BR112019021876B1 - COMPOSITION OF POLYETHYLENE PRODUCT AND FILM LAYER COMPRISING SAID COMPOSITION - Google Patents

Abstract

The present disclosure relates to a polymerization process in three continuous solution reactors. The process solvent, ethylene, optional comonomers, optional hydrogen and a single-site catalyst system are injected into a first and a second reactor configured in parallel with each other. A third reactor receives effluent from the first reactor, the second reactor, or a combination of the first and second reactors. Fresh monomer is charged to the third reactor for further polymerization and to provide a final polyethylene product.

Description

FIELD OF TECHNIQUE

[001] The present invention discloses a polymerization process that uses at least three reactors, where two of these reactors are configured in parallel. Ethylene monomer is charged to each of the three reactors. Using this process, new multimodal polyethylene compositions are obtained while improvements in process efficiency are achieved.

FUNDAMENTALS OF THE TECHNIQUE

[002] Solution polymerization processes are generally carried out at temperatures higher than the melting point of the ethylene homopolymer or copolymer product being produced. In a typical solution polymerization process, catalyst components, solvents, monomers, and hydrogens are charged under pressure to one or more reactors.

[003] For ethylene polymerization or ethylene copolymerization, reactor temperatures can range from about 80 °C to about 300 °C while pressures generally range from about 3 MPag to about 45 MPag. The ethylene homopolymer or copolymer produced remains dissolved in the solvent under reactor conditions. The residence time of the solvent in the reactor is relatively short, for example from about 1 second to about 20 minutes. The solution process can be operated under a wide range of process conditions that allow the production of a wide variety of ethylene polymers. Post-reactor, the polymerization reaction is quenched to prevent further polymerization by adding a catalyst deactivator, and optionally passivated by adding an acid scavenger. Once deactivated (and optionally passivated), the polymer solution is passed to a polymer recovery operation (a devolatilization system) where the ethylene homopolymer or copolymer is separated from the process solvent, unreacted residual ethylene, and α-olefin. unreacted optional(s).

[004] The U.S. Patent 5,236,998 describes the use of a solution polymerization process in three reactors. Two reactors are configured in parallel and their product streams are combined en route to a third reactor. The polymerization process is catalyzed by a Ziegler-Natta catalyst and allows the formation of polyethylene products comprising three components, one from each reactor. However, the disclosure fails to disclose or contemplate advantages that can be achieved by charging fresh monomer (and optionally fresh catalyst) to the third reactor. That is the matter of the present revelation.

SUMMARY OF THE INVENTION

[005] The present disclosure provides a continuous solution polymerization process that improves energy efficiency by reducing the amount of energy consumed. The present disclosure also provides polyethylene product compositions made using a continuous solution polymerization process and films made therefrom.

[006] One embodiment of the disclosure consists of a continuous solution polymerization process comprising: injecting ethylene, a process solvent, a first catalyst system, optionally one or more α-olefins, and optionally hydrogen into each of a first reactor and a second reactor configured in parallel with each other to produce a first output stream containing a first polyethylene made in the first reactor and a second output stream containing a second polyethylene made in the second reactor; passing the first output stream and the second output stream into a third reactor and injecting into the third reactor, ethylene, and optionally each of: a process solvent, one or more α-olefins, hydrogen, and a second catalyst, to produce a third output stream containing a final polyethylene product; passing the third output stream to a devolatilization system to recover the final polyethylene product; wherein the first reactor is operated at a lower temperature than the second reactor; the first catalyst system is a single-site catalyst system; and if injected into the third reactor, the second catalyst system is a single-site catalyst system or a Ziegler-Natta catalyst system.

[007] One embodiment of the disclosure consists of a continuous solution polymerization process comprising: injecting ethylene, a process solvent, a first catalyst system, optionally one or more α-olefins, and optionally hydrogen into each of a first reactor and a second reactor configured in parallel with each other to produce a first output stream containing a first polyethylene made in the first reactor and a second output stream containing a second polyethylene made in the second reactor; passing the first output stream into a third reactor and injecting into the third reactor ethylene and, optionally, each of: a process solvent, one or more α-olefins, hydrogen, and a second catalyst system, to produce a third outflow; combining the second output stream with the third output stream to produce a final product stream containing a final polyethylene product; passing the final product stream to a devolatilization system to recover the final polyethylene product; wherein the first reactor is operated at a lower temperature than the second reactor; the first catalyst system is a single-site catalyst system; and if injected into the third reactor, the second catalyst system is a single-site catalyst system or a Ziegler-Natta catalyst system.

[008] One embodiment of the disclosure consists of a continuous solution polymerization process comprising: injecting ethylene, a process solvent, a first catalyst system, optionally one or more α-olefins, and optionally hydrogen into each of a first reactor and a second reactor configured in parallel with each other to produce a first output stream containing a first polyethylene made in the first reactor and a second output stream containing a second polyethylene made in the second reactor; passing the second output stream into a third reactor and injecting into the third reactor, ethylene, and optionally each of: a process solvent, one or more α-olefins, hydrogen, and a second catalyst system, to produce a third stream about to leave; combining the first output stream with the third output stream to produce a final product stream containing a final polyethylene product; passing the final product stream to a devolatilization system to recover the final polyethylene product; wherein the first reactor is operated at a lower temperature than the second reactor; the first catalyst system is a single-site catalyst system; and if injected into the third reactor, the second catalyst system is a single-site catalyst system or a Ziegler-Natta catalyst system.

em que LA é selecionado a partir do grupo que consiste em ciclopentadienil não substituído, ciclopentadienil substituído, indenil não substituído, indenil substituído, fluorenil não substituído e fluorenil substituído; M é um metal selecionado a partir de titânio, háfnio e zircônio; Pl é um ligante de fosfinimina; e Q é independentemente selecionado a partir do grupo que consiste em um átomo de hidrogênio, um átomo de halogênio, um radical de hidrocarbila C1-10, um radical de alcóxi C1-10 e um radical de óxido de arila C5-10; em que cada um dentre os radicais óxidos de hidrocarbila, alcóxi e arila pode ser não substituído ou adicionalmente substituído por um átomo de halogênio, um radical de alquila C1-18, um radical de alcóxi C1-8, um radical de arila ou arilóxi C6-10, um radical de amido que é não substituído ou substituído por até dois radicais de alquila C1-8 ou um radical fosfido que é não substituído ou substituído por até dois radicais de alquila C1-8; em que a é 1; b é 1; n é 1 ou 2; e (a+b+n) é equivalente à valência do metal M; b) um co-catalisador de alquil aluminoxano; c) um ativador iônico, e; d) opcionalmente, um fenol reticulado.[009] In one embodiment of the disclosure, a first catalyst system is a single-site catalyst system comprising: a) a phosphinine complex defined by the formula

wherein LA is selected from the group consisting of unsubstituted cyclopentadienyl, substituted cyclopentadienyl, unsubstituted indenyl, substituted indenyl, unsubstituted fluorenyl and substituted fluorenyl; M is a metal selected from titanium, hafnium and zirconium; Pl is a phosphinine ligand; and Q is independently selected from the group consisting of a hydrogen atom, a halogen atom, a C1-10 hydrocarbyl radical, a C1-10 alkoxy radical and a C5-10 aryl oxide radical; wherein each of the hydrocarbyl, alkoxy and aryl oxide radicals may be unsubstituted or additionally substituted by a halogen atom, a C1-18 alkyl radical, a C1-8 alkoxy radical, an aryl or C6 aryloxy radical -10, an amido radical which is unsubstituted or substituted by up to two C1-8 alkyl radicals or a phosphide radical which is unsubstituted or substituted by up to two C1-8 alkyl radicals; where a is 1; b is 1; n is 1 or 2; and (a+b+n) is equivalent to the valence of metal M; b) an alkyl aluminoxane co-catalyst; c) an ionic activator, and; d) optionally a cross-linked phenol.

[010] In one embodiment of the disclosure, an alkyl aluminoxane co-catalyst is methylaluminoxane (MAO).

[011] In one embodiment of the disclosure, an ionic activator is trityl tetracis (pentafluoro-phenyl) borate.

[012] In one embodiment of the disclosure, at least 10 percent by weight of the total ethylene injected into reactor 1, reactor 2 and reactor 3 are injected into reactor 3.

[013] In one embodiment of the disclosure, at least 20 percent by weight of the total ethylene injected into reactor 1, reactor 2 and reactor 3 are injected into reactor 3.

[014] In one embodiment of the disclosure, at least 30 percent by weight of the total ethylene injected into reactor 1, reactor 2 and reactor 3 are injected into reactor 3.

[015] In one embodiment of the disclosure, a first, second and third reactor operate at a temperature of about 80 °C to about 300 °C and a pressure of about 3 MPag to about 45 MPag.

[016] In one embodiment of the disclosure, a first reactor operates at a temperature at least 25 °C lower than the temperature at which a second reactor operates.

[017] In one embodiment of the disclosure, a first reactor operates at a temperature at least 45 °C lower than the temperature at which a second reactor operates.

[018] In one embodiment of the disclosure, a first reactor operates at a temperature of about 10 °C to about 100 °C lower than the temperature at which a second reactor operates.

[019] In a development mode, one or more α-olefins are exclusively loaded to the first reactor.

[020] In a development mode, a second catalyst is loaded to the third reactor.

[021] In one embodiment of the development, a first reactor and a second reactor are continuously stirred tank reactors.

[022] In one embodiment of the disclosure, a first reactor and a second reactor are loop reactors.

[023] In one embodiment of the disclosure, a first reactor and a second reactor are independently a continuously stirred tank reactor or a loop reactor.

[024] In one embodiment of the development, a third reactor is a tubular reactor.

em que LA é selecionado a partir do grupo que consiste em ciclopentadienil não substituído, ciclopentadienil substituído, indenil não substituído, indenil substituído, fluorenil não substituído e fluorenil substituído; M é um metal selecionado a partir de titânio, háfnio e zircônio; Pl é um ligante de fosfinimina; e Q é independentemente selecionado a partir do grupo que consiste em um átomo de hidrogênio, um átomo de halogênio, um radical de hidrocarbila C1-10, um radical de alcóxi C1-10 e um radical de óxido de arila C5-10; em que cada um dentre os radicais óxidos de hidrocarbila, alcóxi e arila pode ser não substituído ou adicionalmente substituído por um átomo de halogênio, um radical de alquila C1-18, um radical de alcóxi C1-8, um radical de arila ou arilóxi C6-10, um radical de amido que é não substituído ou substituído por até dois radicais de alquila C1-8 ou um radical fosfido que é não substituído ou substituído por até dois radicais de alquila C1-8; em que a é 1; b é 1; n é 1 ou 2; e (a+b+n) é equivalente à valência do metal M; f) um co-catalisador de alquil aluminoxano; g) um ativador iônico, e; h) opcionalmente, um fenol reticulado.[025] In one embodiment of the disclosure, a second catalyst system is a single-site catalyst system comprising: e) a phosphinine complex defined by the formula

wherein LA is selected from the group consisting of unsubstituted cyclopentadienyl, substituted cyclopentadienyl, unsubstituted indenyl, substituted indenyl, unsubstituted fluorenyl and substituted fluorenyl; M is a metal selected from titanium, hafnium and zirconium; Pl is a phosphinine ligand; and Q is independently selected from the group consisting of a hydrogen atom, a halogen atom, a C1-10 hydrocarbyl radical, a C1-10 alkoxy radical and a C5-10 aryl oxide radical; wherein each of the hydrocarbyl, alkoxy and aryl oxide radicals may be unsubstituted or additionally substituted by a halogen atom, a C1-18 alkyl radical, a C1-8 alkoxy radical, an aryl or C6 aryloxy radical -10, an amido radical which is unsubstituted or substituted by up to two C1-8 alkyl radicals or a phosphide radical which is unsubstituted or substituted by up to two C1-8 alkyl radicals; where a is 1; b is 1; n is 1 or 2; and (a+b+n) is equivalent to the valence of metal M; f) an alkyl aluminoxane co-catalyst; g) an ionic activator, and; h) optionally, a cross-linked phenol.

[026] In one embodiment of the disclosure, a second catalyst system is a Ziegler-Natta catalyst system.

[027] In one embodiment of the disclosure, a process solvent consists of one or more C5 to C12 alkanes.

[028] In one embodiment of the disclosure, one or more α-olefins are selected from α-olefins C3 to C10.

[029] In one embodiment of the disclosure, one or more α-olefins are selected from 1-hexene or 1-octene or a mixture of 1-hexene and 1-octene.

[030] In a development embodiment, a first output stream and a second output stream are combined upstream of a third reactor.

[031] An embodiment of the disclosure consists of a polyethylene product composition comprising: from 35 to 75%, by weight, of a first polyethylene that is an ethylene copolymer having a density of 0.875 to 0.916 g/cm3, an index melting I2 from 0.1 to 5 dg/min, and a molecular weight distribution Mw/Mn from 1.6 to 2.4; from 10 to 40% by weight of a second polyethylene selected from an ethylene copolymer or an ethylene homopolymer having a density of 0.945 to 0.975 g/cm3, a melt index I2 of 1.0 to 20 dg/ min, and an Mw/Mn molecular weight distribution of 1.6 to 2.4; and from 10 to 40% by weight of a third polyethylene which is an ethylene copolymer having a density of 0.880 to 0.936 g/cm3, an I2 melt index of 0.1 to 100 dg/min, and a distribution of molecular weight Mw/Mn that is greater than the molecular weight distribution Mw/Mn of any of the first or second ethylene polymer components; wherein the polyethylene product composition has a density of < 0.939 g/cm3, an I2 melt index of 0.1 to 10 dg/min, a unimodal profile on a gel permeation chromatography (GPC) and a multimodal profile in a TREF analysis.

[032] A development modality consists of a layer of film that has a dart impact strength of > 600 g/mil, a 1% MD secant modulus of > 170 MPa, a slow puncture value of > 65 J/ mm, a machine direction (MD) tear of > 250 g/mil, and a seal initiation temperature (SIT) of < 105 °C.

BRIEF DESCRIPTION OF THE DRAWINGS

[033] Figures 1 to 3 are presented for the purpose of illustrating selected embodiments of this disclosure; it being understood that the embodiments in this disclosure are not limited to the precise arrangement of, or number of, containers shown.

[034] Figure 1 illustrates a continuous solution polymerization process where a first and second polymerization reactors are configured in parallel with each other and are located upstream of a third reactor that receives a combined effluent from the first and second reactors.

[035] Figure 2 illustrates a continuous solution polymerization process where a first and second polymerization reactors are configured in parallel with each other and a third reactor receives effluent from the first reactor.

[036] Figure 3 illustrates a continuous solution polymerization process where a first and second polymerization reactors are configured in parallel and a third reactor receives effluent from the second reactor.

[037] Figure 4A shows the gel permeation chromatographies with Fourier transform infrared detection (GPC-FTIR) obtained for the polyethylene product compositions made in accordance with the present disclosure. The comonomer content, shown as the number of short-chain branches per 1000 carbons (y-axis), is given relative to the molecular weight of the copolymer (x-axis). The upward sloping line (left to right) is the short-chain branching (in short-chain branches per 1000 carbon atoms) determined by FTIR. As can be seen from the Figure, the number of short chain branches increases at higher molecular weights, and therefore comonomer incorporation is said to be "reverse" or "partially reversed" with a peak or maximum present for the Inventive Examples 2, 4 and 5.

[038] Figure 4B shows the gel permeation chromatographies with Fourier transform infrared detection (GPC-FTIR) obtained for comparative polyethylene product compositions.

[039] Figure 5A shows the temperature rise elution fractionation (TREF) analysis and profile of polyethylene product compositions made in accordance with the present disclosure.

[040] Figure 5B shows the temperature rise elution fractionation analysis (TREF) and profile of comparative polyethylene product compositions.

[041] Figure 6A shows the differential scanning calorimetry (DSC) analysis and profile of polyethylene product compositions made in accordance with the present disclosure.

[042] Figure 6B shows the differential scanning calorimetry (DSC) analysis and profile of comparative polyethylene product compositions.

[043] Figure 7A shows the hot melt profiles for films made using the polyethylene product compositions made in accordance with the present invention.

[044] Figure 7B shows the hot melt profiles for films made using comparative polyethylene product compositions.

[045] Figure 8A shows the cold seal profiles for films made using the polyethylene product compositions made in accordance with the present invention.

[046] Figure 8B shows the cold seal profiles for films made using comparative polyethylene product compositions.

Definition of Terms

[047] Unlike the examples or where indicated otherwise, all numbers or expressions referring to amounts of ingredients, extrusion conditions, etc., used in this descriptive report and in the claims shall be understood as modified in all cases by the term "about in." Correspondingly, except where indicated otherwise, the numerical parameters presented in the following specification and in the appended claims are approximations that may vary depending on the desired properties that the various embodiments wish to obtain. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should at least be constructed in view of the reported number of significant digits and applying ordinary rounding techniques. Numeric values presented in specific examples are reported as accurately as possible. Any numerical values, however, inherently contain certain errors that necessarily result from the deviation found in their respective test measurements.

[048] It should be understood that any numerical range quoted in this document is intended to include all subranges integrated therein. For example, a range of “1 to 10” is intended to include all subranges between and including the minimum quoted value of 1 and the maximum quoted value of 10; that is, having a minimum value equal to or greater than 1 and a maximum value equal to or less than 10. Because the revealed numerical ranges are continuous, they include every value between the minimum and maximum values. Except where otherwise noted, the various numerical ranges specified in this order are approximations.

[049] All compositional ranges expressed in this document are limited in total and do not exceed 100 percent (percentage by volume or percent by weight) in practice. Where multiple components may be present in a composition, the sum of the maximum proportions of each component may exceed 100 percent, with the understanding that, and as individuals skilled in the art readily understand, that the proportions of components actually used will conform to the maximum extent. of 100 percent.

[050] In order to form a more complete understanding of this disclosure, the following terms are defined and are to be used with the accompanying figures and with the description of the various embodiments.

[051] According to the use in question, the term "monomer" refers to a small molecule that can chemically react and become chemically bonded to itself or to other monomers to form a polymer.

[052] Depending on the use in question, the term "a-olefin" or "alpha-olefin" is used to describe a monomer having a linear hydrocarbon chain containing from 3 to 20 carbon atoms having a double bond at one end of the chain; an equivalent term is "linear a-olefin".

[053] Depending on the use in question, the term "polyethylene" or "ethylene polymer" refers to macromolecules produced from ethylene monomers and, optionally, one or more additional monomers; regardless of the specific catalyst or specific process used to produce the ethylene polymer. In the polyethylene art, one or more additional monomers are referred to as “comonomer(s)” and generally include α-olefins. The term "homopolymer" refers to a polymer that contains only one type of monomer. An "ethylene homopolymer" is made using only ethylene as a polymerizable monomer. The term "copolymer" refers to a polymer that contains two or more types of monomer. An "ethylene copolymer" is made using ethylene and one or more other types of polymerizable monomer. Common polyethylenes include high density polyethylene (HDPE), medium density polyethylene (MDPE), linear low density polyethylene (LLDPE), very low density polyethylene (VLDPE), ultra-low density polyethylene (ULDPE), plastomer and elastomers . The term polyethylene also includes polyethylene terpolymers which may include two or more comonomers in addition to ethylene. The term polyethylene also includes combinations, or blends, of the previously described polyethylenes.

[054] The term "heterogeneous polyethylene" refers to a subset of polymers in the ethylene polymer group that are produced using a heterogeneous catalyst system; non-limiting examples include Ziegler-Natta or chromium catalysts, both of which are well known in the art.

[055] The term "homogeneous polyethylene" refers to a subset of polymers in the ethylene polymer group that are produced using single-site catalysts; Non-limiting examples of these include metallocene catalysts, phosphinine catalysts, and constrained geometry catalysts, all of which are well known in the art.

[056] Typically, homogeneous polyethylenes have narrow molecular weight distributions, for example, gel permeation chromatography (GPC) Mw/Mn values less than 2.8, although exceptions may arise; Mw and Mn refer to weight and number average molecular weights, respectively. In contrast, Mw/Mn of heterogeneous ethylene polymers are typically larger than Mw/Mn of homogeneous ethylene polymers. In general, homogeneous ethylene polymers also have a narrow comonomer distribution, that is, each macromolecule within the molecular weight distribution has a similar comonomer content. Often, the composition distribution breadth index “CDBI” is used to quantify how the comonomer is distributed within an ethylene polymer, as well as to differentiate ethylene polymers produced with different catalysts or processes. "CDBI50" is defined as the percentage of ethylene polymer whose composition is within 50 percent by weight (% by weight) of the median comonomer composition; this definition is consistent with what is described in WO 93/03093 assigned to Exxon Chemical Patents Inc. The CDBI50 of an ethylene interpolymer can be calculated from TREF (Temperature Elevation Elution Fractionation) curves; the TREF method is described in Wild, et al., J. Polym. Sci., Part B, Polym. Phys., Vol. 20(3), pages 441455. Typically, the CDBI50 of homogeneous ethylene polymers is greater than about 70%. In contrast, the CDBI50 of heterogeneous ethylene polymers containing α-olefin is generally lower than the CDBI50 of homogeneous ethylene polymers.

[057] It is well known to individuals skilled in the art that homogeneous ethylene polymers are often further subdivided into "linear homogeneous ethylene polymers" and "substantially linear homogeneous ethylene polymers". These two subgroups differ in the proportion of long-chain branching: more specifically, homogeneous linear ethylene polymers have less than about 0.01 long-chain branching per 1000 carbon atoms; while substantially linear ethylene polymers have more than about 0.01 to about 3.0 long chain branches per 1000 carbon atoms. A long-chain branch is macromolecular in nature, that is, similar in length to the macromolecule to which the long-chain branch is attached. Hereinafter, in this disclosure, the term "homogeneous polyethylene" refers to linear homogeneous ethylene polymers and substantially linear homogeneous ethylene polymers.

[058] The term “thermoplastic” refers to a polymer that becomes liquid when heated, will flow under pressure and solidify when cooled. Thermoplastic polymers include ethylene polymers as well as other polymers used in the plastics industry; Non-limiting examples of other polymers commonly used in film applications include barrier resins (EVOH), bonding resins, polyethylene terephthalate (PET), polyamides and the like.

[059] According to the use in question, the term "monolayer film" refers to a film containing a single layer of one or more thermoplastics.

[060] According to the use in question, the terms "hydrocarbyl", "hydrocarbyl radical" or "hydrocarbyl group" refer to linear or cyclic, aliphatic, olefinic, acetylenic and aryl (aromatic) radicals that comprise hydrogen and carbon that are deficient on a hydrogen.

[061]According to the use in question, an "alkyl radical" includes linear, branched and cyclic paraffin radicals that are deficient in a hydrogen radical; non-limiting examples include methyl (-CH3) and ethyl (-CH2CH3) radicals. The term "alkenyl radical" refers to linear, branched, and cyclic hydrocarbons containing at least one carbon-carbon double bond that is deficient in a hydrogen radical.

[062]According to the use in question, the term "aryl" group includes phenyl, naphthyl, pyridyl and other radicals whose molecules have an aromatic ring structure; non-limiting examples include naphthylene, phenanthrene and anthracene. An "aryl alkyl" group is an alkyl group having a pendant aryl group; non-limiting examples include benzyl, phenethyl and tolylmethyl; an "alkyl aryl" is an aryl group having one or more pendant alkyl groups; non-limiting examples include tolyl, xylyl, mesityl and cumil.

[063]According to the usage in question, the term “heteroatom” includes any atom other than carbon and hydrogen that can be bonded to carbon. A "heteroatom-containing group" is a hydrocarbon radical that contains a heteroatom and may contain one or more of the same or different heteroatoms. In one embodiment, a heteroatom-containing group is a hydrocarbyl group containing from 1 to 3 atoms selected from the group consisting of boron, aluminum, silicon, germanium, nitrogen, phosphorus, oxygen, and sulfur. Non-limiting examples of heteroatom-containing groups include radicals of imines, amines, oxides, phosphines, ethers, ketones, heterocyclic oxoazolines, oxazolines, thioethers, and the like. The term "heterocyclic" refers to ring systems having a carbon backbone comprising 1 to 3 atoms selected from the group consisting of boron, aluminum, silicon, germanium, nitrogen, phosphorus, oxygen and sulfur.

[064]According to the use in question, the term "unsubstituted" means that hydrogen radicals are attached to the molecular group that follows the unsubstituted term. The term "substituted" means that the group following that term has one or more moieties that have replaced one or more hydrogen radicals at any position within the group; non-limiting examples of moieties include halogen radicals (F, Cl, Br), hydroxyl groups, carbonyl groups, carboxyl groups, amine groups, phosphine groups, alkoxy groups, phenyl groups, naphthyl groups, C1 to C30 alkyl groups, C2 alkyl groups to C30, and combinations thereof. Non-limiting examples of substituted alkyls and aryls include: acyl radicals, alkylamino radicals, alkoxy radicals, aryloxy radicals, alkylthio radicals, dialkylamino radicals, alkoxycarbonyl radicals, aryloxycarbonyl radicals, carbomoyl radicals, alkyl- and dialkylcarbamoyl radicals, acyloxy radicals, acylamino radicals, arylamino radicals and combinations thereof.

[065] In this document, the term "R1" refers to a first reactor in a continuous solution polymerization process; it being understood that R1 is distinctly different from the symbol R1; the latter being used in chemical formula, for example, representing a hydrocarbyl group. Similarly, the term "R2" refers to a second reactor, and; the term “R3” refers to a third reactor.

[066] According to the use in question, the term "oligomers" refers to a low molecular weight ethylene polymer, for example, an ethylene polymer with a weight average molecular weight (Mw) of about 2000 to 3000 daltons. Other commonly used terms for oligomers include "wax" or "grease". As used in this usage, the term "light-end impurities" refers to chemical compounds with relatively low boiling points that may be present in the various vessels and process streams within a continuous solution polymerization process; non-limiting examples include methane, ethane, propane, butane, nitrogen, CO2, chloroethane, HCl, etc.

DESCRIPTION OF MODALITIES

[067] Catalyst systems that are efficient in polymerizing olefins are well known in the art. In the embodiments disclosed herein, at least one catalyst system is employed in a continuous solution polymerization process.

[068] In the embodiment of the disclosure, a first catalyst system is a single-site catalyst system and comprises at least one single-site catalyst that produces a homogeneous ethylene polymer.

[069] The catalyst components that make up the single-site catalyst system are not particularly limited, that is, a wide variety of catalyst components can be used.

[070] In a non-limiting embodiment of the disclosure, a single-site catalyst system comprises the following three or four components: a phosphinine metal complex; an alkyl aluminoxane co-catalyst; an ionic activator and, optionally, a cross-linked phenol.

[071] In one embodiment of the disclosure, and as shown in Table 1, the term "component (a)" refers to a phosphinine metal complex, the term "component (b)" refers to a co-catalyst of alkyl aluminoxane, the term "component (c)" refers to an ionic activator, and; the term "component (d)" refers to an optional cross-linked phenol.

em que (LA) representa um ligante tipo ciclopentadienil; M representa um átomo de metal; PI representa um ligante de fosfinimina; Q representa um ligante ativável; a é 0 ou 1; b é 1 ou 2; (a+b) = 2; n é 1 ou 2, e; a soma de (a+b+n) se iguala à valência do metal M.[072] In one embodiment of the disclosure, non-limiting examples of component (a) are represented by the formula:

wherein (LA) represents a cyclopentadienyl-type linker; M represents a metal atom; PI represents a phosphinine ligand; Q represents an activatable linker; a is 0 or 1; b is 1 or 2; (a+b) = 2; n is 1 or 2, and; the sum of (a+b+n) equals the valence of metal M.

[073]According to the use in question, the term “cyclopentadienyl-type” ligand means to include ligands that contain at least one five-carbon ring that is attached to the metal through an eta-5 (or in some cases eta-3) bond. Thus, the term "cyclopentadienyl-type" includes, for example, unsubstituted cyclopentadienyl, single or multiple substituted cyclopentadienyl, unsubstituted indenyl, single or multiple substituted indenyl, unsubstituted fluorenyl and single or multiple substituted fluorenyl. Hydrogenated versions of indenyl and fluorenyl linkers are also contemplated for use in the present disclosure, provided that the five-carbon ring that attaches to the metal via an eta-5 (or in some cases eta-3) bond remains intact. Substituents for a cyclopentadienyl linker, an indenyl linker (or a hydrogenated version thereof) and a fluorenyl linker (or a hydrogenated version thereof) may be selected from the group consisting of a C1-30 hydrocarbyl radical ( which hydrocarbyl radical may be unsubstituted or additionally substituted by, for example, a halide and/or a hydrocarbyl group, for example a suitable substituted C1-30 hydrocarbyl radical is a pentafluorobenzyl group such as -CH2C6F5); a halogen atom; a C1-6 alkoxy radical; a C6-10 aryl or aryloxy radical (each of which may be further substituted by, for example, a halide and/or a hydrocarbyl group); an amido radical which is unsubstituted or substituted by up to two C1-8 alkyl radicals; a phosphido radical that is unsubstituted or substituted by up to two C1-8 alkyl radicals; a silyl radical of the formula -Si(R')3 wherein each R' is independently selected from the group consisting of hydrogen, a C1-8 alkyl or alkoxy radical, aryl or C610 aryloxy radicals; and a germanyl radical of the formula -Ge(R')3 where R' is as defined directly above.

[074] Non-limiting examples of metal M in the phosphinine metal complex include Group 4 metals, titanium, zirconium, and hafnium.

em que os grupos Rp são independentemente selecionados a partir de: um átomo de hidrogênio; um átomo de halogênio; radicais hidrocarbil C1-20 que são não substituídos ou substituídos por um ou mais átomos de halogênio; um radical alcóxi C1-8; um radical aril C6-10; um radical arilóxi C6-10; um radical amido; um radical silil de fórmula -Si(Rs)3, em que os grupos Rs são independentemente selecionados a partir de um átomo de hidrogênio, um radical alquil ou alcóxi C1-8, um radical aril C6-10, um radical arilóxi C6-10, ou um radical germanil de fórmula -Ge(RG)3, em que os grupos RG são definidos conforme Rs é definido nesse parágrafo.[075] The phosphinine ligand, PI, is defined by the formula:

wherein the Rp groups are independently selected from: a hydrogen atom; a halogen atom; C1-20 hydrocarbyl radicals which are unsubstituted or substituted by one or more halogen atoms; a C1-8 alkoxy radical; a C6-10 aryl radical; a C6-10 aryloxy radical; an amido radical; a silyl radical of the formula -Si(Rs)3, in which the Rs groups are independently selected from a hydrogen atom, a C1-8 alkyl or alkoxy radical, a C6-10 aryl radical, a C6-10 aryloxy radical , or a Germanyl radical of the formula -Ge(RG)3, where the RG groups are defined as Rs is defined in this paragraph.

[076] In the present disclosure, the term "activatable" means that the Q ligand can be cleaved from the M metal center through a protonolysis reaction or extracted from the M metal center by acidic or electrophilic catalyst activating compounds (also known as "co-catalyst" compounds) respectively, examples of which will be described below. The activatable ligand Q can also be transformed into another ligand that is cleaved or extracted from the metal center M (for example, a halide can be converted to an alkyl group). Without wishing to be bound by any theory, protonolysis or extraction reactions generate an active “cationic” metal center that polymerizes olefins.

[077] In the embodiments of the present disclosure, the activatable Q ligand is independently selected from the group consisting of a hydrogen atom; a halogen atom, a C1-10 hydrocarbyl radical; a C110 alkoxy radical; and a C6-10 aryl or aryloxy radical, where each of the hydrocarbyl, alkoxy, aryl or aryl oxide radicals may be unsubstituted or additionally substituted by one or more halogen groups or other groups; a C1-8 alkyl; a C1-8 alkoxy; a C6-10 aryl or aryloxy; an amide or a phosphide radical, but where Q is not a cyclopentadienyl. Two Q linkers can also be joined together to form, for example, a substituted or unsubstituted diene (i.e. 1,3-butadiene) linker; or a delocalized heteroatom-containing group such as an acetate or acetamidinate group. In a convenient embodiment of the disclosure, each X is independently selected from the group consisting of a halide atom, a C1-4 alkyl radical and a benzyl radical.

[078] Particularly suitable activatable linkers are monoanionic such as a halide (eg chloride) or a hydrocarbyl (eg methyl, benzyl).

onde os grupos R podem ser radicais de hidrocarbil lineares, ramificados ou cíclicos iguais ou diferentes contendo 1 a 20 átomos de carbono e n é de 0 a cerca de 50. Um exemplo não limitante de um alquilaluminoxano é metilaluminoxano (ou MAO) em que cada grupo R é um radical metila.[079] In one embodiment of the disclosure, the single-site catalyst component (b) is an alkyl aluminoxane co-catalyst. Although the exact structure of this co-catalyst is uncertain, experts in the art generally agree that an oligomeric species contains repeating units of the general formula:

where the R groups can be the same or different linear, branched or cyclic hydrocarbyl radicals containing 1 to 20 carbon atoms and n is from 0 to about 50. A non-limiting example of an alkylaluminoxane is methylaluminoxane (or MAO) in which each group R is a methyl radical.

[080] In one embodiment of the disclosure, Rdo alkylaluminoxane is a methyl radical and m is from 10 to 40.

[081] In one embodiment of the disclosure, the catalyst activator is modified methylaluminoxane (MMAO).

[082] It is well known in the art that alkylaluminoxane can serve dual roles as an alkylator and an activator. Therefore, an alkylaluminoxane activator is generally used in combination with activatable ligands such as halogens.

onde B representa um átomo de boro, R5 é um hidrocarbil aromático (por exemplo, cátion de trifenil metil) e cada R7 é independentemente selecionado a partir de radicais fenila que são não substituídos ou substituídos por 3 a 5 substituintes selecionados a partir de átomos de flúor, radicais alquil ou alcóxi C1-4 que são não substituídos ou substituídos por átomos de flúor; e um radical silil de fórmula -Si(R9)3, onde cada R9 é independentemente selecionado a partir de átomos de hidrogênio e radicais alquila C1-4, e

onde B é um átomo de boro, H é um átomo de hidrogênio, Z é um átomo de nitrogênio ou fósforo, t é 2 ou 3 e R8 é selecionado a partir de radicais alquila C1-8, radicais fenila que são não substituídos ou substituídos por até três radicais alquila C14, ou um R8 tomado juntamente com o átomo de nitrogênio podem formar um radical de anilínio e R7 é conforme definido acima.[083] In one embodiment of the disclosure, component (c) of the single-site catalyst system is an ionic activator. In general, ionic activators are composed of a cation and a bulky anion; where the latter is substantially non-coordinating. Non-limiting examples of ionic activators are boron ionic activators which have four coordinates with four ligands attached to the boron atom. Non-limiting examples of ionic boron activators include the following formulas shown below;

where B represents a boron atom, R5 is an aromatic hydrocarbyl (e.g., triphenyl methyl cation) and each R7 is independently selected from phenyl radicals that are unsubstituted or substituted by 3 to 5 substituents selected from carbon atoms. fluorine, C1-4 alkyl or alkoxy radicals which are unsubstituted or substituted by fluorine atoms; and a silyl radical of the formula -Si(R9)3, where each R9 is independently selected from hydrogen atoms and C1-4 alkyl radicals, and

where B is a boron atom, H is a hydrogen atom, Z is a nitrogen or phosphorus atom, t is 2 or 3, and R8 is selected from C1-8 alkyl radicals, phenyl radicals that are unsubstituted or substituted by up to three C14 alkyl radicals, or an R8 taken together with the nitrogen atom can form an anilinium radical and R7 is as defined above.

[084] In both formulas, a non-limiting example of R7 is a pentafluorophenyl radical. In general, ionic boron activators can be described as tetra(perfluorophenyl) boron salts; Non-limiting examples include anilinium, carbonium, oxonium, phosphonium and sulphonium salts of tetra(perfluorophenyl)boron with anilinium and trityl (or triphenylmethyl). Additional non-limiting examples of ionic activators include: triethiammonium tetra(phenyl)boron, tripropiammonium tetra(phenyl)boron, tri(n-butyl)ammonium tetra(phenyl)boron, trimethylammonium tetra(p-tolyl)boron, trimethylammonium tetra(o- tolyl)boron, tributiammonium tetra(pentafluorophenyl)boron, tripropiammonium tetra(o,p-dimethylphenyl)boron, tributiammonium tetra(m,m-dimethylphenyl)boron, tributiammonium tetra(p-trifluoromethylphenyl)boron, tributiammonium tetra(pentafluorophenyl)boron, tri (n-butyl)ammonium tetra(o-tolyl)boron, N,N-dimethylanilinium tetra(phenyl)boron, N,N-diethylanilinium tetra(phenyl)boron, N,N-diethylanilinium tetra(phenyl)n-butylboron, N ,N-2,4,6-pentamethylanilinium tetra(phenyl)boron, di-(isopropyl)ammonium tetra(pentafluorophenyl)boron, dicyclohexamonium tetra(phenyl)boron, triphenylphosphonium tetra(phenyl)boron, tri(methylphenyl)phosphonium tetra(phenyl) )boron, tri(dimethylphenyl)phosphonium tetra(phenyl)boron, tropylium tetracispentafluorophenyl borate, triphenylmethyltetracispentafluorophenyl borate, benzene(diazonium)tetracispentafluorophenyl borate, tropylium tetracis(2,3,5,6-tetrafluorophenyl)borate, triphenylmethyltetracis(2,3) ,5,6-tetrafluorophenyl)borate, benzene(diazonium) tetracis(3,4,5-trifluorophenyl)borate, tropylium tetracis(3,4,5-trifluorophenyl)borate, benzene(diazonium)tetracis(3,4,5- trifluorophenyl)borate, tropylium tetracis(1,2,2-trifluoroethenyl)borate, triphenylmethyl tetracis(1,2,2-trifluoroethenyl)borate, benzene(diazonium) tetracis(1,2,2-trifluoroethenyl)borate, tropylium tetracis(2) ,3,4,5-tetrafluorophenyl)borate, triphenylmethyl tetracis(2,3,4,5-tetrafluorophenyl)borate, and benzene(diazonium) tetracis(2,3,4,5-tetrafluorophenyl)borate. Commercially available ionic activators include N,N-dimethylanilinium tetracispentafluorophenyl borate, and triphenylmethyl tetracispentafluorophenyl borate.

[085] The fourth optional catalyst component of the single-site catalyst system is a cross-linked phenol, component (d). Non-limiting examples of cross-linked phenols include butylated phenolic antioxidants, butylated hydroxytoluene, 2,6-di-tertiary butyl-4-ethyl phenol, 4,4'-methylenebis(2,6-di-tertiary-butylphenol), 1,3, 5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl) benzene and octadecyl-3-(3',5'-di-tert-butyl-4'-hydroxyphenyl) propionate.

[086] To produce an active single-site catalyst system, the quality and molar ratios of the three or four components, (a) to (d) are optimized as described below.

[087] In one embodiment of the disclosure, a second catalyst system is a single-site catalyst system as described above or a Ziegler-Natta catalyst as described below.

[088] Ziegler-Natta catalyst systems are well known to those skilled in the art.

[089] In this disclosure, a second catalyst system may be an in-line Ziegler-Natta catalyst system or a branched Ziegler-Natta catalyst system. The term "in-line Ziegler-Natta catalyst system" refers to continuously synthesizing a small amount of an active Ziegler-Natta catalyst system and immediately injecting that catalyst into at least one reactor in continuous operation, in which the catalyst polymerizes ethylene and one or more optional α-olefins to form an ethylene polymer. The terms "batch Ziegler-Natta catalyst system" or "batch Ziegler-Natta pro-catalyst" refer to the synthesis of a much larger amount of catalyst or pro-catalyst in one or more mixing vessels that are external , or isolated, to the polymerization process in solution in continuous operation. Once prepared, the bulk Ziegler-Natta catalyst system, or bulk Ziegler-Natta pro-catalyst, is transferred to a catalyst storage tank. The term "procatalyst" refers to an inactive catalyst system (inactive with respect to ethylene polymerization); the procatalyst is converted into an active catalyst by adding an aluminum alkyl cocatalyst. As needed, the procatalyst is pumped from the storage tank to at least one reactor in continuous operation, where an active catalyst polymerizes ethylene and one or more optional α-olefins to form a polyethylene. The pro-catalyst can be converted into an active catalyst in the reactor or external to the reactor, or en route to the reactor.

[090] A wide variety of compounds can be used to synthesize an active Ziegler-Natta catalyst system. The following describes several compounds that can be combined to produce an active Ziegler-Natta catalyst system. Those skilled in the art will understand that the embodiments of this disclosure are not limited to the specific compounds disclosed.

[091] An active Ziegler-Natta catalyst system can be formed from: a magnesium compound, a chloride compound, a metal compound, an aluminum alkyl co-catalyst and an aluminum alkyl. As will be appreciated by those skilled in the art, Ziegler-Natta catalyst systems can contain additional components; a non-limiting example of an additional component is an electron donor, for example amines or ethers.

em que os grupos R4 podem ser grupos hidrocarbil iguais ou diferentes tendo de 1 a 10 átomos de carbono; os grupos OR9 podem ser grupos alcóxi ou arilóxi iguais ou diferentes em que R9 é um grupo hidrocarbil tendo de 1 a 10 átomos de carbono ligados a oxigênio; X é cloreto ou brometo, e; (p+q+r) = 3, desde que p seja maior que 0. Exemplos não limitantes de co-catalisadores de alquil alumínio comumente usados incluem trimetil alumínio, trietil alumínio, tributil alumínio, metóxido de dimetil alumínio, etóxido de dietil alumínio, butóxido de dibutil alumínio, cloreto ou brometo de dimetil alumínio, cloreto ou brometo de dietil alumínio, cloreto ou brometo de dibutil alumínio e dicloreto ou dibrometo de etil alumínio.[092] A non-limiting example of an active in-line (or batch) Ziegler-Natta catalyst system can be prepared as follows. In the first step, a solution of a magnesium compound (component (e)) is reacted with a solution of a chloride compound (component (f)) to form a magnesium chloride support suspended in solution. Non-limiting examples of magnesium compounds include Mg(R1)2; wherein the R1 groups may be the same or different linear, branched or cyclic hydrocarbyl radicals containing 1 to 10 carbon atoms. Non-limiting examples of chloride compounds include R2Cl; and that R2 represents a hydrogen atom, or a linear, branched or cyclic hydrocarbyl radical containing 1 to 10 carbon atoms. In the first step, the magnesium compound solution may also contain an aluminum alkyl (component (g)). Non-limiting examples of aluminum alkyl include Al(R 3 ) 3 , where the R 3 groups may be the same or different linear, branched or cyclic hydrocarbyl radicals containing from 1 to 10 carbon atoms. In the second step, a solution of the metal compound (component (h)) is added to the magnesium chloride solution and the metal compound is supported on the magnesium chloride. Non-limiting examples of suitable metal compounds include M(X)n or MO(X)n; where M represents a metal selected from Group 4 to Group 8 of the Periodic Table, or mixtures of metals selected from Group 4 to Group 8; O represents oxygen, and; X represents chloride or bromide; n is an integer from 3 to 6 that satisfies the oxidation state of the metal. Additional non-limiting examples of suitable metal compounds include Group 4 to Group 8 metal alkyls, metal alkoxides (which can be prepared by reacting a metal alkyl with an alcohol), and mixed binder metal compounds which contain a mixture of binder ligands. halide, alkyl and alkoxide. In the third step, a solution of an aluminum alkyl co-catalyst (component (i)) is added to the magnesium chloride-supported metal compound. A wide variety of aluminum alkyl co-catalysts are suitable, as expressed by the formula:

wherein the R4 groups can be the same or different hydrocarbyl groups having from 1 to 10 carbon atoms; the OR9 groups may be the same or different alkoxy or aryloxy groups wherein R9 is a hydrocarbyl group having from 1 to 10 carbon atoms bonded to oxygen; X is chloride or bromide, and; (p+q+r) = 3, provided that p is greater than 0. Non-limiting examples of commonly used aluminum alkyl cocatalysts include aluminum trimethyl, aluminum triethyl, aluminum tributyl, aluminum dimethyl methoxide, aluminum diethyl ethoxide, dibutyl aluminum butoxide, dimethyl aluminum chloride or bromide, diethyl aluminum chloride or bromide, dibutyl aluminum chloride or bromide and ethyl aluminum dichloride or dibromide.

[093] The process described in the previous paragraph, to synthesize a Ziegler-Natta catalyst system in active line (or batch), can be carried out in a variety of solvents; non-limiting examples of solvents include linear or branched C5 to C12 alkanes or mixtures thereof.

[094] To produce an active Ziegler-Natta catalyst system, the amount and molar ratios of the components, (e) to (i) are optimized as further described below.

[095] Embodiments of the solution polymerization process of the present disclosure are shown in Figures 1 to 3.

[096] Referring to Figures 1, 2 and 3, a process solvent is injected into two parallel reactors, reactor 1 "R1" and reactor 2 "R2" through flows A and B and into the third reactor, reactor 3 " R3” through flow C. Ethylene is injected into reactors 1, 2 and 3 through flows D, E and F respectively. Optional a-olefin is injected into reactors 1, 2 and 3 through streams G, H and I respectively. As shown in Figures 1 through 3, the process solvent, ethylene, and optional α-olefin feed streams are combined to form reactor feed streams J, K, and L that feed reactors 1, 2, and 3, respectively. Optional hydrogen is injected into reactors 1, 2 and 3 through M, N and O streams respectively.

[097] A single-site catalyst system (the first catalyst system) is injected into reactors 1 and 2 through flows P and Q respectively. When an alpha-olefin is injected into reactors 1 and/or 2, a first and/or second ethylene copolymer is produced in reactors 1 and 2, respectively. If an α-olefin is not added, then ethylene homopolymers are formed.

[098] In one embodiment of the development, an a-olefin is injected into reactor 1, but not into reactor 2, so that a first polyethylene made in reactor 1 is an ethylene copolymer and a second polyethylene made in reactor 2 is a ethylene homopolymer.

[099] R and S catalyst streams contain an ionic activator dissolved in a catalyst component solvent. The T and U catalyst streams contain an organometallic complex, such as a phosphinamine complex, dissolved in a catalyst component solvent. Catalyst streams V and W contain an alkyl aluminoxane cocatalyst dissolved in a catalyst component solvent. Optional catalyst streams X and Y contain a cross-linked phenol dissolved in a catalyst component solvent. The catalyst component solvents for the various catalyst components may be the same or different.

[0100] Optionally, a second catalyst system is injected into reactor 3. The second catalyst system can be a single-site catalyst or a Ziegler-Natta catalyst.

[0101] In one embodiment, a single-site catalyst is injected into reactor 3. Therefore, in one embodiment of the disclosure, the Z catalyst stream contains an ionic activator dissolved in a catalyst component solvent; an AA catalyst stream contains an organometallic complex, such as a phosphinamine complex, dissolved in a catalyst component solvent; a BB catalyst stream contains an alkyl aluminoxane co-catalyst dissolved in a catalyst component solvent; and an optional CC catalyst stream contains a cross-linked phenol dissolved in a catalyst component solvent. The catalyst component solvents for the various catalyst components may be the same or different.

[0102] In one embodiment, a Ziegler-Natta catalyst is injected into reactor 3. The Ziegler-Natta catalyst can be prepared in-line as discussed above and charged to reactor 3 (not shown in the Figures), or the Zielger catalyst -Natta can be prepared in batch mode, stored in a holding tank and activated before entering reactor 3, or en route to reactor 3 as discussed above (not shown in Figures).

[0103] In one embodiment of the continuous solution polymerization process shown in Figure 1, reactor 1 produces an output flow 1' and reactor 2 produces an output flow 2'. Output streams 1' and 2' are then combined en route to Reactor 3. A third ethylene copolymer is produced in reactor 3. Reactor 3 produces an output stream 3' containing a final polyethylene product.

[0104] In one embodiment of the continuous solution polymerization process shown in Figure 1, the reactor 3 produces an output stream 3' containing a final polyethylene product. Downstream of reactor 3, a catalyst scavenger is added through catalyst scavenger tank T2 forming a scavenged stream which is then fed through a pressure reducing device 100 to a devolatilization system. The devolatilization system comprises a vapour/liquid ("V/L") separator 103 (or alternatively a liquid/liquid separator, not shown), downstream of a heat exchanger 101 and a second pressure reducing device 102. Two streams are formed in the V/L separator 103 (or, alternatively, a liquid/liquid separator); an underflow 104 containing an ethylene polymer-rich solution and gaseous overhead stream 105. Optionally, the underflow 104 enters a second V/L separator 105 (or, alternatively, a liquid/liquid separator, not shown) and two streams are formed; bottom flow 106 and gaseous suspended flow 107. Optionally, the bottom flow 106 enters a third V/L separator 107 (or, alternatively, a liquid/liquid separator, not shown) and two flows are formed; product flow 108 and suspended gaseous flow 109.

[0105] The product flow 108 proceeds to polymer recovery. Gaseous overhead streams 105, 107 and 109 are sent to a distillation column where the solvent, ethylene and optional α-olefin are separated and recycled to the solution polymerization process.

[0106] Another embodiment of the continuous solution polymerization process is shown in Figure 2. All charge and output flows are marked analogously to that discussed above in relation to Figure 1. In an embodiment of the continuous solution polymerization process shown in Figure 2, reactor 1 produces output stream 1' which flows into reactor 3. Then reactor 3 produces output stream 3'. Reactor 2 produces an output stream 2' which is combined with an output stream 3' to produce a final product stream containing a final polyethylene product. The final product stream is deactivated by adding a catalyst deactivator from the T2 catalyst deactivator tank forming a deactivated stream. The decommissioned flow is then carried through a pressure reducing device 100 to a devolatilization system. The devolatilization system comprises a vapour/liquid ("V/L") separator 103 (or alternatively a liquid/liquid separator, not shown), a downstream heat exchanger 101 and a second pressure reducing device 102 Two streams are formed in the V/L separator 103 (or, alternatively, a liquid/liquid separator); bottom flow 104 containing an ethylene polymer rich solution and gaseous overhead flow 105. Optionally, the bottom flow 104 enters a second V/L separator 105 (or, alternatively, a liquid/liquid separator, not shown) and two streams are formed; bottom flow 106 and gaseous suspended flow 107. Optionally, the bottom flow 106 enters a third V/L separator 107 (or, alternatively, a liquid/liquid separator, not shown) and two flows are formed; product stream 108 and suspended gaseous stream 109. Product stream 108 proceeds to polymer recovery. The suspended gaseous streams 105, 107 and 109 are sent to a distillation column where solvent, ethylene and optional α-olefin are separated and recycled to the solution polymerization process.

[0107] Another embodiment of the continuous solution polymerization process is shown in Figure 3. All charge and output flows are marked analogously to that discussed above in relation to Figure 1. In an embodiment of the continuous solution polymerization process shown in Figure 3, reactor 2 produces an output stream 2' which flows into reactor 3. Then reactor 3 produces an outlet stream 3'. Reactor 1 produces an output stream 1' which is combined with an output stream 3' to produce a final product stream containing a final polyethylene product. The final product stream is deactivated by adding a catalyst deactivator from the T2 catalyst deactivator tank forming a deactivated stream. The decommissioned flow is then carried through a pressure reducing device 100 to a devolatilization system. The devolatilization system comprises a vapour/liquid ("V/L") separator 103 (or alternatively a liquid/liquid separator, not shown), a downstream heat exchanger 101 and a second pressure reducing device 102 Two streams are formed in the V/L separator 103 (or, alternatively, a liquid/liquid separator); bottom flow 104 containing an ethylene polymer rich solution and gaseous overhead flow 105. Optionally, the bottom flow 104 enters a second V/L separator 105 (or, alternatively, a liquid/liquid separator, not shown) and two streams are formed; bottom flow 106 and gaseous suspended flow 107. Optionally, the bottom flow 106 enters and a third V/L separator 107 (or, alternatively, a liquid/liquid separator, not shown) and two flows are formed; product stream 108 and suspended gaseous stream 109. Product stream 108 proceeds to polymer recovery. The suspended gaseous streams 105, 107 and 109 are sent to a distillation column where solvent, ethylene and optional α-olefin are separated and recycled to the solution polymerization process.

[0108] With reference to Figures 1 to 3, the T2 catalyst deactivator tank can contain a liquid catalyst deactivator (100%), a catalyst deactivator solution in a solvent, or a catalyst deactivator slurry in a solvent. Non-limiting examples of suitable solvents include linear or branched C5 to C12 alkanes. In this disclosure, how the catalyst deactivator is added is not particularly important. Once added, the catalyst deactivator substantially disrupts the polymerization reaction by changing the active catalyst species into inactive forms. Suitable deactivators are well known in the art, non-limiting examples include: amines (e.g., U.S. Patent 4,803,259 by Zboril et al.); alkali or alkaline earth metal salts of carboxylic acid (e.g., U.S. Patent 4,105,609 by Machan et al.); water (e.g., U.S. Patent 4,731,438 by Bernier et al.); hydrotalcites, alcohols and carboxylic acids (e.g., U.S. Patent 4,379,882 by Miyata); or a combination thereof (U.S. Patent 6,180,730 by Sibtain et al.).

[0109] In one embodiment of the disclosure, a passivation agent can be added to the final product stream downstream of the heat exchanger 101, but upstream of the pressure reduction device 102 (not shown in Figures 1 to 3). Without wishing to be bound by any theory, pacification helps to reduce chloride levels in the final polyethylene product. The addition of passivators can be particularly useful when a Ziegler-Natta catalyst system is charged to reactor 3. The passivator can be added in a solvent, or as a slurry of passivator in a solvent. Non-limiting examples of suitable solvents include linear or branched C5 to C12 alkanes. In this disclosure, how a passivator is added is not particularly important. Suitable passivators are well known in the art, non-limiting examples include alkali or alkaline earth metal salts of carboxylic acids or hydrotalcites. The amount of passivator added can vary over a wide range.

[0110] In one embodiment of the continuous solution polymerization process, the first and second reactors are continuously stirred tank reactors (CSTRs).

[0111] In one embodiment of the continuous solution polymerization process, the third reactor is a tubular reactor.

[0112] In one embodiment of the continuous solution polymerization process described in this document, ethylene is added to each of reactors 1, 2 and 3.

[0113] In one embodiment of the continuous solution polymerization process described herein, a single-site catalyst system is added to each of the first and second reactors, but not to the third reactor.

[0114] In one embodiment of the continuous solution polymerization process described in this document, a single-site catalyst system is added to each of the first, second and third reactors.

[0115] In one embodiment of the continuous solution polymerization process described herein, a single-site catalyst system comprises a phosphinine complex.

[0116] Referring to the modalities shown in Figures 1, 2 and 3; an active single-site catalyst system is produced by optimizing the ratio of each of the four single-site catalyst components (a) to (d) as defined above. The term "active" means that the single-site catalyst system is very effective at converting olefins to polyolefins; in practice, the optimization goal is to maximize the following ratio: (pounds of ethylene interpolymer product)/(pounds of catalyst consumed). The amount of the phosphinamine complex, component (a), added to reactors 1 and 2 is expressed as the parts per million (ppm) of component (a) in the total mass of the solutions in reactors 1 and 2; which may be hereinafter referred to as "R1(a) (ppm)" or "R2(a) (ppm)". The upper limit on R1(a) (ppm) or R2(a) (ppm) can be about 5, in some cases about 3, and in other cases about 2. The lower limit on R1(a) ( ppm) and R2(a) (ppm) can be about 0.02, in some cases about 0.05, and in other cases about 0.1.

[0117] The proportion of catalyst component (c), the ionic activator, added to R1 and R2 is optimized by controlling the molar ratio of (ionic activator)/(phosphinine complex) in solution of R1 and R2; hereinafter “R1(c)/(a)” and “R2(c)/(a)”. The upper bound on R1 and R2(c)/(a) can be around 10, in some cases around 5, and in other cases around 2. The lower bound on R1(c)/(a) and R2 (c)/(a) can be about 0.1, in some cases about 0.5, and in other cases about 1.0.

[0118] The proportion of catalyst component (b), alkylaluminoxane is optimized by controlling the molar ratio of (alkylaluminoxane Al)/(phosphinimine complex) in solution of R1 and R2; hereinafter “R1(b)/(a)” and “R2(b)/(a)”. The alkyl aluminoxane co-catalyst is generally added in a molar excess relative to the bulky metal-binder complex. The upper bound on R1(b)/(a) and R2(b)/(a) can be about 1000, in some cases about 500, and in other cases about 200. The lower bound on R1(b )/(a) and R2(b)/(a) can be about 1, in some cases about 10, and in other cases about 30.

[0119] The addition of catalyst component (d), the cross-linked phenol, to R1 and R2 is optional in the embodiments shown in Figures 1 to 3. If added, the proportion of component (d) is optimized by controlling the molar ratio of (crosslinked phenol)/(Al of alkylaluminoxane) in R1 and R2; hereinafter "R1(d)/(b)" and "R2(d)/(b)". The upper bound on R1(d)/(b) and R2(d)/(b) can be about 10, in some cases about 5, and in other cases about 2. The lower bound on R1(d )/(b) and R2 (d)/(b) may be 0.0, in some cases about 0.1 and in other cases about 0.2.

[0120] If a single-site catalyst is loaded into reactor 3, then the phosphinamine complex (a), the ionic activator (c), the alkylaluminoxane (b) and optional cross-linked phenol (d) are optimized as described for the reactors 1 and 2. That is, the following is controlled.

[0121] The amount of phosphinine complex, component (a) added to reactor 3 as expressed as the parts per million (ppm) of component (a) in the total mass of solutions in reactor 3, which may be hereinafter referred to as "R3 (a) (ppm)”; the upper limit on R3(a) (ppm) can be around 5, in some cases around 3, and in other cases around 2. The lower limit on R3(a) (ppm) and R2(a) (ppm ) can be about 0.02, in some cases about 0.05, and in other cases about 0.1.

[0122] The proportion of catalyst component (c), the ionic activator, added to R3 is optimized by controlling the molar ratio of (ionic activator)/(phosphinamine complex) in R3; hereinafter “R3(c)/(a)”. The upper bound on R3(c)/(a) might be about 10, in some cases about 5, and in other cases about 2. The lower bound on R3(c)/(a) might be about 0.1, in some cases around 0.5, and in other cases around 1.0.

[0123] The proportion of catalyst component (b), alkylaluminoxane is optimized by controlling the molar ratio of (alkylaluminoxane Al)/(phosphinine complex) in R3 solution; hereinafter “R3(b)/(a)”. the alkyl aluminoxane co-catalyst is generally added in a molar excess relative to the bulk metal-binder complex. The upper bound on R3(b)/(a) might be about 1000, in some cases about 500, and in other cases about 200. The lower bound on R3(b)/(a) might be about 1, in some cases around 10, and in other cases around 30.

[0124] The addition of catalyst component (d), cross-linked phenol, to R3 is optional in the embodiments shown in Figures 1 to 3. If added, the proportion of component (d) is optimized by controlling the molar ratio of ( cross-linked phenol)/(Al of alkylaluminoxane) in R3; hereinafter “R3(d)/(b)”. The upper bound on R3(d)/(b) might be about 10, in some cases about 5, and in other cases about 2. The lower bound on R3(d)/(b) might be 0, 0, in some cases around 0.1 and in other cases around 0.2.

[0125] Any combination of the single-site catalyst component flows in Figures 1 to 3 may or may not be heated or cooled. The upper limit on catalyst component flow temperatures can be about 70°C; in other cases about 60 °C and in still other cases about 50 °C. The lower limit on catalyst component flow temperatures can be about 0 °C; in other cases about 20 °C and in still other cases about 40 °C.

[0126] For more information on optimizing a single-site catalyst for use with a continuous polymerization process, see the U.S. Patent Application 2016/0108221A1 which is incorporated by way of reference.

[0127] Referring to the modalities shown in Figures 1, 2 and 3; a Ziegler-Natta catalyst system is produced by optimizing the ratio of each of the five Ziegler-Natta catalyst components, (e) to (i) as defined above.

[0128] An efficient in-line Ziegler-Natta catalyst system can be found by optimizing the following molar ratios: (aluminum alkyl)/(magnesium compound) or (g)/(e); (chloride compound)/(magnesium compound) or (f)/(e); (aluminum alkyl co-catalyst)/(metal compound) or (i)/(h), and; (aluminum alkyl)/(metal compound) or (g)/(h); as well as the moment these compounds react and balance. The upper limit on the (aluminum alkyl)/(magnesium compound) molar ratio may be about 70, in some cases about 50, and in other cases about 30. The lower limit on the (aluminum alkyl)/( magnesium compound) may be about 3.0, in some cases about 5.0, and in other cases about 10. The upper limit on the molar ratio (chloride compound)/(magnesium compound) may be about 4, in some cases around 3.5, and in other cases around 3.0. The lower limit on the molar ratio (chloride compound)/(magnesium compound) may be about 1.0, in some cases about 1.5 and in other cases about 1.9. The upper limit on the molar ratio (alkyl aluminum cocatalyst)/(metal compound) may be about 10, in some cases about 7.5, and in other cases about 6.0. The lower limit on the (aluminum alkyl cocatalyst)/(metal compound) mole ratio may be 0, in some cases about 1.0, and in other cases about 2.0.

[0129] For more information on the optimization of an in-line Ziegler-Natta catalyst system and the use of a batch Ziegler-Natta catalyst system for use with a continuous polymerization process, see the U.S. Patent Application 2016/0108221A1 which is incorporated into this document by way of reference.

[0130] In the embodiments of continuous solution processes shown in Figures 1, 2 and 3 a variety of solvents can be used as the process solvent; Non-limiting examples include linear, branched or cyclic C5 to C12 alkanes. Non-limiting examples of α-olefins include 1-propene, 1-butene, 1-pentene, 1-hexene and 1-octene. Suitable catalyst component solvents include aliphatic and aromatic hydrocarbons. Non-limiting examples of aliphatic catalyst component solvent include linear, branched or cyclic C5-12 aliphatic hydrocarbons, for example, pentane, methyl pentane, hexane, heptane, octane, cyclohexane, cyclopentane, methylcyclohexane, hydrogenated naphtha or combinations thereof. Non-limiting examples of aromatic catalyst component solvents include benzene, toluene (methylbenzene), ethylbenzene, o-xylene (1,2-dimethylbenzene), m-xylene (1,3-dimethylbenzene), p-xylene (1,4- dimethylbenzene), isomer mixtures of xylene, hemelitene (1,2,3-trimethylbenzene), pseudocumene (1,2,4-trimethylbenzene), mesitylene (1,3,5-trimethylbenzene), isomer mixtures of trimethylbenzene, prehenitene ( 1,2,3,4-tetramethylbenzene), durene (1,2,3,5-tetramethylbenzene), mixtures of tetramethylbenzene, pentamethylbenzene, hexamethylbenzene and combinations thereof.

[0131] It is well known to individuals experienced in the art that reactor feed streams (solvent, monomer, a-olefin, hydrogen, catalyst system, etc.) must be essentially free of catalyst deactivation poisons; non-limiting examples of poisons include trace amounts of oxygenates such as water, fatty acids, alcohols, ketones and aldehydes. These poisons are removed from the reactor feed streams using standard purification practices, alumina microbeads and oxygen scavenging catalysts for the purification of solvents, ethylene and α-olefins, etc.

[0132] Referring to the first and second reactors in Figures 1, 2 and 3, any combination of reactor load flows 1 or 2 can be heated or cooled. The upper limit on reactor charge flow temperatures can be around 90 °C; in other cases about 80 °C and in still other cases about 70 °C. The lower limit on reactor load flow temperatures can be about -20 °C; in other cases about 0 °C, in other cases about 10 °C, and in still other cases about 20 °C. Any combination of reactor 3 feed streams can be heated or cooled. In some cases, the feed streams from reactor 3 are quenched, i.e. the feed streams from reactor 3 are heated to at least above ambient temperature. The upper temperature limit in the reactor 3 feed streams is in some cases about 200°C, in other cases about 170°C, and in still other cases about 140°C; the lower temperature limit in tubular reactor feed streams in some cases is around 40 °C, in other cases around 60 °C, in other cases around 90 °C, and in still other cases around 120 °C; with the condition that the temperature of the feed streams from reactor 3 is lower than the temperature of the process stream entering reactor 3.

[0133] In the embodiments shown in Figures 1 to 3, the operating temperatures of solution polymerization reactors, reactors 1, 2 and 3 can vary over a wide range. For example, the upper limit on reactor temperatures in some cases may be about 300°C, in other cases about 280°C, and in still other cases about 260°C; and the lower limit in some cases may be about 80°C, in other cases about 100°C, and in still other cases about 125°C.

[0134] In a development mode, the first reactor is operated at a lower temperature than the second reactor.

[0135] The maximum temperature difference between these two reactors, T2 - T1, where "T2" is the operating temperature of R2 and "T1" is the operating temperature of R1, in some cases it is about 120 °C in other cases about 100°C and in still other cases about 80°C; the minimum temperature of T2 - T1 in some cases is about 1 °C, in other cases about 5 °C, and in still other cases about 10 °C.

[0136] In one embodiment of the disclosure, the first reactor operates at a temperature, T1, that is at least 25 °C lower than the temperature at which the second reactor operates, T2.

[0137] In one embodiment of the disclosure, the first reactor operates at a temperature, T1, that is at least 35 °C lower than the temperature at which the second reactor operates, T2.

[0138] In one embodiment of the disclosure, the first reactor operates at a temperature, T1, that is at least 45 °C lower than the temperature at which the reactor operates, T2.

[0139] In one embodiment of the disclosure, the first reactor operates at a temperature, T1, that is at least 55 °C lower than the temperature at which the second reactor operates, T2.

[0140] In one embodiment of the disclosure, the first reactor operates at a temperature, T1, from 10 to 100 °C lower than the temperature at which the second reactor operates, T2.

[0141] In one embodiment of the disclosure, the first reactor operates at a T1 temperature of about 125 °C to about 155 °C and the second reactor operates at a T2 temperature of about 185 °C to about 205 °C .

[0142] In one embodiment of the present disclosure, the third reactor operates at a temperature T3 that is greater than the temperature at which the first reactor operates, T1.

[0143] In one embodiment of the present disclosure, the third reactor operates at a temperature T3 that is greater than the temperature at which the first and second reactors operate, T1 and T2 respectively.

[0144] In one embodiment of the present disclosure, the third reactor operates at a temperature T3 that is lower than the weighted average of the operating temperatures at which the first and second reactors operate.

[0145] In one embodiment of the present disclosure, the third reactor operates at a temperature T3 that is lower than the inlet temperature of the third reactor.

[0146] In one embodiment of the present disclosure, and with reference to Figure 1, the third reactor operates at a temperature T3 that is greater than the temperature of the combined output streams 1' and 2' of reactor 1 and 2 respectively.

[0147] In one embodiment of the present disclosure, and with reference to Figure 1, the third reactor operates at a temperature T3 that is greater than the weighted average temperature of the combined output streams 1' and 2' of reactor 1 and 2 respectively.

[0148] In the embodiments of the disclosure, the third reactor can be operated at at least about 100 °C higher than reactor 1; in other cases at least about 60 °C greater than reactor 1, in still other cases at least about 30 °C greater than reactor 1.

[0149] In the embodiments of the disclosure, the third reactor can be operated at at least about 60 °C higher than reactor 2; in other cases at least about 30 °C higher than reactor 2, in still other cases at least about 10 °C higher than reactor 2, in alternative cases 0 °C higher, i.e. same temperature as reactor two.

[0150] In one embodiment of the disclosure, the first reactor operates at a temperature of about 115 °C to about 155 °C and the second reactor operates at a temperature of about 190 °C to about 205 °C.

[0151] The temperature inside reactor 3 may increase along its length. The maximum temperature difference between the inlet and outlet of R3 in some cases is about 100°C, in other cases about 60°C, and in still other cases about 40°C. The minimum temperature difference between the inlet and outlet of R3 may in some cases be 0 °C, in other cases around 3 °C, and in still other cases around 10 °C. In some cases R3 is operated adiabatically and in other cases R3 is heated.

[0152] The pressure in the polymerization reactors must be high enough to maintain the polymerization solution as a single-phase solution and provide the downstream pressure to force the polymer solution from the reactors through a heat exchanger and into operations polymer recovery. Referring to the embodiments shown in Figures 1, 2 and 3, the operating pressure of solution polymerization reactors can vary over a wide range. For example, the upper limit on reactor pressure in some cases may be about 45 MPag, in other cases about 30 MPag, and in still other cases about 20 MPag; and the lower limit in some cases may be about 3 MPag, in some other cases about 5 MPag, and in still other cases about 7 MPag.

[0153] In one embodiment of the disclosure, one or more solution polymerization reactors may be operated at a pressure that is low enough for the uniphasic polymeric solution to phase separate into a liquid/liquid biphasic polymeric solution.

[0154] The polyethylene product produced in the continuous solution polymerization process can be recovered using conventional devolatilization systems that are well known to individuals skilled in the art, non-limiting examples include instant devolatilization systems and devolatilization extruders.

[0155] Referring to the modalities shown in Figures 1 to 3, before entering the first V/L separator 103, the deactivated solution may have a maximum temperature and, in some cases, around 300 °C, in other cases , about 290°C, and in still other instances about 280°C; the minimum temperature may be in some cases around 150 °C, in other cases around 200 °C, and in still other cases around 220 °C. Immediately before entering the first V/L separator the deactivated solution in some cases may have a maximum pressure of about 40 MPag, in other cases about 25 MPag, and in still other cases about 15 MPag; the minimum pressure in some cases may be about 1.5 MPag, in other cases about 5 MPag, and in still other cases about 6 MPag.

[0156] The first V/L 103 separator can be operated in a relatively wide range of temperatures and pressures. For example, the maximum operating temperature of the first V/L separator in some cases may be about 300°C, in other cases about 285°C, and in still other cases about 270°C; the minimum operating temperature in some cases may be around 100 °C, in other cases around 140 °C, and in still other cases 170 °C. The maximum operating pressure of the first V/L separator in some cases may be about 20 MPag, in other cases about 10 MPag, and in still other cases about 5 MPag; the minimum operating pressure in some cases may be about 1 MPag, in other cases about 2 MPag, and in still other cases about 3 MPag.

[0157] The second V/L 105 separator can be operated in a relatively wide range of temperatures and pressures. For example, the maximum operating temperature of the second V/L separator in some cases may be about 300°C, in other cases about 250°C, and in still other cases about 200°C; the minimum operating temperature in some cases may be around 100 °C, in other cases around 125 °C, and in still other cases around 150 °C. The maximum operating pressure of the second V/L separator in some cases may be about 1000 kPag, in other cases about 900 kPag, and in still other cases about 800 kPag; the minimum operating pressure in some cases may be about 10 kPag, in other cases about 20 kPag, and in still other cases about 30 kPag.

[0158] The third V/L 107 separator can be operated in a relatively wide range of temperatures and pressures. For example, the maximum operating temperature of the third V/L separator in some cases may be about 300°C, in other cases about 250°C, and in still other cases about 200°C; the minimum operating temperature in some cases may be around 100 °C, in other cases around 125 °C, and in still other cases around 150 °C. The maximum operating pressure of the third V/L separator in some cases may be about 500 kPag, in other cases about 150 kPag, and in still other cases about 100 kPag; the minimum operating pressure in some cases may be about 1 kPag, in other cases about 10 kPag, and in still other cases about 25 kPag.

[0159] In one embodiment of the present disclosure, one or more V/L separators can be operated under vacuum pressure.

[0160] The modalities of the continuous solution polymerization process shown in Figures 1 to 3 show three V/L separators. However, continuous solution polymerization embodiments can include configurations comprising at least one V/L separator.

[0161] In another embodiment of the disclosure, a biphasic liquid/liquid polymeric solution may be present or induced to be present downstream of the final polymerization reactor. This biphasic liquid/liquid polymeric solution can be separated into a polymer-poor phase and a polymer-rich phase downstream of the fine polymerization reactor. A liquid/liquid (“L/L”) phase separator can be operated over a relatively wide range of temperatures and pressures. One or more L/L phase separators can be used.

[0162] Any reactor format or design can be used for reactors 1 and 2 in Figures 1 to 3; non-limiting examples include spherical, cylindrical, or unstirred or stirred tank-type vessels, as well as tube reactors or loop reactors. On a commercial scale, the maximum volume of reactors 1 and 2 in some cases can be about 20,000 gallons (about 75,710 L), in other cases about 10,000 gallons (about 37,850 L), and in still other cases about of 5,000 gallons (about 18,930 L). On a commercial scale the minimum volume of reactors 1 and 2 in some cases may be about 100 gallons (about 379 L), in other cases about 500 gallons (about 1893 L), and in still other cases about 1000 gallons (about 3785 L). At pilot plant scales, reactor volumes are typically much smaller, for example, the volume of reactors 1 and 2 at pilot scale can be less than about 10 gallons (less than about 37 L).

[0163] In this disclosure, the volume of reactor R2 can be expressed as a percentage of the volume of reactor R1.

[0164] In the embodiments of the disclosure, the upper limit on the volume of R2 in some cases may be about 600% of R1, in other cases about 400% of R1, and in still other cases about 200% of R1 . For clarity, if the volume of R1 is 5,000 gallons (about 18,925 L) and R2 is 200% of the volume of R1, then R2 has a volume of 10,000 gallons (about 37,850 L).

[0165] In the embodiments of the disclosure, the lower limit on the volume of R2 in some cases may be about 50% of R1, in other cases about 100% of R1, and in still other cases about 150% of R1 . In the case of continuously stirred tank reactors, the stirring rate can vary over a wide range; in some cases from about 10 rpm to about 2000 rpm, in other cases from about 100 to about 1500 rpm, and in still other cases from about 200 to about 1300 rpm.

[0166] In one embodiment of this disclosure, reactor 3 is a tubular reactor, and the volume of R3 may be expressed as a percentage of the volume of reactor R2. The upper limit on the volume of R3 in some cases may be about 500% R2, in other cases about 300% R2, and in still other cases about 100% R2. The lower limit on the volume of R3 in some cases may be about 3% of R2, in other cases about 10% of R2, and in still other cases about 50% of R2.

[0167] The “average residence time in reactor”, a parameter commonly used in the chemical engineering technique, is defined by the first moment of the distribution of residence time in the reactor; the residence time distribution in reactor is a probability distribution function that describes the amount of time a fluid element spends inside the reactor. Average residence time in reactor can vary widely depending on process flow rates and reactor mix, reactor design and capacity.

[0168] In the embodiments of the disclosure, the upper limit on the average residence time of the solution in reactors 1 and 2 is about 720 seconds, or about 600 seconds, or about 480 seconds, or about 360 seconds, or about 240 seconds, or about 180 seconds.

[0169] In the embodiments of the disclosure, the lower limit on the average residence time of the solution in reactors 1 and 2 is about 10 seconds, or about 20 seconds, or about 30 seconds, or about 40 seconds, or about 60 seconds.

[0170] In the embodiments of the disclosure, the upper limit on the average residence time of the solution in reactor 3 is about 600 seconds, or about 360 seconds, or about 180 seconds.

[0171] In the embodiments of the disclosure, the lower limit on the average residence time of the solution in reactor 3 is about 1 second, or about 5 seconds, or about 10 seconds.

[0172] Optionally, additional reactors (for example, CSTRs, loops or tubes, etc.) can be added to the continuous solution polymerization process modalities shown in Figures 1 to 3.

[0173] In operation, in the continuous solution polymerization process modalities shown in Figures 1 to 3, the total proportion of ethylene supplied to the process can be portioned or divided between the three reactors R1, R2 and R3.

[0174] This operational variable is referred to as Ethylene Division (ES), that is, “ESR1”, “ESR2” and “ESR3” refer to the percentage, by weight, of ethylene injected into R1, R2 and R3, respectively; with the condition that ESR1 + ESR2 + ESR3 = 100%. This is accomplished by adjusting the ethylene flow rates on the following streams: D stream (R1), E stream (R2) and F stream (R3).

[0175] In the present disclosure, at least 1 percent by weight of the total ethylene injected into reactor 1, reactor 2, and reactor 3 is injected into reactor 3 (i.e., ESR3 is at least 1%).

[0176] In one embodiment of the disclosure, at least 10 percent by weight of the total ethylene injected into reactor 1, reactor 2, and reactor 3 is injected into reactor 3 (i.e., ESR3 is at least 10%).

[0177] In one embodiment of the disclosure, at least 20 percent by weight of the total ethylene injected into reactor 1, reactor 2, and reactor 3 is injected into reactor 3 (ie, ESR3 is at least 20%).

[0178] In one embodiment of the disclosure, at least 30 percent by weight of the total ethylene injected into reactor 1, reactor 2, and reactor 3 is injected into reactor 3 (i.e., ESR3 is at least 30%).

[0179] In one embodiment of the disclosure, at least 40 percent by weight of the total ethylene injected into reactor 1, reactor 2, and reactor 3 is injected into reactor 3 (ie, ESR3 is at least 40%).

[0180] In one embodiment of the disclosure, at least 50 percent by weight of the total ethylene injected into reactor 1, reactor 2, and reactor 3 is injected into reactor 3 (ie, ESR3 is at least 50%).

[0181] In the embodiments of the disclosure, the upper limit on ESR1 is about 80%, or about 75%, or about 70%, or about 65%; or about 60%, or about 55%; and the lower bound on ESR1 is about 10%, or about 15%, or about 20%.

[0182] In the embodiments of the disclosure, the upper limit on ESR2 is about 60%, or about 55%, or about 50%; or about 45%, or about 40%, or about 35%, or about 30%; and the lower bound on ESR2 is about 5%, or about 10%, or about 15%, or about 20%, or about 25%.

[0183] In the embodiments of the disclosure, the upper limit at ESR3 is about 50%, or about 40%, or about 35%, or about 30%, or about 25%, or about 20%; and the lower bound on ESR3 is about 1%, or about 5%, or about 10%.

[0184] In operation, in the modalities of the continuous solution polymerization process shown in Figures 1 to 3, the ethylene concentration in each reactor can also be controlled. For example, the ethylene concentration in reactor 1, hereinafter “ECR1”, is defined as the weight of ethylene in reactor 1 divided by the total weight of everything added to reactor 1. An “ECR2” and “ECR3” can be similarly defined.

[0185] In the embodiments of the disclosure, the concentration of ethylene in the reactors (ECR1 or ECR2 or ECR3) can vary from about 5 percent by weight to about 25 percent by weight or from about 7 percent by weight (% by weight) to about 25% by weight or from about 8% by weight to about 20% by weight or from about 9% by weight to about 17 % by weight.

[0186] In operation, in the modalities of the continuous solution polymerization process shown in Figures 1 to 3, the total amount of ethylene converted in each reactor can be monitored. The term “QR1” refers to the percentage of the ethylene added to R1 that is converted to a polyethylene polymer by the catalyst system. Similarly, “QR2” and “QR3” represent the percentage of the ethylene added to R2 and R3 that was converted into a polyethylene polymer in the respective reactors.

[0187] Ethylene conversions can vary significantly depending on a variety of process conditions, for example, catalyst concentration, catalyst system, impurities and poisons.

[0188] In the embodiments of the disclosure, the upper limit in QR1 and QR2 may be about 99%, or about 95%, or about 90%; while the lower bound on QR1 and QR2 might be around 65%, or around 70%, or around 75%.

[0189] In the disclosure embodiments, the upper limit on QR3 may be about 99%, or about 95%, or about 90%; while the lower bound in QR3 might be 1%, or around 5%, or around 10%.

[0190] The term “QTOTAL” represents the total or general ethylene conversion throughout the polymerization plant in continuous solution; that is, QT = 100 x [weight of ethylene in the polyethylene product]/([weight of ethylene in the polyethylene product]+[weight of unreacted ethylene]). The upper limit on QT in some cases is about 99%, in other cases about 95%, and in still other cases about 90%; the lower limit on QT in some cases is about 75%, in other cases about 80%, and in still other cases about 85%.

[0191] Optionally, a-olefin can be added to the continuous solution polymerization process. If added, α-olefin can be provided or divided between R1, R2 and R3. This operational variable is referred to as Comonomer Division (CS), i.e. “CSR1”, “CSR2” and “CSR3” refers to the weight percentage of a-olefin comonomer that is injected into R1, R2 and R3 , respectively; with the condition that CSR1 + CSR2 + CSR3 = 100%. This is accomplished by adjusting the α-olefin flow rates in the following streams: G stream (R1), H stream (R2) and I stream (R3).

[0192] The upper limit in CSR1 in some cases is 100% (that is, 100% of the a-olefin is injected into R1), in other cases around 95%, and in still other cases around 90%. The lower limit on CSR1 in some cases is 0% (ethylene homopolymer produced in R1), in other cases around 5%, and in still other cases around 10%. The upper limit on CSR2 is in some cases around 100% (i.e. 100% of the a-olefin is injected into reactor 2), in other cases around 95%, and in still other cases around 90%. The lower limit on CSR2 in some cases is 0% (ethylene homopolymer produced in R2), in other cases about 5%, and in still other cases about 10%. The upper bound on CSR3 is in some cases 100%, in other cases around 95%, and in still other cases around 90%. The lower bound on CSR3 is in some cases 0%, in other cases around 5%, and in still other cases around 10%.

[0193] In one embodiment of the disclosure, a first polyethylene is produced with a single-site catalyst system in reactor 1. Referring to the embodiments shown in Figures 1 to 3, if the optional a-olefin is not added to reactor 1 (R1), so the first polyethylene produced in R1 is an ethylene homopolymer. If an α-olefin is added, then the first polyethylene produced in R1 is an ethylene copolymer and the following weight ratio is a parameter to control the density of the first polyethylene: ((α-olefin)/(ethylene))R1 . The upper limit on ((α-olefin)/(ethylene))R1 can be about 3; in other cases about 2, and in still other cases about 1. The lower limit on ((α-olefin)/(ethylene))R1 may be 0; in other cases about 0.25 and in still other cases about 0.5. Henceforth, the term “d1” refers to the density of the first polyethylene produced in R1. The upper limit on d1 can be about 0.975 g/cm3; in some cases about 0.965 g/cm3 e; in other cases, about 0.955 g/cm3. The lower limit on d1 can be about 0.855 g/cm3, in some cases about 0.865 g/cm3, e; in other cases, about 0.875 g/cm3.

[0194] In the embodiments of the disclosure, the d1 density can be from about 0.875 g/cm3 to about 0.965 g/cm3, or from about 0.875 g/cm3 to about 0.960 g/cm3, or from about 0.875 g /cm3 to 0.950 g/cm3, or from about 0.865 g/cm3 to about 0.940 g/cm3, or from about 0.865 g/cm3 to about 0.936 g/cm3, or from about 0.865 g/cm3 to about from about 0.932 g/cm3, or from about 0.865 g/cm3 to about 0.926 g/cm3, or from about 0.865 g/cm3 to about 0.921 g/cm3, or from about 0.865 g/cm3 to about 0.918 g/cm3, or from about 0.875 g/cm3 to about 0.916 g/cm3, or from about 0.875 g/cm3 to about 0.916 g/cm3, or from about 0.865 g/cm3 to about 0.912 g/cm3 cm3, or from 0.880 g/cm3 to 0.912 g/cm3.

[0195] Methods for determining the CDBI50 (Composition Distribution Branching Index) of an ethylene polymer are well known to those skilled in the art. CDBI50, expressed as a percentage, is defined as the percentage of the ethylene polymer whose comonomer composition is within 50% of the median comonomer composition. It is also well known in the art by those skilled in the art that the CDBI50 of ethylene polymers produced with single-site catalyst systems is superior to the CDBI50 of α-olefin containing ethylene polymers produced with heterogeneous catalyst systems. The upper limit on CDBI50 of the first polyethylene (produced with a single-site catalyst system) may be about 98%, in other cases about 95%, and in still other cases about 90%. The lower limit on the CDBI50 of the first polyethylene may be about 70%, in other cases about 75%, and in still other cases about 80%.

[0196] As is well known to those skilled in the art, the Mw/Mn of ethylene polymers produced with single-site catalyst systems is lower than that of ethylene polymers produced with heterogeneous catalyst systems. The upper limit on the Mw/Mn of the first polyethylene may be about 2.8, in other cases about 2.5, in other cases about 2.4, and in still other cases about 2.2 . The lower limit on the Mw/Mn of the first polyethylene may be about 1.4, in other cases 1.6, in other cases about 1.7, in other cases about 1.8, and in still other cases , about 1.9.

[0197] The first polyethylene may contain catalyst residues that reflect the chemical composition of the single-site catalyst system used. Those skilled in the art will understand that catalyst residues are typically quantified by the parts per million of metal in the first polyethylene, where metal refers to the metal in component (a), for example, the metal in the "phosphinine complex", referred to in this document as M1. The upper limit in ppm of metal M1 in the first polyethylene may be about 5.0 ppm, in other cases about 2.5 ppm, or 2.0 ppm, or 1.0 ppm, or 0.9 ppm, and, in still other cases, about 0.8 ppm. The lower limit on ppm of M1 metal in the first polyethylene may be about 0.01 ppm, in other cases about 0.1 ppm, and in still other cases about 0.2 ppm.

[0198] The proportion of hydrogen added to reactor 1 can vary over a wide range, allowing the continuous solution process to produce polyethylenes that differ considerably in melting index, henceforth I21 (melting index is measured at 190 °C using a load of 2.16 kg following the procedures set out in ASTM D1238). This is accomplished by adjusting the hydrogen flow rate in the M flow (see Figures 1 to 3). The amount of hydrogen added to R1 is expressed as the parts per million (ppm) of hydrogen in R1 relative to the total mass in reactor R1; henceforth H2R1 (ppm). In some cases, H2R1 (ppm) ranges from about 100 ppm to 0 ppm, in other cases from about 50 ppm to 0 ppm, in alternative cases from about 20 ppm to 0 ppm, and in still other cases from about 2 ppm to 0 ppm. The upper limit at I21 can be around 200 dg/min, in some cases around 100 dg/min; in other cases, about 50 dg/min, and; in still other cases, about 1 dg/min. The lower limit on I21 can be about 0.01 dg/min, in some cases about 0.05 dg/min; in other cases about 0.1 dg/min, e; in still other cases, about 0.5 dg/min.

[0199] In the embodiments of the disclosure, the melt index of the first polyethylene I21 can be from about 0.01 dg/min to about 100 dg/min, or from about 0.05 dg/min to about 50 dg /min, or from about 0.10 dg/min to about 50 dg/min, or from about 0.01 dg/min to about 25 dg/min, or from about 0.05 dg/min to about 25 dg/min, or from about 0.10 dg/min to about 25 dg/min, or from about 0.01 dg/min to about 10 dg/min, or from about 0.05 dg/min to about 10 dg/min, or from about 0.10 dg/min to about 10 dg/min, or from about 0.01 dg/min to about 5.0 dg/min, or from about 0.05 dg/min to about 5.0 dg/min, or from about 0.10 dg/min to about 5.0 dg/min, or from about 0.10 dg/min to about 3.0 dg/min, or from about 0.05 dg/min to about 3.0 dg/min, or from about 0.05 to 2.5 dg/min.

[0200] In one embodiment of the disclosure, the melt index of the first polyethylene I21 may be less than about 1.0 dg/min.

[0201] In one embodiment of the disclosure, the first polyethylene has a weight average molecular weight, Mw of from about 40,000 to about 400,000, or from about 45,000 to about 300,000, or from about 50,000 to about 300,000, or from about 50,000 to about 250,000, or from about 50,000 to about 200,000; or from about 60,000 to about 400,000, or from about 60,000 to about 350,000, or from about 60,000 to about 300,000, or from about 60,000 to about 250,000, or from about 60,000 to about 200,000.

[0202] The upper limit on the percentage by weight (% by weight) of the first polyethylene in the final polyethylene polymer product may be about 80% by weight, in other cases about 75% by weight, or about 70% by weight, or about 65% by weight, or about 60% by weight, or about 55% by weight, and in still other instances about 50% by weight . The lower limit on the % by weight of the first polyethylene in the final polyethylene product can be about 15% by weight; in other cases about 25% by weight, in other cases about 30% by weight, in other cases about 35%, in still other cases about 40%.

[0203] In one embodiment of the disclosure, a second polyethylene is produced with a single-site catalyst system in reactor 2. The second polyethylene can be an ethylene homopolymer or an ethylene copolymer. Referring to the embodiments shown in Figures 1 to 3, if optional α-olefin is not added to reactor 2 via the α-olefin H stream, then the second polyethylene produced in reactor 2 is an ethylene homopolymer. If an optional α-olefin is present, then the second polyethylene produced in R2 is an ethylene copolymer and the following weight ratio is a parameter to control the density of the second polyethylene produced in R2: ((α-olefin)/( ethylene))R2. The upper limit on ((α-olefin)/(ethylene))R2 can be about 3; in other cases about 2, and in still other cases about 1. The lower limit on ((α-olefin)/(ethylene))R2 may be 0; in other cases about 0.25 and in still other cases about 0.5. Henceforth, the term "d2" refers to the density of the second polyethylene produced in R2. The upper limit on d2 can be about 0.975 g/cm3; in some cases about 0.965 g/cm3 e; in other cases, about 0.955 g/cm3. Depending on the single site catalyst system used, the lower limit on d2 can be about 0.89 g/cm3, in some cases about 0.90 g/cm3, e; in other cases, about 0.91 g/cm3.

[0204] In the embodiments of the disclosure, the density, d2 can be from about 0.921 g/cm3 to about 0.975 g/cm3, or from about 0.926 g/cm3 to about 0.975 g/cm3, or from about 0.930 g/cm3 to about 0.975 g/cm3, or from about 0.936 g/cm3 to about 0.975 g/cm3, or from about 0.940 g/cm3 to about 0.975 g/cm3, or from about 0.945 g/cm3 cm3 to about 0.975 g/cm3, or from about 0.950 g/cm3 to about 0.975 g/cm3, or from about 0.951 g/cm3 to about 0.975 g/cm3, or from about 0.953 g/cm3 to about 0.970 g/cm3, or from about 0.953 g/cm3 to about 0.959 g/cm3, or from about 0.955 g/cm3 to about 0.975 g/cm3, or from about 0.951 g/cm3 to about 0.959 g/cm3, or from 0.936 to about 0.970 g/cm3, or from about 0.940 g/cm3 to about 0.970 g/cm3, or from about 0.945 g/cm3 to about 0.970 g/cm3, or from about 0.950 g/cm 3 to about 0.970 g/cm 3 .

[0205] The upper limit on CDBI50 of the second polyethylene (produced with a single-site catalyst system) may be about 98%, in other cases about 95%, and in still other cases about 90%. The lower limit on the CDBI50 of the second polyethylene may be about 70%, in other cases about 75%, and in still other cases about 80%.

[0206] The upper limit on the Mw/Mn of the second polyethylene can be about 2.8, in other cases, about 2.5, in other cases, about 2.4, and in still other cases, about 2 ,two. The lower limit on the Mw/Mn of the second polyethylene may be about 1.4, in other cases about 1.6, in other cases about 1.7, in other cases about 1.8, and in still other cases, about 1.9.

[0207] The second polyethylene may contain catalyst residues that reflect on the chemical composition of the single-site catalyst system used. Those skilled in the art will understand that catalyst residues are typically quantified by the parts per million of metal in the second ethylene polymer, where metal refers to the metal in component (a), i.e., the metal in the "phosphinine complex", referred to in this document as M2. The upper limit in ppm of metal M2 in the second polyethylene may be about 5.0 ppm, or about 2.5 ppm, or about 1.0 ppm, or in other cases about 0.9 ppm, and, in still other cases, about 0.8 ppm. The lower limit on ppm of M2 metal in the second polyethylene may be about 0.01 ppm, in other cases about 0.1 ppm, and in still other cases about 0.2 ppm.

[0208] The proportion of hydrogen added to R2 can vary over a wide range allowing the continuous solution process to produce second polyethylenes that differ considerably in melting index, henceforth I22 (melting index is measured at 190 °C using a load of 2.16 kg following the procedures set forth in ASTM D1238). This is accomplished by adjusting the hydrogen flow rate in the N flow (see Figures 1 to 3). The amount of hydrogen added to R2 is expressed as the parts per million (ppm) of hydrogen in R2 relative to the total mass in reactor R2; henceforth H2R2 (ppm). In some cases, H2R2 (ppm) ranges from about 100 ppm to 0 ppm, in other cases from about 50 ppm to 0 ppm, in alternative cases from about 20 ppm to 0 ppm, and in still other cases from about 2 ppm to 0 ppm. The upper limit at I22 may be around 20,000 dg/min; in some cases around 10,000 dg/min; in other cases, around 1,500 dg/min, and; in still other cases, about 1,000 dg/min. The lower limit on I22 can be about 0.3 dg/min, in some cases about 0.4 dg/min, in other cases about 0.5 dg/min, e; in still other cases, about 0.6 dg/min.

[0209] In the embodiments of the disclosure, the melt index of the second polyethylene I22 can be from about 0.5 dg/min to about 10,000 dg/min, or from about 0.5 dg/min to about 1,000 dg /min, or from about 1.0 dg/min to about 10,000 dg/min, or from about 10 dg/min to about 1,000 dg/min, or from about 0.5 dg/min to about 500 dg/min, or from about 1.0 dg/min to about 500 dg/min, or from about 0.5 dg/min to about 100 dg/min, or from about 1.0 dg/min min to about 100 dg/min, or from about 0.5 dg/min to about 75 dg/min, or from about 1.0 dg/min to about 75 dg/min, or from about 0 .5 dg/min to about 50 dg/min, or from about 1.0 dg/min to about 50 dg/min, or from about 0.5 dg/min to about 25 dg/min, or from about 1.0 dg/min to about 25 dg/min, or from about 0.5 dg/min to about 20 dg/min, or from about 1.0 dg/min to about 20 dg /min, or from about 0.5 dg/min to about 15 dg/min, or from about 1.0 dg/min to about 15 dg/min, or from about 0.5 dg/min to about 10 dg/min, or from about 1.0 dg/min to about 12.0 dg/min, or from about 1.0 dg/min to about 10 dg/min.

[0210] In one embodiment of the disclosure, the second polyethylene has a weight average molecular weight, Mw of from about 20,000 to about 150,000, or from about 25,000 to about 130,000, or from about 20,000 to about 120,000, or from about 25,000 to about 100,000, or from about 30,000 to about 120,000; or from about 30,000 to about 100,000.

[0211] The upper limit in percentage, by weight, (%, by weight) of the second polyethylene in the final polyethylene product may be about 85%, by weight, in other cases, about 80%, by weight, in others cases, about 70% by weight, or about 65% by weight, or about 60% by weight, or about 55% by weight, or about 50% by weight, or about 45 % by weight or about 40% by weight or about 35% by weight. The lower limit on % by weight of the second polyethylene in the final polyethylene product can be about 5% by weight or about 10% by weight or about 15% by weight or about 20% by weight, or in other cases about 30% by weight.

[0212] In one embodiment of the disclosure, the first polyethylene may have a weight average molecular weight Mw greater than the weight average molecular weight Mw of the second polyethylene polymer.

[0213] Optionally, a second catalyst system can be added to the third reactor, R3. The second catalyst system can be a single site catalyst system or a Ziegler-Natta catalyst system.

[0214] A third polyethylene is produced in reactor 3. An active catalyst flows from reactor 1 and/or 2, and/or a fresh polymerization catalyst system is added to reactor 3.

[0215] If additional α-olefins are not added to reactor 3, either by fresh α-olefin flow I or transferred from reactors 1 and/or 2 in combined output flows 1' and 2' (Figure 1), or outflow 1' (Figure 2), or outflow 2' (Figure 3), then, the third polymer formed in reactor 3 is an ethylene homopolymer. If additional α-olefins are added to reactor 3, either by fresh α-olefin stream I and/or transferred from reactors 1 and/or 2 in combined outlet streams 1' and 2' (Figure 1), or stream outlet 1' (Figure 2), or outlet flow 2' (Figure 3), then, the third polymer formed in reactor 3 is an ethylene copolymer and the following weight ratio determines the density of the third polyethylene: ((α- olefin)/(ethylene))R3. In the continuous solution polymerization process, ((α-olefin)/(ethylene))R3 is one of two control parameters used to produce a third polyethylene with a desired density. The upper limit on ((α-olefin)/(ethylene))R3 can be about 3; in other cases about 2, and in still other cases about 1. The lower limit on ((α-olefin)/(ethylene))R3 may be 0; in other cases about 0.25 and in still other cases about 0.5. Hereinafter, the term "d3" refers to the density of the ethylene polymer produced in R3. The upper limit on d3 can be about 0.975 g/cm3; in some cases about 0.965 g/cm3 e; in other cases, about 0.955 g/cm3. Depending on the catalyst system used, the lower limit on d3 can be about 0.865 g/cm3, in some cases about 0.875 g/cm3, in some cases about 0.88 g/cm3, in some cases about 0. 89 g/cm3, in some cases about 0.90 g/cm3, and; in other cases, about 0.91 g/cm3.

[0216] In the embodiments of the disclosure, the density of the third polyethylene, d3 can be from about 0.875 g/cm3 to about 0.965 g/cm3, or from about 0.875 g/cm3 to about 0.960 g/cm3, or from from about 0.875 g/cm3 to about 0.955 g/cm3, or from about 0.875 g/cm3 to about 0.950 g/cm3, or from about 0.88 g/cm3 to about 0.945 g/cm3, or from about 0.89 g/cm3 to about 0.941 g/cm3, or from about 0.89 g/cm3 to about 0.940 g/cm3, or from about 0.89 g/cm3 to about 0.936 g/cm cm3, or from about 0.875 g/cm3 to about 0.936 g/cm3, or from about 0.880 g/cm3 to about 0.936 g/cm3, or from about 0.880 g/cm3 to about 0.935 g/cm3, or from about 0.880 g/cm3 to about 0.932 g/cm3, or from about 0.88 g/cm3 to about 0.930 g/cm3, or from about 0.875 g/cm3 to about 0.925 g/cm3, or from about 0.89 g/cm3 to about 0.926 g/cm3.

[0217] The upper limit on the Mw/Mn of the third polyethylene may be about 8.0, or about 7.0, or about 6.5, or about 6.0, in other cases, about 5, 5, or about 5.0, and in still other cases about 4.8. The lower limit on the Mw/Mn of the third polyethylene can be about 4.0, or about 3.5, or about 3.0, or about 2.6, or about 2.5.

[0218] In one embodiment of the disclosure, the Mw/Mn of the third polyethylene can be from about 2.2 to about 7.0, or from about 2.4 to about 6.5, or from about 2 .6 to about 6.0, or from about 2.8 to about 5.5, or from about 3.0 to about 6.0, or from about 3.0 to about 5.5 .

[0219] In one embodiment of the disclosure, the Mw/Mn of the third polyethylene is greater than the Mw/Mn of the first polyethylene.

[0220] In one embodiment of the disclosure, the Mw/Mn of the third polyethylene is greater than the Mw/Mn of the second polyethylene.

[0221] In one embodiment of the disclosure, the Mw/Mn of the third polyethylene is greater than the Mw/Mn of the first and second polyethylenes.

[0222] In one embodiment of the disclosure, the third polyethylene has a weight average molecular weight greater than the weight average molecular weight of the second polyethylene.

[0223] In one embodiment of the disclosure, the first polyethylene and the third polyethylene have a weight average molecular weight greater than the weight average molecular weight of the second polyethylene.

[0224] Referring to the embodiments shown in Figures 1 to 3, optional hydrogen can be added to reactor 3 through the O flow. The proportion of hydrogen added to R3 can vary over a wide range. Adjusting the proportion of hydrogen in R3, henceforth H2R3 (ppm), allows the continuous solution process to produce third polyethylenes that differ considerably in melt index, henceforth I23. The proportion of optional hydrogen added to R3 ranges from about 50 ppm to 0 ppm, in some cases from about 25 ppm to 0 ppm, in other cases from about 10 to 0, and in still other cases from about 2 ppm to 0 ppm. The upper limit at I23 may be around 2000 dg/min; in some cases around 1,500 dg/min; in other cases, about 1,000 dg/min, and; in still other cases, about 500 dg/min. The lower limit on I23 can be about 0.5 dg/min, in some cases about 0.6 dg/min, in other cases about 0.7 dg/min, e; in still other cases, about 0.8 dg/min.

[0225] In the embodiments of the disclosure, the melt index of the third polyethylene I23 can be from about 0.01 dg/min to about 10,000 dg/min or from about 0.05 dg/min to about 10,000 dg/min min, or from about 0.10 to about 10,000, or from about 0.5 dg/min to about 10,000 dg/min, or from about 1.0 dg/min to about 10,000 dg/min, or from about 0.1 dg/min to about 5000 dg/min, or from about 0.5 dg/min to about 5000 dg/min, or from about 0.01 dg/min to about 1000 dg/min, or from about 0.05 to 1000 dg/min, or from about 0.10 dg/min to about 1000 dg/min, or from about 0.5 dg/min to about 1000 dg /min, or from about 1.0 dg/min to about 1000 dg/min, or from about 0.01 dg/min to about 500 dg/min, or from about 0.05 dg/min to about 500 dg/min, or from about 0.10 dg/min to about 500 dg/min, or from about 0.1 dg/min to about 250 dg/min, or from about 0.5 dg/min to about 250 dg/min, or from about 1.0 dg/min to about 250 dg/min, or from about 0.01 dg/min to about 200 dg/min, or from about from about 0.05 dg/min to about 200 dg/min, or from about 0.1 dg/min to about 200 dg/min, or from about 0.01 dg/min to about 100 dg/min , or from about 0.05 dg/min to about 100 dg/min, or from about 0.10 dg/min to 100 dg/min, or from about 0.01 dg/min to about 50 dg /min, or from about 0.05 dg/min to about 50 dg/min, or from about 0.10 dg/min to about 50 dg/min, or from about 0.01 dg/min to about 25 dg/min, or from about 0.05 dg/min to about 25 dg/min, or from about 0.10 dg/min to about 25 dg/min, or from 0.01 dg/min min to about 10 dg/min, or from 0.50 dg/min to about 10 dg/min, or from 0.10 dg/min to about 10 dg/min, or from about 0.01 dg/min min to about 5.0 dg/min, or from about 0.1 dg/min to about 5 dg/min, or from about 0.01 dg/min to about 3 dg/min, or from about from 0.1 dg/min to about 3 dg/min.

[0226] In one embodiment of the disclosure, the third polyethylene has a weight average molecular weight, Mw of from about 20,000 to about 400,000, or from about 20,000 to about 300,000, or from about 20,000 to about 250,000, or from about 25,000 to about 225,000, or from about 25,000 to about 200,000; or from about 20,000 to about 175,000, or from about 20,000 to about 150,000.

[0227] The upper limit in percentage by weight (% by weight) of the third ethylene polymer in the final ethylene polymer product may be about 45% by weight, in other cases, about 40% by weight weight, in other cases about 35% by weight, and in still other cases about 30% by weight. The lower limit on % by weight of optional third ethylene polymer in the final ethylene polymer product can be about 1% by weight; in other cases about 5% by weight, in other cases about 10% by weight, in other cases about 15% by weight, in other cases about 20% by weight, and, in still other cases about 25% by weight.

The composition of the final polyethylene product

[0228] The "final polyethylene product composition" (used interchangeably herein by the terms "polyethylene product composition" and "polyethylene product") comprises a first polyethylene, a second polyethylene and a third polyethylene (as previously described). Despite this fact, in one embodiment of the disclosure, the polyethylene product composition has a unimodal profile on a gel permeation chromatography (GPC) curve generated in accordance with the method of ASTM D6474-99. The term "unimodal" is defined herein to mean that there will be only one significant peak or peak evident in the GPC curve. A unimodal profile includes a wide unimodal profile. In contrast, the use of the term "bimodal" means expressing that in addition to a first peak, there is a secondary peak or ridge that represents a higher or lower molecular weight component (i.e., the molecular weight distribution can be said to have two maxima on a molecular weight distribution curve). Alternatively, the term "bimodal" connotes the presence of two maxima in a molecular weight distribution curve generated according to the method of ASTM D6474-99. The term "multi-modal" denotes the presence of two or more, typically more than two, maxima on a molecular weight distribution curve generated according to the method of ASTM D6474-99.

[0229] In one embodiment of the disclosure, the polyethylene product satisfies the following relationship: [(weight average molecular weight of the second polyethylene) - (weight average molecular weight of the first polyethylene)] / (weight average molecular weight of the second polyethylene) x 100% > -140%. In one embodiment of the disclosure, the polyethylene product satisfies the following relationship: [(weight average molecular weight of the second polyethylene) - (weight average molecular weight of the first polyethylene)] / (weight average molecular weight of the second polyethylene) x 100% > -130%. In one embodiment of the disclosure, the polyethylene product satisfies the following relationship: [(weight average molecular weight of the second polyethylene) - (weight average molecular weight of the first polyethylene)] / (weight average molecular weight of the second polyethylene) x 100% > -120%. In one embodiment of the disclosure, the polyethylene product satisfies the following relationship: [(weight average molecular weight of the second polyethylene) - (weight average molecular weight of the first polyethylene)] / (weight average molecular weight of the second polyethylene) x 100% > -110%. In one embodiment of the disclosure, the polyethylene product satisfies the following relationship: [(weight average molecular weight of the second polyethylene) - (weight average molecular weight of the first polyethylene)] / (weight average molecular weight of the second polyethylene) x 100% > -100%.

[0230] In one embodiment of the disclosure, the polyethylene product satisfies the following relationship: [(weight average molecular weight of the third polyethylene) - (weight average molecular weight of the second polyethylene)] / (weight average molecular weight of the third polyethylene) x 100% > -100%. In one embodiment of the disclosure, the polyethylene product satisfies the following relationship: [(weight average molecular weight of the third polyethylene) - (weight average molecular weight of the second polyethylene)] / (weight average molecular weight of the third polyethylene) x 100% > -75%. In one embodiment of the disclosure, the polyethylene product satisfies the following relationship: [(weight average molecular weight of the third polyethylene) - (weight average molecular weight of the second polyethylene)] / (weight average molecular weight of the third polyethylene) x 100% > -50%. In one embodiment of the disclosure, the polyethylene product satisfies the following relationship: [(weight average molecular weight of the third polyethylene) - (weight average molecular weight of the second polyethylene)] / (weight average molecular weight of the third polyethylene) x 100% > -40%. In one embodiment of the disclosure, the polyethylene product satisfies the following relationship: [(weight average molecular weight of the third polyethylene) - (weight average molecular weight of the second polyethylene)] / (weight average molecular weight of the third polyethylene) x 100% > -30%.

[0231] In one embodiment of the disclosure, the polyethylene composition satisfies the following relationship: [(weight average molecular weight of the third polyethylene) - (weight average molecular weight of the first polyethylene)] / (weight average molecular weight of the third polyethylene) x 100% > -350%. In one embodiment of the disclosure, the polyethylene composition satisfies the following relationship: [(weight average molecular weight of the third polyethylene) - (weight average molecular weight of the first polyethylene)] / (weight average molecular weight of the third polyethylene) x 100% > -300%. In one embodiment of the disclosure, the polyethylene composition satisfies the following relationship: [(weight average molecular weight of the third polyethylene) - (weight average molecular weight of the first polyethylene)] / (weight average molecular weight of the third polyethylene) x 100% > -250%. In one embodiment of the disclosure, the polyethylene composition satisfies the following relationship: [(weight average molecular weight of the third polyethylene) - (weight average molecular weight of the first polyethylene)] / (weight average molecular weight of the third polyethylene) x 100% > -225%. In one embodiment of the disclosure, the polyethylene composition satisfies the following relationship: [(weight average molecular weight of the third polyethylene) - (weight average molecular weight of the first polyethylene)] / (weight average molecular weight of the third polyethylene) x 100% > -200%. In one embodiment of the disclosure, the polyethylene composition satisfies the following relationship: [(weight average molecular weight of the third polyethylene) - (weight average molecular weight of the first polyethylene)] / (weight average molecular weight of the third polyethylene) x 100% > -175%. In one embodiment of the disclosure, the polyethylene composition satisfies the following relationship: [(weight average molecular weight of the third polyethylene) - (weight average molecular weight of the first polyethylene)] / (weight average molecular weight of the third polyethylene) x 100% > -150%. In one embodiment of the disclosure, the polyethylene composition satisfies the following relationship: [(weight average molecular weight of the third polyethylene) - (weight average molecular weight of the first polyethylene)] / (weight average molecular weight of the third polyethylene) x 100% > -100%. In one embodiment of the disclosure, the polyethylene composition satisfies the following relationship: [(weight average molecular weight of the third polyethylene) - (weight average molecular weight of the first polyethylene)] / (weight average molecular weight of the third polyethylene) x 100% > -50%.

[0232] The upper limit on the density of the polyethylene product can be about 0.975 g/cm3; in some cases about 0.965 g/cm3 e; in other cases, about 0.955 g/cm3. The lower limit on the density of the polyethylene product can be about 0.869 g/cm 3 , in some cases about 0.879 g/cm 3 , e; in other cases, about 0.889 g/cm3.

[0233] In the embodiments of the disclosure, the density of the polyethylene product can be from about 0.879 g/cm3 to about 0.940 g/cm3, or from about 0.879 g/cm3 to about 0.939 g/cm3, or from about from about 0.879 g/cm3 to about 0.936 g/cm3, or from about 0.890 g/cm3 to about 0.939 g/cm3, or from about 0.890 to about 0.936 g/cm3, or from about 0.879 g/cm3 to about 0.932 g/cm3, or from about 0.89 g/cm3 to about 0.934 g/cm3, or from about 0.890 g/cm3 to about 0.932 g/cm3, or from about 0.890 g/cm3 to about 0.930 g/cm3, or from about 0.890 to about 0.928 g/cm3, or from about 0.890 to about 0.926 g/cm3, or from about 0.890 g/cm3 to about 0.924 g/cm3, or from about 0.890 g/cm 3 to about 0.921 g/cm 3 , or from about 0.890 g/cm 3 to about 0.918 g/cm 3 .

[0234] In one embodiment of the disclosure, the density of the polyethylene product may be less than about 0.941 g/cm3, or less than about 0.940 g/cm3, or less than about 0.939 g/cm3, or < about 0.939 g/cm3.

[0235] The upper limit on CDBI50 of the final polyethylene product may be about 97%, in other cases about 90%, and in still other cases about 85%. A final polyethylene product with a CDBI50 of 97% can result if an alpha-olefin is not added to the continuous solution polymerization process; in this case, the final polyethylene product is an ethylene homopolymer. The lower limit on the CDBI50 of a final polyethylene product may be about 20%, in other cases about 40%, and in still other cases about 60%.

[0236] In one embodiment of the disclosure, the polyethylene product may have a CDBI50 greater than about 40%. In further embodiments of the disclosure, the polyethylene product can have a CDBI50 of from about 35 to 95%, or from about 40 to 85%, or from about 40 to about 75%.

[0237] The upper limit on the Mw/Mn of the final polyethylene product may be about 25, in other cases about 15, and in still other cases about 9. The lower limit on the Mw/Mn of the polyethylene product end may be 2.0, in other cases about 2.1, or about 2.2.

[0238] In one embodiment of the disclosure, the polyethylene product can have a Mw/Mn of from about 2.1 to about 3.6, or from about 2.0 to about 3.5, or from about 2.1 to about 3.4, or from about 2.1 to about 3.2, or from about 2.1 to about 3.0, or from about 2.0 to about 3, 0, or from about 2.0 to about 2.8.

[0239] In one embodiment of the disclosure, the polyethylene product may have an MZ/MW of less than about 4.0, or less than about 3.5, or less than about 3.0, or less than about 2.5, or less than about 2.3, or less than about 2.1. In embodiments of the disclosure, the polyethylene product can have an MZ/MW of from about 1.6 to about 4.5, or from about 1.6 to about 4.0, or from about 1.6 to about 4.0. about 3.5, or from about 1.6 to about 3.2, or from about 1.6 to about 3.0, or from about 1.8 to about 3.2, or from about 1.8 to about 3.0, or from about 1.6 to about 3.0, or from about 1.8 to about 2.8, or from about 1.8 to about 3.0 2.5, or from about 1.6 to about 2.3, or from about 1.8 to about 2.3.

[0240] In one embodiment of the disclosure, the polyethylene product has a stress exponent less than 1.5, or less than 1.4, or less than 1.3, where the stress exponent is defined by the following relationship : S.Ex.= log(I6/I2)/log(6480/2160); where I6 and I2 are the melt indices measured at 190 °C using loads of 6.48 kg and 2.16 kg, respectively.

[0241] Catalyst residues can be quantified by measuring the parts per million of catalytic metal in the final polyethylene product. Catalytic metals originate from two or, optionally, three sources, specifically: 1) metals originating from component (a) that were used to form the single-site catalyst system used in reactors 1 and 2; and, optionally, “metals” that originate from the second system that can be used in reactor 3.

[0242] The upper limit on the I2 melt index of the polyethylene product may be about 500 dg/min, in some cases about 400 dg/min; in other cases, about 300 dg/min, and; in still other cases, about 200 dg/min. The lower limit on the melt index of the final polyethylene product can be about 0.1 dg/min, or 0.2 dg/min, or 0.3 dg/min, in some cases about 0.4 dg/min ; in other cases about 0.5 dg/min, e; in still other cases, about 0.6 dg/min.

[0243] In the embodiments of the present disclosure, the polyethylene product can have an I2 melt index of from about 0.05 dg/min to about 500 dg/min, or from about 0.1 dg/min to about 400 dg/min, or from 0.1 dg/min to about 300 dg/min, or from about 0.1 dg/min to about 200 dg/min, or from about 0.1 dg/min to about 100 dg/min, or from 0.1 dg/min to about 50 dg/min, or from about 0.1 dg/min to about 25 dg/min, or from about 0.1 dg/min min to about 20 dg/min, or from about 0.1 dg/min to about 15 dg/min, or from about 0.1 dg/min to about 10 dg/min, or from about 0 .1 dg/min to about 5.0 dg/min, or from about 0.1 dg/min to about 3.0 dg/min.

[0244] In one embodiment of the disclosure, the polyethylene product may have a melt index ratio, I21/I2 from about 10 to about 35, where I21 and I2 are the melt indices measured at 190 °C using loads of 21.16 kg and 2.16 kg respectively. In another embodiment of the disclosure, the polyethylene product can have a melt index ratio, I21 /I2 of from about 10 to about 30. In yet another embodiment of the disclosure, the polyethylene product can have a melt index ratio I21/I2 less than about 30.

[0245] In one embodiment of the disclosure, the polyethylene product may have a unimodal profile on a gel permeation chromatography.

[0246] In one embodiment of the disclosure, the polyethylene product may have a multimodal TREF profile in an elution fractionation graph on rising temperature. In the context of TREF analysis, the term “multimodal” connotes a TREF profile in which two or more distinct elution peaks are observable.

[0247] In one embodiment of the disclosure, the polyethylene product may have a trimodal TREF profile in an elution fractionation graph on rising temperature. In the context of TREF analysis, the term “trimodal” connotes a TREF profile in which three distinct elution peaks are observable.

[0248] In one embodiment of the disclosure, the polyethylene product may be at least about 10 percent by weight of the product that elutes at a temperature of 90 °C to 100 °C in a TREE analysis. disclosure, the polyethylene product can be at least about 15 percent by weight of the product that elutes at a temperature of 90°C to 100°C in a TREF analysis. In another embodiment of the disclosure, the polyethylene product can be at least about 17.5 percent by weight of the product that elutes at a temperature of 90°C to 100°C in a TREF analysis. In another embodiment of the disclosure, the polyethylene product can be at least about 20 percent by weight of the product that elutes at a temperature of 90°C to 100°C in a TREF analysis. In another embodiment of the disclosure, the polyethylene product can be at least about 22.5 percent by weight of the product that elutes at a temperature of 90°C to 100°C in a TREF analysis. In another embodiment of the disclosure, the polyethylene product can be at least about 25 percent by weight of the product that elutes at a temperature of 90°C to 100°C in a TREF analysis.

[0249] In one embodiment of the disclosure, the polyethylene product may have a multimodal profile on a differential scanning calorimetry (DSC) graph. In the context of DSC analysis, the term “multimodal” connotes a DSC profile in which two or more distinct peaks are observable.

[0250] In one embodiment of the disclosure, the polyethylene product may have a trimodal profile on a differential scanning calorimetry (DSC) graph. In the context of DSC analysis, the term “trimodal” connotes a DSC profile in which three distinct peaks are observable.

[0251] In one embodiment of the disclosure, the polyethylene product will have an inverse (i.e., "reverse") or partially inverse comonomer distribution profile as measured using GPC-FTIR. If comonomer incorporation decreases with molecular weight, as measured using GPC-FTIR, the distribution is described as "normal". If the comonomer incorporation is approximately constant with molecular weight, as measured using GPC-FTIR, the comonomer distribution is described as "flat" or "uniform". The terms "reverse comonomer distribution" and "partially reverse comonomer distribution" mean that in the GPC-FTIR data obtained for the copolymer, there is one or more higher molecular weight components having a higher comonomer incorporation than one or more higher molecular weight components. bottom. The term "reverse(d) comonomer distribution" is used herein to mean that over the molecular weight range of ethylene copolymer, comonomer contents for the various polymeric fractions are not substantially uniform and the higher molecular weight fractions of the they have proportionately higher comonomer contents (ie, if comonomer incorporation rises with molecular weight, the distribution is described as "reversed" or "reversed"). When comonomer incorporation rises with increasing molecular weight and then declines, the comonomer distribution will still be regarded as "reverse", but will also be described as "partially reversed".

[0252] In one embodiment of the disclosure, the polyethylene product has a reverse comonomer distribution profile as measured using GPC-FTIR.

[0253] In one embodiment of the disclosure, the polyethylene product has a partially reversed comonomer distribution profile as measured using GPC-FTIR.

[0254] In one embodiment of the disclosure, the polyethylene product has a "partially reversed" comonomer distribution profile and shows a peak or a maximum in the comonomer distribution profile as measured using GPC-FTIR.

[0255] In one embodiment of the disclosure, the polyethylene product is produced in a continuous solution polymerization process.

[0256] In one embodiment of the disclosure, the polyethylene product is produced in a continuous solution polymerization process comprising a first and a second reactor configured in parallel with each other.

[0257] In one embodiment of the disclosure, the polyethylene product is produced in a continuous solution polymerization process comprising a first, second and third reactors, where the first and second reactors are configured parallel to each other, and the third reactor receives the combined effluent flows from the first and second reactors.

[0258] In one embodiment of the disclosure, the first polyethylene is produced with a single-site catalyst system.

[0259] In one embodiment of the development, the first polyethylene is a homogeneous polyethylene.

[0260] In one embodiment of the disclosure, the second polyethylene is produced with a single-site catalyst system.

[0261] In one embodiment of the development, the second polyethylene is a homogeneous polyethylene.

[0262] In one embodiment of the disclosure, the third polyethylene is produced with a single-site catalyst system.

[0263] In one embodiment of the development, the third polyethylene is produced with a Ziegler-Natta catalyst system.

[0264] In one embodiment of the disclosure, the first polyethylene and the second polyethylene are produced with a single-site catalyst system.

[0265] In one embodiment of the development, the first polyethylene and the second polyethylene are homogeneous polyethylenes.

[0266] In one embodiment of the disclosure, the first polyethylene, the second polyethylene and the third polyethylene are produced with a single-site catalyst system.

[0267] In one embodiment of the disclosure, the first polyethylene and the second polyethylene are produced with a single-site catalyst system, while the third polyethylene is produced with a Ziegler-Natta catalyst system.

[0268] In one embodiment of the disclosure, the polyethylene product substantially does not have a long chain branch. The phrase "substantially no long-chain branching" means that the polyethylene product has less than 0.03 long-chain branches per thousand carbons.

[0269] In one embodiment of the disclosure, the polyethylene product has a storage modulus value G'(@G”=500 Pa) less than about 38, or less than about 36, or less than about 34.

[0270] In one embodiment of the disclosure, the polyethylene product has a DRI of less than about 0.55, where the DRI is the “dow index of rheology”, defined by the equation: DRI=[365OOO(To/no) -1]/10; where TO is the characteristic relaxation time of polyethylene and no is the zero shear viscosity of the material. The DRI is calculated by least squares fitting of the rheological curve (dynamic complex viscosity versus applied frequency eg. 0.01-100 rads/sec) as described in U.S. Pat. 6,114,486 with the following generalized Cross equation, ie, n(w)=no/[1+(wTo)n]; where n is the power law index of the material, n(w) and w are the measured complex viscosity data and applied frequency, respectively.

[0271] In one embodiment of the disclosure, the polyethylene product has a DRI of < 0.55, or < 0.50, or < 0.45, or < 0.40, or < 0.35, or < 0. 3rd.

[0272] The catalyst residues in the polyethylene product reflect the chemical compositions of the single-site catalyst system used in reactors 1 and 2, and, if present, of the second catalyst system used in reactor 3.

[0273] The polyethylene products disclosed in this document can be converted into flexible manufactured articles such as monolayer or multilayer films, these films are well known to individuals with experience in the art; Non-imitative examples of processes for preparing these films include blown film and cast film processes.

[0274] In the blown film extrusion process, an extruder heats, melts, mixes and transports a thermoplastic, or a thermoplastic blend. Once melted, the thermoplastic is forced through an annular die to produce a thermoplastic tube. In the case of co-extrusion, multiple extruders are employed to produce a multilayer thermoplastic tube. The temperature of the extrusion process is primarily determined by the thermoplastic or thermoplastic blend being processed, for example, the melt temperature or glass transition temperature of the thermoplastic and the desired viscosity of the melt. For polyolefins, typical extrusion temperatures are 330°F to 550°F (166°C to 288°C). Upon exiting the annular die, the thermoplastic tube is inflated with air, cooled, solidified and pulled through a pair of pressure rollers. Due to air inflation, the tube increases in diameter forming a bubble of desired size. Due to the pulling action of the pressure rollers, the bubble is stretched in the machine direction. Thus, the bubble is stretched in two directions: the transverse direction (TD) where the inflation air increases the bubble diameter; and the machine direction (MD) where the pressure rollers stretch the bubble. As a result, the physical properties of blown films are typically anisotropic, that is, the physical properties differ in the MD and TD directions; for example, film tear strength and tensile strength properties typically differ in MD and TD. In some prior art documents, the terms "cross direction" or "CD" are used; these terms are equivalent to the terms "transverse direction" or "TD" used in this disclosure. In the blown film process, air is also blown into the outer bubble circumference to cool the thermoplastic as it exits the annular die. Final film width is determined by controlling inflation air or internal bubble pressure; in other words, increasing or decreasing the bubble diameter. Film thickness is primarily controlled by increasing or decreasing the speed of the pinch rollers to control the drawdown rate. After exiting the pressure rollers, the blister or tube is collapsed and can be split in machine direction, thus creating lamination. Each blade can be rolled onto a roll of film. Each roll can be further divided to create a film of desired width. Each roll is further processed into a variety of consumer products as described below.

[0275] The cast film process is similar to that in which a single extruder or multiple extruders can be used; however, the various thermoplastic materials are measured in a flat die and extruded into a monolayer or multilayer sheet rather than a tube. In the cast film process, the extruded sheet is solidified on a cooling roller.

[0276] Depending on the end-use application, the developed polyethylene products can be converted into films that span a wide range of thicknesses. Non-limiting examples include food packaging films where thicknesses can range from about 0.5 mil (13 µm) to about 4 mil (102 µm), and; in heavy duty bag applications, film thickness can vary from about 2 mil (51 µm) to about 10 mil (254 µm).

[0277] The polyethylene products disclosed in this document can be used in monolayer films; where the monolayer can contain more than one polyethylene product and/or additional thermoplastics; Non-limiting examples of thermoplastics include polyethylene polymers and propylene polymers. The lower limit on the percentage by weight of polyethylene product in a monolayer film may be about 3% by weight, in other cases about 10% by weight, and in still other cases about 30%. % by weight. The upper limit on the percentage by weight of the polyethylene product in the monolayer film may be 100% by weight, in other cases about 90% by weight, and in still other cases about 70% by weight. Weight.

[0278] The polyethylene products disclosed in this document can also be used in one or more layers of a multilayer film; Non-limiting examples of multilayer films include three, five, seven, nine, eleven or more layers. The thickness of a specific layer (containing a polyethylene product) within a multilayer film may be about 5%, in other cases about 15%, and in still other cases about 30% of the film thickness. full multilayer. In other embodiments, the thickness of a specific layer (containing the polyethylene product) within a multilayer film can be about 95%, in other cases about 80%, and in still other cases about 65% of the thickness. total multilayer film thickness. Each individual layer of a multilayer film may contain more than one additional polyethylene and/or thermoplastic product.

[0279] Additional embodiments include include laminations and coatings, in which monolayer or multilayer films containing the disclosed polyethylene products are extrusion laminated or adhesively laminated or extrusion coated. In extrusion lamination or adhesive lamination, two or more substrates are bonded together with a thermoplastic or an adhesive, respectively. In extrusion coating, a thermoplastic is applied to the surface of a substrate. Such processes are well known to those skilled in the art. Often, adhesive lamination or extrusion lamination is used to join dissimilar materials, non-limiting examples include joining a paper web to a thermoplastic web, or joining a web containing aluminum foil to a thermoplastic web, or the joining two thermoplastic mats that are chemically incompatible, for example joining a mat containing polyethylene product to a polyester or polyamide mat. Prior to lamination, the web containing the developed polyethylene products can be monolayer or multilayer. Prior to lamination, individual webs can be surface treated to improve the bond, a non-limiting example of a surface treatment is corona treatment. A primary mat or film can be laminated to its top surface, its bottom surface, or both its top and bottom surfaces with a secondary mat. A secondary mat and a tertiary mat can be laminated to the primary mat; in which the secondary and tertiary mats differ in chemical composition. As non-limiting examples, secondary or tertiary webs can include polyamide, polyester and polypropylene, or webs containing layers of barrier resin such as EVOH. Such mats may also contain a vapor deposited barrier layer; for example, a layer of thin silicon oxide (SiOx) or aluminum oxide (AlOx). Multi-layer batts (or films) may contain three, five, seven, nine, eleven or more layers.

[0280] The polyethylene products disclosed in this document can be used in a wide range of manufactured articles comprising one or more films or layers of films (monolayer or multilayer). Non-limiting examples of these articles of manufacture include: films for food packaging (fresh and frozen food, liquid and granular food), backing pouches, retortable packaging and bag-in-box packaging; barrier films (oxygen, moisture, aroma, oil, etc.) and modified atmosphere packaging, collating shrink films, pallet shrink films, shrink bags, shrink packs and shrink wraps; light and heavy stretch films, manual stretch film, machine stretch wrap and stretch cover films; high clarity films; heavy bags; household wraps, packaging films and sandwich bags; industrial and institutional films, garbage bags, can liners, magazine wrappers, newspaper bags, mailing bags, bags and envelopes, bubble wrap, carpet films, furniture bags, garment bags, coin purses, panel films of automobiles; medical applications such as aprons, drapery and surgical clothing; construction films and sheets, asphalt films, insulation bags, masking films, landscaping films and bags; geomembrane liners for municipal waste disposal and mining applications; batch inclusion bags; agricultural films, mulch films and greenhouse films; store packaging, self-service bags, boutique bags, grocery bags, tote bags and t-shirt bags; oriented films, machine direction oriented and biaxially oriented films and functional film layers on oriented polypropylene (OPP) films, eg sealant and/or toughness layers. Additional articles of manufacture comprising one or more films containing at least one polyethylene product include laminates and/or multilayer films; sealants and bonding layers in films and multilayer composites; paper laminations; aluminum foil laminates or laminates containing vacuum deposited aluminum; polyamide laminates; polyester laminates; extrusion coated laminates, and; hot melt adhesive formulations. The articles of manufacture summarized in this paragraph contain at least one film (monolayer or multilayer) comprising at least one embodiment of the disclosed polyethylene products.

[0281] The desired film physical properties (monolayer or multilayer) typically depend on the application of interest. Non-limiting examples of desirable film properties include: optical properties (gloss, haze, and clarity), dart impact, Elmendorf tear, modulus (1% and 2% secant modulus), puncture propagation tear resistance, tensile strength (yield strength, breaking strength, elongation at break, stiffness, etc.) and heat seal properties (heat seal initiation temperature and hot melt strength). The specific heat sealing and heat sealing properties are desired in vertical and horizontal sealing processes for high speed form filling that load and seal a commercial product (liquid, solid, pasty, partial, etc.) within a type package. handbag.

[0282] In addition to the desired film physical properties, it is desired that the developed polyethylene products are easy to process in film lines. Those skilled in the art often use the term "processability" to differentiate polymers with improved processability versus polymers with lower processability. A commonly used measure to quantify processability is extrusion pressure; More specifically, a polymer with an improved processability has a lower extrusion pressure (on a blown film or cast film extrusion line) than a polymer with a lower processability.

[0283] In one embodiment of development, a film or film layer comprises the previously described polyethylene product.

[0284] In the development modalities, a film will have a dart impact of > 500 g/mil, or > 550 g/mil, or > 600 g/mil, or > 650 g/mil, or > 700 g/mil. In another embodiment of development, a film will have a dart impact of 500 g/mil to 950 g/mil. In an additional mode of development, a film will have a dart impact of 550 g/mil to 850 g/mil. In yet another mode of development, the film will have a dart impact of 600 g/mil to 850 g/mil. In yet another embodiment of development, a film will have a dart impact of 600 g/mil to 800 g/mil.

[0285] In the development modalities, a 1 mil film will have a secant modulus in machine direction (MD) at 1% strain of > 150 MPa, or > 160 MPa, or > 170 MPa, or > 175 MPa, or > 180 MPa, or > 185 MPa, or > 190 MPa, or > 195 MPa, or > 200 MPa. In one development embodiment, a 1 mil film will have a machine direction (MD) secant modulus at 1% strain from 150 MPa to 240 MPa. In one development embodiment, a 1 mil film will have a machine direction (MD) secant modulus at 1% strain from 160 MPa to 230 MPa. In another development mode, a 1 mil film will have a secant modulus in machine direction (MD) at 1% strain from 170 MPa to 230 MPa. In yet another development embodiment, a 1 mil film will have a secant modulus in machine direction (MD) at 1% strain from 170 MPa to 220 MPa.

[0286] In a development mode, a 1 mil film will have a secant modulus in the transverse direction (TD) at 1% strain of > 190 MPa, or > 200 MPa, or > 210 MPa, or > 220 MPa, or > 230 MPa. In one development embodiment, a 1 mil film will have a secant modulus in the transverse direction (TD) at 1% strain from 180 MPa to 400 MPa. In another development embodiment, a 1 mil film will have a secant modulus in the transverse direction (TD) at 1% strain from 180 MPa to 300 MPa. In yet another embodiment of development, a 1 mil film will have a secant modulus in the transverse direction (TD) at 1% strain from 200 MPa to 280 MPa.

[0287] In the development modalities, a 1 mil film will have a tensile strength in machine direction (MD) at rupture of > 35 MPa, or > 40 MPa, or > 45 MPa, or > 50 MPa, or > 55 MPa. In one development embodiment, a 1 mil film will have a tensile strength in machine direction at break of 30 MPa to 70 MPa. In one development embodiment, a 1 mil film will have a machine direction (MD) tensile strength at break of 35 MPa to 65 MPa. In another development embodiment, a 1 mil film will have a machine direction (MD) tensile strength at break of 40 MPa to 65 MPa.

[0288] In the development modalities, a film will have a resistance to tearing in the machine direction (MD) of > 200 g/mil, or > 210 g/mil, or > 220 g/mil, or > 230 g/mil, or > 240 g/mil, or > 250 g/mil, or > 260 g/mil, or > 270 g/mil, or > 275 g/mil. In one development embodiment, a film will have a machine direction (MD) tear strength of 220 g/mil to 375 g/mil. In one development embodiment, a film will have a machine direction (MD) tear strength of 230 g/mil to 375 g/mil. In one development embodiment, a film will have a machine direction (MD) tear strength of 240 g/mil to 375 g/mil. In one development embodiment, a film will have a machine direction (MD) tear strength of 250 g/mil to 375 g/mil. In one development embodiment, a film will have a machine direction (MD) tear strength of 250 g/mil to 350 g/mil.

[0289] In the development modalities, a 1 mil film will have a slow puncture resistance value of > 55 J/mm, or > 60 J/mm, or > 65 J/mm, or > 70 J/mm, or > 75 J/mm, or > 80 J/mm, or > 85 J/mm. In development modes, a 1 mil film will have a slow pierce value of 55 J/mm to 95 J/mm, or 60 J/mm to 90 J/mm, or 65 J/mm to 90 J/mm .

[0290] In development modalities, a 1 mil film will have a haze of < 16%, or < 15%, < 14%, or < 13%, or < 12%, or < 11%, or < 10%. In development modes, a 1 mil film will have a haze of 6% to 16%, or 8% to 14%.

[0291] In the development modalities, a 1 mil film will have a seal initiation temperature of < 115 °C, or < 110 °C, or < 105 °C, or < 100 °C. In one development embodiment, a 1 mil film will have a seal initiation temperature (SIT) between 90°C and 115°C. In one development embodiment, a film will have a seal initiation temperature (SIT) between 95°C and 105°C. In one development embodiment, a film will have a seal initiation temperature (SIT) between 95°C and 100°C. In one development embodiment, a film will have a seal initiation temperature (SIT) between 90°C and 100°C.

[0292] Some embodiments of the present disclosure provide the films with improvements in at least two or more of the following properties: dart impact, modulus in machine direction (MD) (1% and/or 2%), tensile strength in direction machine direction (MD) at break, machine direction (MD) tear, slow puncture resistance, fog, and seal initiation temperature relative to films formed from comparative polyethylenes. Therefore, in one development embodiment, a 1 mil film has a dart impact strength of > 600 g/mil, a secant modulus in 1% MD of > 170 MPa, a tensile strength in MD at break of > 40 MPa, a machine direction (MD) tear of > 250 g/mil, a slow pierce value of > 65 J/mm, a haze of less than < 14%, and a seal initiation temperature (SIT) of < 105 °C. In another embodiment of development, a 1 mil film has a dart impact strength of > 600 g/mil, a secant modulus in 1% MD of > 170 MPa, a slow pierce value of > 65 J/mm, a machine direction (MD) tear of > 250 g/mil, and seal initiation temperature (SIT) of < 105 °C.

[0293] In a development mode, films manufactured using the inventive compositions will have good hot-sticking performance. Good heat seal performance is generally associated with good film performance on pouch or bag packaging lines such as form fill vertical seal application lines (VFFS). Without wishing to be bound by any theory, in the hot melt profile (seal temperature vs. force), good hot melt performance is indicated by an early (or slow) hot melt initiation temperature, so a relatively high strength over a wide range of sealing temperatures.

[0294] The films used in manufactured articles described in this section may optionally include, depending on their intended use, additives and adjuvants. Non-limiting examples of additives and adjuvants include, antiblocking agents, antioxidants, heat stabilizers, glidants, processing aids, antistatic additives, colorants, colorants, fillers, light stabilizers, light absorbers, lubricants, pigments, plasticizers, agents of nucleation and combinations thereof.

[0295] The following examples are presented for the purpose of illustrating selected embodiments of this disclosure; it being understood that the examples presented are not limited to the claims presented.

EXAMPLES test methods

[0296] Before testing, each specimen was conditioned for at least 24 hours at 23 ±2 °C and 50 ±10% relative unit and a subsequent test was conducted at 23 ±2 °C and 50 ±10% relative unit . In this document, the term “ASTM conditions” refers to a laboratory that is maintained at 23 ±2 °C and 50 ±10% relative humidity; and specimens to be tested were conditioned for at least 24 hours in that laboratory prior to testing. ASTM refers to the North American Society for Testing and Materials.

[0297] Polyethylene product densities were determined using ASTM D792-13 (November 1, 2013).

[0298] The melt index of polyethylene product was determined using ASTM D1238 (August 1, 2013). Melt indices, I2 , I6 , I10 and I21 were measured at 190°C using weights of 2.16 kg, 6.48 kg, 10 kg and 21.6 kg respectively. In this document, the term “voltage exponent” or its acronym “S.Ex.”, is defined by the following relationship: S.Ex.= log (I6/I2)/log(6480/2160); where I6 and I2 are the melt flow rates measured at 190 °C using 6.48 kg and 2.16 kg charges, respectively.

[0299] Molecular weights of polyethylene product, Mn, Mw and Mz, as well as polydispersity (Mw/Mn), were determined using ASTM D6474-12 (December 15, 2012). This method clarifies the molecular weight distributions of polyethylene polymer products by high temperature gel permeation chromatography (GPC). The method uses commercially available polystyrene standards to calibrate the GPC.

[0300] The “Composition Distribution Branching Index” or “CDBI” of the Inventive Examples and Comparative Examples were determined using a crystalline TREF unit commercially available from Polymer Char (Valencia, Spain). The acronym “TREF” refers to Temperature Rise Elution Fractionation. A sample of ethylene polymer product (80 to 100 mg) was placed in the reactor of the Polymer Char crystalline TREF unit, the reactor was charged with 35 ml of 1,2,4-trichlorobenzene (TCB), heated to 150° C and held at that temperature for 2 hours to dissolve the sample. An aliquot of the TCB solution (1.5 mL) was then loaded onto the Polymer Char TREF column loaded with stainless steel microspheres and the column was equilibrated for 45 minutes at 110 °C. The polyethylene product was then crystallized from the TCB solution on the TREF column by slowly cooling the column from 110°C to 30°C using a cooling rate of 0.09°C per minute. The TREF column was then equilibrated at 30°C for 30 minutes. The crystallized polyethylene product was then eluted from the TREF column by passing pure TCB solvent through the column at a flow rate of 0.75 mL/minute as the column temperature was slowly increased from 30 °C to 120 °C using a heating rate of 0.25 °C per minute. Using Polymer ChAR software, a TREF distribution curve was generated as the polyethylene product was eluted from the TREF column, i.e., a TREF distribution curve is a graphical representation of the amount (or intensity) ) of polyethylene product eluting from the column as a function of TREF elution temperature. A CDBI50 was calculated from the TREF distribution curve for each polyethylene product analyzed. The "CDBI50" is defined as the percentage, by weight, of ethylene polymer whose composition is within 50% of the median comonomer composition (50% on each side of the median comonomer composition); The same is calculated from the TREF compositional distribution curve and the normalized cumulative integral of the TREF compositional distribution curve. Those skilled in the art will understand that a calibration curve is necessary to convert a TREF elution temperature into comonomer content, ie, the proportion of comonomer in the fraction of polyethylene product that elutes at a specific temperature. The generation of these calibration curves is described in the prior art, eg Wild, et al., J. Polym. Sci., Part B, Polym. Phys., Vol. 20(3), pages 441-455: incorporated herein in its entirety by reference. The "CDBI25" is defined as the percentage, by weight, of the polyethylene product whose composition is within 25% of the median comonomer composition (25% on either side of the median comonomer composition).

[0301] Dynamic mechanical analyzes were performed with a rheometer, that is, Rheometrics Dynamic Spectrometer (RDS-II) or Stresstech SR5 or ATS Rheometrics, on samples modeled by compression under a nitrogen atmosphere at 190 °C, using a conical and plane geometry of 25 mm diameter. The oscillatory shear experiments were performed within the linear viscoelastic strain range (10% strain) at frequencies from 0.05 to 100 rad/s. The values of storage modulus (G'), loss modulus (G”), complex modulus (G*) and complex viscosity (q*) were obtained as a function of frequency. The same rheological data can also be obtained using a 25 mm diameter parallel plane geometry at 190 °C under a nitrogen atmosphere.

[0302]The impact strength of the film dart was determined using ASTM Method D1709-09 A (May 1, 2009). In this disclosure, the dart impact test employed a 1.5 inch (38 mm) diameter hemispherical head dart.

[0303] Film “perforation”, or “slow perforation” which is the energy (J/mm) required to break the film was determined using ASTM D5748-95 (originally adopted in 1995, reapproved in 2012).

[0304] The “lubricated piercing” test was performed as follows: the energy (J/mm) to pierce a film sample was determined using a fluorocarbon-coated probe with a pear shape and a diameter of 0.75 inches (1 .9 cm) moving at 10 inches per minute (25.4 cm/minute). ASTM conditions were employed. Before testing the specimens, the probe head was manually lubricated with Muko lubricating gel to reduce friction. Muko Lubricating Gel is a water soluble personal lubricant available from Cardinal Health Inc., 1000 Tesma Way, Vaughan, ON L4K 5R8 Canada. The probe was mounted on an Instron Model 5 SL Universal Testing Machine and a 1000 N load cell as per use. Film samples (1.0 mil (25 µm) thick, 5.5 inches (14 cm) wide, and 6 inches (15 cm) long) were mounted in the Instron and perforated.

[0305] The following film tensile properties were determined using ASTM D882-12 (August 1, 2012): tensile strength at break (MPa), elongation at break (%), yield strength (MPa) , tensile elongation in yield (%) and film stiffness or total energy at break (footdb/in3). Tensile properties were measured in machine direction (MD) and transverse direction (TD) of blown films.

[0306] The secant modulus is a measure of film stiffness. The secant modulus is the slope of a line drawn between two points on the stress-strain curve, ie the secant line. The first point on the stress-strain curve is the origin, that is, the point that corresponds to the origin (the point of zero percent strain and zero stress), and; the second point on the stress-strain curve is the point corresponding to 1% strain; given these two points the secant modulus at 1% is calculated and expressed in terms of force per unit area (MPa). The 2% secant modulus is calculated similarly. This method is used to calculate film modulus because the stress-strain relationship for polyethylene does not follow Hook's law; that is, the stress-strain behavior of polyethylene is non-linear due to its viscoelastic nature. The secant modulus was measured using a conventional Instron tensile tester equipped with an 889.64 N (200 lbf) load cell. Strips of monolayer film samples were cut for testing to the following dimensions: 35.56 centimeters (14 inches) long, 2.54 centimeters (1 inch) wide, and 1 mil thick; ensuring that there were no cracks or cuts on the edges of the samples. The film samples were cut in machine direction (MD) and cross direction (TD) and tested. ASTM conditions were used to condition the samples. The thickness of each film was precisely measured with a handheld micrometer and entered along with the sample name into the Instron software. Samples were loaded into the Instron with a grip separation of 25.4 centimeters (10 inches) pulled at a rate of 2.54 cm/min (1 inch/min) generating the strain-strain curve. The 1% and 2% secant modulus were calculated using Instron software.

[0307] The puncture propagation tear resistance of blown film was determined using ASTM D2582-09 (May 1, 2009). This test measures the resistance of a blown film to obstacles, or more precisely, to dynamic puncture and puncture propagation resulting in a tear. The puncture propagation tear resistance was measured in the machine direction (MD) and in the transverse direction (TD) of the blown films.

[0308]Film tearing performance was determined by ASTM D1922-09 (May 1, 2009); an equivalent term for tear is "Elmendorf tear". Film tearing was measured in the machine direction (MD) and transverse direction (TD) of blown films.

[0309] The optical properties of film were measured as follows: Haze, ASTM D1003-13 (November 15, 2013), and; Gloss ASTM D2457-13 (April 1, 2013).

[0310] In this disclosure, the “Hot Sticking Test” was performed as follows, using ASTM conditions. Hot stick data was generated using a J&B Hot Stick Tester which is commercially available from Jbi Hot Tack, Geloeslaan 30, B-3630 Maamechelen, Belgium. In the heat seal test, the strength of a polyolefin seal to the polyolefin is measured immediately after heat sealing the two film samples together (the two film samples were cut from the same 2.0 mil (51- μm) thick), i.e. when the polyolefin macromolecules comprising the film are in a semi-molten state. This model simulates the heat sealing of polyethylene films on high speed automatic packaging machines, for example vertically or horizontally filling and sealing equipment. The following parameters were used in the J&B Hot Seal Test: film specimen width, 1 inch (25.4 mm); film sealing time, 0.5 second; film sealing pressure, 0.27 N/mm2; delay time, 0.5 second; film shift speed, 7.9 inch/second (200 mm/second); test temperature range, 203°F to 293°F (95°C to 145°C); temperature increments, 9°F (5°C); and five film samples were tested at each temperature increment to calculate average values at each temperature. The following data were recorded for the Inventive Example films and Comparative Example films: “Principle of Bonding @ 1.0 N (°C)”, the temperature at which a hot bond strength of 1N was observed (mean of 5 film samples); “Maximum Hot Bond Strength (N)”, the maximum observed hot bond strength (average of 5 film samples) over the test temperature range, and; “Temperature - maximum hot glue (°C)”, the temperature at which the maximum hot glue strength was observed.

[0311] In this disclosure, the “Hot Seal Strength Test” (also known as “cold seal test”) has been performed as follows. ASTM conditions were employed. The heat seal data was generated using a conventional Instron Tensile Tester. In this test, two film samples are sealed over a range of temperatures (both film samples were cut from the same 2.0 mil (51-μm) thick roll). The following parameters were used in the Heat Seal (or Cold Seal) Strength Test: film specimen width, 1 inch (25.4 mm); film sealing time, 0.5 second; film seal pressure, 40 psi (0.28 N/mm2); temperature range, 212°F to 302°F (100°C to 150°C) and temperature step, 9°F (5°C). After aging for at least 24 hours under ASTM conditions, the seal strength was determined using the following tensile parameters: crosshead pull speed, 12 inches/min (2.54 cm/min); pulling direction, 90° to seal, and; 5 film samples were tested at each temperature increment. The Seal Initiation Temperature, hereinafter S.I.T., is defined as the temperature required to form a commercially viable seal; a commercially viable seal has a seal strength of 2.0 lbs per inch of seal (8.8 N per 25.4 mm of seal).

[0312] Hexane extractables were determined in accordance with the Federal Registration Code 21 CFR §177.1520 For (c) 3.1 and 3.2; wherein the amount of hexane extractable material in a film is determined gravimetrically. Elaborating, 2.5 grams of 3.5 mil (89 µm) monolayer film was placed in a stainless steel basket, the film and basket were weighed (wi), while in the basket the film was: extracted with n-hexane at 49.5°C for two hours; dried at 80 °C in a vacuum oven for 2 hours; cooled in a desiccator for 30 minutes, and; heavy (wf). Percent weight loss is the percentage of hexane extractables (wC6): wC6 = 100 x (wi-wf)/wi.

Polymerization

[0313] The embodiments of polyethylene products were prepared in a pilot plant using two CSTR reactors configured in parallel (reactors 1 and 2), followed by a tubular reactor (reactor 3) as represented by the continuous solution polymerization process shown in Figure 1. In the inventive examples, ethylene was charged to reactor 3. Comparative polyethylene products were prepared similarly and according to the continuous solution polymerization process shown in Figure 1, except that ethylene was not charged to reactor 3.

[0314] Methylpentane was used as the process solvent (a commercial blend of methylpentane isomers). The volume of the first CSTR reactor (R1) was 3.2 gallons (12 L), the volume of the second CSTR reactor (R2) was 5.8 gallons (22 L), and the volume of the tubular reactor (R3) it was 0.58 gallons (2.2 L) or 4.8 gallons (18 L). The pressure of R1 was from about 14 MPa to about 18 MPa; the pressure of R2 was from about 14 MPa to about 18 MPa. Reactor 3 was operated at a lower pressure to facilitate continuous flow from reactors 1 and 2 towards reactor 3. R1 and R2 were configured in parallel with each other, and the combined output flows from reactor 1 and 2 , streams 1' and 2' respectively were charged to reactor 3. Both CSTR's were agitated to provide conditions where the reactor contents were well mixed. The process was operated continuously by charging fresh process solvent, ethylene, 1-octene and hydrogen to the reactors as described under the reactor conditions given in Table 1.

[0315] The components of the single-site catalyst system were loaded into reactors 1 and 2 and included: component (a), cyclopentadienyl tri(tertiary butyl)phosphinemine titanium dichloride, Cp((t-Bu)3PN)TiCl2; component (b), modified methylaluminoxane (MMAO-07); component (c), trityl tetracis(pentafluorophenyl), and; component (d), 2,6-di-tert-butyl-4-ethylphenol.

[0316] The single-site catalyst system component solvents used were methylpentane for catalyst components (b) and (d) and xylene for catalyst components (a) and (c).

[0317] The average residence time of the solvent in a reactor was primarily influenced by the proportion of solvent flowing through each reactor and the total proportion of solvent flowing through the solution process. The following are representative or typical values for the examples shown in Table 1: Average residence times in reactors were: about 8.2 seconds in R1, about 36 seconds in R2, about 6 seconds for an R3 volume of 0 .58 gallons (2.2 L), and about 65 seconds for an R3 volume of 4.8 gallons (18L). Therefore, if the polymerization reaction was allowed to proceed in reactor 3 for a relatively short period of time, then a catalyst deactivator was added to reactor 3 at a point where about 2.2 L of reactor volume was used for polymerization. (Comparative Example 1); alternatively, if the polymerization reaction was allowed to proceed in reactor 3 for a relatively long period of time, then a catalyst deactivator was added to reactor 3 to stop the reaction near the outlet of the tubular reactor (R3), at a point where about 18L of reactor volume was used for polymerization (Comparative Example 2, and Inventive Examples 1-5). For the Inventive Examples, ethylene monomer was charged to the third reactor at a point where about 2.2 L of reactor volume was used for polymerization (Inventive Examples 1 to 5). For Comparative Examples 1 and 2, no ethylene monomer was charged to the third reactor.

[0318] The catalyst deactivator used was octanoic acid (caprylic acid), commercially available from P&G Chemicals, Cincinnati, OH, USA. Catalyst deactivator was added so that the moles of fatty acid added were 50% of the total molar ratio of titanium and aluminum added to the polymerization process; clearly, the added octanoic acid moles = 0.5 x (titanium moles + aluminum moles); this molar ratio was consistently used in all examples.

[0319] A two-stage devolitilization process was employed to recover the final polyethylene product from the process solvent, that is, two vapor/liquid separators were used and the second bottom stream (from the second vapor separator V/L) was passed through a gear pump/pelletizer combination.

[0320] Before pelletizing, the polyethylene product was stabilized by adding 500 ppm of IRGANOX 1076 (a primary antioxidant) and 500 ppm of IRGAFOS 168 (a secondary antioxidant), based on the weight of the polyethylene polymer product. Antioxidants were dissolved in process solvent and added between the first and second V/L separators.

[0321] Catalyst system details, reactor conditions and some final polyethylene product properties are given in Table 1. Table 1 also reveals process parameters such as ethylene and comonomer divisions (ie, 1-octene) (“ ES" and "CS") between reactors, ethylene concentrations in each reactor, ethylene ("Q") conversions in each reactor, etc. When carrying out the polymerization process for each of the examples in Table 1, the target polyethylene product was one having a melt index (I2) (ASTM D1239, 2.16 kg load, 190 °C) or 1 g/10min and a density of 0.917 g/cm 3 (ASTM D792). TABLE 1

[0322] As noted in the data provided in Table 1, in each of the inventive examples, where fresh ethylene is charged directly to reactor 3, the productivity (kg of polyethylene product per hour) of the polymerization reaction improved in relation to any one of the Comparative Examples, in which no fresh ethylene was charged to reactor 3. In general, productivity increased as the proportion of ethylene charged to reactor 3 increased.

[0323] Similarly, and importantly, the Inventive Examples show that as the splitting of ethylene from reactor 3 ESR3 increased, the temperature of the effluent stream from reactor 3 also increased (the “R3 outlet temperature”), which successively reduced the energy burden on the downstream heat exchanger. Or, put another way, since the outlet temperature of reactor 3 has increased, less heat must be added through the heat exchanger before charging the final polyethylene product stream to the solvent separation system (i.e., the devolatilization process) in order to carry out an efficient separation. This is further evidenced by the reduction in the temperature difference between the outlet temperature of reactor 3 and the outlet temperature of the heat exchanger as well as the corresponding relative percentage reduction in the temperature difference thereof in relation to Comparative Example 1 (see Table 1).

[0324] As the high heat exchanger outlet temperature is desired for efficient solvent/polymer separation, the present Inventive Examples provide improvements in energy consumption by increasing the reactor outlet flow temperature 3 in relation to to Comparative Examples. These enhancements reduce energy inputs, save costs and reduce environmental impacts.

[0325] The polyethylene product composition properties are provided in Table 2. The details of the polyethylene product composition components, the first, second and third polyethylenes, were calculated using Copolymerization Reactor modeling in substantially the same manner as described in US patent 9,074,082 except for the fact that the model was adapted to use three reactors instead of two. The results of this modeling are provided in Table 3.

[0326] With reference to Figures 4A and 4B, a person skilled in the art will recognize that the inventive polyethylene product compositions have a reverse comonomer incorporation, and, in fact, that in some cases (inventive examples 2, 4 and 5) the Comonomer incorporation is partially reversed (i.e., it first rises as the molecular weight increases, and then falls as the molecular weight increases further).

[0327] With reference to Figures 5A and 5B, one skilled in the art will recognize that the inventive polyethylene product compositions have a multimodal TREF profile. For comparative examples 1 and 2 as well as inventive examples 1 and 2 the TREF profile is bimodal. For inventive examples 3, 4 and 5, the TREF profile is trimodal. In each of the inventive examples 1, 2, 3, 4 and 5, greater than 10 weight percent of the polyethylene product composition elutes at a temperature between about 90°C and about 100°C.

[0328] With reference to Figures 6A and 6B, one skilled in the art will recognize that the inventive polyethylene product compositions have a multimodal DSC profile. For examples 1, 2, 3, 4 and 5, the DSC profile is at least trimodal.

[0329] Blown films were generated using a Gloucester blown film line of 6.35 centimeters (2.5 inches) (L/D = 24) with a die diameter of 10.16 centimeters (4 inches). The die was coated with a polymer processing aid (PPA) by fixing the line with a high concentration of PPA masterbatch to prevent melt fracture. The fixed conditions were 35 mils (0.0889 cm) die spans, about 43.18 centimeters (17 inches) freeze line height, and 45.36 kg/hr (100 lbs/hr) output. Films were collected under different orientation conditions. The 1-mil monolayer film was produced with a blown ratio (BUR) of 2.5 and the 1-mil films were used to obtain the physical properties of the films. The 2-mil monolayer film (BUR = 2.5) was used to obtain the cold seal and hot glue profiles. Data for blown film from the polyethylene product compositions of the present disclosure are provided in Table 4, along with data for films made from various comparative resins.

[0330] Comparative Example A is a film made from SURPASS® FP117-C, a resin commercially available from NOVA Chemicals Corporation. SURPASS FP117-C has a density of 0.917 g/cm3 and an I2 melt index of 1 dg/min. Comparative Example B is a film made from EXCEED® 1018CA, a resin commercially available from ExxonMobil. EXCEED 1018CA has a density of about 0.918 g/cm3 and an I2 melt index of about 0.94 dg/min. Comparative Example C is a film made from MARLEX® D139, a resin commercially available from ChevronPhillips. MARLEX D139 has a density of about 0.918 g/cm3 and an I2 melt index of about 0.9 dg/min. Comparative Example D is a film made from ELITE® 5400G, a resin commercially available from the Dow Chemical Company. ELITE 5400G has a density of about 0.916 g/cm3 and an I2 melt index of about 1 dg/min. Comparative Example E is a film made from a resin made in accordance with US Patent Application 2016/0108221. The resin has a density of about 0.917 g/cm3, an I2 melt index of about 0.96 dg/min, and is made in a multireactor solution process where a first reactor and a second reactor are configured in series. each other. The resin is an ethylene/1-octene copolymer. In Table 4, Comparative Examples 1 and 2 are films that were made from Comparative Polyethylenes 1 and 2. As described earlier, these comparative resins were made using a three-reactor process, where the first and second reactors are configured in parallel , but in which the ethylene monomer was not added to the third reactor. In Table 4, Inventive Examples 1 to 5 are films made from the inventive polyethylene product compositions 1 to 5. TABLE 4

[0331] The data provided in Table 4 demonstrate that the inventive polyethylene product compositions have a good balance of film properties, including good dart impact, stiffness, piercing, tearing and sealing properties. Ugly films from inventive polyethylene products also have good tensile strength and optical properties.

[0332] Finally, films made from inventive polyethylene products also have good hot-sealing and cold-sealing performance. Without wishing to be bound by any theory, in the hot melt (or cold seal) profile (seal temperature vs. force), good hot glue (or cold seal) performance is indicated by an initiation temperature of early (or slow) hot-sealing (or cold-sealing), so a relatively high strength over a wide range of hot-sealing temperatures. See, for example, the shape of the curves in Figure 7A for inventive compositions 1, 2, 3, 4 and 5, in relation to comparative resins 1 and 2 and comparative resins A, B, C and D, in Figure 7B. The shape of the hot melt sealing curve for the inventive composition 5 is particularly good and has an early hot melt sealing initiation temperature combined with high strength over a wide range of hot melt sealing temperatures.

[0333] Good cold sealing properties are evidenced by the curves provided in Figure 8A for the inventive polyethylene compositions. The cold seal properties of some comparative polyethylene compositions are provided in Table 8B. One skilled in the art will recognize that inventive example 5 has an early cold seal initiation temperature in combination with relatively high strength over a wide range of cold seal temperatures.

[0334] Non-limiting embodiments of the present disclosure include the following:

[0335] Embodiment A. Polyethylene product composition comprising: from 35 to 75% by weight of a first polyethylene which is an ethylene copolymer having a density of 0.875 to 0.916 g/cm3, a melt index I2 of 0.1 to 5 dg/min, and an Mw/Mn molecular weight distribution of 1.6 to 2.4; from 10 to 40% by weight of a second polyethylene selected from an ethylene copolymer or an ethylene homopolymer having a density of 0.945 to 0.975 g/cm3, a melt index I2 of 1.0 to 20 dg/ min and a Mw/Mn molecular weight distribution of 1.6 to 2.4; and from 10 to 40% by weight of a third polyethylene which is an ethylene copolymer having a density of 0.880 to 0.936 g/cm3, an I2 melt index of 0.1 to 100 dg/min, and a distribution of molecular weight Mw/Mn that is greater than the molecular weight distribution Mw/Mn of any of the first and second ethylene polymer components; wherein the polyethylene product composition has a density of < 0.939 g/cm3, an I2 melt index of 0.1 to 10 dg/min, a unimodal profile on a gel permeation chromatography (GPC) and a multimodal profile in a TREF analysis.

[0336] Modality B. Polyethylene product composition, according to Modality A, in which at least 15 percent, by weight, of the composition elutes at a temperature of 90 °C to 100 °C in a TREF analysis .

[0337] Modality C. Composition of polyethylene product, according to Modality A or B, wherein the composition has a multimodal DSC profile.

[0338] Modality D. Polyethylene product composition, according to Modality A, B or C, in which the composition has a trimodal profile in a TREF analysis.

[0339] Method E. Polyethylene product composition, according to Method A, B, C or D, in which the first polyethylene has a weight average molecular weight greater than the weight average molecular weight of the second polyethylene.

[0340] Embodiment F. Composition of polyethylene product, according to Embodiment A, B, C, or D, in which the first polyethylene and the third polyethylene have a weight average molecular weight greater than the weight average molecular weight of the second polyethylene.

[0341] Type G. Polyethylene product composition, according to Type A, B, C, D, E or F, in which the first polyethylene has a weight average molecular weight, Mw, from 50,000 to 200,000; the second polyethylene has a weight average molecular weight, Mw of 25,000 to 100,000; and the third polyethylene has a weight average molecular weight, Mw of 25,000 to 200,000.

[0342] Type H. Composition of polyethylene product, according to Type A, B, C, D, E, F or G, in which the first polyethylene and the second polyethylene are homogeneous polyethylenes.

[0343] Type I. Polyethylene product composition, according to Type A, B, C, D, E, F, or G, in which the first polyethylene, the second polyethylene and the third polyethylene are homogeneous polyethylenes.

[0344] Type J. Composition of polyethylene product, according to Type A, B, C, D, E, F or G, in which the first polyethylene and the second polyethylene are produced with a single-site catalyst system .

[0345] Type K. Polyethylene product composition, according to Type A, B, C, D, E, F or G, in which the first polyethylene, the second polyethylene and the third polyethylene are produced with a system of single site catalyst.

[0346] Type L. Polyethylene product composition, according to Type A, B, C, D, E, F, G, H, I, J or K, in which the second polyethylene is a homopolymer.

[0347] Type M. Polyethylene product composition, according to Type A, B, C, D, E, F, G, H, I, J, K or L, in which the third polyethylene is present from 15 to 40% by weight.

[0348] Modality N. Composition of polyethylene product, according to Modality A, B, C, D, E, F, G, H, I, J, K or L, in which the third polyethylene is present from 20 to 40% by weight.

[0349] Type O. Composition of polyethylene product, according to Type A, B, C, D, E, F, G, H, I, J, K, L, M or N, in which the composition substantially does not have a long chain branch.

[0350] Type P. Composition of polyethylene product, according to Type A, B, C, D, E, F, G, H, I, J, K, L, M, N or O, in which the third polyethylene has an Mw/Mn molecular weight distribution of 2.6 to 8.0.

[0351] Type Q. Composition of polyethylene product, according to Type A, B, C, D, E, F, G, H, I, J, K, L, M, N, O or P, in that the first polyethylene has a density of 0.880 to 0.912 g/cm3.

[0352] Type R. Composition of polyethylene product, according to Type A, B, C, D, E, F, G, H, I, J, K, L, M, N, O, P or Q , wherein the first polyethylene has a melt index, I2 of less than 1.0 dg/min.

[0353] Type S. Composition of polyethylene product, according to Type A, B, C, D, E, F, G, H, I, J, K, L, M, N, O, P, Q or R, wherein the second polyethylene has a density of 0.951 to 0.959 g/cm3.

[0354] Type T. Composition of polyethylene product, according to Type A, B, C, D, E, F, G, H, I, J, K, L, M, N, O, P, Q , R, S, wherein the second polyethylene has a melt index, I 2 of 1.0 to 12.0 dg/min.

[0355] Type U. Composition of polyethylene product, according to Type A, B, C, D, E, F, G, H, I, J, K, L, M, N, O, P, Q , R, S or T, wherein the composition has a density of 0.890 to 0.936 g/cm 3 .

[0356] Type V. Composition of polyethylene product, according to Type A, B, C, D, E, F, G, H, I, J, K, L, M, N, O, P, Q , R, S, or T, wherein the composition has a density of 0.890 to 0.926 g/cm 3 .

[0357] Type W. Composition of polyethylene product, according to Type A, B, C, D, E, F, G, H, I, J, K, L, M, N, O, P, Q , R, S, T, U or V, wherein the composition has a melt index, I 2 of 0.1 to 3.0 dg/min.

[0358] Type X. Polyethylene product composition, according to Type A, B, C, D, E, F, G, H, I, J, K, L, M, N, O, P, Q , R, S, T, U, V or W, wherein the composition has an MW/Mn molecular weight distribution of 2.0 to 3.5.

[0359] Type Y. Composition of polyethylene product, according to Type A, B, C, D, E, F, G, H, I, J, K, L, M, N, O, P, Q , R, S, T, U, V or W, wherein the composition has an MW/Mn molecular weight distribution of 2.0 to 3.0.

[0360] Type Z. Composition of polyethylene product, according to Type A, B, C, D, E, F, G, H, I, J, K, L, M, N, O, P, Q , R, S, T, U, V, W, X or Y, wherein the composition has an MZ/Mw less than 2.5.

[0361] AA modality. Polyethylene product composition, according to Modality A, B, C, D, E, F, G, H, I, J, K, L, M, N, O, P, Q, R, S, T , U, V, W, X or Y, where the composition has an MZ/Mw less than 2.3.

[0362] BB mode. Polyethylene product composition, according to Modality A, B, C, D, E, F, G, H, I, J, K, L, M, N, O, P, Q, R, S, T , U, V, W, X, Y, Z or AA, and that the composition has a voltage exponent less than 1.3.

[0363] CC mode. Polyethylene product composition, according to Modality A, B, C, D, E, F, G, H, I, J, K, L, M, N, O, P, Q, R, S, T , U, V, W, X, Y, Z, AA or BB, wherein the composition has a melt index ratio, I21/I2 of 10 to 35.

[0364] DD modality. Polyethylene product composition, according to Modality A, B, C, D, E, F, G, H, I, J, K, L, M, N, O, P, Q, R, S, T , U, V, W, X, Y, Z, AA or BB, wherein the composition has a melt index ratio, I21/I2 of 10 to 30.

[0365] EE modality. Polyethylene product composition, according to Modality A, B, C, D, E, F, G, H, I, J, K, L, M, N, O, P, Q, R, S, T , U, V, W, X, Y, Z, AA or BB, wherein the composition has an I21/I2 melt index ratio of less than 30.

[0366] FF mode. Polyethylene product composition, according to Modality A, B, C, D, E, F, G, H, I, J, K, L, M, N, O, P, Q, R, S, T , U, V, W, X, Y, Z, AA, BB, CC, DD or EE, wherein the composition has a CDBI50 of 40 to 75% by weight.

[0367] Type GG. Polyethylene product composition, according to Modality A, B, C, D, E, F, G, H, I, J, K, L, M, N, O, P, Q, R, S, T , U, V, W, X, Y, Z, AA, BB, CC, DD, EE or FF that satisfies the following relation:

[0368][(weight average molecular weight of the second polyethylene) - (weight average molecular weight of the first polyethylene)] / (weight average molecular weight of the second polyethylene) x 100% > -100 %.

[0369] HH mode. Polyethylene product composition, according to Modality A, B, C, D, E, F, G, H, I, J, K, L, M, N, O, P, Q, R, S, T , U, V, W, X, Y, Z, AA, BB, CC, DD, EE, FF or GG that satisfies the following relationship: [(weight average molecular weight of the third polyethylene) - (weight average molecular weight of the second polyethylene)] / (weight average molecular weight of the third polyethylene) x 100% > -50%.

[0370] Type II. Polyethylene product composition, according to Modality A, B, C, D, E, F, G, H, I, J, K, L, M, N, O, P, Q, R, S, T , U, V, W, X, Y, Z, AA, BB, CC, DD, EE, FF, GG or HH satisfying the following relationship: [(weight average molecular weight of the third polyethylene) - (weight average molecular weight of the first polyethylene)] / (weight average molecular weight of the third polyethylene) x 100% > -200%.

[0371] JJ modality. Polyethylene product composition, according to Modality A, B, C, D, E, F, G, H, I, J, K, L, M, N, O, P, Q, R, S, T , U, V, W, X, Y, Z, AA, BB, CC, DD, EE, FF, GG, HH or II, wherein the composition is produced in a continuous solution polymerization process.

[0372] KK mode. Polyethylene product composition, according to Modality A, B, C, D, E, F, G, H, I, J, K, L, M, N, O, P, Q, R, S, T , U, V, W, X, Y, Z, AA, BB, CC, DD, EE, FF, GG, HH or II, wherein the composition is produced in a continuous solution polymerization process comprising a first reactor , a second reactor and a third reactor, wherein the first and second reactors are configured in parallel with each other and wherein the third reactor receives the combined effluent flows from the first and second reactors.

[0373] LL modality. Film layer comprising the ethylene polymer composition as defined in Embodiment A.

[0374] Modality MM. Film layer, according to Modality LL, where the film has a 1% secant modulus in machine direction (MD) of > 170 MPa.

[0375] NN modality. Film layer, according to Modality LL or MM, where the film has a dart impact resistance of > 500 g/mil.

[0376] OO modality. Film layer, according to Modality LL, MM or NN, where the film has a seal initiation temperature (SIT) of < 105 °C.

[0377] PP modality. Film layer, according to Modality LL, MM, NN or OO, where the film has a slow puncture resistance value of > 65 J/mm.

[0378] QQ mode. Film layer, according to Modality LL, MM, NN, OO or PP, where the film has a machine direction (MD) tear of > 250 g/mil.

[0379] RR mode. Film layer, according to Modality LL, MM, NN, OO, PP or QQ, where the film has a machine direction (MD) tensile strength at break of > 40 MPa.

[0380] SS mode. Film layer, according to Modality LL, MM, NN, OO, PP, QQ or RR, where the film has a haze of < 14%.

[0381] TT mode. Film layer that has a dart impact strength of > 600 g/mil, a 1% MD secant modulus of > 170 MPa, a slow pierce value of > 65 J/mm, a machine direction tear ( MD) of > 250 g/mil, and a seal initiation temperature (SIT) of < 105 °C.

[0382] UU mode. Film layer, according to Modality TT, where the film has an MD tensile strength at break of > 40 MPa.

[0383] VV mode. Film layer, according to TT or UU Modality, where the film has a haze of < 14%.

INDUSTRIAL APPLICABILITY

[0384] A continuous solution polymerization process is revealed in which ethylene is polymerized in three different reactors. The polymers produced using the disclosed process are suitable for making a variety of commercial goods, such as plastic films.

Claims (46)

1. Polyethylene product composition, CHARACTERIZED by the fact that it comprises: from 35 to 75% by weight of a first polyethylene which is an ethylene copolymer having a density of 0.875 to 0.916 g/cm3, an I2 melt index of 0 .1 to 5 dg/min, and an Mw/Mn molecular weight distribution of 1.6 to 2.4; from 10 to 40% by weight of a second polyethylene selected from an ethylene copolymer or an ethylene homopolymer having a density of 0.945 to 0.975 g/cm3, a melt index I2 of 1.0 to 20 dg/min and a Mw/Mn molecular weight distribution of 1.6 to 2.4; and from 10 to 40% by weight of a third polyethylene which is an ethylene copolymer having a density of 0.880 to 0.936 g/cm3, an I2 melt index of 0.1 to 100 dg/min, and a molecular weight distribution Mw/Mn which is greater than the Mw/Mn molecular weight distribution of the first or second ethylene polymer components; wherein the polyethylene product composition has a density of < 0.939 g/cm3, an I2 melt index of 0.1 to 10 dg/min, a unimodal profile on a gel permeation chromatography (GPC) and a multimodal profile in a TREF analysis; wherein the density is determined in accordance with ASTM D792-13; wherein melt index I2 is determined in accordance with ASTM D1238 at 190°C using a 2.16 kg weight; and wherein the molecular weight distribution, MW/Mn is determined using gel permeation chromatography in accordance with ASTM D6474-12. 2. The polyethylene product composition according to claim 1, CHARACTERIZED by the fact that at least 15 percent by weight of the composition elutes at a temperature of 90°C to 100°C in a TREF analysis. 3. Composition of polyethylene product, according to claim 1 or 2, CHARACTERIZED by the fact that the composition has a multimodal DSC profile. 4. Polyethylene product composition, according to any one of claims 1 to 3, CHARACTERIZED by the fact that the composition has a trimodal profile in a TREF analysis. 5. Polyethylene product composition, according to any one of claims 1 to 4, characterized by the fact that the first polyethylene has a weight average molecular weight greater than the weight average molecular weight of the second polyethylene. 6. Polyethylene product composition, according to any one of claims 1 to 5, characterized by the fact that each of the first polyethylene and the third polyethylene has a weight average molecular weight greater than the weight average molecular weight of the second polyethylene. 7. Composition of polyethylene product, according to any one of claims 1 to 6, characterized by the fact that the first polyethylene has a weight average molecular weight, Mw, from 50,000 to 200,000; the second polyethylene has a weight average molecular weight, Mw, from 25,000 to 100,000; and the third polyethylene has a weight average molecular weight, Mw, of 25,000 to 200,000. 8. Polyethylene product composition, according to any one of claims 1 to 7, characterized by the fact that the first polyethylene and the second polyethylene are homogeneous polyethylenes. 9. Composition of polyethylene product, according to any one of claims 1 to 8, characterized by the fact that the first polyethylene, the second polyethylene and the third polyethylene are homogeneous polyethylenes. 10. Polyethylene product composition, according to any one of claims 1 to 9, characterized by the fact that the second polyethylene is a homopolymer. 11. Polyethylene product composition, according to any one of claims 1 to 10, characterized by the fact that the third polyethylene is present in 15 to 40% by weight. 12. Polyethylene product composition, according to any one of claims 1 to 11, characterized by the fact that the third polyethylene is present in 20 to 40% by weight. 13. Polyethylene product composition according to any one of claims 1 to 12, characterized by the fact that the composition has substantially no long chain branching. 14. Polyethylene product composition, according to any one of claims 1 to 13, characterized by the fact that the third polyethylene has a molecular weight distribution Mw/Mn of 2.6 to 8.0. 15. Polyethylene product composition, according to any one of claims 1 to 14, characterized by the fact that the first polyethylene has a density of 0.880 to 0.912 g/cm3. 16. Polyethylene product composition, according to any one of claims 1 to 15, characterized by the fact that the first polyethylene has a melting index, I2, less than 1.0 dg/min. 17. Polyethylene product composition, according to any one of claims 1 to 16, characterized by the fact that the second polyethylene has a density of 0.951 to 0.959 g/cm3. 18. Polyethylene product composition, according to any one of claims 1 to 17, characterized by the fact that the second polyethylene has a melting index, I2, from 1.0 to 12.0 dg/min. 19. Polyethylene product composition, according to any one of claims 1 to 18, characterized by the fact that the composition has a density of 0.890 to 0.936 g/cm3. 20. Polyethylene product composition, according to any one of claims 1 to 19, characterized by the fact that the composition has a density of 0.890 to 0.926 g/cm3. 21. Polyethylene product composition, according to any one of claims 1 to 20, characterized by the fact that the composition has a melting index, I2, from 0.1 to 3.0 dg/min. 22. Polyethylene product composition, according to any one of claims 1 to 21, characterized by the fact that the composition has a molecular weight distribution MW/Mn of 2.0 to 3.5. 23. Composition of polyethylene product, according to any one of claims 1 to 22, characterized by the fact that the composition has a molecular weight distribution MW/Mn of 2.0 to 3.0. 24. Polyethylene product composition, according to any one of claims 1 to 23, characterized by the fact that the composition has an MZ/Mw less than 2.5. 25. Polyethylene product composition, according to any one of claims 1 to 24, characterized by the fact that the composition has an MZ/Mw less than 2.3. 26. Polyethylene product composition, according to any one of claims 1 to 25, CHARACTERIZED by the fact that the composition has a stress exponent less than 1.3. 27. Polyethylene product composition, according to any one of claims 1 to 26, characterized by the fact that the composition has a melt index ratio, I21/I2, from 10 to 35. 28. Polyethylene product composition, according to any one of claims 1 to 27, characterized by the fact that the composition has a melt index ratio, I21/I2, from 10 to 30. 29. Polyethylene product composition, according to any one of claims 1 to 28, characterized by the fact that the composition has a melting index ratio I21/I2, less than 30. 30. Polyethylene product composition, according to any one of claims 1 to 29, CHARACTERIZED by the fact that the composition has a composition distribution breadth index (CDBI50) of 40 to 75% by weight, as determined by the analysis temperature rise elution fractionation (TREF). 31. Polyethylene product composition, according to any one of claims 1 to 30, CHARACTERIZED by the fact that it satisfies the following relationship: [(weight average molecular weight of the second polyethylene) - (weight average molecular weight of the first polyethylene)] / (weight average molecular weight of the second polyethylene) x 100% > -100%. 32. Polyethylene product composition, according to any one of claims 1 to 31, CHARACTERIZED by the fact that it satisfies the following relationship: [(weight average molecular weight of the third polyethylene) - (weight average molecular weight of the second polyethylene)] / (weight average molecular weight of the third polyethylene) x 100% > -50%. 33. Polyethylene product composition, according to any one of claims 1 to 32, CHARACTERIZED by the fact that it satisfies the following relationship: [(weight average molecular weight of the third polyethylene) - (weight average molecular weight of the first polyethylene)] / (weight average molecular weight of the third polyethylene) x 100% > -200%. 34. Polyethylene product composition, according to any one of claims 1 to 33, characterized by the fact that the composition is produced in a continuous solution polymerization process. 35. Polyethylene product composition, according to any one of claims 1 to 34, characterized by the fact that the composition is produced in a continuous solution polymerization process comprising a first reactor, a second reactor and a third reactor, wherein the first and second reactors are configured in parallel with each other and wherein the third reactor receives the combined effluent streams from the first and second reactors. 36. Film layer CHARACTERIZED by the fact that it comprises the ethylene polymer composition as defined in claim 1. 37. Film layer, according to claim 36, CHARACTERIZED by the fact that the film has a 1% secant modulus in machine direction (MD) of > 170 MPa. 38. Film layer, according to claim 37, CHARACTERIZED by the fact that the film has a dart impact resistance of > 500 g/mil. 39. Film layer, according to claim 38, CHARACTERIZED by the fact that the film has a seal initiation temperature (SIT) of < 105°C. 40. Film layer, according to claim 39, CHARACTERIZED by the fact that the film has a slow puncture resistance value of > 65 J/mm. 41. Film layer, according to claim 40, CHARACTERIZED by the fact that the film has a machine direction (MD) tear of > 250 g/mil. 42. Film layer, according to claim 41, CHARACTERIZED by the fact that the film has a tensile strength in machine direction (MD) at rupture of > 40 MPa. 43. Film layer according to claim 42, CHARACTERIZED by the fact that the film has a haze of < 14%. 44. Film layer, according to claim 36, CHARACTERIZED by the fact that it has a dart impact strength of > 600 g/mil, a 1% secant modulus in MD of > 170 MPa, a slow puncture value of > 65 J/mm, a machine direction (MD) tear of > 250 g/mil, and a seal initiation temperature (SIT) of < 105 °C. 45. Film layer, according to claim 44, CHARACTERIZED by the fact that the film has a tensile strength in MD at rupture of > 40 MPa. 46. Film layer according to claim 45, CHARACTERIZED by the fact that the film has a haze of < 14%.

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