Multimodal ethylene-based copolymer compositions and processes for producing same

Abstract

An embodiment of the present disclosure includes a process for polymerizing a multimodal polyethylene polymer. The process includes contacting ethylene and optionally one or more α-olefin monomers with at least two catalyst systems in a solution reactor at a reactor temperature greater than 150° C. The at least two catalyst systems produce greater than 0.3 vinyl end groups per 1000 carbon atoms. A first catalyst system of the at least two catalyst systems includes a first procatalyst and a second catalyst system of the at least two catalyst systems includes a second procatalyst having a reactivity ratio less than 20, the reactivity ratio of the first procatalyst being measured using only the first catalyst system in a single reactor in the presence of 1250 grams of ISOPAR-E with a mole fraction of ethylene in solution of 0.709 at a reactor temperature of at least 150° C.

Description

[Technical field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims the benefit of U.S. Provisional Application No. 63 / 295,182, filed December 30, 2021, the entire disclosure of which is incorporated herein by reference.

[0002] FIELD OF THE DISCLOSURE Embodiments of the present disclosure relate generally to polymer compositions and, more specifically, to multimodal ethylene-based copolymer compositions and processes for producing the same. [Background technology]

[0003] The use of polyolefin compositions in industries such as packaging applications is generally known. A variety of conventional methods can be used to produce such polyolefin compositions. A variety of polymerization techniques using different catalyst systems have been used to produce such polyolefin compositions suitable for packaging applications. However, in some embodiments, despite the research efforts in developing compositions suitable for packaging applications, there is still a need for improved polyethylene compositions suitable for packaging applications that can have a good balance of physical properties and melt strength at desired polymer composition density. Summary of the Invention

[0004] Melt strength and processability are interrelated properties of polyethylene resins. Generally, higher melt strength provides a polyethylene resin with improved processability.

[0005] In addition, conventional polyethylene resins produced by conventional processes typically exhibit a trade-off between the mechanical properties and melt strength of the resin. For example, conventional radical processes typically produce low density polyethylenes (LDPE) that exhibit high melt strength but have poor mechanical properties. In contrast, linear low-density polyethylenes (LLDPE) made via solution or gas phase processes typically have poor melt strength but excellent mechanical properties.

[0006] Therefore, to increase processability, some amount of LDPE may typically be blended with LLDPE to improve the processability and melt strength of the LLDPE resin. Unfortunately, the addition of LDPE results in a decrease in the mechanical properties of the resulting blend when compared to the pure LLDPE resin.

[0007] Thus, there is a need for a solution polymerization process that produces polyethylene resins that can have melt strengths comparable to those produced via radical processes.Due to the potential hazards associated with radical polymerization on an industrial scale, there is a need for a solution polymerization process that produces polyethylene resins that can have melt strengths comparable to those of LDPE resins produced via radical processes.

[0008] Embodiments of the present disclosure meet these needs by providing multimodal ethylene-based copolymers that include a bulk low molecular weight (LMW) ethylene-based component made by one catalyst or multiple catalysts and a high molecular weight (HMW) ethylene-based component made by a different catalyst or multiple catalysts.

[0009] The multimodal ethylene-based copolymers described herein, along with the HMW ethylene-based component, can have long chain branching that allows melt strengths comparable to or higher than various LDPEs produced via conventional processes to be achieved.

[0010] An embodiment of the present disclosure includes a process for making a multimodal ethylene-based copolymer. In an embodiment, the process for polymerizing a multimodal polyethylene polymer includes contacting ethylene and optionally one or more α-olefin monomers with at least two catalyst systems in a solution reactor at a reactor temperature greater than 150° C. The at least two catalyst systems produce a vinyl end group count greater than 0.3 per 1000 carbon atoms, where the vinyl end groups per 1000 carbon atoms are measured by a 600 MHz nuclear magnetic resonance (NMR) instrument. A first catalyst system of the at least two catalyst systems includes a first procatalyst and a second catalyst system of the at least two catalyst systems includes a second procatalyst having a reactivity ratio less than 20, where the reactivity ratio of the first procatalyst is measured using only the first catalyst system in a single reactor in the presence of 1250 grams of ISOPAR-E with a mole fraction of ethylene in solution of 0.709 at a reactor temperature of at least 150° C. In some embodiments, the multimodal polyethylene polymer has at least 10% weight fraction greater than 500 kg / mole. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011] Described herein are embodiments of multimodal ethylene-based copolymer compositions and processes for producing the same. An ethylene-based polymer of ethylene and optionally one or more comonomers, such as an α-olefin, can comprise at least 50 mole percent (mol %) monomer units derived from ethylene. All individual values ​​and subranges encompassed by "at least 50 mole percent" are disclosed herein as separate embodiments, for example, an ethylene-based polymer can comprise at least 60 mole percent monomer units derived from ethylene, at least 70 mole percent monomer units derived from ethylene, at least 80 mole percent monomer units derived from ethylene, or from 50 to 100 mole percent monomer units derived from ethylene, or from 80 to 100 mole percent monomer units derived from ethylene.

[0012] process

[0013] In an embodiment, a process for polymerizing a multimodal polyethylene polymer includes contacting ethylene and optionally one or more α-olefin monomers with at least two catalyst systems in a solution reactor at a reactor temperature greater than 150° C. The at least two catalyst systems produce a vinyl end group count greater than 0.3 per 1000 carbon atoms, where the vinyl end groups per 1000 carbon atoms are measured by a 600 MHz nuclear magnetic resonance (NMR) instrument. A first catalyst system of the at least two catalyst systems includes a first procatalyst and a second catalyst system of the at least two catalyst systems includes a second procatalyst having a reactivity ratio less than 20, where the reactivity ratio of the first procatalyst is measured using only the first catalyst system in a single reactor in the presence of 1250 grams of ISOPAR-E with a mole fraction of ethylene in solution of 0.709 at a reactor temperature of at least 150° C. In some embodiments, the multimodal polyethylene polymer has a weight fraction of at least 10% greater than 500 kg / mole.

[0014] In embodiments, the solution polymerization reactor system may include one or more reactors. In embodiments, the solution polymerization reactor system may be a single reactor system. In embodiments, the solution polymerization reactor system may be a dual reactor system. In embodiments including a dual reactor system, the solution polymerization reactor system may include a first reactor and a second reactor, and the first reactor and the second reactor may have various orders. For example, the second reactor may be downstream of the first reactor. However, the reverse is also contemplated. Such a solution polymerization process may include, for example, using one or more conventional reactors, such as loop reactors, isothermal reactors, adiabatic reactors, fluidized bed gas phase reactors, stirred tank reactors, batch reactors, for example, in parallel, in series, or in any combination thereof.

[0015] In an embodiment, at least two catalyst systems are present in one reaction vessel. A single reactor has one reaction vessel and a dual reactor has two reaction vessels.

[0016] In one or more embodiments, when the solution reactor is a single reactor, the at least two catalyst systems include a first catalyst system and a second catalyst system. In some embodiments, when the solution reactor is a dual reactor, the first catalyst system and the second catalyst system are present in a first reactor of the dual reactor, and the second reactor of the dual reactor includes a third catalyst system. In various embodiments, when the solution reactor is a dual reactor, the first catalyst system and the second catalyst system can be present in one reactor of the dual reactor, and the other reactor of the dual reactor includes a third catalyst system. In other embodiments, when the solution reactor is a dual reactor, the first catalyst system can be present in one reactor of the dual reactor, and the other reactor of the dual reactor includes a second catalyst system and a third catalyst system.

[0017] In embodiments, the first catalyst system includes the reaction product, a first procatalyst, and an activator, the second catalyst system includes the reaction product, a second procatalyst, and an activator, and the third catalyst system includes the reaction product, a third procatalyst, and an activator. In some embodiments, the activators in each catalyst system are the same. In other embodiments, the activators in each catalyst system are not the same. In various embodiments, the activators present in the first catalyst system and the second catalyst system are the same and different in the third catalyst system. In some embodiments, the activator in the first catalyst system is different from the activator in the second catalyst system.

[0018] In one or more embodiments, the first procatalyst is different from the second procatalyst, which is different from the third procatalyst, hi various embodiments, the first procatalyst is different from the third procatalyst.

[0019] In one or more embodiments, the at least two catalyst systems produce greater than 0.4, or greater than 0.45, vinyl end groups per 1000 carbon atoms, where the vinyl end groups per 1000 carbon atoms are measured by a 600 MHz nuclear magnetic resonance (NMR) instrument. The phrase "vinyl end groups per 1000 carbon atoms" refers to the number of vinyl (carbon-carbon double bond) groups in the reactor solution on a 600 MHz nuclear magnetic resonance (NMR) instrument.

[0020] The multimodal polyethylene-based composition of the present disclosure has increased melt strength compared to a typical LLDPE composition, and superior mechanical properties to a typical LDPE composition. Without being bound by theory, it is believed that one of the at least two catalyst systems in the multimodal polyethylene-based composition creates a high molecular weight fraction. At least one of the catalysts in the first, second, and optionally third catalyst systems, or a combination of catalyst systems, produces a vinyl end group number greater than 0.3, greater than 0.4, or greater than 0.45 per 1000 carbon atoms. Some of the vinyl end groups produced by at least one of the at least two catalyst systems can be reinserted into the polymer chain to create long chain branches, and some of the vinyl groups remain in the final composition. The combination of long chain branching and high molecular weight fraction increases the melt strength of the polymer of the embodiments of the present invention.

[0021] In embodiments, the multimodal ethylene-based copolymer composition may be produced via a solution polymerization process. In embodiments, a process for making a multimodal ethylene-based copolymer may include contacting at least two α-olefin monomers in the presence of a catalyst system including at least one low molecular weight catalyst and at least one high molecular weight catalyst in a solution polymerization reactor system.

[0022] In embodiments, ethylene and at least one α-olefin monomer may be polymerized in the presence of a catalyst to produce the multimodal ethylene-based copolymer composition described herein. Typically, the α-olefin monomer has 20 or fewer carbon atoms. For example, the α-olefin comonomer may have 3 to 10 carbon atoms, or 3 to 8 carbon atoms. Exemplary α-olefin comonomers include, but are not limited to, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, and 4-methyl-1-pentene. For example, the one or more α-olefin comonomers may be selected from the group consisting of propylene, 1-butene, 1-hexene, and 1-octene, or alternatively, from the group consisting of 1-hexene and 1-octene. In some embodiments, the α-olefin is not a diene. In embodiments, the α-olefin comonomer and process solvent may be purified using molecular sieves prior to introduction into the solution polymerization reactor system. The solvent, monomer, comonomer, and hydrogen may be combined and fed to the solution polymerization reactor system. Exemplary solvents include, but are not limited to, isoparaffins. For example, such solvents are commercially available from ExxonMobil Chemical under the name ISOPAR E. In some embodiments, the combined feed may be temperature controlled at temperatures between 5°C and 50°C, 5°C and 25°C, 5°C and 10°C, 10°C and 50°C, 10°C and 25°C, or 25°C and 50°C.

[0023] The catalyst system, described in more detail in the following sections, is utilized in the polymerization of olefins to produce the multimodal ethylene-based copolymer compositions described herein. As previously described, the catalyst system in the solution polymerization reactor system can include at least one first catalyst that produces a high molecular weight (HMW) ethylene-based component and at least one second catalyst that produces a bulk low molecular weight (LMW) ethylene-based component. The term "bulk" with respect to "bulk low molecular weight" means greater than 50% by weight of the total composition.

[0024] In one embodiment, the multimodal ethylene-based copolymer composition may be produced via a solution polymerization process, where ethylene, and optionally one or more α-olefins, are polymerized in the presence of a first catalyst to produce a high molecular weight (HMW) ethylene-based component. In one or more embodiments, the first catalyst may have a first efficiency of from 1,000 kg polymer / g metal to 30,000 kg polymer / g metal. In further embodiments, the first catalyst is at a concentration of from 1,000 kg polymer / g metal to 25,000 kg polymer / g metal, from 1,000 kg polymer / g metal to 20,000 kg polymer / g metal, from 1,000 kg polymer / g metal to 15,000 kg polymer / g metal, from 1,000 kg polymer / g metal to 10,000 kg polymer / g metal, from 1,000 kg polymer / g metal to 5,000 kg polymer / g metal, from 5,000 kg polymer / g metal to 25,000 kg polymer / g metal, from 5,000 kg polymer / g metal to 20,000 kg polymer / g metal, from 5,000 kg polymer / g metal to 1 The first catalyst may have a first efficiency of 5,000 kg polymer / g metal, 5,000 kg polymer / g metal to 10,000 kg polymer / g metal, 10,000 kg polymer / g metal to 25,000 kg polymer / g metal, 10,000 kg polymer / g metal to 20,000 kg polymer / g metal, 10,000 kg polymer / g metal to 15,000 kg polymer / g metal, 15,000 kg polymer / g metal to 25,000 kg polymer / g metal, 15,000 kg polymer / g metal to 20,000 kg polymer / g metal, or 1,000 kg polymer / g metal to 25,000 kg polymer / g metal. In one or more embodiments, the first catalyst may exhibit a first reactivity ratio of less than 20. In further embodiments, the first catalyst may exhibit a first reactivity ratio of less than 20, less than 15, or less than 10. In further embodiments, the first catalyst may exhibit a first reactivity ratio of from 10 to 20, or from 10 to 15, or from 15 to 20.

[0025] In one embodiment, the multimodal ethylene-based copolymer composition may be produced via a solution polymerization process, where ethylene, and optionally one or more α-olefins, are polymerized in the presence of a second catalyst to produce a bulk low molecular weight (LMW) ethylene-based component. In one or more embodiments, the second catalyst may have a second catalyst efficiency of from 1,000 kg polymer / g metal to 30,000 kg polymer / g metal. In further embodiments, the second catalyst is at a concentration of from 1,000 kg polymer / g metal to 25,000 kg polymer / g metal, from 1,000 kg polymer / g metal to 20,000 kg polymer / g metal, from 1,000 kg polymer / g metal to 15,000 kg polymer / g metal, from 1,000 kg polymer / g metal to 10,000 kg polymer / g metal, from 1,000 kg polymer / g metal to 5,000 kg polymer / g metal, from 5,000 kg polymer / g metal to 25,000 kg polymer / g metal, from 5,000 kg polymer / g metal to 20,000 kg polymer / g metal, from 5,000 kg polymer / g metal to 15, The catalyst may have a low molecular weight catalyst efficiency of from 1,000 kg polymer / g metal, 5,000 kg polymer / g metal to 10,000 kg polymer / g metal, 10,000 kg polymer / g metal to 25,000 kg polymer / g metal, 10,000 kg polymer / g metal to 20,000 kg polymer / g metal, 10,000 kg polymer / g metal to 15,000 kg polymer / g metal, 15,000 kg polymer / g metal to 25,000 kg polymer / g metal, 15,000 kg polymer / g metal to 20,000 kg polymer / g metal, or 1,000 kg polymer / g metal to 25,000 kg polymer / g metal.

[0026] In one embodiment, the multimodal ethylene-based copolymer composition can be produced via a solution polymerization process in a dual reactor system, e.g., a dual loop reactor system, where ethylene and optionally one or more α-olefins are polymerized in the first reactor in the presence of a low molecular weight catalyst system to produce a bulk low molecular weight (LMW) ethylene-based component and ethylene, and optionally one or more α-olefins are polymerized in the second reactor in the presence of a high molecular weight catalyst system to produce a high molecular weight ethylene-based component. In addition, one or more cocatalysts may be present. In another embodiment, the multimodal ethylene-based copolymer composition can be produced via a solution polymerization process in a single reactor system, e.g., a single loop reactor system, where ethylene and optionally one or more α-olefins are polymerized in the presence of a low molecular weight catalyst system and a high molecular weight catalyst system. In addition, one or more cocatalysts may be present.

[0027] In embodiments, the solution polymerization reactor system may include one or more reactors operating at temperatures above 150°C. In embodiments, the solution polymerization reactor system may include one or more reactors operating at temperatures between 160°C and 200°C, between 160°C and 190°C, between 160°C and 180°C, between 160°C and 170°C, between 170°C and 200°C, between 170°C and 190°C, between 170°C and 180°C, between 180°C and 200°C, between 180°C and 190°C, or between 190°C and 200°C. Further improvements to solution polymerization systems involving multi-catalyst systems making high melt strength polyethylene may be made. One improvement to the process is to operate at high reactor temperatures (above 150°C) to increase production rates and reduce energy consumption while still producing desirable polyethylene products with commercially acceptable catalyst efficiency and process control. Such improvements have not been demonstrated in the state of the art.

[0028] The reactor monomer feed (ethylene) stream is pressurized via a mechanical compressor to a pressure above the reaction pressure of 525 psig. The solvent and comonomer (1-octene) feeds are pressurized via mechanical positive displacement pumps to a pressure above the reaction pressure of 525 psig.

[0029] Immediately after each fresh injection point, the feed stream is mixed with the contents of the circulating polymerization reactor using static mixing elements. The effluent from the polymerization reactor (containing solvent, monomer, comonomer, hydrogen, catalyst components, and molten polymer) exits the first reactor loop and passes through a control valve (responsible for maintaining the pressure of the first reactor at a specified target). As the stream exits the reactor, it is contacted with water to stop the reaction. In addition, various additives such as antioxidants may be added at this point. The stream then passes through another set of static mixing elements to uniformly distribute the catalyst kill and additives.

[0030] Following the addition of additives, the effluent (containing solvent, monomer, comonomer, hydrogen, catalyst components, and molten polymer) passed through a heat exchanger to increase the stream temperature in preparation for separation of the polymer from other lower boiling reaction components. The stream then enters a two-stage separation and devolatilization system where the polymer is stripped from the solvent, hydrogen, and unreacted monomer and comonomer. The separated, devolatilized polymer melt is pumped through a die specially designed for underwater pelletization, cut into uniform solid pellets, dried, and transported to boxes for storage.

[0031] Catalyst system

[0032] In one or more embodiments, specific embodiments of catalyst systems that can be used to produce the multimodal ethylene-based copolymer compositions described herein are described herein. It is understood that the catalyst systems of the present disclosure may be embodied in different forms and should not be construed as limited to the specific embodiments described in this disclosure. Rather, the embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the subject matter to those skilled in the art.

[0033] The term "independently selected" means 1 , R 2 , R 3 , R 4 , and R 5The R groups, such as R 1 , R 2 , R 3 , R 4 , and R 5 are all substituted alkyl, or R 1 and R 2 is a substituted alkyl; R 3 The terms "aryl" and "aryl" are used herein to indicate that an R group is an aryl group, and the like. The use of the singular includes the use of the plural and vice versa (e.g., a hexane solvent includes a plurality of hexanes). A named R group will generally have a structure recognized in the art as corresponding to the R group having that name. These definitions are intended to supplement and illustrate, not preclude, definitions known to those of skill in the art.

[0034] The term "procatalyst" refers to a compound that has catalytic activity when combined with an activator. The term "activator" refers to a compound that chemically reacts with a procatalyst to convert the procatalyst into a catalytically active catalyst. As used herein, the terms "cocatalyst" and "activator" are interchangeable terms.

[0035] When used to describe a chemical group that contains a specific carbon atom, the term "(C x ~C y A bracketed expression having the form "(C1-C)" means that the unsubstituted form of the chemical group has from x carbon atoms to y carbon atoms, inclusive of x and y. For example, (C1-C 40 ) Alkyl is an alkyl group having 1 to 40 carbon atoms in its unsubstituted form. In some embodiments and general structures, certain chemical groups are R S The parenthetical "(C x -C y ) for the chemical group R S The substituted version can be any group R S Depending on the identity of each of the groups, the group may contain more than y carbon atoms. For example, "R SExactly one group R is phenyl (-C6H5) S (C1~C 40 "(C)alkyl" can contain from 7 to 46 carbon atoms. Thus, the parenthetical "(C)alkyl" is generally used. x ~C y )" is a substituent R S When a chemical group is substituted by x, the minimum and maximum total number of carbon atoms in the group is determined by the presence of both x and y in the substituent R S It is determined by adding the total number of carbon atoms derived from the

[0036] The term "substituted" refers to the replacement of at least one hydrogen atom (-H) bonded to a carbon or heteroatom or functional group of the corresponding unsubstituted compound with a substituent (e.g., R S The term "persubstituted" means that all hydrogen atoms (H) attached to carbon or heteroatoms of the corresponding unsubstituted compound or functional group are replaced by a substituent (e.g., R S The term "polysubstituted" means that at least two, but fewer than all, of the hydrogen atoms bonded to a carbon or heteroatom of the corresponding unsubstituted compound or functional group are replaced by a substituent.

[0037] The term "-H" means a hydrogen or hydrogen radical that is covalently bonded to another atom. "Hydrogen" and "-H" are interchangeable and mean the same thing unless otherwise specified.

[0038] "(C1~C 40 The term "(C1-C)hydrocarbyl" means a hydrocarbon radical of 1 to 40 carbon atoms. 40The term "hydrocarbylene" means a hydrocarbon diradical of 1 to 40 carbon atoms, each of which may be aromatic or non-aromatic, saturated or unsaturated, straight or branched chain, cyclic (including monocyclic and polycyclic, fused and non-fused polycyclic, including bicyclic, 3 or more carbon atoms) or acyclic, unsubstituted or substituted with one or more R S has been replaced by

[0039] In the present disclosure, (C1 to C 40 ) Hydrocarbyl is unsubstituted or substituted (C1-C 40 ) Alkyl, (C3-C 40 )Cycloalkyl, (C3-C 20 )Cycloalkyl-(C1-C 20 ) Alkylene, (C6-C 40 ) aryl, or (C6-C 20 )Aryl-(C1-C 20 In some embodiments, the alkylene group may be any of the alkylene groups (C1-C 40 Each of the hydrocarbyl groups has up to 20 carbon atoms (i.e., (C1-C 20 ) hydrocarbyl), in embodiments having up to 12 carbon atoms.

[0040] "(C1~C 40 ) alkyl" and "(C1-C 18 The term "alkyl" refers to an unsubstituted or substituted alkyl group having 1 to 40 carbon atoms or 1 to 18 carbon atoms, respectively, and one or more R S means a saturated linear or branched hydrocarbon radical substituted by 40 Examples of alkyl are unsubstituted (C1-C 20 ) Alkyl, unsubstituted (C1-C 10 ) alkyl, unsubstituted (C1-C5) alkyl, methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2-butyl, 2-methylpropyl, 1,1-dimethylethyl, 1-pentyl, 1-hexyl, 1-heptyl, 1-nonyl, and 1-decyl. 40 Examples of substituted (C1-C20 ) Alkyl, Substituted (C1-C 10 ) alkyl, trifluoromethyl, and [C 45 ] alkyl. 45 The term "alkyl" (with brackets) means that there are up to 45 carbon atoms in the radical, including the substituents, e.g., one R that is (C1-C5) alkyl, S Replaced by (C 27 ~C 40 )alkyl. Each (C1-C5)alkyl can be methyl, trifluoromethyl, ethyl, 1-propyl, 1-methylethyl, or 1,1-dimethylethyl.

[0041] "(C6~C 40 The term "aryl" refers to an unsubstituted or substituted aryl group having 6 to 40 carbon atoms, of which at least 6 to 14 carbon atoms are aromatic ring carbon atoms. S means a monocyclic, bicyclic, or tricyclic aromatic hydrocarbon radical substituted (by C6-C 40 Examples of alkyl are unsubstituted (C6-C 20 ) Alkyl Unsubstituted (C6-C 18 ) alkyl, 2-(C1-C5) alkylphenyl, 2,4-bis(C1-C5) alkylphenyl, phenyl, fluorenyl, tetrahydrofluorenyl, indacenyl, hexahydroindacenyl, indenyl, dihydroindenyl, naphthyl, tetrahydronaphthyl, and phenanthrene. 40 Examples of substituted (C1-C 20 ) Alkyl, Substituted (C6-C 18 )aryl, 2,4-bis[(C 20 )alkyl]-phenyl, polyfluorophenyl, pentafluorophenyl, and fluoren-9-on-1-yl.

[0042] "(C3~C 40 The term "cycloalkyl" means unsubstituted or substituted with one or more R S means a saturated cyclic hydrocarbon radical of 3 to 40 carbon atoms, substituted with other cycloalkyl groups, such as (C x ~C y )Cycloalkyl) has x to y carbon atoms and is unsubstituted or has one or more R S Unsubstituted (C3-C 40 Examples of cycloalkyl are unsubstituted (C 20 )Cycloalkyl, unsubstituted (C3-C 10 ) cycloalkyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, and cyclodecyl. 40 Examples of cycloalkyl are substituted (C3-C 20 )Cycloalkyl, substituted (C3-C 10 ) cycloalkyl, cyclopentanon-2-yl, and 1-fluorocyclohexyl.

[0043] (C1~C 40 Examples of hydrocarbylenes include unsubstituted or substituted (C6-C 40 )Arylene, (C3-C 40 ) cycloalkylene, and (C1-C 40 ) Alkylene (e.g. (C1-C 20 ) alkylene). In some embodiments, the diradicals are on the same carbon atom (e.g., -CH2-), or on adjacent carbon atoms (i.e., 1,2-diradicals), or separated by one, two, or more than two intervening carbon atoms (e.g., 1,3-diradicals, 1,4-diradicals, etc., respectively). Some diradicals include α,ω-diradicals. α,ω-diradicals are diradicals with the greatest carbon backbone spacing between the radical carbons. (C2-C 20Some examples of alkylene α,ω-diradicals include ethane-1,2-diyl (i.e., -CH2CH2-), propane-1,3-diyl (i.e., -CH2CH2CH2-), 2-methylpropane-1,3-diyl (i.e., -CH2CH(CH3)CH2-). (C6-C 50 ) Some examples of arylene α,ω-diradicals include phenyl-1,4-diyl, naphthalene-2,6-diyl, or naphthalene-3,7-diyl.

[0044] "(C1~C 40 The term "alkylene" may be unsubstituted or may contain one or more R S means a saturated straight or branched diradical (i.e., the radical is not on a ring atom) of 1 to 40 carbon atoms, which is substituted with 50 Examples of alkylene are unsubstituted (C1-C) alkylenes, including unsubstituted -CH2CH2-, -(CH2)3-, -(CH2)4-, -(CH2)5-, -(CH2)6-, -(CH2)7-, -(CH2)8-, -CH2C*HCH3, and -(CH2)4C*(H)CH3. 20 ) alkylene, where "C*" represents a carbon atom from which a hydrogen atom is removed to form a secondary or tertiary alkyl radical. 50 Examples of alkylene are substituted (C1-C 20 ) alkylene, -CF2-, -C(O)-, and -(CH2) 14 C(CH3)2(CH2)5- (i.e., 6,6-dimethyl-substituted normal-1,20-eicosylene). As mentioned above, the two R S Together (C1~C 18 ) alkylene, so that the substitution (C1-C 50 Examples of alkylene also include 1,2-bis(methylene)cyclopentane, 1,2-bis(methylene)cyclohexane, 2,3-bis(methylene)-7,7-dimethyl-bicyclo[2.2.1]heptane, and 2,3-bis(methylene)bicyclo[2.2.2]octane.

[0045] "(C3~C 40 The term "cycloalkylene" may be unsubstituted or may contain one or more R S "R" means a cyclic diradical (i.e., the radicals are on ring atoms) of 3 to 40 carbon atoms substituted by

[0046] The term "heteroatom" refers to an atom other than hydrogen or carbon. Examples of heteroatoms include O, S, S(O), S(O), Si(R C )2, P(R P ), N(R N ), -N=C(R C )2, -Ge(R C )2-, or -Si(R C )-, wherein each R C , each R N , and each R P is unsubstituted (C1 to C 18 ) hydrocarbyl or -H. The term "heterohydrocarbon" refers to a molecule or molecular skeleton in which one or more carbon atoms are replaced with a heteroatom. "(C1-C 40 The term "heterohydrocarbyl" means a heterohydrocarbon radical of 1 to 40 carbon atoms, and is used interchangeably with "(C1-C 40 The term "heterohydrocarbylene" means a heterohydrocarbon diradical of 1 to 40 carbon atoms, each heterohydrocarbon having one or more heteroatoms. The heterohydrocarbyl radical can be present on a carbon atom or a heteroatom, and the heterohydrocarbyl diradical can be present on (1) one or two carbon atoms, (2) one or two heteroatoms, or (3) one carbon atom and one heteroatom. Each (C1 to C 50 ) heterohydrocarbyl and (C1-C 50 ) Heterohydrocarbylene is unsubstituted or substituted (one or more R S The ring structure may be aromatic or non-aromatic, saturated or unsaturated, straight or branched chain, cyclic (including monocyclic and polycyclic, fused polycyclic and non-fused polycyclic) or acyclic.

[0047] (C1~C 40) Heterohydrocarbyl is unsubstituted or substituted (C1-C 40 )heteroalkyl, (C1-C 40 ) hydrocarbyl-O-, (C1-C 40 ) Hydrocarbyl-S-, (C1-C 40 ) hydrocarbyl-S(O)-, (C1-C 40 ) hydrocarbyl-S(O)2-, (C1-C 40 ) Hydrocarbyl-Si(R C )2-, (C1~C 40 )hydrocarbyl-N(R N )-, (C1~C 40 ) hydrocarbyl-P(R P )-, (C2~C 40 )heterocycloalkyl, (C2-C 19 )Heterocycloalkyl-(C1-C 20 ) alkylene, (C3-C 20 )Cycloalkyl-(C1-C 19 ) Heteroalkylene, (C2-C 19 )Heterocycloalkyl-(C1-C 20 ) Heteroalkylene, (C1-C 40 ) Heteroaryl, (C1-C 19 )Heteroaryl-(C1-C 20 ) Alkylene, (C6-C 20 )Aryl-(C1-C 19 ) heteroalkylene, or (C1-C 19 )Heteroaryl-(C1-C 20 ) heteroalkylene.

[0048] "(C4~C 40 The term "heteroaryl" refers to an unsubstituted or substituted heteroaryl group consisting of a total of 4 to 40 carbon atoms and 1 to 10 heteroatoms (one or more R S (C) means a monocyclic, bicyclic, or tricyclic heteroaromatic hydrocarbon radical, the monocyclic, bicyclic, or tricyclic radical containing, respectively, one, two, or three rings, the two or three rings being independently fused or non-fused, and at least one of the two or three rings being heteroaromatic. Other heteroaryl groups, such as, for example, generally (C x ~Cy ) Heteroaryl, for example (C4-C 12 ) Heteroaryl) similarly has x to y carbon atoms (e.g., 4 to 12 carbon atoms) and is unsubstituted or has one or more R S The monocyclic heteroaromatic hydrocarbon radical is a 5- or 6-membered ring. The 5-membered ring has 5 minus h carbon atoms, where h is the number of heteroatoms, which can be 1, 2, or 3, and each heteroatom can be O, S, N, or P. Examples of 5-membered heteroaromatic hydrocarbon radicals include pyrrol-1-yl, pyrrol-2-yl, furan-3-yl, thiophen-2-yl, pyrazol-1-yl, isoxazol-2-yl, isothiazol-5-yl, imidazol-2-yl, oxazol-4-yl, thiazol-2-yl, 1,2,4-triazol-1-yl, 1,3,4-oxadiazol-2-yl, 1,3,4-thiadiazol-2-yl, tetrazol-1-yl, tetrazol-2-yl, and tetrazol-5-yl. The 6-membered ring has 6 minus h carbon atoms, where h is the number of heteroatoms, which may be 1 or 2, and the heteroatoms may be N or P. Examples of 6-membered heteroaromatic hydrocarbon radicals include pyridin-2-yl, pyrimidin-2-yl, and pyrazin-2-yl. The bicyclic heteroaromatic hydrocarbon radicals may be fused 5,6- or 6,6-ring systems. Examples of fused 5,6-ring bicyclic heteroaromatic hydrocarbon radicals are indol-1-yl and benzimidazol-1-yl. Examples of fused 6,6-ring bicyclic heteroaromatic hydrocarbon radicals are quinolin-2-yl and isoquinolin-1-yl. The tricyclic heteroaromatic hydrocarbon radicals may be fused 5,6,5-, 5,6,6-, 6,5,6-, or 6,6,6-ring systems. An example of a fused 5,6,5-ring system is 1,7-dihydropyrrolo[3,2-f]indol-1-yl. An example of a fused 5,6,6-ring system is 1H-benzo[f]indol-1-yl. An example of a fused 6,5,6-ring system is 9H-carbazol-9-yl. An example of a fused 6,5,6-ring system is 9H-carbazol-9-yl. An example of a fused 6,6,6-ring system is acridine-9-yl.

[0049] The heteroalkyl referred to above is (C1-C 50 ) carbon atoms or fewer and one or more heteroatoms. Similarly, heteroalkylene can be a saturated straight or branched chain diradical containing 1 to 50 carbon atoms and one or more heteroatoms. Heteroatoms as defined above include Si(R C )3, Ge(R C )3, Si(R C )2, Ge(R C )2, P(R P )2, P(R P ), N(R N )2, N(R N ), N, O, OR C , S, S.R. C , S(O), and S(O), each of the heteroalkyl and heteroalkylene groups can be unsubstituted or can include one or more R S is replaced by

[0050] Unsubstituted (C2~C 40 Examples of heterocycloalkyl are unsubstituted (C-C 20 )Heterocycloalkyl, unsubstituted (C2-C 10 ) heterocycloalkyl, aziridin-l-yl, oxetan-2-yl, tetrahydrofuran-3-yl, pyrrolidin-l-yl, tetrahydrothiophene-S,S-dioxid-2-yl, morpholin-4-yl, 1,4-dioxan-2-yl, hexahydroazepin-4-yl, 3-oxa-cyclooctyl, 5-thio-cyclononyl, and 2-aza-cyclodecyl.

[0051] The term "halogen atom" or "halogen" refers to a radical of a fluorine atom (F), a chlorine atom (Cl), a bromine atom (Br), or an iodine atom (I). The term "halide" refers to a halogen atom: fluoride (F - ), chloride (Cl - ), bromide (Br - ), or iodide (I - ) means the anionic form of

[0052] The term "saturated" means lacking carbon-carbon double bonds, carbon-carbon triple bonds, and (in heteroatom-containing groups) carbon-nitrogen, carbon-phosphorus, and carbon-silicon double bonds. A saturated chemical group is one or more substituents R S When substituted by, one or more double and / or triple bonds may optionally be replaced by a substituent R S The term "unsaturated" refers to the inclusion of one or more carbon-carbon double bonds, carbon-carbon triple bonds, and (in heteroatom-containing groups) carbon-nitrogen, carbon-phosphorus, and carbon-silicon double bonds, provided that the substituents R, if present, are not included in the formula (I). S It is meant to exclude any double bonds that may be present in or, if present, in a (hetero)aromatic ring.

[0053] According to some embodiments, the first catalyst system, the second catalyst system, or the third catalyst system may comprise a metal-ligand complex according to formula (I). [ka]

[0054] In formula (I), M is a metal selected from titanium, zirconium, or hafnium, the metal is in a formal oxidation state of +2, +3, or +4, n is 0, 1, or 2, when n is 1, X is a monodentate or bidentate ligand, and when n is 2, each X is a monodentate ligand and is the same or different, the metal-ligand complex is overall charge neutral, and each Z is independently selected from -O-, -S-, -N(R N )- or -P(R P )-, and L is selected from (C1 to C 40 ) hydrocarbylene or (C1-C 40 ) heterohydrocarbylene, (C1-C 40 ) Hydrocarbylene has a moiety containing a linker skeleton of 1 to 10 carbon atoms connecting the two Z groups in formula (I) (to which L is attached), or40 Heterohydrocarbylene has a moiety containing a linker skeleton of 1 to 10 atoms connecting the two Z groups in formula (I), and (C1 to C 40 Each of the 1 to 10 atoms of the 1 to 10 atom linker backbone of the heterohydrocarbylene is independently a carbon atom or a heteroatom, and each heteroatom is independently O, S, S(O), S(O), Si(R C )2, Ge(R C )2, P(R C ), or N(R C ), and independently, each R C is (C1~C 30 ) hydrocarbyl or (C1-C 30 ) heterohydrocarbyl, R 1 and R 8 are independently -H, (C1 to C 40 ) hydrocarbyl, (C1-C 40 ) heterohydrocarbyl, -Si(R C )3, -Ge(R C )3, -P(R P )2, -N(R N )2, -OR C , -SR C , -NO2, -CN, -CF3, R C S(O)-, R C S(O)2-, (R C )2C=N-, R C C(O)O-, R C OC(O)-, R C C(O)N(R N )-, (R N ) 2NC(O)-, halogen, and a radical having formula (II), formula (III), or formula (IV): [ka]

[0055] In formulas (II), (III), and (IV), R 31~35 , R 41~48 , or R 51~59 Each of the following is independently: 40 ) hydrocarbyl, (C1-C40 ) heterohydrocarbyl, -Si(R C )3, -Ge(R C )3, -P(R P )2, -N(R N )2, -N=CHR C , -OR C , -SR C , -NO2, -CN, -CF3, R C S(O)-, R C S(O)2-, (R C )2C=N-, R C C(O)O-, R C OC(O)-, R C C(O)N(R N )-, (R N ) 2NC(O)-, halogen, or -H, with the proviso that R 1 or R 8 is a radical having formula (II), formula (III), or formula (IV).

[0056] In formula (I), R 2~4 , R 5~7 , and R 9~16 Each of the following is independently: 40 ) hydrocarbyl, (C1-C 40 ) heterohydrocarbyl, -Si(R C )3, -Ge(R C )3, -P(R P )2, -N(R N )2, -N=CHR C , -OR C , -SR C , -NO2, -CN, -CF3, R C S(O)-, R C S(O)2-, (R C )2C=N-, R C C(O)O-, R C OC(O)-, R C C(O)N(R N )-, (R C ) 2NC(O)-, halogen, and -H.

[0057] In some embodiments, the multimodal ethylene-based copolymer composition is formed using a first catalyst according to Formula (I) in a first reactor and a different catalyst according to Formula (I) in a second reactor.

[0058] In one exemplary embodiment in which a dual loop reactor is used, the procatalyst used in the first loop is zirconium, [[2,2''-[[bis[1-methylethyl]germylene]bis(methyleneoxy-κO)]bis[3'',5,5''-tris(1,1-dimethylethyl)-5'-octyl[1,1':3',1''-terphenyl]-2'-olato-κO]](2-)]dimethyl-, having the chemical formula C 86 H 128 F2GeO4Zr and has the following structure (V): [ka]

[0059] In such an embodiment, the procatalyst used in the second loop is zirconium, [[2,2'''-[1,3-propanediylbis(oxy-κO)]bis[3-[2,7-bis(1,1-dimethylethyl)-9H-carbazol-9-yl]]-5'-(dimethyloctylsilyl)-3'-methyl-5-(1,1,3,3-tetramethylbutyl)[1,1]-biphenyl]-2-olato-κO]](2-)]dimethyl, having the chemical formula C 107 H 154 N2O4Si2Zr and having the following structure (VI): [ka]

[0060] According to some embodiments, the first catalyst system, the second catalyst system, or the third catalyst system may comprise a constrained geometry metal-ligand complex according to formula (XI).

[0061] Lp i MX m X' n X” p, or its dimer (XI).

[0062] In formula (XI), Lp is an anionic delocalized π-bonded group containing up to 50 non-hydrogen atoms and attached to M. In some embodiments of formula (XI), two Lp groups may be bonded together to form a bridged structure, and optionally one Lp may be bonded to X.

[0063] In formula (XI), M is a Group 4 metal of the Periodic Table of the Elements in a formal oxidation state of +2, +3, or +4. X is an optional divalent substituent of up to 50 non-hydrogen atoms that together with Lp forms a metallocycle containing M. X' is an optional neutral ligand having up to 20 non-hydrogen atoms, and each X'' is independently a monovalent anionic moiety having up to 40 non-hydrogen atoms. Optionally, two X'' groups may be covalently bonded together to form a divalent dianionic moiety with both valencies bonded to M, or optionally, two X'' groups may be covalently bonded together to form a neutral, conjugated, or non-conjugated diene π-bonded to M, where M is in the +2 oxidation state. In other embodiments, one or more X'' and one or more X' groups may be bonded together, thereby forming a moiety that is covalently bonded to M and coordinated by a Lewis base functionality.

[0064] Illustrative Group IV complexes having constrained geometry that can be used in the practice of the present invention include, but are not limited to, cyclopentadienyltitanium trimethyl, cyclopentadienyltitanium triethyl, cyclopentadienyltitanium triisopropyl, cyclopentadienyltitanium triphenyl, cyclopentadienyltitanium tribenzyl, cyclopentadienyltitanium-2,4-dimethylpentadienyl.

[0065] According to some embodiments, the first catalyst system, the second catalyst system, or the third catalyst system may comprise a metal-ligand complex according to formula (XII). [ka]

[0066] In formula (XII), M is a metal selected from titanium, zirconium, or hafnium, the metal having a formal oxidation state of +2, +3, or +4, and each X is independently an unsaturated (C2-C 50 ) Heterohydrocarbons, unsaturated (C2-C 50 ) Hydrocarbons, (C1-C 50 ) hydrocarbyl, (C6-C 50 )Aryl, (C6-C 50 ) Heteroaryl, cyclopentadienyl, substituted cyclopentadienyl, (C4-C 12 ) Diene, halogen, -N(R N )2, and -NCOR C (X) is a monodentate or bidentate ligand selected from the group consisting of n The subscript n is an integer 1, 2, or 3. The subscript m is 1 or 2. The metal-ligand complexes of formula (I) have up to six metal-ligand bonds and may be charge neutral or may have a positive charge associated with the metal center. Each Y is independently selected from oxygen or sulfur.

[0067] In formula (XII), each R 1 are independently 50 ) hydrocarbyl, (C1-C 50 ) Heterohydrocarbyl, (C6-C 50 )Aryl, (C4-C 50 )heteroaryl, -Si(R C )3, -Ge(R C )3, -P(R P )2, -N(R N )2, -OR C , -SR C , -NO2, -CN, -CF3, R C S(O)-, R C S(O)2-, (R P )2P(O)-, (R C )2C=N-, R C C(O)O-, R C OC(O)-, R C C(O)N(R)-, (R C )2NC(O)-, halogen, and -H.2 are independently 50 ) hydrocarbyl, (C1-C 50 ) Heterohydrocarbyl, (C6-C 50 )Aryl, (C4-C 50 )heteroaryl, -Si(R C )3, and -Ge(R C ) 3, and when m is 2, two R 2 are optionally covalently linked, and for each individual ring containing groups z1 and z2, each of z1 and z2 is independently sulfur, oxygen, -N(R R )- and -C(R R )-, with the proviso that at least one of z1 and z2 is -C(R R )-.

[0068] In formula (XII), each A is independently -z3-z4-z5- or -C(R 3 )C(R 4 )C(R 5 )C(R 6 When A is -z3-z4-z5-, each of z3, z4, and z5 is sulfur, oxygen, -N(R R )- and -C(R R )-, with the proviso that exactly one of z3, z4, or z5 is -C(R R )-, and exactly two of z3, z4, or z5 are -C(R R )-. A is -C(R 3 )C(R 4 )C(R 5 )C(R 6 )-, then each R 3 , R 4 , R 5 , and R 6 are independently 50 ) hydrocarbyl, (C1-C 50 ) Heterohydrocarbyl, (C6-C 50 )Aryl, (C4-C 50 )heteroaryl, -Si(R C )3, -Ge(R C)3, -P(R P )2, -N(R N )2, -OR C , -SR C , -NO2, -CN, -CF3, R C S(O)-, R C S(O)2-, (R P )2P(O)-, (R C )2C=N-, R C C(O)O-, R C OC(O)-, R C C(O)N(R)-, (R C ) 2NC(O)-, halogen, or -H.

[0069] In formula (XII), each R C , R N , and R P are independently 50 ) hydrocarbyl, and each R R are independently 50 ) hydrocarbyl, (C1-C 50 ) Heterohydrocarbyl, (C6-C 50 )Aryl, (C4-C 50 )heteroaryl, -Si(R C )3, -Ge(R C )3, -P(R P )2, -N(R N )2, -OR C , -SR C , -NO2, -CN, -CF3, R C S(O)-, R C S(O)2-, (R P )2P(O)-, (R C )2C=N-, R C C(O)O-, R C OC(O)-, R C C(O)N(R)-, (R C )2NC(O)-, halogen, or -H, and any two R bonded to adjacent atoms are selected from R The groups are optionally linked.

[0070] According to some embodiments, the first catalyst system, the second catalyst system, or the third catalyst system may comprise a metal-ligand complex according to formula (XIII). [ka]

[0071] In formula (XIII), M is a metal selected from titanium, zirconium, or hafnium, the metal having a formal oxidation state of +2, +3, or +4. Each X is independently selected from (C1 to C 50 ) Hydrocarbons, (C1-C 50 ) Heterohydrocarbons, (C1-C 50 ) hydrocarbyl, (C6-C 50 )Aryl, (C6-C 50 ) Heteroaryl, cyclopentadienyl, substituted cyclopentadienyl, (C4-C 12 ) Diene, halogen, -N(R N )2, and -NCOR C The subscript n is 1, 2, or 3. The subscript m is 1 or 2. The metal-ligand complexes of formula (XIII) have six or fewer metal-ligand bonds and are overall charge neutral.

[0072] In embodiments of Formula (XIII), each Y is independently selected from oxygen or sulfur. 1 , R 2 , R 3 , and R 4 are independently 50 ) hydrocarbyl, (C1-C 50 ) Heterohydrocarbyl, (C6-C 50 )Aryl, (C4-C 50 )heteroaryl, -Si(R C )3, -Ge(R C )3, -P(R P )2, -N(R N )2, -OR C , -SR C , -NO2, -CN, -CF3, R C S(O)-, R C S(O)2-, (RC )2C=N-, R C C(O)O-, R C OC(O)-, R C C(O)N(R)-, (R C )2NC(O)-, halogen, and -H. 5 are independently 50 ) hydrocarbyl, (C1-C 50 ) Heterohydrocarbyl, (C6-C 50 )Aryl, (C4-C 50 )heteroaryl, -Si(R C )3, and -Ge(R C ) 3, and when m is 2, two R 5 are optionally covalently linked.

[0073] In embodiments of Formula (XIII), for each individual ring containing groups z1, z2, and z3, each of z1, z2, and z3 is independently sulfur, oxygen, -N(R R )- or -C(R R At least one and no more than two of z1, z2, and z3 are selected from the group consisting of -C(R R )- and R R is -H or (C1-C 30 ) hydrocarbyl, and any two R R In formula (XIII), each R C , R N , and R P are independently 30 ) hydrocarbyl.

[0074] In catalyst systems according to embodiments of the present disclosure, the molar ratio of bimetallic activator complex to Group IV metal-ligand complex can be from 1:10,000 to 1000:1, such as 1:5000 to 100:1, 1:100 to 100:1, 1:10 to 10:1, 1:5 to 1:1, or 1.25:1 to 1:1, etc. The catalyst systems can include a combination of one or more bimetallic activator complexes described in the present disclosure.

[0075] cocatalyst component

[0076] The catalyst system comprising the metal-ligand complex of formula (I) can be catalytically activated by any technique known in the art for activating metal-based catalysts for olefin polymerization reactions. For example, the system comprising the metal-ligand complex of formula (I) can be catalytically activated by contacting the complex with an activating cocatalyst or combining the complex with an activating cocatalyst. Suitable activating cocatalysts for use herein include alkylaluminum, polymeric or oligomeric alumoxanes (also known as aluminoxanes), neutral Lewis acids, and non-polymeric, non-coordinating, ion-forming compounds, including the use of such compounds under oxidizing conditions. A suitable activation technique is bulk electrolysis. Combinations of one or more of the foregoing activating cocatalysts and techniques are also contemplated. The term "alkylaluminum" means monoalkylaluminum dihydrides or dihalides, dialkylaluminum hydrides or halides, or trialkylaluminum. Examples of polymeric or oligomeric alumoxanes include methylalumoxane, triisobutylaluminum modified methylalumoxane, and isobutylalumoxane.

[0077] The Lewis acid activator (cocatalyst) is, as described herein, a compound having 1 to 3 (C1 to C 20 In one embodiment, the Group 13 metal compound includes a tri((C1-C) hydrocarbyl substituent. 20 )hydrocarbyl)substituted aluminum or tri((C1-C 20 In an embodiment, the Group 13 metal compound is a tri(hydrocarbyl)-substituted aluminum, tri((C1-C 20 )hydrocarbyl)-boron compounds, tri((C1-C 10 ) alkyl) aluminum, tri((C6-C 18)aryl)boron compounds and their halogenated (including perhalogenated) derivatives. In further embodiments, the Group 13 metal compound is tris(fluoro-substituted phenyl)borane, tris(pentafluorophenyl)borane. In some embodiments, the activating cocatalyst is tris((C1-C 20 ) hydrocarbyl borate (e.g. trityl tetrafluoroborate) or tri((C 20 )hydrocarbyl)ammonium tetra((C1-C 20 As used herein, the term "ammonium" refers to a ((C1-C2) hydrocarbyl) borane (e.g., bis(octadecyl)methylammonium tetrakis(pentafluorophenyl)borane). 20 ) Hydrocarbyl) 4N + , ((C1~C 20 )hydrocarbyl)3N(H) + , ((C1~C 20 )hydrocarbyl)2N(H)2 + , (C1~C 20 ) HydrocarbylN(H)3 + , or N(H)4 + In the formula, each of (C1 to C 20 ) Hydrocarbyls, when present more than once, may be the same or different.

[0078] As a combination of neutral Lewis acid activators (cocatalysts), tri((C1-C4) alkyl)aluminum and tri((C6-C 18)aryl)boron compounds, particularly tris(pentafluorophenyl)borane. Embodiments include such neutral Lewis acid mixtures in combination with polymeric or oligomeric alumoxanes, and a single neutral Lewis acid, particularly tris(pentafluorophenyl)borane in combination with polymeric or oligomeric alumoxanes. The molar ratio of (metal-ligand complex):(tris(pentafluorophenylborane):(alumoxane) [e.g., Group 4 metal-ligand complex):(tris(pentafluorophenylborane):(alumoxane)] is 1:1:1 to 1:10:30, in embodiments 1:1:1.5 to 1:5:10.

[0079] Catalyst systems comprising the metal-ligand complexes of formula (I) may be activated to form active catalyst compositions by combination with one or more cocatalysts, such as cation-forming cocatalysts, strong Lewis acids, or combinations thereof. Suitable activating cocatalysts include polymeric or oligomeric aluminoxanes, particularly methylaluminoxane, as well as inert, compatible, non-coordinating, ion-forming compounds. Examples of suitable cocatalysts include modified methylaluminoxane (MMAO), bis(hydrogenated tallow alkyl)methyl, tetrakis(pentafluorophenyl)borate (1 - ) amines, and combinations thereof.

[0080] In some embodiments, one or more of the aforementioned activating cocatalysts are used in combination with each other. Particularly preferred combinations are mixtures of tri((C1-C4)hydrocarbyl)aluminum, tri((C1-C4)hydrocarbyl)borane, or ammonium borate with an oligomeric or polymeric alumoxane compound. The ratio of the total number of moles of the one or more metal-ligand complexes of formula (I) to the total number of moles of the one or more activating cocatalysts is 1:10,000 to 100:1. In some embodiments, this ratio is at least 1:5000, in some embodiments at least 1:1000, and not more than 10:1, and in some embodiments, not more than 1:1. When an alumoxane is used alone as the activating cocatalyst, it is preferred that the number of moles of alumoxane used is at least 100 times the number of moles of the metal-ligand complex of formula (I). When tris(pentafluorophenyl)borane is used alone as the activating cocatalyst, in some embodiments the number of moles of tris(pentafluorophenyl)borane used relative to the total number of moles of one or more metal-ligand complexes of Formula (I) is from 0.5:1 to 10:1, from 1:1 to 6:1, or from 1:1 to 5:1. The remaining activating cocatalyst is generally used in a molar amount approximately equal to the total molar amount of one or more metal-ligand complexes of Formula (I).

[0081] composition

[0082] It has been found that by carrying out the process described above, multimodal ethylene-based copolymer compositions having improved melt strength can be produced. Properties of the multimodal ethylene-based copolymer compositions according to the embodiments disclosed and described herein are provided herein. It should be understood that by varying the various process conditions described in the embodiments above, multimodal ethylene-based copolymer compositions having different and desirable properties can be produced. Although the properties listed below are described in separate paragraphs, it should be understood that the properties of any of the following paragraphs can be combined with the properties of any of the other paragraphs below by varying the various process conditions discussed above. Thus, multimodal ethylene-based copolymer compositions having any combination of the various properties listed below are envisioned and can be produced according to the embodiments.

[0083] In one or more embodiments, the multimodal ethylene-based copolymer composition has a viscosity of 0.900 g / cm 3 ~0.930g / cm 3 For example, embodiments of the multimodal ethylene-based copolymer compositions of the present disclosure may have a density of 0.900 g / cm 3 ~0.925g / cm 3 , 0.900g / cm 3 ~0.920g / cm 3 , 0.900g / cm 3 ~0.918g / cm 3 , 0.900g / cm 3 ~0.916g / cm 3 , 0.900g / cm 3 ~0.914g / cm 3 , 0.900g / cm 3 ~0.912g / cm 3 , 0.900g / cm 3 ~0.910g / cm 3 , 0.900g / cm 3 ~0.908g / cm 3 , 0.900g / cm 3 ~0.906g / cm 3 , 0.900g / cm 3~0.904g / cm 3 、0.900g / cm 3 ~0.902g / cm 3 、0.902g / cm 3 ~0.920g / cm 3 、0.902g / cm 3 ~0.918g / cm 3 、0.902g / cm 3 ~0.916g / cm 3 、0.902g / cm 3 ~0.914g / cm 3 、0.902g / cm 3 ~0.912g / cm 3 、0.902g / cm 3 ~0.910g / cm 3 、0.902g / cm 3 ~0.908g / cm 3 、0.902g / cm 3 ~0.906g / cm 3 、0.902g / cm 3 ~0.904g / cm 3 、0.904g / cm 3 ~0.920g / cm 3 、0.904g / cm 3 ~0.918g / cm 3 、0.904g / cm 3 ~0.916g / cm 3 、0.904g / cm 3 ~0.914g / cm 3 、0.904g / cm 3 ~0.912g / cm 3 、0.904g / cm 3 ~0.910g / cm 3 、0.904g / cm 3 ~0.908g / cm 3 、0.904g / cm 3 ~0.906g / cm 3 、0.906g / cm 3 ~0.920g / cm 3 、0.906g / cm 3 ~0.918g / cm 3 、0.906g / cm 3 ~0.916g / cm 3 、0.906g / cm3 ~0.914g / cm 3 、0.906g / cm 3 ~0.912g / cm 3 、0.906g / cm 3 ~0.910g / cm 3 、0.906g / cm 3 ~0.908g / cm 3 、0.908g / cm 3 ~0.920g / cm 3 、0.908g / cm 3 ~0.918g / cm 3 、0.908g / cm 3 ~0.916g / cm 3 、0.908g / cm 3 ~0.914g / cm 3 、0.908g / cm 3 ~0.912g / cm 3 、0.908g / cm 3 ~0.910g / cm 3 、0.910g / cm 3 ~0.920g / cm 3 、0.910g / cm 3 ~0.918g / cm 3 、0.910g / cm 3 ~0.916g / cm 3 、0.910g / cm 3 ~0.914g / cm 3 、0.910g / cm 3 ~0.912g / cm 3 、0.912g / cm 3 ~0.920g / cm 3 、0.912g / cm 3 ~0.918g / cm 3 、0.912g / cm 3 ~0.916g / cm 3 、0.912g / cm 3 ~0.914g / cm 3 、0.914g / cm 3 ~0.920g / cm 3 、0.914g / cm 3 ~0.918g / cm 3 、0.914g / cm 3 ~0.916g / cm 3, 0.916g / cm 3 ~0.920g / cm 3 , 0.916g / cm 3 ~0.918g / cm 3 , 0.918g / cm 3 ~0.920g / cm 3 , or any combination of these ranges.

[0084] In one or more embodiments, the multimodal ethylene-based copolymer composition can have a melt index (I2) from 0.50 g / 10 minutes (g / 10 min) to 10.0 g / 10 min, as measured according to ASTM D-1238 at 190° C. and 2.16 kg. ... When measured according to D-1238, the following are available: 0.5g / 10min - 10.0g / 10min, 0.5g / 10min - 9.0g / 10min, 0.5g / 10min - 8.0g / 10min, 0.5g / 10min - 7.0g / 10min, 0.5g / 10min - 6.0g / 10min, 0.5g / 10min - 5.0g / 10min, 0.5g / 10min - 4.0g / 10min, 0.5g / 10min - 3.0g / 10min, 0.5g / 10min - 2.0g / 10min, 0.5g / 10min - 1.0g / 10min, 1.0g / 10 min~10.0g / 10min, 1.0g / 10min~9.0g / 10min, 1.0g / 10min~8.0g / 10min, 1.0g / 10min~7.0g / 10min, 1.0g / 10min~6.0g / 10min, 1.0g / 10min~5.0g / 10min, 1 .0g / 10min~4.0g / 10min, 1.0g / 10min~3.0g / 10min, 1.0g / 10min~2.0g / 10min, 2.0g / 10min~10.0g / 10min, 2.0g / 10min~9.0g / 10min, 2.0g / 10min~8.0g / 10 minutes, 2.0g / 10 minutes ~ 7.0g / 10 minutes, 2.0g / 10 minutes ~ 6.0g / 10 minutes, 2.0g / 10 minutes ~ 5.0g / 10 minutes, 2.0g / 10 minutes ~ 4.0g / 10 minutes, 2.0g / 10 minutes ~ 3.0g / 10 minutes, 3.0g / 10 minutes ~ 10.0g / 10min, 3.0g / 10min~9.0g / 10min, 3.0g / 10min~8.0g / 10min, 3.0g / 10min~7.0g / 10min, 3.0g / 10min~6.0g / 10min, 3.0g / 10min~5.0g / 10min, 3.0g / 10 minutes~4.0g / 10 minutes, 4.0g / 10 minutes~10.0g / 10 minutes, 4.0g / 10 minutes~9.0g / 10 minutes, 4.0g / 10 minutes~8.0g / 10 minutes, 4.0g / 10 minutes~7.0g / 10 minutes, 4.0g / 10 minutes~6.0g / 10 min, 4.0g / 10min~5.0g / 10min, 5.0g / 10min~10.0g / 10min, 5.0g / 10min~9.0g / 10min, 5.0g / 10min~8.0g / 10min, 5.0g / 10min~7.0g / 10min, 5.0g / 10min~6.The melt index (I2) may be 0 g / 10 min, 6.0 g / 10 min to 10.0 g / 10 min, 6.0 g / 10 min to 9.0 g / 10 min, 6.0 g / 10 min to 8.0 g / 10 min, 6.0 g / 10 min to 7.0 g / 10 min, 7.0 g / 10 min to 10.0 g / 10 min, 7.0 g / 10 min to 9.0 g / 10 min, 7.0 g / 10 min to 8.0 g / 10 min, 8.0 g / 10 min to 10.0 g / 10 min, 8.0 g / 10 min to 9.0 g / 10 min, 9.0 g / 10 min to 10.0 g / 10 min, or any combination of these ranges.

[0085] According to embodiments, the multimodal ethylene-based copolymer composition may have a molecular weight distribution (expressed as the ratio of weight average molecular weight to number average molecular weight (Mw / Mn)) in the range of 2.0 to 6.0. For example, the multimodal ethylene-based copolymer composition may have a molecular weight distribution (expressed as the ratio of weight average molecular weight to number average molecular weight (Mw / Mn)) in the range of 2.0 to 5.5, 2.0 to 5.0, 2.0 to 4.5, 2.0 to 4.0, 2.0 to 3.5, 2.0 to 3.0, 2.0 to 2.5, 2.5 to 6.0, 3.0 to 5.5, 3.0 to 5.0, 3.0 to 4.5, 3.0 to 4.0, 3.0 to 3.5, 3.5 to 6.0, 3.5 The molecular weight distribution may be 0.01 to 0.5, ...

[0086] Long Chain Branching Frequency (LCB f ) refers to the degree of long chain branching per 1000 carbons. In embodiments, the long chain branching frequency (LCB) of a multimodal ethylene-based copolymer composition is f In one or more embodiments, the long chain branching frequency (LCB) of the multimodal ethylene-based copolymer composition is greater than or equal to 1.0 and less than or equal to 1.8. f) may be 1.0 to 1.8, 1.0 to 1.6, 1.0 to 1.4, 1.0 to 1.2, 1.2 to 1.8, 1.2 to 1.6, 1.2 to 1.4, 1.4 to 1.8, 1.4 to 1.6, 1.6 to 1.8, or any combination of these ranges.

[0087] According to embodiments, the multimodal ethylene-based copolymer compositions can have a compositional activation energy (Ea), as determined from dynamic mechanical analysis, that can be greater than 30 kJ / mol. In further embodiments, the multimodal ethylene-based copolymer compositions can have a compositional activation energy (Ea), as determined from dynamic mechanical analysis, that can be from 30 kJ / mol to 60 kJ / mol, from 30 kJ / mol to 50 kJ / mol, from 30 kJ / mol to 40 kJ / mol, from 40 kJ / mol to 60 kJ / mol, from 40 kJ / mol to 50 kJ / mol, or from 50 kJ / mol to 60 kJ / mol.

[0088] The activation energy is calculated from the rheological time-temperature superimposed viscosity data obtained from the melt rheological frequency sweep. These measurements are performed using a TA Instruments Advanced Rheometric Expansion System (ARES) equipped with 25 mm parallel plates using pure nitrogen. The linear viscoelastic response is measured at three different temperatures, 150°C, 190°C, and 230°C, using frequencies of 0.1-500 rad / s, 0.1-100 rad / s, and 0.01-100 rad / s, respectively. The strain is modified based on the torque output of the transducer to ensure that the torque remains within an acceptable range. The stress response is analyzed in terms of amplitude and phase, from which the storage and loss moduli, as well as the dynamic melt viscosity, are calculated. The temperature dependence of the linear viscoelastic curve can be predicted by shifting the modulus curve across the frequency axis (X-axis) relative to a reference using a set of shift coefficients. This concept is commonly known as time-temperature superimposition. This technique involves shifting the curves at different temperatures so that they overlap and form a single curve, also known as the master curve. The shift coefficients were generated using RepTate software. The reference temperature was chosen to be 190° C. The Arrhenius equation relates the horizontal shift coefficient to the activation energy and the reference temperature according to the following equation:

number

[0089] According to embodiments, the multimodal ethylene-based copolymer composition may have a melt strength (MS) that satisfies Equation 1:

number

[0090] where x is greater than or equal to 8, y is greater than or equal to 3, and I2 is the melt index of the copolymer measured according to ASTM 1238 at 2.16 kg and 190° C. According to one or more embodiments, the multimodal ethylene-based copolymer composition may have a melt strength of at least 5 centiNewtons (cN). In further embodiments, the multimodal ethylene-based copolymer composition has a viscosity of 5 cN to 50 cN, 5 cN to 45 cN, 5 cN to 40 cN, 5 cN to 35 cN, 5 cN to 30 cN, 5 cN to 25 cN, 5 cN to 20 cN, 5 cN to 15 cN, 5 cN to 10 cN, 10 cN to 50 cN, 10 cN to 45 cN, 10 cN to 40 cN, 10 cN to 35 cN, 10 cN to 30 cN, 10 cN to 25 cN, 10 cN to 20 cN, 10 cN to 15 cN, 15 cN to 50 cN, 15 cN to 45 cN, 15 cN to 40 cN, 15 cN to 35 cN, 15 cN to 30 cN , 15cN to 25cN, 15cN to 20cN, 20cN to 50cN, 20cN to 45cN, 20cN to 40cN, 20cN to 35cN, 20cN to 30cN, 20cN to 25cN, 25cN to 50cN, 25cN to 45cN, 25cN to 40cN, 25cN to 35cN, 25cN to 30cN, 30cN to 50cN, 30cN to 45cN, 30cN to 40cN, 30cN to 35cN, 35cN to 50cN, 35cN to 45cN, 35cN to 40cN, 40cN to 50cN, 40cN to 45cN, or 45cN to 50cN.

[0091] In embodiments, the multimodal ethylene-based copolymer compositions can have a ratio of viscosity measured at 0.1 rad / sec and 190° C. to viscosity measured at 100 rad / sec and 190° C. (V0.1 / V100), as determined by dynamic mechanical analysis, of greater than 5. In further embodiments, the multimodal ethylene-based copolymer compositions can have a (V0.1 / V100), as determined by dynamic mechanical analysis, of 5 to 30, 5 to 25, 5 to 20, 5 to 15, 5 to 10, 10 to 30, 10 to 25, 10 to 20, 10 to 15, 15 to 30, 15 to 25, 15 to 20, 20 to 30, 20 to 25, or 25 to 30.

[0092] In an embodiment, the cumulative distribution fractions (CDF) of the light scattering analysis at molecular weights above 500,000 g / mol (CDF LS ) is 8% or more.

[0093] In embodiments, the multimodal ethylene-based copolymer composition can have a high molecular weight fraction of 8% to 50%, calculated using a GPC molecular weight distribution to measure the area fraction of a low angle light scattering (LALLS) detector chromatogram above 500,000 g / mole. In embodiments, the high molecular weight fraction, calculated using a GPC molecular weight distribution to measure the area fraction of a low angle light scattering (LALLS) detector chromatogram above 500,000 g / mole, can be 8% to 40%, 8% to 30%, 8% to 20%, 8% to 10%, 10% to 50%, 10% to 40%, 10% to 30%, 10% to 20%, 20% to 50%, 20% to 40%, 20% to 30%, 30% to 50%, 30% to 40%, or 40% to 50%.

[0094] In an embodiment, the multimodal ethylene-based copolymer composition may have a low molecular weight fraction of greater than 50%, calculated using a GPC molecular weight distribution to measure the area fraction of a low angle light scattering (LALLS) detector chromatogram less than 500,000 g / mole. In an embodiment, the low molecular weight fraction, calculated using a GPC molecular weight distribution to measure the area fraction of a low angle light scattering (LALLS) detector chromatogram less than 500,000 g / mole, may be 50% to 92%, 50% to 90%, 50% to 80%, 50% to 70%, 50% to 60%, 60% to 92%, 60% to 90%, 60% to 80%, 60% to 70%, 70% to 92%, 70% to 90%, 70% to 80%, 80% to 92%, 80% to 90%, or 90% to 92%. Traditionally, having as much high molecular weight material as possible was considered ideal because the higher molecular weight results in a higher level of entanglement that improves the properties of LLDPE. Thus, low molecular weight material was minimized. However, multimodal ethylene-based copolymer compositions according to embodiments disclosed and described herein exhibit unique and unexpected properties compared to commercial LDPE products when the high molecular weight fraction is between 8% and 50%, as calculated by using GPC molecular weight distribution to measure the area fraction of the low angle light scattering (LALLS) detector chromatogram above 500,000 g / mole.

[0095] In embodiments, the amount of long chain branching, derived from the concentration of vinyl end groups in the resultant multimodal ethylene-based copolymer composition, expressed as vinyl groups / 1000 carbon atoms, can be from 0.475 to 0.600. In embodiments, the amount of long chain branching, derived from the concentration of vinyl groups in the resulting multimodal ethylene-based copolymer composition, expressed as vinyl / 1000 carbon atoms, can be 0.475-0.575, 0.475-0.550, 0.475-0.525, 0.475-0.500, 0.500-0.600, 0.500-0.575, 0.500-0.550, 0.500-0.525, 0.525-0.600, 0.525-0.575, 0.525-0.550, 0.550-0.600, 0.550-0.575, or 0.575-0.600. Without wishing to be bound by theory, it is believed that the vinyl end groups allow for the formation of long chain branches, which is a contributing factor to the melt strength achieved.

[0096] The multimodal ethylene-based copolymer composition may further comprise one or more additives. Such additives include, but are not limited to, antistatic agents, color enhancers, dyes, lubricants, pigments, primary antioxidants, secondary antioxidants, processing aids, UV stabilizers, and combinations thereof. The multimodal ethylene-based copolymer composition may contain any amount of additives. The multimodal ethylene-based copolymer composition may comprise from about 0 to about 10 percent by combined weight of such additives, based on the total weight of the multimodal ethylene-based copolymer composition. The multimodal ethylene-based copolymer composition may further comprise a filler, which may include, but is not limited to, organic or inorganic fillers. The multimodal ethylene-based copolymer composition may contain from about 0 to about 20 percent by weight of a filler, such as, for example, calcium carbonate, talc, or Mg(OH)2, based on the total weight of the multimodal ethylene-based copolymer composition. The multimodal ethylene-based copolymer composition may further be blended with one or more polymers to form a blend.

[0097] Test Method

[0098] Unless otherwise indicated herein, the following analytical methods are used in describing aspects of the present disclosure.

[0099] Melt Index

[0100] The melt index I2 (or I2) and I 10 (or I10) were measured according to ASTM D-1238 (Method B) at 190° C. and loads of 2.16 kg and 10 kg, respectively, and the values ​​are reported in g / 10 min.

[0101] density

[0102] Samples for density measurements were prepared according to ASTM D4703. Measurements were performed according to ASTM D792, Method B, within 1 hour of sample pressing.

[0103] Triple Detector Gel Permeation Chromatography (GPC)

[0104] The chromatographic system consisted of a PolymerChar GPC-IR (Valencia, Spain) high temperature GPC chromatograph equipped with an internal IR5 infra-red detector (IR5) and a 4-capillary viscometer (DV) coupled to a Precision Detectors (now Agilent Technologies) 2-angle laser light scattering (LS) detector model 2040. For all absolute light scattering measurements, a 15 degree angle is used for the measurements. The autosampler oven compartment was set to 160°C and the column and detector compartments were set to 150°C. The columns used were four Agilent "Mixed A" 30 cm, 20 micron linear mixed bed columns. The chromatographic solvent used was 1,2,4-trichlorobenzene containing 200 ppm butylated hydroxytoluene (BHT). The solvent source was nitrogen sparged. The injection volume employed was 200 microliters and the flow rate was 1.0 milliliters / minute.

[0105] The total plate count of the GPC column set was performed with decane introduced in the blank sample via a micropump controlled using a PolymerChar GPC-IR system. The plate count of the chromatographic system should exceed 18,000 for four Agilent "Mixed A" 30 cm 20 micron linear mixed bed columns.

[0106] Samples were prepared in a semi-automated fashion using PolymerChar's "Instrument Control" software to target sample weights of 2 mg / ml and add solvent (containing 200 ppm BHT) via a PolymerChar high temperature autosampler to pre-nitrogen sparged capped vials with septa. Samples were dissolved at 160° C. for 2 hours under "slow" shaking.

[0107] To monitor deviations over time, a flow rate marker (decane) was introduced into each sample via a micropump controlled by a PolymerChar GPC-IR system. This flow rate marker (FM) was used to linearly correct the pump flow rate (flow rate (apparent)) of each sample by RV matching the respective decane peak in the sample (RV (FM sample)) with that of the decane peak in the narrow standard calibration (RV (FM calibrated)). Any change in the time of the decane marker peak is then assumed to be related to a linear shift in the flow rate (flow rate (effective)) throughout the run. After calibrating the system based on the flow rate marker peak, the effective flow rate (relative to the narrow standard calibration) is calculated as per Equation 1. Processing of the flow rate marker peak was performed via PolymerChar GPCOne™ software. An acceptable flow rate correction is such that the effective flow rate should be within ±0.5% of the apparent flow rate.

[0108] With respect to the determination of viscometer and light scattering detector offsets from the IR5 detector, a systematic approach for the determination of multi-detector offsets has been described by Balke, Mourey et al. (Mourey and Balke, Chromatography Polym. Chpt 12, (1992)) (Balke, Thitiratsakul, Lew, Cheung, Mourey, Chromatography Polym. Chpt 13, (1992)), in which triple detector log (MW and IV) results obtained from linear homopolymer polyethylene standards (3.5>Mw / Mn>2.2) having molecular weights in the range of 115,000-125,000 g / mol are optimized to narrow standard column calibration results obtained from a narrow standard calibration curve using PolymerChar GPCOne™ software.

[0109] Absolute molecular weight data was obtained using PolymerChar GPCOne™ software in a manner consistent with that published by Zimm (Zimm, BH, J. Chem. Phys., 16, 1099 (1948)) and Kratochvil (Kratochvil, P., Classical Light Scattering from Polymer Solutions, Elsevier, Oxford, NY (1987)). The total injected concentration used in determining the molecular weight was obtained from the mass detector area and mass detector constant derived from a suitable linear polyethylene homopolymer or one of the polyethylene standards of known weight average molecular weight. The calculated molecular weight (using GPCOne™) was obtained using the light scattering constant and refractive index concentration coefficient, dn / dc, of -0.104, derived from one or more of the polyethylene standards mentioned below. In general, the mass detector response (IR5) and light scattering constant (determined using GPCOne™) should be determined from a linear standard with a molecular weight greater than about 50,000 g / mol. Calibration of the viscometer (determined using GPCOne™) can be accomplished using the method described by the manufacturer, or alternatively, by using the published values ​​of a suitable linear standard, such as Standard Reference Material (SRM) 1475 (available from the National Institute of Standards and Technology (NIST)). The specific viscosity area (DV) for the calibration standard and the injected mass are used to calculate the viscometer constant (obtained using GPCOne™) that relates to its intrinsic viscosity. The chromatographic concentration is assumed to be low enough to preclude addressing the second viral coefficient effect (concentration effect on molecular weight).

[0110] Absolute weight average molecular weight (MW (Abs)) is obtained (using GPCOne™) from the light scattering (LS) area integrated chromatogram (factored by the light scattering constant) divided by the mass recovered from the mass detector (IR5) area and the mass constant. The molecular weight and intrinsic viscosity responses are linearly extrapolated (using GPCOne™) at the chromatographic end where the signal to noise is low. The other respective moments, Mn (Abs) and Mz (Abs) is calculated according to the following Equations 8 to 10.

number

number

number

[0111] How to calculate the CDF

[0112] Low angle laser light scattering detector (CDF LS Cumulative detector fractions (CDF) for the low angle laser light scattering (CDF LS ") is accomplished by the following steps:

[0113] 1) Linearly flow correct the chromatogram based on the decane flow marker injection described above.

[0114] 2) Implement detector offset as described above.

[0115] 3) Calculate absolute molecular weight from light scattering as described above.

[0116] 4) According to Equation 13, for each data slice (j), a low angle laser light scattering (LALLS) chromatogram (CDF) is calculated based on the baseline subtracted peak heights (H) of the high to low molecular weight (low to high retention volume). LS ) to calculate the cumulative detector fraction (CDF).

number

[0117] LCB frequency (LCB f ) calculation

[0118] The long chain branching frequency was calculated based on the difference between g', the ratio of the intrinsic viscosity of the polymer sample to that of a linear polymer standard having the same molecular weight. In the 3D GPC run, a reference polyethylene homopolymer, containing no detectable LCB or SCB and having a Mw of approximately 120,000 g / mol and a polydispersity of about 3.0, was injected at the beginning of each run queue to establish a Mark-Houwink linear baseline. A first-order linear fit was applied to the log of the resulting intrinsic viscosity and the log of the molecular weight data within the log of the molecular weight range of 4.5 to 5.8 g / mol to obtain linear reference K and α values.

[0119] The polyethylene sample of interest was analyzed to obtain intrinsic viscosity, molecular weight values, and g i Calculate the value of ' for each chromatographic slice (i) according to Equation 14.

number

[0120] Here, the calculation is based on linear standards within the log molecular weight range of 4.5 to 5.8 g / mol, with IV values ​​at equal absolute molecular weight values ​​and the same SCB content values. 試料、i If there is a difference in SCB content, IV 線形基準、i The line is IV 試料、iThe K values ​​from the Mark-Houwink plot are shifted vertically by adjusting them to account for the SCB correction compared to the 4.5 log molecular weight. The shift is performed until the linear baseline creates a single point of contact that makes a tangent to the sample Mark-Houwink line at 4.5 log molecular weight.

[0121] The Zimm-Stockmayer branching factor g is g',g'=g, using an epsilon factor of 0.5. ε The number of branches along the polymer sample in each data slice (i) (B n ) can be determined by using Equation 15. (BH Zimm and WH Stockmayer, J. Chem. Phys. 17, 1301 (1949)):

number

[0122] Finally, the average amount of LCBf per 1000 carbon atoms in the polymer across all slices (i) can be determined using Equation 16:

number

[0123] Procedures for NMR end group analysis including vinyl number determination.

[0124] Approximately 7 mg of polymer sample was loaded into a 5 mm NMR tube along with 0.6 ml of tetrachloroethane-d2 and 0.008 M chromium(III) acetylacetonate. The tube was purged with N2 and the cap secured with Teflon tape. The prepared sample tube was heated in a heating block set at 125°C and repeatedly vortexed until a homogenous solution was achieved as evidenced by consistent flow when the tube was tilted horizontally. The completed sample was inserted into a Bruker AVANCE 600 MHz system equipped with a 10 mm high temperature cryoprobe set at 120°C. 1The acquisition parameters for the H NMR spectra were: 90 degree pulse, 1.8 s acquisition time, 10 s relaxation delay, spectral center set at 2 ppm, spectral width of 20 ppm, and 128 scans for signal averaging. The resulting raw FIDs were exponentially multiplied, Fourier transformed, phased, baseline corrected, and integrated using MNOVA software.

[0125] Semi-batch reactor polymerization procedure The feedstocks (ethylene, 1-octene) and process solvent (high purity narrow boiling range isoparaffinic solvent commercially available from ExxonMobil Corporation under the trademark ISOPAR E) were purified with molecular sieves. A 1 gallon (3.79 L) stirred autoclave reactor was charged with ISOPAR E and 1-octene. The reactor was then heated to the desired temperature and charged with ethylene to reach the desired pressure. If desired, hydrogen was also added at this point. The catalyst composition was prepared in a dry box under an inert atmosphere by mixing the desired procatalyst and, optionally, one or more additives, when desired, with additional solvent to obtain a total volume of about 15-20 mL. The activated catalyst mixture was then rapidly injected into the reactor. The reactor pressure and temperature were kept constant by feeding ethylene during the polymerization and cooling the reactor as needed. After 10 minutes, the ethylene feed was stopped and the solution was transferred to a nitrogen purged resin kettle. The polymer was thoroughly dried in a vacuum oven and the reactor was thoroughly rinsed with hot ISOPAR E between polymerization runs.

[0126] Procedure for polymerization in a continuous reactor The feedstocks (ethylene, 1-octene) and process solvent (high purity narrow boiling range isoparaffinic solvent commercially available under the trademark Isopar E from ExxonMobil Corporation) were purified with molecular sieves before being introduced into the reaction environment. Hydrogen was supplied in pressurized cylinders as a high purity grade without further purification. The reactor monomer feed (ethylene) stream was pressurized to a pressure higher than the reaction pressure via a mechanical compressor. The solvent and comonomer (1-octene) feeds were pressurized to a pressure higher than the reaction pressure via mechanical positive displacement pumps. MMAO-3A, ​​commercially available from Nouryon, was used as an impurity scavenger. The individual catalyst components (procatalyst or cocatalyst) were manually batch diluted to the specific component concentrations with purified solvent (Isopar E) and pressurized to a pressure higher than the reaction pressure. The cocatalyst was [HNMe(C 18 H 37 )]2[B(C6F5)4], used in a ratio of 1.2 relative to the catalyst metal unless otherwise specified. All reaction feed flows were measured by mass flow meters and independently controlled by computerized automated valve control systems.

[0127] Continuous solution polymerizations were carried out in one or more of CSTRs, loops, and / or plug flow reactors. CSTRs and loop reactors have independent control of all fresh solvent, monomer, comonomer, hydrogen, and catalyst component feeds. Plug flow reactors have independent control of catalyst component feeds. The combined solvent, monomer, comonomer, and hydrogen feeds to the reactors are temperature controlled anywhere between 5°C and 50°C, typically 25°C. Fresh comonomer feed to the polymerization reactor is fed along with the solvent feed. Fresh solvent feed is typically controlled with each injector receiving half of the total fresh feed mass flow rate. Cocatalyst is fed to the procatalyst based on a calculated designated molar ratio. Immediately after the location of each fresh injection, the feed streams are mixed with the contents of the circulating polymerization reactor using static mixing elements. The ratio of catalyst feeds is adjusted to obtain the desired polymer MI, density, and melt strength. The effluent from the polymerization reactor system (containing solvent, monomer, comonomer, hydrogen, catalyst components, and molten polymer) exits and passes through a control valve (responsible for maintaining the pressure of the reactor system at a specified target). As the stream exits the reactor, it is contacted with water to quench the reaction. Additionally, various additives such as antioxidants could be added at this point. The stream then passes through another set of static mixing elements to uniformly distribute the catalyst kill and additives.

[0128] Following the addition of the additives, the effluent (containing solvent, monomer, comonomer, hydrogen, catalyst components, and molten polymer) passed through a heat exchanger to raise the stream temperature in preparation for separation of the polymer from other low boiling reaction components. The stream then entered a two-stage separation and devolatilization system where the polymer was stripped from the solvent, hydrogen, and unreacted monomer and comonomer. The separated, devolatilized polymer melt was pumped through a die specially designed for underwater pelletization, cut into uniform solid pellets, dried, and transported to boxes for storage. EXAMPLES

[0129] One or more features of the present disclosure will be illustrated in light of the following examples.

[0130] The following catalysts were utilized in one or more of the examples described in more detail below. [ka] [ka] [ka]

[0131] Example 1: Preparation of Compositions 1-9

[0132] Multimodal ethylene-based copolymer compositions 1-9 described according to one or more embodiments of the Detailed Description were prepared by a process utilizing the catalysts and reactors described below.

[0133] The reactor and feed conditions for the synthesis of compositions 1-9 are provided in Table 1. [Table 1]

[0134] Example 2: Preparation of Comparative Compositions C1 to C3

[0135] Comparative compositions C1-C3 were prepared by a process utilizing the catalyst and reactor described below.

[0136] All raw materials (monomers and comonomers) and process solvents (high purity isoparaffinic solvent with narrow boiling range, Isopar-E) were purified with molecular sieves prior to introduction into the reaction environment. Hydrogen was supplied under pressure as a high purity grade and no further purification was performed. The reactor monomer feed stream was pressurized above the reaction pressure via a mechanical compressor. The solvent and comonomer feeds were pressurized by pumps to a pressure above the reaction pressure. The individual catalyst components were manually batch diluted with purified solvent and pressurized to the reaction pressure above. All reaction feed streams were metered with mass flow meters and independently controlled with a computerized automated valve control system. The reactor and feed conditions for the synthesis of comparative compositions C1-C3 are provided in Table 3. [Table 2]

[0137] Example 3: Comparative compositions C4 to C8

[0138] Table 3 identifies commercially available comparative compositions C4-C8. [Table 3]

[0139] Example 4: Preparation of comparative compositions C9 to C19

[0140] Comparative compositions 9-19 were prepared by a process utilizing the catalyst and reactor described below. [Table 4]

[0141] Example 5: Analysis of Compositions 1-10 and Comparative Compositions 1-19

[0142] In Example 5, multimodal ethylene-based polymer compositions 1-10 and comparative compositions 1-19 were tested for the properties listed in Tables 6-8 according to the test methods described herein. [Table 5] Conditions: 160° C. run: 320 psi ethylene, 60 g 1-octene, 0 H2, 1250 mL Isopar E solvent. 190° C. run: 410 psi ethylene, 65 g 1-octene, 0 H2, 1250 mL Isopar E solvent. All runs: mole fraction of ethylene in solution = 0.709. *Reactivity ratio r1 is the reactivity ratio for monomer insertion after ethylene and is calculated using the Mayo-Lewis equation.

number

number

[0143] For catalyst E, 25 g of 1-octene was added along with 1442 g of ISOPAR-E. The reactor was heated to 165° C. and saturated with ethylene at a total reactor pressure of about 169 psi. A catalyst solution was prepared by combining solutions of catalyst E, RIBS-II, and MMAO-3A to give 6 μmol Ti, 7.2 μmol RIBS-II, and 30 μmol Al.

[0144] For Catalyst C and Catalyst D, 1.47 kg Isopar-E, 100 g octene, 100 g ethylene, temperature was 160° C., total pressure was 410 psi, precatalyst:activator ratio was 1:1.2, activator was [HNMe(C 18 H 37 )2][B(CF)4]. MMAO-3A was used as an impurity scavenger at a molar ratio (Al:procatalyst) of 50:1. The reaction duration was 10 min. The efficiency (Eff) is in kilograms of polymer per gram of active metal (Zr or Hf) in the catalyst. [Table 6] *Values ​​from absolute GPC analysis **Values ​​from conventional GPC analysis [Table 7] [Table 8]

[0145] As shown in Tables 6-8, Samples 1-10 exhibited improved melt strength compared to Comparative Samples C1-C19. C1-C3, C9, and C12-C19 all failed to exhibit sufficient high molecular weight fractions, calculated by the area fraction of MWD greater than 500,000 g / mol obtained by absolute molecular weight from GPC light scattering analysis. In addition, Comparative Samples C4-C5 exhibited high molecular weight fractions greater than 50% of the area fraction of MWD greater than 500,000 g / mol obtained by absolute molecular weight from light scattering. In addition, Samples 1-10 exhibited a higher amount of vinyl end groups per 1000 carbon atoms when compared to Comparative Samples C12-C19. An increase in the number of vinyl end groups correlates with an increase in the frequency of long chain branching. In addition, Samples 1-10 exhibited a higher amount of vinyl end groups per 1000 carbon atoms ...-C 10The samples exhibited I10 / I2 (melt flow ratios) comparable to or exceeding I10 / I2, indicating comparable or improved processability of the resins, respectively. Although long chain branching was present in comparable amounts in both Samples 1-8 and Comparative Samples C1-C3, only Samples 1-8 having the high molecular weight component described herein exhibited improved melt strength and melt flow ratios. Similarly, both Samples 1-8 and Comparative Samples C1-C3 have similar LCBf, but only Samples 1-8 having the high molecular weight component described herein exhibited improved melt strength.

Claims

1. 1. A process for polymerizing a multimodal polyethylene polymer, said process comprising: contacting ethylene and optionally one or more α-olefin monomers with at least two catalyst systems in a solution reactor at a reactor temperature greater than 150° C.; the at least two catalyst systems produce greater than 0.3 vinyl end groups per 1000 carbon atoms, wherein the vinyl end groups per 1000 carbon atoms are measured by a 600 MHz nuclear magnetic resonance (NMR) instrument; a first catalyst system of the at least two catalyst systems comprises a first procatalyst; a second catalyst system of said at least two catalyst systems comprises a second procatalyst having a reactivity ratio of less than 20, said reactivity ratio of said first procatalyst being measured in a single reactor using only said first catalyst system, in the presence of 1250 grams of ISOPAR-E, with a mole fraction of ethylene in solution of 0.709, and at a reactor temperature of at least 150°C.

2. 10. The process of claim 1, wherein the at least two catalyst systems are present in one reactor.

3. 3. The process of claim 1 or 2, wherein at least 10% of the multimodal polyethylene polymer is greater than 500 kg / mol.

4. The process according to any one of claims 1 to 3, wherein the solution reactor is a dual reactor.

5. 5. The process of claim 4, wherein a first reactor comprises a first catalyst system and a second catalyst system, and a second reactor of the dual reactor comprises a third catalyst system.

6. 6. The process of claim 4 or 5, wherein the first catalyst system comprises the reaction product, a first procatalyst, and an activator, the second catalyst system comprises the reaction product, a second procatalyst, and an activator, and the third catalyst system comprises the reaction product, a third procatalyst, and an activator.

7. 7. The process of claim 6, wherein the first procatalyst is different from the second procatalyst, and the second procatalyst is different from the third procatalyst.

8. The process of claim 7 , wherein the first procatalyst is different from the third procatalyst.

9. 9. The process of any one of claims 2 to 8, wherein the reactor temperature of the first reactor is greater than 150°C and the second reactor temperature of the other reactor is less than 150°C.

10. 10. The process of claim 1, wherein the solution reactor is a single reactor.

11. 11. The process of claim 10, wherein the single reactor has a reactor temperature greater than 160°C.

12. 12. The process of any one of claims 9 to 11, wherein the number of vinyl end groups per 1000 carbon atoms is greater than 0.40 as measured by a 600 MHz nuclear magnetic resonance (NMR) instrument.

13. 12. The process of any one of claims 9 to 11, wherein the number of vinyl end groups per 1000 carbon atoms is greater than 0.45 as measured by a 600 MHz nuclear magnetic resonance (NMR) instrument.

14. The process of any one of claims 1 to 13, wherein the α-olefin monomer is not a diene.

15. The process of any one of claims 1 to 12, wherein the α-olefin monomer contains a single vinyl group.

16. The process of any one of claims 1 to 15, wherein the α-olefin monomer is linear.

17. The α-olefin monomer is ３ ~C １２ 17. The process of any one of claims 1 to 16, wherein the monomer is an α-olefin monomer.

18. The process of any one of claims 1 to 17, wherein the at least two catalyst systems comprise at least one co-catalyst.

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