CARNAHAN EDMUND M (US)
KLOSIN JERZY (US)
ROSEN MARI S (US)
HAMAD FAWZI G (US)
WO2021128126A1 | 2021-07-01 | |||
WO2021133613A1 | 2021-07-01 | |||
WO2023272545A1 | 2023-01-05 |
BALKETHITIRATSAKULLEWCHEUNGMOUREY: "Chromatography Polym", 1992
ZIMM, B.H., J. CHEM. PHYS., vol. 16, 1948, pages 1099
KRATOCHVIL, P.: "Classical Light Scattering from Polymer Solutions", 1987, ELSEVIER
B. H. ZIMMW. H. STOCKMAYER, J. CHEM. PHYS., vol. 17, 1949, pages 1301
CLAIMS 1. A process of polymerizing a multi-modal polyethylene polymer, the 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 of greater than 150°C; wherein: the at least two catalyst systems produce a vinyl end group count per 1000 carbon atoms is greater than 0.3, wherein the vinyl end group count per 1000 carbon atoms is measured by 600 MHz nuclear magnetic resonance (NMR) instrument; a first catalyst system of the at least two catalyst systems comprises a first procatalyst; and a second catalyst system of the at least two catalyst systems comprises a second procatalyst having a reactivity ratio of less than 20, wherein the reactivity ratio of the first procatalyst is measured in a single reactor with only the first catalyst system in the presence of 1250 grams of ISOPAR-E, with a mol fraction of ethylene in solution of 0.709, and at a reactor temperature of at least 150°C. 2. The process of claim 1, wherein the at least two catalyst systems are in one reactor. 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 of any one of the proceeding claims, wherein the solution reactor is a dual reactor. 5. The process of claim 4, wherein the first reactor comprises a first catalyst system and a second catalyst system; and the second reactor of the dual reactor comprises a third catalyst system. 6. The process of claim 4 or claim 5, wherein the first catalyst system comprises a reaction product a first procatalyst and an activator; the second catalyst system comprises a reaction product a second procatalyst and an activator, and a third catalyst system comprises a reaction product a third procatalyst and an activator. 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. 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 an other reactor is less than 150°C. 10. The process of claim 1, wherein the solution reactor is a single reactor. 11. The process of claim 10, wherein the single reactor has a reactor temperature of greater than 160°C. 12. The process of any one of claims 9 to 11, wherein the vinyl end group count per 1000 carbon atoms is greater than 0.40 when measured 600 MHz nuclear magnetic resonance (NMR) instrument. 13. The process of any one of claims 9 to 11, wherein the vinyl end group count per 1000 carbon atoms is greater than 0.45 when measured 600 MHz nuclear magnetic resonance (NMR) instrument. 14. The process of any one of the preceding claims, 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 comprises a single vinyl group. 16. The process of any one of the preceding claims, wherein the α-olefin monomer is linear. 17. The process of any one of the preceding claims, wherein the α-olefin monomer is a (C3−C12)α-olefin monomer. 18. The process of anyone of the preceding claims, wherein the at least two catalyst systems comprises at least one co-catalyst. |
[0054] In formula (I), M is a metal chosen from titanium, zirconium, or hafnium, the metal being in a formal oxidation state of +2, +3, or +4; n is 0, 1, or 2; when n is 1, X is a monodentate ligand or a bidentate ligand; when n is 2, each X is a monodentate ligand and is the same or different; the metal–ligand complex is overall charge-neutral; each Z is independently chosen from −O−, −S−, −N(R N )−, or –P(R P )−; L is (C 1 −C 40 )hydrocarbylene or (C 1 −C 40 )heterohydrocarbylene, wherein the (C 1 −C 40 )hydrocarbylene has a portion that comprises a 1-carbon atom to 10-carbon atom linker backbone linking the two Z groups in Formula (I) (to which L is bonded) or the (C 1 −C 40 )heterohydrocarbylene has a portion that comprises a 1-atom to 10-atom linker backbone linking the two Z groups in Formula (I), wherein each of the 1 to 10 atoms of the 1-atom to 10-atom linker backbone of the (C 1 −C 40 )heterohydrocarbylene independently is a carbon atom or heteroatom, wherein each heteroatom independently is O, S, S(O), S(O) 2 , Si(RC) 2 , Ge(RC) 2 , P(RC), or N(R C ), wherein independently each R C is (C −C )hydrocarbyl or (C −C )hetero 1 8 1 30 1 30 hydrocarbyl; R and R are independently selected from the group consisting of –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−, R C OC(O)−, R C C(O)N(R N )−, (R N ) 2 NC(O)−, halogen, and radicals having formula (II), formula (III), or formula (IV): [0055] In formulas (II), (III), and (IV), each of R 31–35 , R 41–48 , or R 51–59 is independently chosen from (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 , – 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, provided at least one of R 1 or R 8 is a radical having formula (II), formula (III), or formula (IV). [0056] In formula (I), each of R 2–4 , R 5–7 , and R 9–16 is independently selected from (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 , –– 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 NC(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 where a dual loop reactor is used, the procatalyst used in the first loop is zirconium, [[2,2’’’-[[bis[1-methylethyl)germylene]bis(methyleneox y- κO)]bis[3’’,5,5’’-tris(1,1-dimethylethyl)-5’-octy l[1,1’:3’,1’’-terphenyl]-2’-olato-κO]](2- )]dimethyl-, having the chemical formula C 86 H 128 F 2 GeO 4 Zr and the following structure (V): [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-dimethylethy l)-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 N 2 O 4 Si 2 Zr and the following structure (VI): [0060] According to some embodiments, the first catalyst system, the second catalyst system, or the third catalyst system may include a metal−ligand complex having a constrained geometry structure according to formula (XI): [0061] Lp i MX m X' n X" p , or a dimer thereof (XI). [0062] In formula (XI), Lp is an anionic, delocalized, π-bonded group that is bound to M, containing up to 50 non-hydrogen atoms. In some embodiments of formula (XI), two Lp groups may be joined together forming a bridged structure, and further optionally one Lp may be bound to X. [0063] In formula (XI), M is a metal of Group 4 of the Periodic Table of the Elements in the +2, +3 or +4 formal oxidation state. X is an optional, divalent substituent of up to 50 non-hydrogen atoms that together With Lp forms a metallocycle with M. X' is an optional neutral ligand having up to 20 non hydrogen atoms; each X" is independently a monovalent, anionic moiety having up to 40 non-hydrogen atoms. Optionally, two X" groups may be covalently bound together forming a divalent dianionic moiety having both valences bound to M, or, optionally two X" groups may be covalently bound together to form a neutral, conjugated or nonconjugated diene that is π- bonded to M, in which 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 both covalently bound to M and coordinated thereto by means of Lewis base functionality. [0064] Illustrative Group IV complexes having a constrained geometry structure that may be employed in the practice of the present invention include, but are not limited to: cyclopentadienyltitaniumtrimethyl; cyclopentadienyltitaniumtriethyl; cyclopentadienyltitaniumtriisopropyl; cyclopentadienyltitaniumtriphenyl; cyclopentadienyltitaniumtribenzyl; cyclopentadienyltitanium-2,4-dimethylpentadienyl. [0065] According to some embodiments, the first catalyst system, the second catalyst system, or the third catalyst system may include a metal−ligand complex according to formula (XII): [0066] In formula (XII), M is a metal chosen from titanium, zirconium, or hafnium, the metal having a formal oxidation state of +2, +3, or +4; and each X is a monodentate or bidentate ligand independently chosen from unsaturated (C 2 −C 50 )heterohydrocarbon, unsaturated (C 2 −C 50 )hydrocarbon, (C 1 −C 50 )hydrocarbyl, (C 6 −C 50 )aryl, (C 6 −C 50 )heteroaryl, cyclopentadienyl, substituted cyclopentadienyl, (C 4 −C 12 )diene, halogen, −N(R N ) 2 , and −NCOR C . Subscript n of (X) n is an interger 1, 2, or 3. Subscript m is 1 or 2. The metal–ligand complex of formula (I) has 6 or fewer metal−ligand bonds and may be charge nuetral or 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 is independently selected from the group consisting of (C 1 −C 50 )hydrocarbyl, (C 1 −C 50 )heterohydrocarbyl, (C 6 −C 50 )aryl, (C 4 −C 50 )heteroaryl, −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 P ) 2 P(O)−, (R C ) 2 C=N−, R C C(O)O−, R C OC(O)−, R C C(O)N(R)−, (R C ) 2 NC(O)−, halogen, and –H. Each R 2 is independently chosen from (C 1 −C 50 )hydrocarbyl, (C 1 −C 50 )heterohydrocarbyl, (C 6 −C 50 )aryl, (C 4 −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 z 1 and z 2 , each of z 1 and z 2 is independently selected from the group consisting of sulfur, oxygen, −N(R R )−, and −C(R R )−, provided that at least one of z or z is −C(R R 1 2 )−. [0068] In formula (XII), each A is independently chosen from −z 3 −z 4 −z 5 − or −C(R 3 )C(R 4 )C(R 5 )C(R 6 )−, such that when A is −z 3 −z 4 −z 5 −, each of z 3 , z 4 , and z 5 is selected from the group consisting of sulfur, oxygen, −N(R R )−, and −C(R R )−, provided that exactly one of z 3 , z , or z is −C(R R )− or that exactly two of z , z R 4 5 3 4 , or z 5 are −C(R )−. When A is −C(R 3 )C(R 4 )C(R 5 )C(R 6 )−, each R 3 , R 4 , R 5 , and R 6 is independently chosen from (C 1 −C 50 )hydrocarbyl, (C 1 −C 50 )heterohydrocarbyl, (C 6 −C 50 )aryl, (C 4 −C 50 )heteroaryl, −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 P ) 2 P(O)−, (R C ) 2 C=N−, R C C(O)O−, R C OC(O)−, R C C(O)N(R)−, (R C ) 2 NC(O)−, halogen, or −H. [0069] Each R C , R N , and R P in formula (XII) is independently a (C 1 −C 50 )hydrocarbyl; and each R R is independently chosen from (C 1 −C 50 )hydrocarbyl, (C 1 −C 50 )heterohydrocarbyl, (C 6 −C 50 )aryl, (C 4 −C 50 )heteroaryl, −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 P ) 2 P(O)−, (R C ) 2 C=N−, R C C(O)O−, R C OC(O)−, R C C(O)N(R)−, (R C ) 2 NC(O)−, halogen, or −H, wherein any two R R groups bonded to neighboring atoms are optionally linked. [0070] According to some embodiments, the first catalyst system, the second catalyst system, or the third catalyst system may include a metal−ligand complex according to formula (XIII): [0071] In formula (XIII), M is a metal chosen from titanium, zirconium, or hafnium, the metal having a formal oxidation state of +2, +3, or +4. Each X is a monodentate or bidentate ligand independently chosen from (C 1 −C 50 )hydrocarbon, (C 1 −C 50 )heterohydrocarbon, (C 1 −C 50 )hydrocarbyl, (C 6 −C 50 )aryl, (C 6 −C 50 )heteroaryl, cyclopentadienyl, substituted cyclopentadienyl, (C 4 −C 12 )diene, halogen, −N(R N ) 2 , and −NCOR C . Subscript n is 1, 2 or 3. Subscript m is 1 or 2. The metal–ligand complex of formula (XIII) has 6 or fewer metal−ligand bonds and is overall charge-neutral. [0072] In embodiments of formula (XIII), each Y is independently selected from oxygen or sulfur. Each R 1 , R 2 , R 3 , and R 4 is independently selected from the group consisting of (C 1 −C 50 )hydrocarbyl, (C 1 −C 50 )heterohydrocarbyl, (C 6 −C 50 )aryl, (C 4 −C 50 )heteroaryl, −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−, R C OC(O)−, R C C(O)N(R)−, (R C ) 2 NC(O)−, halogen, and −H. Each R 5 is independently chosen from (C 1 −C 50 )hydrocarbyl, (C 1 −C 50 )heterohydrocarbyl, (C 6 −C 50 )aryl, (C 4 −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 z 1 , z 2 , and z 3 , each of z 1 , z 2 , and z 3 is independently selected from the group consisting of sulfur, oxygen, −N(R R )−, or −C(R R )− and at least one and not more than two of z 1 , z 2 , and z 3 are −C(R R R R is –H or (C 1 –C 30 )hydrocarbyl, wherein any two R R groups bonded to neighboring atoms are optionally linked. In formula (XIII), each R C , R N , and R P in formula (XIII) is independently a (C 1 −C 30 )hydrocarbyl. [0074] In the catalyst systems according to embodiments of this disclosure, the molar ratio of the bimetallic activator complex to Group IV metal−ligand complex may be from 1:10,000 to 1000:1, such as, for example, from 1:5000 to 100:1, from 1:100 to 100:1 from 1:10 to 10:1, from 1:5 to 1:1, or from 1.25:1 to 1:1. The catalyst systems may include combinations of one or more bimetallic activator complex described in this disclosure. [0075] Co-Catalyst Component [0076] The catalyst system comprising a metal–ligand complex of formula (I) may be rendered catalytically active by any technique known in the art for activating metal-based catalysts of olefin polymerization reactions. For example, the system comprising a metal–ligand complex of formula (I) may be rendered catalytically active by contacting the complex to, or combining the complex with, an activating co-catalyst. Suitable activating co-catalysts for use herein include alkyl aluminums; 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 activating technique is bulk electrolysis. Combinations of one or more of the foregoing activating co-catalysts and techniques are also contemplated. The term “alkyl aluminum” means a monoalkyl aluminum dihydride or monoalkylaluminum dihalide, a dialkyl aluminum hydride or dialkyl aluminum halide, or a trialkylaluminum. Examples of polymeric or oligomeric alumoxanes include methylalumoxane, triisobutylaluminum-modified methylalumoxane, and isobutylalumoxane. [0077] Lewis acid activators (co-catalysts) include Group 13 metal compounds containing from 1 to 3 (C 1 –C 20 )hydrocarbyl substituents as described herein. In one embodiment, Group 13 metal compounds are tri((C 1 –C 20 )hydrocarbyl)-substituted-aluminum or tri((C 1 – C 20 )hydrocarbyl)-boron compounds. In embodiments, Group 13 metal compounds are tri(hydrocarbyl)-substituted-aluminum, tri((C 1 –C 20 )hydrocarbyl)-boron compounds, tri((C 1 – C10)alkyl)aluminum, tri((C 6 –C 18 )aryl)boron compounds, and halogenated (including perhalogenated) derivatives thereof. In further embodiments, Group 13 metal compounds are tris(fluoro-substituted phenyl)boranes, tris(pentafluorophenyl)borane. In some embodiments, the activating co-catalyst is a tris((C 1 –C 20 )hydrocarbyl borate (e.g. trityl tetrafluoroborate) or a tri((C 1 –C 20 )hydrocarbyl)ammonium tetra((C 1 –C 20 )hydrocarbyl)borane (e.g. bis(octadecyl)methylammonium tetrakis(pentafluorophenyl)borane). As used herein, the term “ammonium” means a nitrogen cation that is a ((C 1 –C 20 )hydrocarbyl) 4 N + a ((C 1 – C 20 )hydrocarbyl) 3 N(H) + , a ((C 1 –C 20 )hydrocarbyl) 2 N(H) 2 + , (C 1 –C 20 )hydrocarbylN(H) 3 + , or N(H) 4 + , wherein each (C 1 –C 20 )hydrocarbyl, when two or more are present, may be the same or different. [0078] Combinations of neutral Lewis acid activators (co-catalysts) include mixtures comprising a combination of a tri((C 1 –C 4 )alkyl)aluminum and a halogenated tri((C 6 – C 18 )aryl)boron compound, especially a tris(pentafluorophenyl)borane. Embodiments are combinations of such neutral Lewis acid mixtures with a polymeric or oligomeric alumoxane, and combinations of a single neutral Lewis acid, especially tris(pentafluorophenyl)borane with a polymeric or oligomeric alumoxane. Ratios of numbers of moles of (metal–ligand complex): (tris(pentafluoro-phenylborane): (alumoxane) [e.g., (Group 4 metal–ligand complex) :(tris(pentafluoro-phenylborane):(alumoxane)] are from 1:1:1 to 1:10:30, in embodiments, from 1:1:1.5 to 1:5:10 [0079] The catalyst system comprising the metal–ligand complex of formula (I) may be activated to form an active catalyst composition by combination with one or more co-catalysts, for example, a cation forming co-catalyst, a strong Lewis acid, or combinations thereof. Suitable activating co-catalysts include polymeric or oligomeric aluminoxanes, especially methyl aluminoxane, as well as inert, compatible, noncoordinating, ion forming compounds. Exemplary suitable co-catalysts include, but are not limited to: modified methyl aluminoxane (MMAO), bis(hydrogenated tallow alkyl)methyl, tetrakis(pentafluorophenyl)borate(1 − ) amine, and combinations thereof. [0080] In some embodiments, one or more of the foregoing activating co-catalysts are used in combination with each other. An especially preferred combination is a mixture of a tri((C 1 – C 4 )hydrocarbyl)aluminum, tri((C 1 –C 4 )hydrocarbyl)borane, or an ammonium borate with an oligomeric or polymeric alumoxane compound. The ratio of total number of moles of one or more metal-ligand complexes of formula (I) to total number of moles of one or more of the activating co-catalysts 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 10:1 or less, and in some embodiments, 1:1 or less. When an alumoxane alone is used as the activating co-catalyst, preferably the number of moles of the alumoxane that are employed is at least 100 times the number of moles of the metal–ligand complex of formula (I). When tris(pentafluorophenyl)borane alone is used as the activating co- catalyst, in some embodiments, the number of moles of the tris(pentafluorophenyl)borane that are employed to the total number of moles of one or more metal–ligand complexes of formula (I) from 0.5: 1 to 10:1, from 1:1 to 6:1, or from 1:1 to 5:1. The remaining activating co-catalysts are generally employed in approximately mole quantities equal to the total mole quantities of one or more metal-ligand complexes of formula (I). [0081] Compositions [0082] It was discovered that by performing processes as described above, multimodal ethylene-based copolymer compositions with improved melt strength can be produced. Properties of the multimodal ethylene-based copolymer composition according to embodiments disclosed and described herein will now be provided. It should be understood that by modifying the various process conditions described above embodiments of the multimodal ethylene-based copolymer composition with differing and desirable properties can be produced. Although the properties listed below are recited in separate paragraphs, it should be understood that any property from any paragraph below may be combined with any other property from any paragraph below by modifying the various process conditions discussed above. Therefore, the multimodal ethylene- based copolymer composition having any combination of various properties listed below are envisioned and can be produced, according to embodiments. [0083] In one or more embodiments, the multimodal ethylene-based copolymer composition may have a density of 0.900 g/cm 3 to 0.930 g/cm 3 . For example, embodiments of the presently- disclosed multimodal ethylene-based copolymer composition may have densities of from 0.900 g/cm 3 to 0.925 g/cm 3 , from 0.900 g/cm 3 to 0.920 g/cm 3 , from 0.900 g/cm 3 to 0.918 g/cm 3 , from 0.900 g/cm 3 to 0.916 g/cm 3 , from 0.900 g/cm 3 to 0.914 g/cm 3 , from 0.900 g/cm 3 to 0.912 g/cm 3 , from 0.900 g/cm 3 to 0.910 g/cm 3 , from 0.900 g/cm 3 to 0.908 g/cm 3 , from 0.900 g/cm 3 to 0.906 g/cm 3 , from 0.900 g/cm 3 to 0.904 g/cm 3 , from 0.900 g/cm 3 to 0.902 g/cm 3 , from 0.902 g/cm 3 to 0.920 g/cm 3 , from 0.902 g/cm 3 to 0.918 g/cm 3 , from 0.902 g/cm 3 to 0.916 g/cm 3 , from 0.902 g/cm 3 to 0.914 g/cm 3 , from 0.902 g/cm 3 to 0.912 g/cm 3 , from 0.902 g/cm 3 to 0.910 g/cm 3 , from 0.902 g/cm 3 to 0.908 g/cm 3 , from 0.902 g/cm 3 to 0.906 g/cm 3 , from 0.902 g/cm 3 to 0.904 g/cm 3 , from 0.904 g/cm 3 to 0.920 g/cm 3 , from 0.904 g/cm 3 to 0.918 g/cm 3 , from 0.904 g/cm 3 to 0.916 g/cm 3 , from 0.904 g/cm 3 to 0.914 g/cm 3 , from 0.904 g/cm 3 to 0.912 g/cm 3 , from 0.904 g/cm 3 to 0.910 g/cm 3 , from 0.904 g/cm 3 to 0.908 g/cm 3 , from 0.904 g/cm 3 to 0.906 g/cm 3 , from 0.906 g/cm 3 to 0.920 g/cm 3 , from 0.906 g/cm 3 to 0.918 g/cm 3 , from 0.906 g/cm 3 to 0.916 g/cm 3 , from 0.906 g/cm 3 to 0.914 g/cm 3 , from 0.906 g/cm 3 to 0.912 g/cm 3 , from 0.906 g/cm 3 to 0.910 g/cm 3 , from 0.906 g/cm 3 to 0.908 g/cm 3 , from 0.908 g/cm 3 to 0.920 g/cm 3 , from 0.908 g/cm 3 to 0.918 g/cm 3 , from 0.908 g/cm 3 to 0.916 g/cm 3 , from 0.908 g/cm 3 to 0.914 g/cm 3 , from 0.908 g/cm 3 to 0.912 g/cm 3 , from 0.908 g/cm 3 to 0.910 g/cm 3 , from 0.910 g/cm 3 to 0.920 g/cm 3 , from 0.910 g/cm 3 to 0.918 g/cm 3 , from 0.910 g/cm 3 to 0.916 g/cm 3 , from 0.910 g/cm 3 to 0.914 g/cm 3 , from 0.910 g/cm 3 to 0.912 g/cm 3 , from 0.912 g/cm 3 to 0.920 g/cm 3 , from 0.912 g/cm 3 to 0.918 g/cm 3 , from 0.912 g/cm 3 to 0.916 g/cm 3 , from 0.912 g/cm 3 to 0.914 g/cm 3 , from 0.914 g/cm 3 to 0.920 g/cm 3 , from 0.914 g/cm 3 to 0.918 g/cm 3 , from 0.914 g/cm 3 to 0.916 g/cm 3 , from 0.916 g/cm 3 to 0.920 g/cm 3 , from 0.916 g/cm 3 to 0.918 g/cm 3 , from 0.918 g/cm 3 to 0.920 g/cm 3 , or any combination of these ranges. [0084] In one or more embodiments, the multimodal ethylene-based copolymer composition may have a melt index (I 2 ) of from 0.50 g/10 minutes (g/10 min) to 10.0 g/10 min when measured according to ASTM D-1238 at 190 °C and 2.16 kg. In one or more embodiments, the multimodal ethylene-based copolymer composition may have a melt index (I 2 ) of from 0.5 g/10 min to 10.0 g/10 min, from 0.5 g/10 min to 9.0 g/10 min, from 0.5 g/10 min to 8.0 g/10 min, from 0.5 g/10 min to 7.0 g/10 min, from 0.5 g/10 min to 6.0 g/10 min, from 0.5 g/10 min to 5.0 g/10 min, from 0.5 g/10 min to 4.0 g/10 min, from 0.5 g/10 min to 3.0 g/10 min, from 0.5 g/10 min to 2.0 g/10 min, from 0.5 g/10 min to 1.0 g/10 min, from 1.0 g/10 min to 10.0 g/10 min, from 1.0 g/10 min to 9.0 g/10 min, from 1.0 g/10 min to 8.0 g/10 min, from 1.0 g/10 min to 7.0 g/10 min, from 1.0 g/10 min to 6.0 g/10 min, from 1.0 g/10 min to 5.0 g/10 min, from 1.0 g/10 min to 4.0 g/10 min, from 1.0 g/10 min to 3.0 g/10 min, from 1.0 g/10 min to 2.0 g/10 min, from 2.0 g/10 min to 10.0 g/10 min, from 2.0 g/10 min to 9.0 g/10 min, from 2.0 g/10 min to 8.0 g/10 min, from 2.0 g/10 min to 7.0 g/10 min, from 2.0 g/10 min to 6.0 g/10 min, from 2.0 g/10 min to 5.0 g/10 min, from 2.0 g/10 min to 4.0 g/10 min, from 2.0 g/10 min to 3.0 g/10 min, from 3.0 g/10 min to 10.0 g/10 min, from 3.0 g/10 min to 9.0 g/10 min, from 3.0 g/10 min to 8.0 g/10 min, from 3.0 g/10 min to 7.0 g/10 min, from 3.0 g/10 min to 6.0 g/10 min, from 3.0 g/10 min to 5.0 g/10 min, from 3.0 g/10 min to 4.0 g/10 min, from 4.0 g/10 min to 10.0 g/10 min, from 4.0 g/10 min to 9.0 g/10 min, from 4.0 g/10 min to 8.0 g/10 min, from 4.0 g/10 min to 7.0 g/10 min, from 4.0 g/10 min to 6.0 g/10 min, from 4.0 g/10 min to 5.0 g/10 min, from 5.0 g/10 min to 10.0 g/10 min, from 5.0 g/10 min to 9.0 g/10 min, from 5.0 g/10 min to 8.0 g/10 min, from 5.0 g/10 min to 7.0 g/10 min, from 5.0 g/10 min to 6.0 g/10 min, from 6.0 g/10 min to 10.0 g/10 min, from 6.0 g/10 min to 9.0 g/10 min, from 6.0 g/10 min to 8.0 g/10 min, from 6.0 g/10 min to 7.0 g/10 min, from 7.0 g/10 min to 10.0 g/10 min, from 7.0 g/10 min to 9.0 g/10 min, from 7.0 g/10 min to 8.0 g/10 min, from 8.0 g/10 min to 10.0 g/10 min, from 8.0 g/10 min to 9.0 g/10 min, from 9.0 g/10 min to 10.0 g/10 min, or any combination of these ranges, when measured according to ASTM D-1238 at 190 °C and 2.16 kg. [0085] According to embodiments, the multimodal ethylene-based copolymer composition may have a molecular weight distribution, expressed as the ratio of the weight average molecular weight to number average molecular weight (Mw/Mn), in the range of from 2.0 to 6.0. For example, the multimodal ethylene-based copolymer composition may have a molecular weight distribution of from 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 to 5.5, 3.5 to 5.0, 3.5 to 4.5, 3.5 to 4.0, 4.0 to 6.0, 4.0 to 5.5, 4.0 to 5.0, 4.0 to 4.5, 4.5 to 6.0, 4.5 to 5.5, 4.5 to 5.0, 5.0 to 6.0, 5.0 to 5.5, or 5.5 to 6.0, or any combination of these ranges. As presently described, the molecular weight distribution may be calculated according to gel permeation chromatography (GPC) techniques as described herein. [0086] The long chain branching frequency (LCB f ) refers to the level of long chain branches per 1000 carbons. In embodiments, the long chain branching frequency (LCB f ) of the multimodal ethylene-based copolymer composition is greater than or equal to 1.0 and less than or equal to 1.8. In one or more embodiments, the long chain branching frequency (LCB f ) of the multimodal ethylene-based copolymer composition may be from 1.0 to 1.8, from 1.0 to 1.6, from 1.0 to 1.4, from 1.0 to 1.2, from 1.2 to 1.8, from 1.2 to 1.6, from 1.2 to 1.4, from 1.4 to 1.8, from 1.4 to 1.6, from 1.6 to 1.8, or any combination of these ranges. [0087] According to embodiments, the multimodal ethylene-based copolymer composition may have an activation energy (Ea) of the composition as determined from dynamic mechanical analysis may be greater than 30 kJ/mol. In further embodiments, the multimodal ethylene-based copolymer compositions may have an activation energy (Ea) of the composition as determined from dynamic mechanical analysis may 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 rheology time-temperature superposition viscosity data obtained from melt rheology frequency sweeps. These measurements are performed using TA Instruments Advanced Rheometric Expansion System (ARES) equipped with 25 mm parallel plates using nitrogen pure. The linear viscoelastic response are 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 altered based on transducer torque output, making sure torque remained with acceptable range. The stress response is analyzed in terms of amplitude and phase, from which the storage and loss moduli and dynamic melt viscosity are calculated. The temperature dependence of linear viscoelastic curve can be predicted by shifting the modulus curves across the frequency axis (X-axis) against a reference using sets of shift factors. This concept is generally known as time-temperature superposition. This technique involves shifting curves at different temperatures in such a way that they overlap and form a single curve, also known as the master curve. The shift factors were generated using RepTate software. Reference temperature was chosen at 190 °C. The Arrhenius equation associates the horizontal shift factors to the activation energy and a reference temperature according to the following equation: [0089] According to embodiments, the multimodal ethylene-based copolymer composition may have a melt strength (MS) that satisfies the following equation 1: [0090] wherein x is greater than or equal to 8, y is greater than or equal to 3, and I 2 is a 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 may have a melt strength of from 5 cN to 50 cN, from 5 cN to 45 cN, from 5 cN to 40 cN, from 5 cN to 35 cN, from 5 cN to 30 cN, from 5 cN to 25 cN, from 5 cN to 20 cN, from 5 cN to 15 cN, from 5 cN to 10 cN, from 10 cN to 50 cN, from 10 cN to 45 cN, from 10 cN to 40 cN, from 10 cN to 35 cN, from 10 cN to 30 cN, from 10 cN to 25 cN, from 10 cN to 20 cN, from 10 cN to 15 cN, from 15 cN to 50 cN, from 15 cN to 45 cN, from 15 cN to 40 cN, from 15 cN to 35 cN, from 15 cN to 30 cN, from 15 cN to 25 cN, from 15 cN to 20 cN, from 20 cN to 50 cN, from 20 cN to 45 cN, from 20 cN to 40 cN, from 20 cN to 35 cN, from 20 cN to 30 cN, from 20 cN to 25 cN, from 25 cN to 50 cN, from 25 cN to 45 cN, from 25 cN to 40 cN, from 25 cN to 35 cN, from 25 cN to 30 cN, from 30 cN to 50 cN, from 30 cN to 45 cN, from 30 cN to 40 cN, from 30 cN to 35 cN, from 35 cN to 50 cN, from 35 cN to 45 cN, from 35 cN to 40 cN, from 40 cN to 50 cN, from 40 cN to 45 cN, or from 45 cN to 50 cN. [0091] In embodiments, the multimodal ethylene-based copolymer composition may have a ratio of viscosity measured at 0.1 radians/second and 190 °C to viscosity measured at 100 radians/second and 190 °C (V0.1/V100), as determined by dynamic mechanical analysis, of greater than 5. In further embodiments, the multimodal ethylene-based copolymer composition may have a (V0.1/V100), as determined by dynamic mechanical analysis, of from 5 to 30, from 5 to 25, from 5 to 20, from 5 to 15, from 5 to 10, from 10 to 30, from 10 to 25, from 10 to 20, from 10 to 15, from 15 to 30, from 15 to 25, from 15 to 20, from 20 to 30, from 20 to 25, or from 25 to 30. [0092] In embodiments, the cumulative distribution fractions (CDF) for light scattering analysis (CDF LS ) at a molecular weight greater than 500,000 g/mol is greater than or equal to 8%. [0093] In embodiments, the multimodal ethylene-based copolymer composition may have a high molecular weight fraction, computed by measuring an area fraction of a low angle light scattering (LALLS) detector chromatogram greater than 500,000 g/mol using GPC molecular weight distribution, of from 8% to 50%. In embodiments, the high molecular weight fraction, computed by measuring an area fraction of a low angle light scattering (LALLS) detector chromatogram greater than 500,000 g/mol using GPC molecular weight distribution, may be from 8% to 40%, from 8% to 30%, from 8% to 20%, from 8% to 10%, from 10% to 50%, from 10% to 40%, from 10% to 30%, from 10% to 20%, from 20% to 50%, from 20% to 40%, from 20% to 30%, from 30% to 50%, from 30% to 40%, or from 40% to 50%. [0094] In embodiments, the multimodal ethylene-based copolymer composition may have a low molecular weight fraction, computed by measuring an area fraction of a low angle light scattering (LALLS) detector chromatogram less than 500,000 g/mol using GPC molecular weight distribution, of greater than 50%. In embodiments, the low molecular weight fraction, computed by measuring an area fraction of a low angle light scattering (LALLS) detector chromatogram less than 500,000 g/mol using GPC molecular weight distribution, may be from 50% to 92%, from 50% to 90%, from 50% to 80% from 50% to 70%, from 50% to 60%, from 60% to 92%, from 60% to 90%, from 60% to 80%, from 60% to 70%, from 70% to 92%, from 70% to 90%, from 70% to 80%, from 80% to 92%, from 80% to 90%, or from 90% to 92%. Traditionally, it was thought that having as much high molecular weight material as possible was ideal because high molecular weight would lead to higher levels of entanglements that improve the properties of the LLDPE. Accordingly, low molecular weight material was kept to a minimum. However, the multimodal ethylene-based copolymer compositions according to embodiments disclosed and described herein exhibit unique and unexpected characteristics compared to commercially available LDPE products when the high molecular weight fraction, computed by measuring an area fraction of a low angle light scattering (LALLS) detector chromatogram greater than 500,000 g/mol using GPC molecular weight distribution, is from 8% to 50%. [0095] In embodiments, the amount of long-chain branching derived from the concentration of vinyl end groups in the multimodal ethylene-based copolymer composition produced expressed in the vinyl groups/1,000 carbon atoms may be from 0.475 to 0.600. In embodiments, the amount of long-chain branching derived from the concentration of vinyl groups in the multimodal ethylene-based copolymer composition produced expressed in vinyls/1,000 carbon atoms may be from 0.475 to 0.575, from 0.475 to 0.550, from 0.475 to 0.525, from 0.475 to 0.500, from 0.500 to 0.600, from 0.500 to 0.575, from 0.500 to 0.550, from 0.500 to 0.525, from 0.525 to 0.600, from 0.525 to 0.575, from 0.525 to 0.550, from 0.550 to 0.600, from 0.550 to 0.575, or from 0.575 to 0.600. Without intent to be bound by theory, it is believed that the vinyl end groups enable the formation of long chain branching, which is a contributing factor to the melt strengths achieved. [0096] The multimodal ethylene-based copolymer compositions 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 compositions may contain any amounts of additives. The multimodal ethylene-based copolymer compositions may compromise from about 0 to about 10 percent by the combined weight of such additives, based on the total weight of the multimodal ethylene-based copolymer compositions. The multimodal ethylene-based copolymer compositions may further comprise fillers, which may include, but are not limited to, organic or inorganic fillers. The multimodal ethylene-based copolymer compositions may contain from about 0 to about 20 weight percent fillers such as, for example, calcium carbonate, talc, or Mg(OH) 2 , based on the total weight of the multimodal ethylene-based copolymer compositions. The multimodal ethylene-based copolymer compositions may further be blended with one or more polymers to form a blend. [0097] TEST METHODS [0098] Unless otherwise indicated herein, the following analytical methods are used in describing aspects of the present disclosure: [0099] Melt index [00100] Melt indices I 2 (or I2) and I 10 (or I10) of polymer samples were measured in accordance to ASTM D-1238 (method B) at 190 °C and at 2.16 kg and 10 kg load, respectively. Their values are reported in g/10 min. [00101] Density [00102] Samples for density measurement were prepared according to ASTM D4703. Measurements were made, according to ASTM D792, Method B, within one hour of sample pressing. [00103] Triple Detector Gel Permeation Chromatography (GPC) [00104] 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 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, the 15 degree angle is used for measurement. The autosampler oven compartment was set at 160º Celsius and the column and detector compartment were set at 150º Celsius. The columns used were 4 Agilent “Mixed A” 30cm 20-micron linear mixed-bed columns. The chromatographic solvent used was 1,2,4 trichlorobenzene and contained 200 ppm of butylated hydroxytoluene (BHT). The solvent source was nitrogen sparged. The injection volume used was 200 microliters and the flow rate was 1.0 milliliters/minute. [00105] The total plate count of the GPC column set was performed with decane which was introduced into blank sample via a micropump controlled with the PolymerChar GPC-IR system. The plate count for the chromatographic system should be greater than 18,000 for the 4 Agilent “Mixed A” 30cm 20-micron linear mixed-bed columns. [00106] Samples were prepared in a semi-automatic manner with the PolymerChar “Instrument Control” Software, wherein the samples were weight-targeted at 2 mg/ml, and the solvent (contained 200ppm BHT) was added to a pre nitrogen-sparged septa-capped vial, via the PolymerChar high temperature autosampler. The samples were dissolved for 2 hours at 160º Celsius under “low speed” shaking. [00107] In order to monitor the deviations over time, a flowrate marker (decane) was introduced into each sample via a micropump controlled with the PolymerChar GPC-IR system. This flowrate marker (FM) was used to linearly correct the pump flowrate (Flowrate(nominal)) for each sample by RV alignment of the respective decane peak within the sample (RV(FM Sample)) to that of the decane peak within the narrow standards calibration (RV(FM Calibrated)). Any changes in the time of the decane marker peak are then assumed to be related to a linear-shift in flowrate (Flowrate(effective)) for the entire run. After calibrating the system based on a flow marker peak, the effective flowrate (with respect to the narrow standards calibration) is calculated as Equation 1. Processing of the flow marker peak was done via the PolymerChar GPCOne™ Software. Acceptable flowrate correction is such that the effective flowrate should be within +/- 0.5% of the nominal flowrate. [00108] For the determination of the viscometer and light scattering detector offsets from the IR5 detector, the Systematic Approach for the determination of multi-detector offsets is done in a manner consistent with that published by Balke, Mourey, et. al. (Mourey and Balke, Chromatography Polym. Chpt 12, (1992)) (Balke, Thitiratsakul, Lew, Cheung, Mourey, Chromatography Polym. Chpt 13, (1992)), optimizing triple detector log (MW and IV) results from a linear homopolymer polyethylene standard (3.5 > Mw/Mn > 2.2) with a molecular weight in the range of 115,000 to 125,000 g/mol to the narrow standard column calibration results from the narrow standards calibration curve using PolymerChar GPCOne™ Software. [00109] The absolute molecular weight data was obtained in a manner consistent with that published by Zimm (Zimm, B.H., J. Chem. Phys., 16, 1099 (1948)) and Kratochvil (Kratochvil, P., Classical Light Scattering from Polymer Solutions, Elsevier, Oxford, NY (1987)) using PolymerChar GPCOne™ software. The overall injected concentration, used in the determination of the molecular weight, was obtained from the mass detector area and the 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 weights (using GPCOne™) were obtained using a light scattering constant, derived from one or more of the polyethylene standards mentioned below, and a refractive index concentration coefficient, dn/dc, of -0.104. Generally, the mass detector response (IR5) and the light scattering constant (determined using GPCOne™) should be determined from a linear standard with a molecular weight in excess of about 50,000 g/mole. The viscometer calibration (determined using GPCOne™) can be accomplished using the methods described by the manufacturer, or, alternatively, by using the published values of suitable linear standards, such as Standard Reference Materials (SRM) 1475 (available from National Institute of Standards and Technology (NIST)). A viscometer constant (obtained using GPCOne™) is calculated which relates specific viscosity area (DV) and injected mass for the calibration standard to its intrinsic viscosity. The chromatographic concentrations are assumed low enough to eliminate addressing 2nd viral coefficient effects (concentration effects on molecular weight). [00110] The absolute weight average molecular weight (MW (Abs) ) is obtained (using GPCOne™) from the Area of the Light Scattering (LS) integrated chromatogram (factored by the light scattering constant) divided by the mass recovered from the mass constant and the mass detector (IR5) area. The molecular weight and intrinsic viscosity responses are linearly extrapolated at chromatographic ends where signal to noise becomes low (using GPCOne™). Other respective moments, Mn (Abs) and Mz (Abs) are be calculated according to equations 8-10 as follows: [00111] CDF Calculation Method [00112] The calculation of the cumulative detector fractions (CDF) for the low angle laser light scattering detector (“CDF LS ”) are accomplished by the following steps: [00113] 1) Linearly flow correct the chromatogram based on decane flow marker injection as described above. [00114] 2) Perform detector offsets as described above. [00115] 3) Calculate absolute molecular weights from light scattering as described above. [00116] 4) Calculate the cumulative detector fraction (CDF) of the Low-Angle Laser Light Scattering (LALLS) chromatogram (CDF LS ) based on its baseline-subtracted peak height (H) from high to low molecular weight (low to high retention volume) at each data slice (j) according to Equations 13. [00117] Calculation of LCB frequency (LCBf) [00118] The long chain branching frequency was calculated based on the differences between the g’, which is a ratio of the intrinsic viscosity of a polymer sample over a linear polymer reference with the same molecular weight. In 3D GPC practice, a reference polyethylene homopolymer, containing no detectable LCB or SCB, and with a Mw of approximately 120,000 g/mol and polydispersity around 3.0, is injected at the beginning of each run queue to establish the Mark-Houwink linear reference line. A first-order linear fit is applied to the obtained log of the intrinsic viscosity and log of the molecular weight data within the log of the molecular weight range of 4.5 to 5.8 g/mol to provide the linear reference K and α values. [00119] A polyethylene sample of interest is analyzed to obtain intrinsic viscosity, molecular weight values, and the value of g i ’ is calculated at each chromatographic slice (i) according to Equation 14: [00120] where the calculation utilizes the IV Sample,i at equivalent absolute molecular weight values and same SCB content values to the linear reference within the log molecular weight range of 4.5 to 5.8 g/mol. If a difference in SCB content exists, the IV linear reference,i line is vertically shifted by adjusting the K value from the Mark-Houwink Plot to account for the SCB correction compared to the IV Sample,i . The shift is done until the linear reference line makes a single point of contact to make a tangent with the sample Mark-Houwink line at a log molecular weight of 4.5. [00121] A Zimm-Stockmayer branching factor g was calculated from g’, g’= g ε , using an epsilon factor of 0.5. The number of branches along the polymer sample (B n ) at each data slice (i) can be determined by using Equation 15, (B. H. Zimm and W. H. Stockmayer, J. Chem. Phys. 17, 1301 (1949)): [00122] Finally, the average LCBf quantity per 1000 carbons in the polymer across all of the slices (i) can be determined using Equation 16: [00123] Procedure for NMR end group analysis including vinyl count determination [00124] Approximately 7 mg of polymer sample was loaded into a 5mm NMR tube with 0.6 ml tetrachloroethane-d 2 with 0.008 M chromium(III) acetylacetonate. The tube was purged with N 2 , and the cap was secured with Teflon tape. The prepared sample tube was heated in a heating block set at 125 °C and repeatedly vortexed until a homogeneous solution was achieved evidenced by consistent flow when the tube was tipped horizontally. The finished sample was inserted into a Bruker AVANCE 600 MHz system equipped with a 10 mm high-temperature cryo-probe set at 120 °C. The acquisition parameters for the 1 H NMR spectra are: 90 degree pulse, 1.8 second acquisition time, 10 seconds relaxation delay, center of spectrum set at 2 ppm, spectral width of 20 ppm and 128 scans for signal averaging. The resulting raw FID was exponential multiplied, Fourier transformed, phased, baseline corrected, and integrated using MNOVA software. Semi-Batch Reactor Polymerization Procedure [00125] Raw materials (ethylene, 1-octene) and the process solvent (a narrow boiling range high-purity isoparaffinic solvent trademarked ISOPAR E commercially available from ExxonMobil Corporation) are purified with molecular sieves before introduction into the reaction environment. A one 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. Hydrogen was also added at this point if desired. The catalyst composition was prepared in a drybox under inert atmosphere by mixing the desired pro-catalyst and optionally one or more addtives as desired, with additional solvent to give a total volume of about 15-20 mL. The activated catalyst mixture was then quick-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 shut off and the solution transferred into 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. Procedure for Polymerization in a Continuous Reactor [00126] Raw materials (ethylene, 1-octene) and the process solvent (a narrow boiling range high-purity isoparaffinic solvent trademarked Isopar E commercially available from ExxonMobil Corporation) are purified with molecular sieves before introduction into the reaction environment. Hydrogen is supplied in pressurized cylinders as a high purity grade and is not further purified. The reactor monomer feed (ethylene) stream is pressurized via mechanical compressor to above reaction pressure. The solvent and comonomer (1-octene) feed are pressurized via a mechanical positive displacement pump to above reaction pressure. MMAO-3A, commercially available from Nouryon, was used as an impurity scavenger. The individual catalyst components (procatalyst or cocatalyst) were manually batch diluted to specified component concentrations with purified solvent (Isopar E) and pressured to above reaction pressure. The cocatalyst is [HNMe(C 18 H 37 )] 2 [B(C 6 F 5 ) 4 ], commercially available from Boulder Scientific, and is used at a 1.2 ratio to catalyst metal unless otherwise specified. All reaction feed flows were measured with mass flow meters and independently controlled with computer automated valve control systems. [00127] The continuous solution polymerizations were carried out in one or more of a CSTR, loop, and/or a plug flow reactor. The CSTR and loop reactors have independent control of all fresh solvent, monomer, comonomer, hydrogen, and catalyst component feeds. The plug flow reactor has independent control of catalyst component feeds. The combined solvent, monomer, comonomer and hydrogen feed to the reactors is temperature controlled to anywhere between 5 °C to 50 °C and typically 25 °C. The fresh comonomer feed to the polymerization reactor is fed in with the solvent feed. The fresh solvent feed is controlled typically with each injector receiving half of the total fresh feed mass flow. The cocatalyst is fed based on a calculated specified molar ratio to the procatalysts. Immediately following each fresh injection location, the feed streams are mixed with the circulating polymerization reactor contents with static mixing elements. The ratio of the 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 stop the reaction. In addition, various additives, such as antioxidants, could be added at this point. The stream then goes through another set of static mixing elements to evenly disperse the catalyst kill and additives. [00128] Following additive addition, the effluent (containing solvent, monomer, comonomer, hydrogen, catalyst components, and molten polymer) passes through a heat exchanger to raise the stream temperature in preparation for separation of the polymer from the other lower boiling reaction components. The stream then entered a two-stage separation and devolatization system where the polymer was removed from the solvent, hydrogen, and unreacted monomer and comonomer. The separated and devolatized polymer melt was pumped through a die specially designed for underwater pelletization, cut into uniform solid pellets, dried, and transferred into a box for storage. EXAMPLES [00129] One or more features of the present disclosure are illustrated in view of the examples as follows. [00130] The following catalysts were utilized in one or more of the examples described subsequently in more detail:
[00131] Example 1: Preparation of Compositions 1–9 [00132] Multimodal Ethylene-based Polymer Compositions 1–9, which are described according to the one or more embodiments of the detailed description, were prepared by a process utilizing the catalysts and reactors described below. [00133] The reactor and feed conditions for the synthesis of Compositions 1–9 are provided in Table 1. Table 1: Reactor and Feed Conditions for the Synthesis of Compositions 1–9.
[00134] Example 2: Preparation of Comparative Compositions C1–C3 [00135] Comparative Compositions C1–C3 were prepared by a process utilizing the catalysts and reactors described below. [00136] All raw materials (monomer and comonomer) and the process solvent (a narrow boiling range high-purity isoparaffinic solvent, Isopar-E) were purified with molecular sieves before introduction into the reaction environment. Hydrogen was supplied pressurized as a high purity grade and was not further purified. The reactor monomer feed stream was pressurized via a mechanical compressor to above reaction pressure. The solvent and comonomer feed was pressurized via a pump to above reaction pressure. The individual catalyst components were manually batch diluted with purified solvent and pressured to above reaction pressure. All reaction feed flows were measured with mass flow meters and independently controlled with computer automated valve control systems. The reactor and feed conditions for the synthesis of Comparative Compositions C1–C3 are provided in Table 3. Table 2: Reactor and Feed Conditions for the Synthesis of Comparative Comp. C1–C3.
[00137] Example 3: Comparative Compositions C4–C8 [00138] Table 3 identifies the commercially-available Comparative Compositions C4–C8. Table 3: Commercially-available Comparative Compositions C4–C8. [00139] Example 4: Preparation of Comparative Compositions C9–C19 [00140] Comparative Compositions 9–19 were prepared by a process utilizing the catalysts and reactors described below. Table 5: Reactor and Feed Conditions for the Synthesis of Comparative Comp. C9–C19.
[00141] Example 5: Analysis of Compositions 1–10 and Comparative Compositions 1–19. [00142] In Example 5, the 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: Evaluation of Catalysts A−E in a Semi-Batch Reactor Conditions: 160 °C runs: 320 psi ethylene, 60 g 1-octene, 0 H2, 1250 mL Isopar E solvent.190 °C runs: 410 psi ethylene, 65 g 1-octene, 0 H2, 1250 mL Isopar E solvent. All runs: mol fraction of ethylene in solution = 0.709. *Reactivity ratio r 1 is the reactivity ratio for a monomer insertion after ethylene, and is calculated using the Mayo-Lewis equation: where r 2 is the reactivity ratio for a monomer insertion after the comonomer (here 1-octene), f 1 is the mol fraction of ethylene in the feed, f 2 is the mol fraction of comonomer (1-octene) in the feed, and F 1 is the mol fraction of ethylene in the polymer. F 1 = 1 – F 2 where F 2 is the mol fraction of 1-octene in the polymer. This value can be obtained experimentally by GPC analysis of the polymer. The Mayo-Lewis equation can be solved using the GRG Nonlinear solving method available in Microsoft Excel to find the r 1 and r 2 values that give the best fit. [00143] 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 about 169 psi total reactor pressure. A catalyst solution was prepared by combining solutions of Catalyst E, RIBS-II, and MMAO-3A to give 6 µmoles of Ti, 7.2 µmoles of RIBS-II, and 30 µmoles of Al. [00144] For Catalyst C and Catalyst D, 1.47 Kg Isopar-E; 100 g octene; 100g ethylene; temperature was 160 °C; total pressure was 410 psi; procatalyst:activator ratio was 1:1.2; activator was [HNMe(C 18 H 37 ) 2 ][B(C 6 F 5 ) 4 ]; MMAO-3A was used as an impurity scavenger at a 50:1 molar ratio (Al:procatalyst); reaction time was 10 min. Efficiency (Eff) in units of kilograms of polymer per gram of active metal (Zr or Hf) in the catalyst. Table 6: Analysis of Compositions 1–10 and Comparative Compositions 1–19. * Mw/ Mz/ Mn** M Mw (abs) / a) Mn* Mw** w** Mz** Mw (GPC) 4 2.6 2.7 20.3 53.2 141.5 1.21
*Values from absolute GPC analysis **Values from conventional GPC analysis Table 7: Analysis of Compositions 1–9 and Comparative Compositions 1–19.
Table 8: Analysis of Compositions 1–10 and Comparative Compositions 1–19. [00145] As shown in Tables 6–8, Samples 1–10 exhibited improved melt strength in comparison to Comparative Samples C1–C19. C1–C3, C9, and C12–C19 all failed to exhibit enough high molecular weight fraction, computed by the area fraction of the MWD greater than 500,000 g/mol as obtained by absolute molecular weights from GPC light scattering analysis. Additionally, Comparative Samples C4–C5 exhibited a high molecular weight fraction of greater than 50% of the area fraction of the MWD greater than 500,000 g/mol as obtained by absolute molecular weights from light scattering. Additionally, Samples 1–10 exhibited higher amount of vinyl end groups per 1000 carbon atoms when compared to Comparative Examples C12–C19. The increase in the number of vinyl end group count correlates to the increase in long chain branching frequency. Additionally, Samples 1–10 exhibited I10/I2 (melt flow ratio) comparable to or higher than the I 10 /I 2 of C1–C19, which is indicative of the resin’s comparable or improved processability, respectively. Long chain branching is present in both Samples 1–8 and Comparative Samples C1–C3) in comparable quantities; however, only Samples 1–8, having high molecular weight component described herein, exhibited improved melt strength and melt flow ratio. Similarly, both Samples 1–8 and Comparative Samples C1 – C3 have similar LCBf, but only Samples 1–8, having high molecular weight component described herein, exhibited improved melt strength.