Multimodal ethylene-based copolymer compositions and processes for producing same

Abstract

An embodiment of a process for making a multimodal ethylene-based copolymer can include contacting at least two olefin monomers in the presence of at least a first catalyst to produce a bulk low molecular weight component and a second catalyst to produce a high molecular weight component in a solution polymerization reactor system at a reactor temperature of 150° C. or greater. The multimodal ethylene-based copolymer can include a long chain branching frequency of 1.0 to 1.8, a melt index of 0.5 g / 10 minutes (g / 10 min) to 10.0 g / 10 min, and a molecular weight distribution as determined by GPC-LALLS CDF that includes a high molecular weight fraction of greater than 8%, where the high molecular weight fraction is calculated by measuring the area fraction of a low angle light scattering (LALLS) detector chromatogram greater than 500,000 g / mole using GPC.

Description

[Technical field]

[0001] (CROSS REFERENCE TO RELATED APPLICATIONS) This application claims the benefit of U.S. Provisional Application No. 63 / 295,187, filed December 30, 2021, the entire disclosure of which is incorporated herein by reference.

[0002] FIELD OF THEINVENTION 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, which are known to be hazardous, 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. In particular, 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] The embodiments of the present disclosure meet these demands by providing a multimodal ethylene-based copolymer that includes a bulk low molecular weight (LMW) ethylene-based component made by one catalyst or catalysts and a high molecular weight (HMW) ethylene-based component made by a different catalyst or catalysts. 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 those of various LDPEs produced via conventional processes to be achieved. As a result, the multimodal ethylene-based copolymers described herein can be used as blend components with LLDPE in amounts less than those required for conventional LDPE resins, thereby resulting in improved mechanical properties of the resulting LLDPE blends when compared to those in conventional LLDPE / LDPE blends. In an embodiment, the multimodal ethylene-based copolymers are produced via a solution polymerization process.

[0009] An embodiment of the present disclosure includes a process for making a multimodal ethylene-based copolymer. In an embodiment, the process includes contacting at least two olefin monomers in the presence of at least a first catalyst to produce a bulk low molecular weight component and a second catalyst to produce a high molecular weight (HMW) component in a solution polymerization reactor system at a first reactor temperature of 150° C. or greater. The multimodal ethylene-based copolymer comprises a long chain branching frequency of 0.3 to 1.0, a melt index of 0.5 grams per 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, and a molecular weight distribution as determined by GPC low angle light scattering (LALLS) cumulative distribution fraction (CDF) that comprises a high molecular weight fraction of greater than 8%, where the high molecular weight fraction is calculated by measuring the area fraction of a low angle light scattering (LALLS) detector chromatogram greater than 500,000 g / mole using GPC. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] 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%) of 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 of monomer units derived from ethylene, at least 70 mole percent of monomer units derived from ethylene, at least 80 mole percent of monomer units derived from ethylene, or from 50 to 100 mole percent of monomer units derived from ethylene, or from 80 to 100 mole percent of monomer units derived from ethylene.

[0011] process 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 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.

[0012] 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. 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 any combination thereof.

[0013] In an embodiment, ethylene and at least one olefin monomer may be polymerized in the presence of a catalyst to produce a multimodal ethylene-based copolymer composition described herein. The olefin monomer may be an α-olefin comonomer. 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 an embodiment, 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 a 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.

[0014] The catalyst systems described in more detail in subsequent sections are 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 bulk low molecular weight (LMW) ethylene-based component and at least one second catalyst that produces a high molecular weight (HMW) ethylene-based component.

[0015] In one embodiment, the multimodal ethylene-based copolymer composition may be produced via a solution polymerization process, in which ethylene, and optionally one or more α-olefins, are polymerized in the presence of a first catalyst to produce a bulk low molecular weight (LMW) ethylene-based component. As used herein, "bulk" may refer to a component that constitutes greater than 50% of the composition, based on the total weight of the composition. In one or more embodiments, the first catalyst may have a first catalyst efficiency of 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 15, The low molecular weight catalyst efficiency may be 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.

[0016] 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 high molecular weight (HMW) ethylene-based component. In one or more embodiments, the second catalyst may have a second efficiency of from 1,000 kg polymer / g metal to 100,000 kg polymer / g metal. In further embodiments, the second catalyst may have a second efficiency of from 1,000 kg polymer / g metal to 75,000 kg polymer / g metal, from 1,000 kg polymer / g metal to 50,000 kg polymer / g metal, or from 1,000 kg polymer / g metal to 25,000 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 1 The second catalyst may have a second 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 second catalyst may exhibit a second reactivity ratio of less than 20. In further embodiments, the second catalyst may exhibit a second reactivity ratio of less than 20, less than 15, or less than 10. In further embodiments, the second catalyst may exhibit a first reactivity ratio of from 10 to 20, or from 10 to 15, or from 15 to 20.

[0017] 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 (HMW) 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.

[0018] In embodiments, a solution polymerization reactor system may include one or more reactors operating at temperatures above 150° C. In embodiments, a solution polymerization reactor system may include one or more reactors operating at temperatures from 160° C. to 200° C., 160° C. to 190° C., 160° C. to 180° C., 160° C. to 170° C., 170° C. to 200° C., 170° C. to 190° C., 170° C. to 180° C., 180° C. to 200° C., 180° C. to 190° C., or 190° C. to 200° C. Operating a solution polymerization reactor at high reactor temperatures (>150° C.) may increase production rates and reduce energy consumption while still producing polyethylene product with acceptable catalyst efficiency and process control.

[0019] 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.

[0020] 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.

[0021] 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.

[0022] Catalyst system 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.

[0023] The term "independently selected" means 1 , R 2 , R 3 , R 4 , and R 5 The R groups, such as R1 , 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.

[0024] 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.

[0025] When used to describe a chemical group that contains a particular carbon atom, the term "(C x ~C y A bracketed expression having the form "(C)" means that the unsubstituted form of the chemical group has from x carbon atoms to y carbon atoms, inclusive. For example, (C 1 ~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 represented by any group R S Depending on the identity of R, R may contain more than y carbon atoms. For example, S is phenyl (-C 6 H 5), exactly one group R S Replaced by (C 1 ~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

[0026] 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.

[0027] 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.

[0028] "(C 1 ~C 40 The term "(C)hydrocarbyl" means a hydrocarbon radical of 1 to 40 carbon atoms. 1 ~C 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

[0029] In this disclosure, 1 ~C 40 ) Hydrocarbyl is unsubstituted or substituted (C 1 ~C 40 ) alkyl, (C 3 ~C 40 ) cycloalkyl, (C 3 ~C 20 )Cycloalkyl-(C 1 ~C 20 ) alkylene, (C 6 ~C 40 ) aryl, or (C 6 ~C 20 )Aryl-(C 1 ~C 20 In some embodiments, the alkylene group may be the alkylene group mentioned above. 1 ~C 40 Each of the hydrocarbyl groups has up to 20 carbon atoms (i.e., (C 1 ~C 20 ) hydrocarbyl), in embodiments having up to 12 carbon atoms.

[0030] "(C 1 ~C 40 ) alkyl" and "(C 1 ~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 1 ~C 40 Examples of alkyl groups include unsubstituted (C 1 ~C 20 ) Alkyl, unsubstituted (C1 ~C 10 ) Alkyl, unsubstituted (C 1 ~C 5 ) 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. 1 ~C 40 Examples of substituted (C 1 ~C 20 ) Alkyl, Substituted (C 1 ~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., (C 1 ~C 5 ) one R that is alkyl S Replaced by (C 27 ~C 40 ) alkyl. 1 ~C 5 ) Alkyl can be methyl, trifluoromethyl, ethyl, 1-propyl, 1-methylethyl, or 1,1-dimethylethyl.

[0031] "(C 6 ~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) with one, two, or three rings, respectively, in which one ring is aromatic and two or three rings are independently fused or non-fused, and at least one of the two or three rings is aromatic. 6 ~C 40 Examples of alkyl groups include unsubstituted (C 6 ~C 20 ) Alkyl unsubstituted (C 6 ~C 18) alkyl, 2-(C 1 ~C 5 ) alkylphenyl, 2,4-bis(C 1 ~C 5 ) alkylphenyl, phenyl, fluorenyl, tetrahydrofluorenyl, indacenyl, hexahydroindacenyl, indenyl, dihydroindenyl, naphthyl, tetrahydronaphthyl, and phenanthrene. 6 ~C 40 Examples of substituted (C 1 ~C 20 ) Alkyl, Substituted (C 6 ~C 18 )aryl, 2,4-bis[(C 20 )alkyl]-phenyl, polyfluorophenyl, pentafluorophenyl, and fluoren-9-on-1-yl.

[0032] "(C 3 ~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 The unsubstituted (C 3 ~C 40 Examples of cycloalkyl are unsubstituted (C 3 ~C 20 ) Cycloalkyl, unsubstituted (C 3 ~C 10 ) cycloalkyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, and cyclodecyl. 3 ~C 40 Examples of cycloalkyl are substituted (C 3 ~C 20 ) Cycloalkyl, substituted (C 3 ~C 10) cycloalkyl, cyclopentanon-2-yl, and 1-fluorocyclohexyl.

[0033] (C 1 ~C 40 Examples of hydrocarbylenes include unsubstituted or substituted (C 6 ~C 40 ) arylene, (C 3 ~C 40 ) cycloalkylene, and (C 1 ~C 40 ) alkylene (e.g. (C 1 ~C 20 In some embodiments, the diradicals are on the same carbon atom (e.g., —CH 2 -), 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 largest carbon backbone spacing between the radical carbons. (C 2 ~C 20 Some examples of alkylene α,ω-diradicals are ethane-1,2-diyl (i.e., -CH 2 CH 2 -), propane-1,3-diyl (i.e., -CH 2 CH 2 CH 2 -), 2-methylpropane-1,3-diyl (i.e., -CH 2 CH(CH 3 )CH 2 -) is one of them. (C 6 ~C 50 ) Some examples of arylene α,ω-diradicals include phenyl-1,4-diyl, naphthalene-2,6-diyl, or naphthalene-3,7-diyl.

[0034] "(C 1 ~C 40 The term "alkylene" may be unsubstituted or may contain one or more R Smeans a saturated straight or branched diradical (i.e., the radicals are not on ring atoms) of 1 to 40 carbon atoms, which is substituted with 1 ~C 50 An example of an alkylene is an unsubstituted —CH 2 CH 2 -, -(CH 2 ) 3 -, -(CH 2 ) 4 -, -(CH 2 ) 5 -, -(CH 2 ) 6 -, -(CH 2 ) 7 -, -(CH 2 ) 8 -, -CH 2 C * HCH 3 , and -(CH 2 ) 4 C * (H)CH 3 Non-substituted (C 1 ~C 20 ) alkylene, * " represents a carbon atom from which a hydrogen atom is removed to form a secondary or tertiary alkyl radical. 1 ~C 50 Examples of alkylenes are substituted (C 1 ~C 20 ) alkylene, -CF 2 -, -C(O)-, and -(CH 2 ) 14 C(CH 3 ) 2 (CH 2 ) 5 - (i.e., 6,6-dimethyl-substituted normal-1,20-eicosylene). As mentioned above, two R S Let's get together (C 1 ~C 18 ) alkylene, so the substitution (C 1 ~C 50Examples 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.

[0035] "(C 3 ~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

[0036] The term "heteroatom" refers to an atom other than hydrogen or carbon. Examples of heteroatoms include O, S, S(O), S(O) 2 , 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 non-substituted (C 1 ~C 18 ) hydrocarbyl or -H. The term "heterohydrocarbon" refers to a molecule or molecular backbone in which one or more carbon atoms are replaced with a heteroatom. 1 ~C 40 The term "heterohydrocarbyl" means a heterohydrocarbon radical of 1 to 40 carbon atoms, and 1 ~C 40The term "heterohydrocarbylene" means a heterohydrocarbon diradical of 1 to 40 carbon atoms, each heterohydrocarbon having one or more heteroatoms. The heterohydrocarbyl radical may be present on a carbon atom or a heteroatom, and the heterohydrocarbyl diradical may be present on (1) one or two carbon atoms, (2) one or two heteroatoms, or (3) one carbon atom and one heteroatom. Each (C 1 ~C 50 ) heterohydrocarbyl and (C 1 ~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.

[0037] (C 1 ~C 40 ) Heterohydrocarbyl is unsubstituted or substituted (C 1 ~C 40 )heteroalkyl, (C 1 ~C 40 ) hydrocarbyl-O-, (C 1 ~C 40 ) hydrocarbyl-S-, (C 1 ~C 40 ) hydrocarbyl-S(O)-, (C 1 ~C 40 ) Hydrocarbyl-S(O) 2 -, (C 1 ~C 40 ) Hydrocarbyl-Si(R C ) 2 -, (C 1 ~C 40 )hydrocarbyl-N(R N )-, (C 1 ~C 40 ) hydrocarbyl-P(R P )-, (C 2 ~C 40 )heterocycloalkyl, (C 2 ~C 19 )Heterocycloalkyl-(C 1 ~C 20 ) alkylene, (C3 ~C 20 )Cycloalkyl-(C 1 ~C 19 ) heteroalkylene, (C 2 ~C 19 )Heterocycloalkyl-(C 1 ~C 20 ) heteroalkylene, (C 1 ~C 40 ) heteroaryl, (C 1 ~C 19 ) Heteroaryl-(C 1 ~C 20 ) alkylene, (C 6 ~C 20 )Aryl-(C 1 ~C 19 ) heteroalkylene, or (C 1 ~C 19 ) Heteroaryl-(C 1 ~C 20 ) heteroalkylene.

[0038] "(C 4 ~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 ~C y ) heteroaryl, for example (C 4 ~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 SThe 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.

[0039] The heteroalkyl referred to above is (C 1 ~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) 2 wherein each of the heteroalkyl and heteroalkylene groups can be unsubstituted or can include one or more R S is replaced by

[0040] Unsubstituted (C 2 ~C 40 Examples of heterocycloalkyl are unsubstituted (C 2 ~C 20 )Heterocycloalkyl, unsubstituted (C 2 ~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.

[0041] 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

[0042] 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.

[0043] According to some embodiments, a catalyst system for producing a multimodal ethylene-based copolymer composition comprises a metal-ligand complex according to Formula (I).

[0044] [ka]

[0045] 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 )-, L is selected from (C 1 ~C 40 ) hydrocarbylene or (C 1 ~C40 ) heterohydrocarbylene, (C 1 ~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), or 1 ~C 40 ) Heterohydrocarbylene has a moiety that includes a linker skeleton of 1 atom to 10 atoms that connects the two Z groups in formula (I), 1 ~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) 2 , Si(R C ) 2 , Ge(R C ) 2 , P(R C ), or N(R C ), and independently, each R C is (C 1 ~C 30 ) hydrocarbyl or (C 1 ~C 30 ) heterohydrocarbyl, R 1 and R 8 are independently -H, (C 1 ~C 40 ) hydrocarbyl, (C 1 ~C 40 ) heterohydrocarbyl, -Si(R C ) 3 , -Ge(R C ) 3 , -P(R P ) 2 , -N(R N ) 2 , -OR C , -SR C , -NO 2 , -CN, -CF 3 , R C S(O)-, R C S(O) 2 -, (R C ) 2 C=N-, R C C(O)O-, RC OC(O)-, R C C(O)N(R N )-, (R N ) 2 is selected from the group consisting of NC(O)-, halogen, and a radical having formula (II), formula (III), or formula (IV).

[0046] [ka]

[0047] In formulas (II), (III), and (IV), R 31~35 , R 41~48 , or R 51~59 Each of the above may be independently selected from the group consisting of: 1 ~C 40 ) hydrocarbyl, (C 1 ~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 , -NO 2 , -CN, -CF 3 , R C S(O)-, R C S(O) 2 -, (R C ) 2 C=N-, R C C(O)O-, R C OC(O)-, R C C(O)N(R N )-, (R N ) 2 NC(O)-, halogen, or -H, with the proviso that R 1 or R 8 is a radical having formula (II), formula (III), or formula (IV).

[0048] In formula (I), R 2~4 , R 5~7 , and R 9~16 Each of the above may be independently selected from the group consisting of: 1 ~C 40 ) hydrocarbyl, (C 1 ~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 , -NO 2 , -CN, -CF 3 , R C S(O)-, R C S(O) 2 -, (R C ) 2 C=N-, R C C(O)O-, R C OC(O)-, R C C(O)N(R N )-, (R C ) 2 is selected from NC(O)-, halogen, and -H.

[0049] 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.

[0050] cocatalyst component 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.

[0051] The Lewis acid activator (cocatalyst) may be any of 1 to 3 (C 1 ~C 20 In one embodiment, the Group 13 metal compound includes a tri((C 1 ~C 20 )hydrocarbyl)-substituted aluminum or tri((C 1 ~C 20 In an embodiment, the Group 13 metal compound is a tri(hydrocarbyl)-substituted aluminum, tri((C 1 ~C 20 )hydrocarbyl)-boron compounds, tri((C 1 ~C 10 ) alkyl) aluminum, tri((C 6 ~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((C 1 ~C 20 ) hydrocarbyl borates (e.g. trityl tetrafluoroborate) or tri((C 1 ~C 20 )hydrocarbyl)ammonium tetra((C 1 ~C 20 )hydrocarbyl)boranes (e.g., bis(octadecyl)methylammonium tetrakis(pentafluorophenyl)borane). As used herein, the term "ammonium" refers to a borane having a tetrakis(pentafluorophenyl) group and a tetrakis(pentafluorophenyl) group. 1 ~C 20 )hydrocarbyl) 4 N + , ((C 1 ~C 20 )hydrocarbyl) 3 N(H) + , ((C 1 ~C 20 )hydrocarbyl) 2 N(H) 2 + , (C 1 ~C 20 ) Hydrocarbyl N(H) 3 + , or N(H) 4 + wherein each (C 1 ~C 20 ) Hydrocarbyls, when present more than once, may be the same or different.

[0052] As a combination of neutral Lewis acid activators (cocatalysts), tri((C 1 ~C 4 ) alkyl) aluminum and tri((C) halide 6 ~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.

[0053] 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.

[0054] In some embodiments, one or more of the aforementioned activating cocatalysts are used in combination with each other. Particularly preferred combinations are tri((C 1 ~C 4 )hydrocarbyl)aluminum, tri((C 1 ~C 4)hydrocarbyl)borane, or a mixture of ammonium borate and 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 from 1:10,000 to 100:1. In some embodiments, the ratio is at least 1:5000, in some embodiments at least 1:1000, and up to 10:1, and in some embodiments up to 1:1. When an alumoxane is used alone as the activating cocatalyst, the number of moles of alumoxane used is preferably 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).

[0055] composition 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.

[0056] In one or more embodiments, the multimodal ethylene-based copolymer composition has a viscosity of 0.900 g / cm 3 ~0.940g / 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 / cm 3 ~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 / cm3 , 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.

[0057] In one or more embodiments, the multimodal ethylene-based copolymer composition has a melt index (I ) of 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. 2In one or more embodiments, the multimodal ethylene-based copolymer composition may have an ASTM Dye Strength 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 / 10min - 10.0g / 10min, 1.0g / 10min - 9.0g / 1 0 minutes, 1.0g / 10 minutes ~ 8.0g / 10 minutes, 1.0g / 10 minutes ~ 7.0g / 10 minutes, 1.0g / 10 minutes ~ 6.0g / 10 minutes, 1 .0g / 10 minutes~5.0g / 10 minutes, 1.0g / 10 minutes~4.0g / 10 minutes, 1.0g / 10 minutes~3.0g / 10 minutes, 1.0g / 1 0min~2.0g / 10min, 2.0g / 10min~10.0g / 10min, 2.0g / 10min~9.0g / 10min, 2.0g / 10min~8 .0g / 10min, 2.0g / 10min~7.0g / 10min, 2.0g / 10min~6.0g / 10min, 2.0g / 10min~5.0g / 1 0 minutes, 2.0g / 10 minutes~4.0g / 10 minutes, 2.0g / 10 minutes~3.0g / 10 minutes, 3.0g / 10 minutes~10.0g / 10 minutes, 3.0g / 10 minutes~9.0g / 10 minutes, 3.0g / 10 minutes~8.0g / 10 minutes, 3.0g / 10 minutes~7.0g / 10 minutes, 3.0g / 10 minutes~6.0g / 10 minutes, 3.0g / 10 minutes~5.0g / 10 minutes, 3.0g / 10 minutes~4.0g / 10 minutes, 4.0g / 10 minutes~ 10.0g / 10min, 4.0g / 10min~9.0g / 10min, 4.0g / 10min~8.0g / 10min, 4.0g / 10min~7.0g / 10 minutes, 4.0g / 10 minutes~6.0g / 10 minutes, 4.0g / 10 minutes~5.0g / 10 minutes, 5.0g / 10 minutes~10.0g / 10 min, 5.0g / 10min~9.0g / 10min, 5.0g / 10min~8.0g / 10min, 5.0g / 10min~7.0g / 10min, 5.0 g / 10 minutes~6.0g / 10 minutes, 6.0g / 10 minutes~10.0g / 10 minutes, 6.0g / 10 minutes~9.0g / 10 minutes, 6.0g / 10 min~8.0g / 10min, 6.0g / 10min~7.0g / 10min, 7.0g / 10min~10.0g / 10min, 7.0g / 10min~9.A melt index (I.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. 2 ).

[0058] 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, ...

[0059] 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 0.3 and less than or equal to 1.0. f ) may be 0.3 to 1.0, 0.3 to 0.8, 0.3 to 0.7, 0.3 to 0.6, 0.5 to 1.0, 0.5 to 0.9, 0.5 to 0.8, 0.8 to 1.0, or any combination of these ranges.

[0060] According to embodiments, the multimodal ethylene-based copolymer composition may have an activation energy (Ea) of the composition as determined from dynamic mechanical analysis that may exceed 30 kJ / mol. The activation energy is calculated from rheological time-temperature superimposed viscosity data obtained from melt rheological frequency sweeps. These measurements were performed using a TA Instruments Advanced Rheometric Expansion System (ARES) equipped with 25 mm parallel plates using pure nitrogen. The linear viscoelastic response was measured at three different temperatures, 150°C, 190°C, and 230°C, using frequencies of 0.1-500 rad / sec, 0.1-100 rad / sec, and 0.01-100 rad / sec, respectively. The strain was varied based on the torque output of the transducer to ensure that the torque remained within an acceptable range. The stress response was analyzed in terms of amplitude and phase from which the storage and loss moduli, as well as the dynamic melt viscosity, were calculated. The temperature dependence of a 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 superposition. 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 selected to be 190° C. The Arrhenius equation relates the horizontal shift coefficients to the activation energy and the reference temperature according to the following equation:

[0061]

number

[0062] In further embodiments, the multimodal ethylene-based copolymer composition can have an activation energy (Ea) of the composition, 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.

[0063] According to embodiments, the multimodal ethylene-based copolymer composition may have a melt strength (MS) that satisfies Equation 1:

[0064]

number

[0065] In the formula, x is 8 or more, y is 3 or more, and I 2is the melt index of the copolymer as 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.

[0066] 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.

[0067] In an embodiment, the cumulative distribution fraction (CDF) of the light scattering analysis at molecular weights above 500,000 g / mol (CDF LS ) is 8% or more.

[0068] In embodiments, the multimodal ethylene-based copolymer composition may 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, may 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%. 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.

[0069] 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 from 0.475 to 0.600. The amount of long chain branching derived from the concentration of vinyl groups in the multimodal ethylene-based copolymer composition can be described according to the test methods described later in this specification. In embodiments, the amount of long chain branching, derived from the concentration of vinyl groups in the resultant 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, the vinyl end groups may enable the formation of long chain branches that are a contributing factor to the melt strength achieved in the multimodal ethylene-based copolymer compositions described herein.

[0070] 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 comprise, for example, calcium carbonate, talc, or Mg(OH) , based on the total weight of the multimodal ethylene-based copolymer composition. 2and the like, from about 0 to about 20 weight percent. The multimodal ethylene-based copolymer composition may be further blended with one or more polymers to form a blend.

[0071] Test Method Unless otherwise indicated herein, the following analytical methods are used in describing aspects of the present disclosure.

[0072] Melt Index Melt index I of polymer sample 2 (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.

[0073] density 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.

[0074] Triple detector gel permeation chromatography (GPC) 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.

[0075] 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.

[0076] 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.

[0077] To monitor deviations over time, a flow marker (decane) was introduced into each sample via a micropump controlled by a PolymerChar GPC-IR system. This flow marker (FM) was used to linearly calibrate the pump flow rate (Flow (apparent)) of each sample by RV matching the respective decane peak in the sample (RV (FM sample)) with the decane peak in the narrow standard calibration (RV (FM calibrated)). Any change in time of the decane marker peak is then assumed to be related to a linear shift in flow rate (Flow (effective)) throughout the run. After calibrating the system based on the flow marker peak, the effective flow rate (relative to the narrow standard calibration) is calculated as per Equation 1. Processing of the flow marker peak was performed via PolymerChar GPCOne™ software. An acceptable flow correction is such that the effective flow rate should be within ±0.5% of the apparent flow rate. Flow (effective) = Flow (apparent) * (RV(FM calibrated) / RV(FM sample)) (Equation 3)

[0078] 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.

[0079] 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).

[0080] 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.

[0081]

number

[0082] How to calculate the CDF Low angle laser light scattering detector (CDF) LS Calculation of the cumulative detector fractions (CDF) of the 100 Hz to 100 Hz radians is accomplished by the following steps: 1) Linearly flow correct the chromatogram based on the decane flow marker injection described above. 2) Implement detector offset as described above. 3) Calculate absolute molecular weight from light scattering as described above. 4) According to Equation 14, 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).

[0083]

number

[0084] LCB frequency (LCB f ) calculation 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.

[0085] 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 15: g i '=(IV 試料、i / IV 線形基準、i ) (Formula 8) 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、i The 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.

[0086] 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 16, (BH Zimm and WH Stockmayer, J. Chem. Phys. 17, 1301 (1949)).

[0087]

number

[0088] Finally, the average amount of LCBf per 1000 carbon atoms in the polymer across all slices (i) can be determined using Equation 17:

[0089]

number

[0090] Procedures for NMR end group analysis including vinyl number determination. To determine the vinyl number, approximately 7 mg of polymer sample was dissolved in 0.6 ml of tetrachloroethane-d 2 and 0.008 M chromium(III) acetylacetonate were packed into a 5 mm NMR tube. The tube was sealed with N 2 The tubes were purged with 500 psi and the caps secured with Teflon tape. The prepared sample tubes were 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 samples were inserted into a Bruker AVANCE 600MHz system equipped with a 10mm high temperature cryoprobe set at 120°C. 1 The 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.

[0091] Procedure for polymerization in a continuous reactor: Setup 1 Feedstocks (ethylene, 1-octene) and process solvents (high purity narrow boiling range isoparaffinic solvent commercially available under the trademark Isopar E from ExxonMobil Corporation) were purified with molecular sieves prior to introduction 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. Individual catalyst components (27re catalyst 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(C 6 F 5 ) 4

[0033] and is 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.

[0092] 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.

[0093] 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.

[0094] Procedure for polymerization in a continuous reactor: Setup 2 All raw materials (monomers and comonomers) as well as process solvents (high purity narrow boiling range isoparaffinic solvent, Isopar-E) are purified with molecular sieves prior to introduction into the reaction environment. Hydrogen is supplied under pressure as a high purity grade and is not further purified. The monomer feed stream to the reactor is pressurized to a pressure above the reaction pressure by a mechanical compressor. The solvent and comonomer feeds are pressurized to a pressure above the reaction pressure by pumps. The individual catalyst components are manually batch diluted with purified solvent and pressurized above the reaction pressure. All reaction feed streams are metered with mass flow meters and independently controlled by computer automated valve control systems.

[0095] Two reactor systems are used in a series configuration. The first reactor is a continuous solution polymerization reactor consisting of a liquid-filled adiabatic continuously stirred tank reactor (CSTR). Independent control of all fresh solvent, monomer, comonomer, hydrogen, and catalyst component feeds is possible. All fresh feed streams to the second reactor (solvent, monomer, comonomer, and hydrogen) are temperature controlled to maintain a single solution phase by passing the feed streams through heat exchangers. All fresh feeds to the second polymerization reactor are injected into the reactor at one location. Catalyst components are injected into the second polymerization reactor separately from the fresh feeds. The feed of the primary catalyst component is computer controlled to maintain the monomer conversion of the reactor at a specific value. The cocatalyst component is fed based on a molar ratio relative to the primary catalyst component. Mixing in the second reactor is provided by an agitator. The effluent from the first polymerization reactor (containing solvent, monomer, comonomer, hydrogen, catalyst components, and polymer) exits the first reactor loop and is added to the second reactor separately from the fresh feed and separately from the catalyst feed components.

[0096] The second reactor is a continuous solution polymerization reactor consisting of a liquid-filled, non-adiabatic, isothermal, circulating, loop reactor that mimics a continuous stirred tank reactor (CSTR) with heat removal. Independent control of all fresh solvent, monomer, comonomer, hydrogen, and catalyst component feeds is possible. All fresh feed streams to the first reactor (solvent, monomer, comonomer, and hydrogen) are temperature controlled to maintain a single solution phase by passing the feed streams through heat exchangers. All fresh feed to the first polymerization reactor is injected into the reactor at two locations with approximately equal reactor volume between each injection location. The fresh feed is controlled with each injector receiving half of the total fresh feed mass flow rate. Catalyst components are injected into the polymerization reactor separately from the fresh feed. Primary catalyst component feed is computer controlled to maintain reactor monomer conversion at a specific value and produce polymer with desired MI, density, and melt strength. Cocatalyst components are fed based on a molar ratio relative to the primary catalyst component. Immediately after the injection point of each first reactor feed, the feed stream is mixed with the contents of a circulation polymerization reactor with a static mixing element. The contents of the first reactor are continuously circulated to a heat exchanger, which serves to remove most of the heat of reaction, at a temperature on the coolant side, which serves to maintain an isothermal reaction environment at a specific temperature. Circulation around the first reactor loop is provided by a pump.

[0097] The second reactor effluent enters a zone where a suitable reagent (water) is added to deactivate the effluent by reacting with it. Antioxidant addition may also occur at this same addition point. Following catalyst deactivation and additive addition, the reactor effluent enters a devolatilization system where polymer is removed from the non-polymer stream. The isolated polymer melt is pelletized and recovered. The non-polymer stream passes through various equipment that separates most of the ethylene removed from the system. Most of the solvent and unreacted comonomer are recycled to the reactor after passing through a purification system. Small amounts of solvent and comonomer are purged from the process.

[0098] Reactor stream feed data flows correspond to the values ​​in Table 2. The data is displayed to allow for the complexity of the solvent recycle system and to make the reaction system more easily treatable as a once-through flow diagram. EXAMPLES

[0099] One or more features of the present disclosure will be illustrated in light of the following examples.

[0100] The following catalysts were utilized in one or more of the examples described in more detail below.

[0101] [ka]

[0102] Example 1: Preparation of Compositions 1-8 Multimodal ethylene-based copolymer compositions 1-8 described according to one or more embodiments of the Detailed Description were prepared by a process utilizing the catalysts and reactors described below. The reactor and feed conditions for the synthesis of compositions 1-8 are provided in Table 1, and composition 9 is provided in Table 2.

[0103] [Table 1]

[0104] [Table 2]

[0105] Example 2: Preparation of Comparative Compositions C1 to C3 Comparative compositions C1-C3 were prepared by a process utilizing the catalyst and reactor described below.

[0106] 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.

[0107] [Table 3]

[0108] Example 3: Comparative compositions C4 to C8 Table 4 identifies commercially available comparative compositions C4-C8.

[0109] [Table 4]

[0110] Example 4: Preparation of comparative compositions C9 to C19 Comparative compositions 9-19 were prepared by a process utilizing the catalyst and reactor described below.

[0111] [Table 5]

[0112] Example 5: Analysis of Compositions 1-8 and Comparative Compositions 1-19. In Example 5, multimodal ethylene-based polymer compositions 1-8 and comparative compositions 1-19 were tested for the properties listed in Tables 6-8 according to the test methods described herein.

[0113] [Table 6] * Absolute values ​​from GPC analysis ** Values ​​from conventional GPC analysis

[0114] [Table 7]

[0115] [Table 8]

[0116] As shown in Tables 6-8, Samples 1-9 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 / mole 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 / mole obtained by absolute molecular weight from light scattering. In addition, Samples 1-8 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 long chain branching frequency. In addition, Samples 1-8 exhibited I10 / I2 (melt flow ratios) comparable to or exceeding the I10 / I2 of C1-C19, indicating comparable or improved processability of the resins, respectively. Long chain branching was present in comparable amounts in both Samples 1-8 and Comparative Samples C1-C3, but only Samples 1-8 with the higher molecular weight component described herein exhibited improved melt strength and melt flow ratio. Similarly, both Samples 1-9 and Comparative Samples C1-C3 have similar LCBf, but only Samples 1-9 with the higher molecular weight component described herein exhibited improved melt strength.

Claims

1. 1. A process for making a multimodal ethylene-based copolymer, comprising: contacting ethylene with at least one olefin monomer in the presence of at least a first catalyst system to produce a bulk low molecular weight component, and in the presence of a second catalyst system in a solution polymerization reactor system at a reactor temperature of 150° C. or greater to produce a high molecular weight component; the multimodal ethylene-based copolymer comprising: A long chain branching frequency of 0.3 to 1.0; a melt index of 0.5 g / 10 minutes (g / 10 min) to 10.0 g / 10 min, as measured in accordance with ASTM D-1238 at 190° C. and 2.16 kg; and 8% to 50% high molecular weight fraction, based on a total percent of the multimodal ethylene-based copolymer, calculated by using GPC molecular weight distribution to measure the area fraction of a molecular weight distribution obtained from absolute molecular weight by low angle light scattering that is greater than 500,000 g / mole.

2. 10. The process of claim 1, wherein the composition has an activation energy (Ea) greater than 47 kJ / mol as determined from dynamic mechanical analysis.

3. 3. The process of claim 1 or 2, wherein the multimodal ethylene-based copolymer further comprises a low molecular weight fraction that is 50% or greater, based on a total percent of the multimodal ethylene-based copolymer, calculated by using GPC molecular weight distribution to measure an area fraction of a molecular weight distribution obtained from absolute molecular weight by low angle light scattering that is less than 500,000 g / mole.

4. 4. The process of any one of claims 1 to 3, wherein the amount of long chain branching, derived from the concentration of vinyl groups in the produced multimodal ethylene-based copolymer, expressed as vinyl / thousand carbon atoms, is from 0.475 to 0.

600.

5. The process of any one of claims 1 to 4, wherein the first catalyst system has a first catalytic efficiency of from 1,000 kg polymer / g metal to 100,000 kg polymer / g metal.

6. The process of any one of claims 1 to 5, wherein the second catalyst has a second catalytic efficiency of from 1,000 kg polymer / g metal to 100,000 kg polymer / g metal.

7. The process of any one of claims 1 to 6, wherein the solution polymerization reactor system comprises a single reactor.

8. The process of any one of claims 1 to 7, wherein the solution polymerization reactor system comprises a first reactor and a second reactor.

9. The process of any one of claims 1 to 8, wherein the second catalyst has a reactivity ratio of less than 20.

10. The process of any one of claims 1 to 9, wherein the multimodal ethylene-based copolymer has a density, measured in accordance with ASTM D792, of 0.900 g / cc to 0.940 g / cc.

11. The multimodal ethylene-based copolymer has a melt strength of at least 5 cN, and a melt index (I ) of at least 0.5 g / 10 min, measured according to ASTM 1238 at 2.16 kg and 190° C. ２ 11. The process according to claim 1, wherein

12. The multimodal ethylene-based copolymer has a melt strength (MS) that satisfies the following formula: [0010] In the formula, x is 8 or more, y is 3 or more, and I ２ The process of any one of claims 1 to 11, wherein x is the melt index of the copolymer measured according to ASTM 1238 at 2.16 kg and 190°C.

13. The process of any one of claims 1 to 12, wherein the V0.1 / V100 value is greater than 10 as determined by dynamic mechanical analysis.

14. The process of any one of claims 1 to 13, wherein the temperature of the first reactor is from 160°C to 200°C.

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