Long-chain branched ethylene polymer

Abstract

Abstract Ethylene-based polymers have an absolute molecular weight distribution (MWD) curve determined by gel permeation chromatography (GPC). max The low molecular weight polymer fraction and the high molecular weight polymer fraction are divided by the following equation: log[η]=log(β)+αlog(M)-L, which follows the Mark-Hwink-Sakurada curve. * The ladder characteristic L is defined for a given absolute molecular weight (MW) as the fit of the logarithm of the intrinsic viscosity [η] versus the logarithm of the absolute MW (M) using αlog(2), where log(β) is the intercept and α is the slope. The low molecular weight polymer fraction is S max The MW of the polymer fractions is below 1000, and all L values ​​are between -0.35 and 0.35. The high molecular weight polymer fractions are max It has a MW greater than 0.8 and a maximum L value of 0.8 to 1.5.

Description

[Technical Field]

[0001] (CROSS-REFERENCE TO RELATED APPLICATIONS) This application claims priority to U.S. Provisional Patent Application No. 63 / 000,954, filed March 27, 2020, the entire disclosure of which is incorporated herein by reference.

[0002] FIELD OF THE INVENTION FIELD OF THE DISCLOSURE Embodiments of the present disclosure generally relate to polymer compositions having long chain branching and processes by which the ethylene-based polymer compositions are synthesized. [Background technology]

[0003] Ethylene-based polymers, such as polyethylene polymers, are produced via a variety of catalyst systems, and the selection of such catalyst system used in the polymerization process of an ethylene-based polymer is an important factor contributing to the characteristics and properties of such an ethylene-based polymer.

[0004] Ethylene-based polymers are manufactured for a wide variety of articles. The polymerization process can be varied in many ways to produce a wide variety of resulting polymer resins with different physical properties that make them suitable for use in a variety of applications. The effect of branching on the properties of an ethylene-based polymer depends on the length and amount of branching. For example, short-chain branching affects the physical properties of the ethylene-based polymer. Short branches primarily affect mechanical and thermal properties. As the frequency of short-chain branching increases, the polymer is unable to form layered crystals, resulting in decreased mechanical and thermal properties. A small amount of long-chain branching can significantly alter the processing properties of the polymer.

[0005] To form long-chain branches (LCBs), the vinyl or terminal double bond of a polymer chain is incorporated into a new polymer chain. Reincorporation of vinyl-terminated polymers and the introduction of diene comonomers are two mechanisms by which vinyl groups on a polymer strand are incorporated into a second polymer strand. In addition, long-chain branching can be induced via radicals. In all three mechanisms, it is difficult to control the amount of branching. When radicals or dienes are used to initiate long-chain branching, too much branching can occur, which can lead to gelation and reactor fouling. The reincorporation mechanism does not produce many branches, and branching can occur only after a polymer strand has been created, thereby further limiting the amount of branching that can occur.

[0006] Increasing the amount of long-chain branching (LCB) increases melt processing properties. Long-chain branched materials (e.g., low-density polyethylene, LDPE) are added to LLDPE as processing aids. Generally, LDPE has good processing properties, but films made from it have poor physical properties, such as tear strength and dart strength. Films made from linear low-density polyethylene (LLDPE) have good physical properties, such as tear strength and dart strength, but cannot be processed efficiently. While blending with LDPE to a certain extent is necessary for processing (melt strength, shear thinning), this reduces the physical properties of LLDPE films. When blending LLDPE and LDPE, researchers have attempted to balance processability and physical properties, but have not achieved the ideal combination. Summary of the Invention

[0007] There is a continuing need to produce polymer compositions with high melt strength and normal to low viscosity as indicated by melt index that allow for polymer formation that provides better processability but without reactor fouling. Accordingly, the processes and ethylene-based polymers of the present disclosure seek to form long chain branches without gelling the ethylene-based polymer or fouling the reactor.

[0008] Embodiments of the present disclosure are directed to ethylene-based polymers. The ethylene-based polymers include a low molecular weight polymer fraction and a high molecular weight polymer fraction. The low molecular weight fraction and the high molecular weight fraction are defined as S on a molecular weight distribution (MWD) curve as determined by absolute gel permeation chromatography. max Divide by S max is the maximum absolute slope on the high molecular weight side of the main peak of the MWD curve, the main peak being the peak of greatest magnitude in the MWD curve.

[0009] The low molecular weight polymer fraction and the high molecular weight polymer fraction of an ethylene-based polymer each follow the Mark-Hwink-Sakurada curve, log[η]=log(β)+αlog(M)-L * The ladder characteristic L is defined for a given absolute molecular weight (MW) as the fit of the logarithm of the intrinsic viscosity [η] versus the logarithm of the absolute MW (M) using αlog(2), where log(β) is the intercept and α is the slope. The low molecular weight polymer fraction is S max The MW of the polymers is below 0.35, and all L values ​​are between 0.35 and 0.35. The high molecular weight polymer fraction is max It has a MW greater than 0.8 and a maximum L value of 0.8 to 1.5. [Brief explanation of the drawings]

[0010] [Figure 1] 1 is a graphical representation of polymer molecular weights with increasing number of branched methines per 1000 carbons. [Figure 2] 1 is a graphical model predicting the dependence of molecular weight distribution (MWD) curves on branching level. [Figure 3] 1 is a molecular weight distribution (MWD) curve of two-catalyst bimodal ethylene-based polymer distribution with and without diene. [Figure 4] 1 is a Mark-Hwink-Sakurada plot of a conventional long-chain branching (LCB) polymer and LDPE, specifically DOW™ LDPE6621. [Figure 5]1 is a diagram of an ethylene-based ladder polymer with the polymer backbone shown as a solid line and the long-chain branches shown as dotted lines, which provides a visual depiction of the molecular weight difference calculated by traditional standards versus absolute weight average molecular weight (MW) for the long-chain branched polymers of the present disclosure. [Figure 6] 1 is a Mark-Fwink-Sakurada plot showing the definitions of parameters and variables characterizing the long chain branching polymers of the present disclosure in a Mark-Fwink-Sakurada plot. [Figure 7] 1 is a Mark-Hwink-Sakurada plot of a series of bimodal ethylene-based polymers in which the low MW fraction is produced by a single-chain catalyst and the high MW fraction is produced by a dual-chain catalyst. [Figure 8] 1 is a graph showing plots of intrinsic viscosity and slope of intrinsic viscosity as a function of absolute MW for Examples 1-11. [Figure 9] 1 shows the ladder characteristics L as a function of absolute Mw for Examples 1-11. [Figure 10] 10 is a graph of rudder characteristics as a function of log(M) before (left) and after (right) Smax for a bimodal embodiment. [Figure 11] 10 is a graph of rudder characteristics as a function of log(M) before (left) and after (right) Smax for the comparative example. [Figure 12] 1 is a graph of an absolute molecular weight distribution (MWD) curve showing how the high MWD tail area metric is defined using the maximum point of slope. [Figure 13] 1 is a graph containing a three-parameter linear least-squares fit of melt strength versus the amount of catalyst 1, hydrogen, and diene. [Figure 14] 1 is a plot of melt strength versus melt index (MI) for autoclave and tubular LDPE. [Figure 15] 1 is a plot of melt strength versus melt index (MI) for a tetrafunctional long chain branched polymer and a comparative LDPE resin. DETAILED DESCRIPTION OF THE INVENTION

[0011] Specific embodiments of processes for synthesizing polymers and polymers synthesized by the processes of the present disclosure are described herein. It is understood that the processes for synthesizing polymers 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.

[0012] definition As used herein, "multimodal" refers to a composition that can be characterized as having at least two polymer fractions with different densities and weight average molecular weights, and that may optionally also have different melt index values. In one embodiment, multimodal can be defined by having at least two distinct peaks in a gel permeation chromatography (GPC) chromatogram that indicates a molecular weight distribution. Specifically, in this embodiment, the GPC measurement is calculated by absolute GPC. In another embodiment, multimodal can be defined by having at least three distinct peaks in a crystallization elution fractionation (CEF) chromatogram that indicates a short-chain branching distribution. Multimodal includes resins with three peaks and resins with more than three peaks.

[0013] The term "bimodal polymer" refers to a multimodal ethylene-based polymer having two major fractions: a first ethylene-based polymer fraction, which may be a low molecular weight fraction, and a second ethylene-based polymer fraction, which may be a high molecular weight fraction.

[0014] The term "trimodal polymer" refers to a multimodal ethylene-based polymer having three major fractions: a first ethylene-based polymer fraction, a second ethylene-based polymer fraction, and a third ethylene-based polymer fraction.

[0015] The term "polymer" refers to a polymeric compound prepared by polymerizing monomers, whether the monomers are the same or different. Thus, the generic term "polymer" encompasses the term "homopolymer," which is commonly used to refer to a polymer prepared from only one type of monomer, as well as "copolymer," which refers to a polymer prepared from two or more different monomers. As used herein, the term "interpolymer" refers to a polymer prepared by polymerization of at least two different types of monomers. Thus, the generic term "interpolymer" includes copolymers and polymers prepared from three or more different types of monomers, such as terpolymers. The term "bimodal polymer" refers to two polymers, each formed from a different catalyst.

[0016] "Polyethylene" or "ethylene-based polymer" shall mean a polymer containing more than 50 mole percent units derived from ethylene monomers. This includes polyethylene homopolymers or copolymers (meaning units derived from two or more comonomers). Common forms of polyethylene known in the art include low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), ultra-low-density polyethylene (ULDPE), very low-density polyethylene (VLDPE), single-site catalyzed linear low-density polyethylene (m-LLDPE), including both linear and substantially linear low-density resins, medium-density polyethylene (MDPE), and high-density polyethylene (HDPE).

[0017] The term "diene" refers to a monomer or molecule that contains two alkenes (double bonds).

[0018] Embodiments of the present disclosure comprise a process for the production of ethylene, at least one diene, and optionally at least one C3-C olefin, in the presence of at least one multi-chain catalyst, at least one single-chain catalyst, and optionally a solvent. 12 This involves a process for synthesizing long-chain branched polymers by adding an α-olefin comonomer, and the multi-chain catalyst comprises a molecule with multiple polymerization sites.

[0019] The process for synthesizing polymers according to the present disclosure differs from conventional long-chain branching. The term "long-chain branching" refers to a branch having more than 100 carbon atoms. A "branch" refers to a portion of a polymer extending from a tertiary or quaternary site. When a branch extends from a tertiary site, there are two other branches, which collectively can be the polymer strand from which the branch extends. Conventionally, long-chain branching (LCB) can occur naturally during the polymerization process, as shown in Scheme 1. This can occur through vinyl termination of the polymer chain and reinsertion of the polymeric vinyl to form trifunctional long-chain branches. Depending on the degree of branching, various methods, such as nuclear magnetic resonance (NMR), can determine LCB or identify the effect of LCB in a polymer. For example, the effect of LCB is observed in shear flow in van Gurp-Palmen analysis, and the increase in shear viscosity at low angular frequencies and the increase in the degree of shear thinning behavior can be attributed to LCB. In extensional flow, the effect of LCB is usually discerned in the degree of hardening (strain hardening) or strength of the melt (melt strength) and the maximum deformation achieved. Due to the limited concentration of vinyl-terminated polymers (maximum one per polymer chain) and the need to carry out high ethylene conversion to ensure the formation of LCB, it is difficult to achieve high levels of natural LCB in the polymer (polymers with g' values ​​less than 0.5). To ensure that more vinyl-terminated polymers can be reinserted into second polymer chains, there is a low level of ethylene concentration in the reactor.

[0020] Scheme 1: Spontaneous long-chain branching: Chain transfer events leading to vinyl-terminated polymers

[0021] [ka]

[0022] In Scheme 1, "Cat" is the catalyst and "P" is the polymer chain.

[0023] There is minimal long-chain branching formed through naturally occurring branching. One way to enhance naturally occurring LCB is to add α,ω-dienes to the polymerization system, whether it is a radical, heterogeneous, or homogeneous process. Generally, dienes are added to the polymer chain in a manner similar to α-olefins, but leave pendant vinyl groups, which can be inserted back into the polymer chain to create LCB, as illustrated in Scheme 2. Generally, the length of the diene is not important; only that it can link two polymer chains together is important. In principle, the concentration of pendant vinyl can be controlled through the amount of diene added to the reactor. Therefore, the degree of LCB can be controlled by the concentration of pendant vinyl.

[0024] Scheme 2: Long-chain branching via diene incorporation

[0025] [ka]

[0026] In Scheme 2, "Cat" is the catalyst, "P" is the polymer chain, and the diene in this example is 1,5-hexadiene.

[0027] Conventional processes incorporating dienes into polymer synthesis systems suffer from fundamental drawbacks, such as gel formation or reactor fouling. Previously described kinetic modeling (Guzman-2010 (J.D. Guzman, D.J. Arriola, T. Karjala, J. Gaubert, B.W.S. Kolthammer, AIChE 2010, 56, 1325), International Application Nos. US2019 / 053524 (filed September 27, 2019), US2019 / 053527 (filed September 27, 2019), US2019 / 053529 (filed September 27, 2019), and US2019 / 053537 (filed September 27, 2019)) can provide good predictive results, enabling a better understanding of gel formation. For example, longer polymer chains have more inserted olefins, and therefore more inserted dienes, and therefore more pendant vinyls, meaning that the longer polymer chains are more likely to reinsert into the catalyst to form LCBs. Therefore, the longer polymer chains are preferentially reinserted to form tetrafunctional long-chain branches, which are even larger polymer molecules, resulting in gel problems. As shown in Scheme 2, tetrafunctional LCBs have a short segment (the number of carbons between the two double bonds of the diene) that bridges the two long chains on either side of the short segment. The weight average molecular weight (M) as a function of branching can be calculated using the following formula: w ) and number average molecular weight (M n A simulation of M is shown in Figure 1 for polyethylene in a constant pressure semi-batch reactor. n is M w As goes to infinity, it only increases slightly. w increases to numbers above 200,000 grams per mole (g / mol), there is polymer gel, gelation, or reactor fouling.

[0028] The term "gel" or "gelation" refers to a solid composed of at least two components: a three-dimensional cross-linked polymer and a medium in which the polymer is not completely soluble. If the polymer gels and does not completely dissolve, the reactor may become fouled with the polymer gel.

[0029] The term "ladder branched" polymer refers to a tetrafunctional long chain branched polymer as disclosed in this application, and the term "ladder branching mechanism" refers to how the "ladder branched" polymer is formed.

[0030] In one or more embodiments of the present disclosure, a process for synthesizing a long-chain branched polymer achieves long-chain branching and avoids gel formation or reactor fouling. Without intending to be bound by theory, it is believed that reactor fouling is avoided by reacting two alkenes of a diene in a concerted manner across two proximal polymer chains. For example, as shown in Scheme 3, one alkene of a diene reacts before the second alkene, which reacts before too many ethylene molecules are added to the polymer strand, thereby removing the second alkene from proximity to the reaction site. The reaction of the first alkene of a diene to one polymer chain and the second alkene of a diene to the adjacent polymer chain before too many ethylene monomers are inserted is referred to as concerted addition of a diene to the proximal polymer chain.

[0031] Scheme 3: Description of the incorporation of dienes in a concerted manner, also referred to as the "ladder branching" mechanism (P is the polymer chain).

[0032] [ka]

[0033] A polymer strand is a linear segment of a polymer, or more specifically a copolymer, optionally joined at its ends by a branched junction. For example, as shown in Scheme 1, a tetrafunctional branched junction joins the ends of four polymer strands, in contrast to a trifunctional branched junction, which joins the ends of three polymer strands.

[0034] The combination of multi-chain catalysts and dienes affects the amount and type of branching. Embodiments of the present disclosure relate to controlling polymer properties, such as 1) the use of multiple diene species, 2) the use of multi-chain catalysts and other catalyst species, or 3) a combination of polymerization environments, including multiple reactor zones or zone gradients.

[0035] The use of multiple catalysts, including single-chain catalysts, can allow for some degree of conventional long-chain branching. The use of multiple diene species also includes those dienes that do not create ladder branching or tend to result in "conventional" LCB. The process for synthesizing polymers according to the present disclosure differs from conventional long-chain branching.

[0036] In one or more embodiments, the process for polymerizing long-chain branched polymers includes a catalyst having at least two active sites in close proximity (a multi-chain catalyst). To bring the two active sites into close proximity, the two active sites can be less than 18.5 angstroms (Å) apart. In some embodiments, the two active sites comprise a distance of 2.5 angstroms (Å) to 18.5 Å, 9 Å to 14 Å, or about 11 Å. In various embodiments, the process for polymerizing long-chain branched polymers includes a multi-chain catalyst. In one or more embodiments, the multi-chain catalyst can include at least one metal center, where the two active sites are on the same metal center. In some embodiments, the multi-chain catalyst can include a metal-ligand complex, where the two active sites (two polymer chains) are on the same metal center.

[0037] In one or more embodiments, the diene is a non-conjugated diene, and the non-conjugated diene is acyclic. In some embodiments, the diene is an α,ω-diene, meaning that both double bonds are terminal. In other embodiments, the non-conjugated diene comprises a branched group, and the branched group is a C1-C4 alkyl. The branched group can be an sp 2 alkyl group, such as 2-methyl-1,4-pentadiene. 2 Hybridized carbon atoms, or sp in dienes such as 3-methyl-1,4-pentadiene 3It may occur on a hybridized carbon atom. In various embodiments, the diene is selected from 1,4-pentadiene, 1,5-hexadiene, 1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, 1,10-undecadiene, 1,11-dodecadiene, dimethyldivinylsilane, dimethyldiallylsilane, dimethylallylvinylsilane.

[0038] According to the X-ray crystal structure (AD Bond, Chem. Comm. 2002, 1664), 1,9-decadiene has a terminal carbon-to-carbon distance of 10.8 Å. While there is data that 1,9-decadiene forms rungs between two polymer chains via a "ladder branching" mechanism, it is believed that linear α,ω-dienes with more than 10 carbon atoms may also form rungs via the "ladder branching" mechanism. Without intending to be bound by theory, the question of whether α,ω-dienes with more than 10 carbon atoms can form rungs may be determined by the distance between the two polymer chains. For example, if the two polymer chains are present on different metal atoms of the catalyst (e.g., bimetallic, heterogeneous), the α,ω-dienes may contain additional methylene units (same C-C bond length and angle) to extend this structure to 1,15-hexadecadiene. Without intending to be bound by theory, it is postulated that this 16-carbon analog may form rungs via a "ladder branching" mechanism. In this manner, the dienes 1,11-dodecadiene (terminal carbon-to-terminal distance of 13.3 Å), 1,13-tetradecadiene (terminal carbon-to-terminal distance of 15.9 Å), and 1,15-hexadecadiene (terminal carbon-to-terminal distance of 18.5 Å) may be considered. In some embodiments, when the double-stranded catalyst of the "ladder branching" mechanism is a bimetallic catalyst, the diene is 18.5 Å or less.

[0039] Modern computational techniques are known to be able to reproduce known experimental crystal structures with high accuracy as a way to estimate the interchain distance of a catalyst. In the case of heterogeneous systems, the surface concentration of the metal can be estimated, which is often expressed as metal atoms per nanometer squared (M / nm). 2) This surface coverage provides an estimate of the accessible metal on the surface, which, if uniformly dispersed, can be converted to mm distances, which reflect the distance between polymer chains. For extended surfaces, it is 1 metal / nm 2 yields a distance of 10 Å between metal atoms, which is well within the desired cutoff. At 18.5 Å, this gives 0.3 metal / nm 2 The coverage at the surface can be determined.

[0040] Examples of catalysts having at least two adjacent active sites include, but are not limited to, bimetallic transition metal catalysts, heterogeneous catalysts, dianionic activators with two related active catalysts, linked transition metal catalysts with two or more growing polymer chains, Group IV olefin polymerization catalysts containing a monoanionic group, a bidentate monoanionic group, a tridentate monoanionic group, or a monodentate, bidentate, or tridentate monoanionic group with an external donor.

[0041] The catalysts in Table 1 are exemplary embodiments of the aforementioned catalyst classes and specific catalysts contemplated. The examples in Table 1 are not intended to be limiting, but rather merely illustrative and specific examples of the aforementioned catalyst classes.

[0042] [Table 1]

[0043] Without wishing to be bound by theory, the mechanism described in this section describes how multi-chain catalysts can create unique cross-linked molecular structures when diene comonomers are polymerized under the desired conditions. A kinetic illustration is shown in Scheme 4, in which a catalyst center generates two polymer strands. Scheme 4 illustrates how a diene "ladder-branched" polymer structure can be created through a combination of diene cross-linking and chain transfer. The term "ladder-branched" polymer refers to a long-chain branch in which a short chain or rung containing 1 to 12 carbon atoms links two long chains together. As shown, a metal-ligand catalyst with at least two polymer chain sites grows two separate polymer chains. It is believed that one alkene of the diene is incorporated into one of the catalyst sites, and due to the proximity of the propagation sites, the second alkene of the diene is then rapidly incorporated into the second polymer chain, thereby forming a bridge or rung. This sequential addition of dienes is referred to as "concerted" addition of dienes, to distinguish it from catalysts that do not have two proximal chains, where the addition of dienes results in the concentration of vinyl-containing polymers that react later in the reactor. The term "rung" refers to the diene, once incorporated into two separate polymer strands, thereby linking the strands together. The first and second polymer strands continue to grow until the polymer transfers to another catalyst, the polymer is released from the catalyst, the catalyst dies, or another diene is added.

[0044] Scheme 4: Illustration of the "branching ladder" reaction kinetics, including the resulting molecular structures. Metal-ligand catalysts are + are collectively expressed as

[0045] [ka]

[0046] In one or more embodiments, the single-site catalyst may include, but is not limited to, a Ziegler-Natta catalyst, a chromium catalyst, a metallocene catalyst, a post-metallocene catalyst, a constrained geometry complex (CGC) catalyst, a phosphinimine catalyst, or a bis(phenylphenoxy) catalyst. Details and examples of CGC catalysts are provided in U.S. Patent Nos. 5,272,236, 5,278,272, 6,812,289, and WO 93 / 08221, which are incorporated herein by reference in their entireties. Details and examples of bis(phenylphenoxy) catalysts are provided in U.S. Patent Nos. 6,869,904, 7,030,256, 8,101,696, 8,058,373, and 9,029,487, which are incorporated herein by reference in their entireties.

[0047] Bis(phenylphenoxy) catalysts are an example of a homogeneous catalyst. Other examples of homogeneous catalysts include constrained geometry catalysts. Examples of heterogeneous catalysts include heterogeneous Ziegler-Natta catalysts. Examples of such Ziegler-Natta catalysts are those derived from organomagnesium compounds, alkyl halides or aluminum halides or hydrogen chloride, and transition metal compounds. Examples of such catalysts are described in U.S. Pat. Nos. 4,314,912 (Lowery, Jr. et al.), 4,547,475 (Glass et al.), and 4,612,300 (Coleman, III), the teachings of which are incorporated herein by reference.

[0048] 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.

[0049] The term "independently selected" refers to 1 , R 2 , R 3 , R 4 , and R 5 and the R groups may be the same or different (e.g., R 1 , R 2 , R 3 , R 4 , and R 5 are all substituted alkyl, or R 1 and R 2 is a substituted alkyl, and R 3 The terms "a" and "an" are used herein to indicate that an R group is an alkyl group, and the R group may be an aryl group, etc. The use of the singular includes the use of the plural and vice versa (e.g., 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 with that name. These definitions are intended to supplement and illustrate, not preclude, definitions known to those of skill in the art.

[0050] 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.

[0051] When used to describe a chemical group containing a particular carbon atom, "(C x ~C y A bracketed expression having the form "(C1-C )" means that the unsubstituted form of the chemical group has from x carbon atoms to y carbon atoms, inclusive of x and y. For example, (C1-C 40 ) Alkyl is an alkyl group having 1 to 40 carbon atoms in its unsubstituted form. In some embodiments and general structures, specific chemical groups are S The parenthesized "(C x ~C y )" for the chemical group RS Substituted versions may be formed by adding any group R S may contain more than y carbon atoms depending on the identity of S Exactly one group R is phenyl (-C6H5) S (C1~C 40 A "(C ) alkyl" can contain from 7 to 46 carbon atoms. Therefore, the parenthesized "(C ) alkyl" is generally used. x ~C y )" is a substituent R S When substituted by, the minimum and maximum total number of carbon atoms in the chemical group are the substituents R containing all carbon atoms in both x and y. S It is determined by adding the total number of carbon atoms from

[0052] The term "substituted" means that at least one hydrogen atom (-H) bonded to a carbon or heteroatom or functional group of the corresponding unsubstituted compound is replaced by a substituent (e.g., R S The term "hypersubstituted" means that all hydrogen atoms (H) bonded to carbon atoms 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, hydrogen atoms bonded to carbon atoms or heteroatoms of the corresponding unsubstituted compound or functional group are replaced by substituents.

[0053] 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.

[0054] "(C1~C 40 The term "(C1-C)hydrocarbyl" means a hydrocarbon radical of 1 to 40 carbon atoms. 40The term "hydrocarbylene" means a hydrocarbon diradical of 1 to 40 carbon atoms, wherein each hydrocarbon radical and each hydrocarbon diradical is 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

[0055] In the present disclosure, (C1 to C 40 ) Hydrocarbyl is unsubstituted or substituted (C1-C 40 ) Alkyl, (C3-C 40 ) cycloalkyl, (C3-C 20 )Cycloalkyl-(C1-C 20 ) Alkylene, (C6-C 40 ) aryl, or (C6-C 20 )Aryl-(C1-C 20 In some embodiments, the above (C1-C) alkylene may be 40 Each of the hydrocarbyl groups has up to 20 carbon atoms (i.e., (C1-C 20 ) hydrocarbyl), in embodiments having up to 12 carbon atoms.

[0056] "(C1~C 40 ) alkyl" and "(C1-C 18 The term "alkyl" refers to an alkyl group of 1 to 40 carbon atoms or 1 to 18 carbon atoms, unsubstituted or substituted with one or more R S means a saturated linear or branched hydrocarbon radical substituted by an unsubstituted (C1-C 40 Examples of alkyl are unsubstituted (C1-C 20 ) Alkyl, unsubstituted (C1-C 10 ) alkyl, unsubstituted (C1-C5) alkyl, methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2-butyl, 2-methylpropyl, 1,1-dimethylethyl, 1-pentyl, 1-hexyl, 1-heptyl, 1-nonyl, and 1-decyl. 40 Examples of substituted (C1-C 20) Alkyl, substituted (C1-C 10 ) alkyl, trifluoromethyl, and [C 45 ] alkyl. 45 The term "(C1-C5) alkyl" (with brackets) means that there are up to 45 carbon atoms in the radical, including the substituents, e.g., one R S replaced by (C 27 ~C 40 Each (C1-C5)alkyl can be methyl, trifluoromethyl, ethyl, 1-propyl, 1-methylethyl, or 1,1-dimethylethyl.

[0057] "(C6~C 40 The term "aryl" refers to an unsubstituted or (one or more R)aryl 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) a monocyclic, bicyclic, or tricyclic radical containing one, two, or three rings, respectively, wherein the monocyclic ring is aromatic and the two or three rings are independently fused or non-fused, and at least one of the two or three is aromatic. 40 Examples of aryl are unsubstituted (C-C 20 ) Unsubstituted aryl (C6-C 18 )aryl, 2-(C1-C5)alkylphenyl, 2,4-bis(C1-C5)alkylphenyl, phenyl, fluorenyl, tetrahydrofluorenyl, indakenyl, hexahydroindenyl, indenyl, dihydroindenyl, naphthyl, tetrahydronaphthyl, and phenanthrene. 40 Examples of aryl are substituted (C1-C 20 ) Aryl, substituted (C6-C 18 )aryl, 2,4-bis[(C 20 ) alkyl]-phenyl, polyfluorophenyl, pentafluorophenyl, and fluoren-9-on-1-yl.

[0058] "(C3~C 40The term "cycloalkyl" refers to a group that is unsubstituted or has one or more R S means a saturated cyclic hydrocarbon radical of 3 to 40 carbon atoms, substituted with other cycloalkyl groups, such as (C x ~C y )cycloalkyl) has x to y carbon atoms and is unsubstituted or has one or more R S Unsubstituted (C3-C 40 Examples of cycloalkyl are unsubstituted (C-C 20 ) Cycloalkyl, unsubstituted (C3-C 10 ) cycloalkyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, and cyclodecyl. 40 Examples of cycloalkyl are substituted (C3-C 20 ) Cycloalkyl, substituted (C3-C 10 ) cycloalkyl, cyclopentanon-2-yl, and 1-fluorocyclohexyl.

[0059] (C1~C 40 Examples of hydrocarbylene include unsubstituted or substituted (C6-C 40 )Arylene, (C3-C 40 ) cycloalkylene, and (C1-C 40 ) alkylene (e.g. (C1-C 20 ) alkylene). In some embodiments, the diradicals are on the same carbon atom (e.g., —CH2—), on adjacent carbon atoms (i.e., 1,2-diradicals), or separated by one, two, or more than two intervening carbon atoms (e.g., 1,3-diradicals, 1,4-diradicals, etc., respectively). Some diradicals include α,ω-diradicals. α,ω-diradicals are diradicals with the greatest carbon backbone spacing between the radical carbons. (C2-C 20Some examples of alkylene α,ω-diradicals include ethane-1,2-diyl (i.e., -CHCH-), propane-1,3-diyl (i.e., -CHCHCH-), and 2-methylpropane-1,3-diyl (i.e., -CHCH(CH)CH-). (C6-C 50 Some examples of arylene α,ω-diradicals include phenyl-1,4-diyl, naphthalene-2,6-diyl, or naphthalene-3,7-diyl.

[0060] "(C1~C 40 The term "alkylene" refers to an unsubstituted or substituted group having one or more R S means a saturated straight or branched chain diradical (i.e., the radical is not a ring atom) having 1 to 40 carbon atoms substituted with 50 Examples of alkylene are unsubstituted (C1-C 20 ) alkylene, and is unsubstituted —CH2CH2—, —(CH2)3—, —(CH2)4—, —(CH2)5—, —(CH2)6—, —(CH2)7—, —(CH2)8—, —CH2C * HCH3 and -(CH2)4C * (H)(CH3) and "C * " represents a carbon atom from which a hydrogen atom is removed to form a secondary or tertiary alkyl radical. 50 Examples of alkylene are substituted (C1-C 20 ) alkylene, -CF2-, -C(O)-, and -(CH2) 14 C(CH3)2(CH2)5- (i.e., 6,6-dimethyl-substituted normal-1,20-eicosylene). As mentioned above, the two R S are combined, (C1~C 18 ) alkylene, so that substituted (C1-C 50 Examples of )alkylene also include 1,2-bis(methylene)cyclopentane, 1,2-bis(methylene)cyclohexane, 2,3-bis(methylene)-7,7-dimethyl-bicyclo[2.2.1]heptane, and 2,3-bis(methylene)bicyclo[2.2.2]octane.

[0061] "(C3~C 40 The term "cycloalkylene" may be unsubstituted or may contain one or more R S means a cyclic diradical (i.e., the radicals are on ring atoms) of 3 to 40 carbon atoms substituted by

[0062] The term "heteroatom" refers to an atom other than hydrogen or carbon. Examples of heteroatoms include O, S, S(O), S(O), Si(R c )2, P(R P ), N(R N ), -N=C(R C )2, -Ge(R C )2-, or -Si(R C )-, and each R C , each R N , and each R P is unsubstituted (C1 to C 18 ) hydrocarbyl or -H. The term "heterohydrocarbon" refers to a molecule or molecular skeleton in which one or more carbon atoms are replaced with a heteroatom. 40 The term "(C1-C)heterohydrocarbyl" means a heterohydrocarbon radical of 1 to 40 carbon atoms. 40 The term "heterohydrocarbylene" means a heterohydrocarbon diradical of 1 to 40 carbon atoms, each heterohydrocarbon having one or more heteroatoms. The heterohydrocarbyl radical can be present on a carbon atom or a heteroatom, and the heterohydrocarbyl diradical can be present on (1) one or two carbon atoms, (2) one or two heteroatoms, or (3) one carbon atom and one heteroatom. Each (C1 to C 50 ) heterohydrocarbyl and (C1-C 50 ) heterohydrocarbylene is unsubstituted or substituted (one or more R S The aromatic ring may be aromatic or non-aromatic, saturated or unsaturated, straight or branched chain, cyclic (including monocyclic and polycyclic, fused and non-fused polycyclic) or acyclic.

[0063] (C1~C 40) Heterohydrocarbyl is unsubstituted or substituted (C1-C 40 ) heteroalkyl, (C1-C 40 ) hydrocarbyl-O-, (C1-C 40 ) hydrocarbyl-S-, (C1-C 40 ) hydrocarbyl-S(O)-, (C1-C 40 ) hydrocarbyl-S(O)2-, (C1-C 40 ) Hydrocarbyl-Si(R C )2-, (C1~C 40 )hydrocarbyl-N(R N )-, (C1~C 40 ) hydrocarbyl-P(R P )-, (C2~C 40 ) heterocycloalkyl, (C2-C 19 )Heterocycloalkyl-(C1-C 20 ) alkylene, (C3-C 20 )Cycloalkyl-(C1-C 19 ) heteroalkylene, (C2-C 19 )Heterocycloalkyl-(C1-C 20 ) heteroalkylene, (C1-C 40 ) heteroaryl, (C1-C 19 )Heteroaryl-(C1-C 20 ) Alkylene, (C6-C 20 )Aryl-(C1-C 19 ) heteroalkylene, or (C1-C 19 )Heteroaryl-(C1-C 20 ) heteroalkylene.

[0064] "(C4~C 40 The term "heteroaryl" refers to an unsubstituted or substituted (one or more R) heteroaryl group of a total of 4 to 40 carbon atoms and 1 to 10 heteroatoms. S

[0033] The term "heteroaromatic hydrocarbon radical" refers to a monocyclic, bicyclic, or tricyclic heteroaromatic hydrocarbon radical (according to the formula (C)), wherein the monocyclic, bicyclic, or tricyclic radical contains one, two, or three rings, respectively, which are independently fused or unfused, and at least one of the two or three rings is heteroaromatic. Other heteroaryl groups (e.g., generally (C) x~C y ) heteroaryl, (C4-C 12 ) heteroaryl, etc.) has x to y carbon atoms (e.g., 4 to 12 carbon atoms) and is unsubstituted or has one or more R S The monocyclic heteroaromatic hydrocarbon radical is defined in the same manner as when substituted by . The monocyclic heteroaromatic hydrocarbon radical is a 5-membered or 6-membered ring. The 5-membered ring has 5 minus h carbon atoms, where h is the number of heteroatoms and can be 1, 2, or 3, and each heteroatom can be O, S, N, or P. Examples of 5-membered heteroaromatic hydrocarbon radicals are 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. A 6-membered ring has 6 minus h carbon atoms, where h is the number of heteroatoms and can be 1 or 2, and the heteroatoms can be N or P. Examples of 6-membered heteroaromatic hydrocarbon radicals are pyridin-2-yl, pyrimidin-2-yl, and pyrazin-2-yl. Bicyclic heteroaromatic hydrocarbon radicals can 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. Tricyclic heteroaromatic hydrocarbon radicals can 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.

[0065] The heteroalkyl group may be any of (C1-C 50 ) or fewer carbon atoms and one or more heteroatoms. Similarly, heteroalkylene may 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, each of the heteroalkyl and heteroalkylene groups being unsubstituted or containing one or more R S is replaced by

[0066] Unsubstituted (C2~C 40 Examples of heterocycloalkyl include unsubstituted (C-C 20 ) Heterocycloalkyl, unsubstituted (C2-C 10 ) heterocycloalkyl, aziridin-1-yl, oxetan-2-yl, tetrahydrofuran-3-yl, pyrrolidin-1-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.

[0067] The term "halogen atom" or "halogen" means 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 radical of a fluoride (F - ), chloride (Cl - ), bromide (Br - ), or iodide (I -) refers to the anionic form of a halogen atom.

[0068] 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 substituted by a substituent R S The term "unsaturated" refers to the presence 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 present in the group. S It is meant to exclude any double bonds that may be present in, or, if present, in, a (hetero)aromatic ring.

[0069] According to some embodiments, a single chain catalyst in a process for polymerizing an ethylene-based polymer comprises a metal-ligand complex according to Formula (I).

[0070] [ka]

[0071] In formula (I), M is a metal selected from titanium, zirconium, or hafnium, the metal being in a +2, +3, or +4 formal oxidation state; n is 0, 1, or 2; when n is 1, X is a monodentate or 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; and each Z is selected from -O-, -S-, -N(R N )-, or -P(R P )-, and L is independently selected from (C1 to C 40 ) hydrocarbylene or (C1-C 40 ) heterohydrocarbylene, where (C1-C 40) Hydrocarbylene has a moiety containing a linker skeleton of 1 to 10 carbon atoms that connects the two Z groups in formula (I) (to which L is bonded), or (C1 to C 40 ) Heterohydrocarbylene has a moiety containing a linker skeleton of 1 to 10 atoms that connects the two Z groups in formula (I), and (C1 to C 40 Each of the 1 to 10 atoms of the 1- to 10-atom linker backbone of the heterohydrocarbylene is independently a carbon atom or a heteroatom, and each heteroatom is independently O, S, S(O), S(O), Si(R C )2, Ge(R C )2, P(R C ), or N(R C ) and independently each R C is (C1~C 30 ) hydrocarbyl or (C1-C 30 ) heterohydrocarbyl, and R 1 and R 8 are independently -H, (C1~C 40 ) hydrocarbyl, (C1-C 40 ) heterohydrocarbyl, -Si(R C )3, -Ge(R C )3, -P(R P )2, -N(R N )2, -OR C , -SR C , -NO2, -CN, -CF3, R C S(O)-, R C S(O)2-, (R C )2C=NR C C(O)O-, R C OC(O)-, R C C(O)N(R N )-, (R N )2NC(O)-, halogen, and a radical having formula (II), formula (III), or formula (IV).

[0072] [ka]

[0073] In formulas (II), (III), and (IV), R 31~35 , R 41~48 , or R 51~59 Each of (C1 to C 40 ) hydrocarbyl, (C1-C 40 ) heterohydrocarbyl, -Si(R C )3, -Ge(R C )3, -P(R P )2, -N(R N )2, -N=CHR C , -OR C , -SR C , -NO2, -CN, -CF3, R C S(O)-, R C S(O)2-, (R C )2C=N-, R C C(O)O-, R C OC(O)-, R C C(O)N(R N )-, (R N )2NC(O)—, halogen, or —H, provided that R 1 or R 8 is a radical having formula (II), formula (III), or formula (IV).

[0074] In formula (I), R 2~4 , R 5~7 , and R 9~16 Each of (C1 to C 40 ) hydrocarbyl, (C1-C 40 ) heterohydrocarbyl, -Si(R C )3, -Ge(R C )3, -P(R P )2, -N(R N )2, -N=CHR C , -OR C , -SR C , -NO2, -CN, -CF3, R C S(O)-, R C S(O)2-, (R C )2C=N-, R C C(O)O-, R C OC(O)-, R C C(O)N(R N)-, (R C )2NC(O)-, halogen, and -H.

[0075] An illustrative example of a metal-ligand complex according to formula (I) is catalyst 4.

[0076] [ka]

[0077] In one or more embodiments, the single chain catalyst comprises a metal-ligand complex according to formula (V).

[0078] [ka]

[0079] In formula (V), M is hafnium, zirconium, titanium, a Group III or lanthanide metal. A are independently (C1~C 40 ) hydrocarbyl, (C1-C 40 ) heterohydrocarbyl, -Si(R B )3, -Ge(R B )3, -P(R B )2, -N(R B )2, -OR B , -SR B , -NO2, -CN, CF3, R B S(O)-, R B S(O)2-, (R B )2C=N-, R B C(O)O-, R B OC(O)-, R B C(O)N(R)-, (R B )NC(O)-, a halogen atom, and a hydrogen atom. Optionally, two or more R A The groups can be attached together in one or more ring structures. B are independently (C1~C 30 ) hydrocarbyl or (C1-C 30 ) heterohydrocarbyl.

[0080] In formula (V), Z is [(R D ) n G] m where the subscript m is 1 or 2, and each G is independently selected from carbon, silicon, germanium, or boron, with the proviso that when G is carbon, silicon, or germanium, n is 2, and when G is boron, n is 1. D are independently (C1~C 30 ) hydrocarbyl or (C1-C 30 ) heterohydrocarbyl.

[0081] In formula (V), Y is —O—, —S—, or —NR E - and -PR E -, and each R b , R d , or R E are independently (C1~C 30 ) hydrocarbyl or (C1-C 30 ) heterohydrocarbyl.

[0082] In formula (V), each X is (C1 to C 40 ) Hydrocarbons, (C1-C 40 ) Heterohydrocarbons, (C1-C 40 ) hydrocarbyl, (C1-C 40 ) heterohydrocarbyl, Si(-Si(R C )3, -Ge(R C )3, -P(R C )2, -N(R C )2, -OR C , -SR C , -NO2, -CN, CF3, R C S(O)-, R C S(O)2-, (R C )2C=N-, R C C(O)O-, R C OC(O)-, R C C(O)N(R)-, (R C )NC(O)-, a halogen atom, and a hydrogen atom. C are independently (C1~C 30) hydrocarbyl or (C1-C 30 ) heterohydrocarbyl.

[0083] An illustrative example of a metal-ligand complex according to formula (V) is catalyst 2.

[0084] [ka]

[0085] In one or more embodiments, the single chain catalyst comprises a metal-ligand complex according to formula (VI).

[0086] [ka]

[0087] In formula (VI), M is hafnium, zirconium, titanium, a Group III or lanthanide metal. Each X is (C1 to C 40 ) Hydrocarbons, (C1-C 40 ) Heterohydrocarbons, (C1-C 40 ) hydrocarbyl, (C1-C 40 ) heterohydrocarbyl, Si(-Si(R C )3, -Ge(R C )3, -P(R C )2, -N(R C )2, -OR C , -SR C , -NO2, -CN, CF3, R C S(O)-, R C S(O)2-, (R C )2C=N-, R C C(O)O-, R C OC(O)-, R C C(O)N(R)-, (R C )NC(O)-, a halogen atom, and a hydrogen atom. C and R P are independently (C1~C 30 ) hydrocarbyl or (C1-C 30 ) heterohydrocarbyl. Each R Pare independently (C1~C 30 ) hydrocarbyl or (C1-C 30 ) heterohydrocarbyl. (X) n The subscript n in is 1 or 2. Cp is cyclopentadienyl, which may be unsubstituted or substituted with up to five substituents. Each of the five substituents may be a (C1-C5) hydrocarbyl, a (C1-C5) heterohydrocarbyl, or a halogen. Optionally, two of the five substituents may be joined together to form a ring.

[0088] In some embodiments, Cp is selected from cyclopentadienyl, indenyl, and fluorenyl.

[0089] In formula (VI), N is nitrogen, P is phosphorus, and each R P are independently (C1~C 30 ) hydrocarbyl.

[0090] An illustrative example of a metal-ligand complex according to formula (VI) is catalyst 3.

[0091] [ka]

[0092] In embodiments, the multi-chain catalyst comprises a metal-ligand complex according to formula (VII).

[0093] [ka]

[0094] In formula (VII), M is hafnium, zirconium, titanium, a Group III or lanthanide metal. Each X is (C1 to C 40 ) Hydrocarbons, (C1-C 40 ) Heterohydrocarbons, (C1-C 40 ) hydrocarbyl, (C1-C 40 ) heterohydrocarbyl, Si(-Si(R C )3, -Ge(RC )3, -P(R C )2, -N(R C )2, -OR C , -SR C , -NO2, -CN, CF3, R C S(O)-, R C S(O)2-, (R C )2C=N-, R C C(O)O-, R C OC(O)-, R C C(O)N(R)-, (R C )NC(O)-, a halogen atom, and a hydrogen atom. C are independently (C1~C 30 ) hydrocarbyl or (C1-C 30 ) heterohydrocarbyl.

[0095] In formula (VII), R 71 ~R 76 is (C1~C 40 ) hydrocarbyl, (C1-C 40 ) heterohydrocarbyl.

[0096] An illustrative example of a metal-ligand complex according to formula (VII) is catalyst 1.

[0097] [ka]

[0098] In catalyst systems according to embodiments of the present disclosure, the molar ratio of bimetallic activator complex to Group IV metal-ligand complex can be from 1:10,000 to 1000:1, such as 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 system can include a combination of one or more bimetallic activator complexes described in this disclosure.

[0099] cocatalyst component Catalyst systems containing the metal-ligand complex of formula (I) can be made catalytically active by any technique known in the art for activating metal-based catalysts for olefin polymerization reactions. For example, systems containing the metal-ligand complex of formula (I) can be made catalytically active by contacting the complex with an activating cocatalyst or combining the complex with an activating cocatalyst. Activating cocatalysts suitable for use herein include alkylaluminums, 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" refers to monoalkylaluminum dihydrides or dihalides, dialkylaluminum hydrides or halides, or trialkylaluminums. Examples of polymeric or oligomeric alumoxanes include methylalumoxane, methylalumoxane modified with triisobutylaluminum, and isobutylalumoxane.

[0100] The Lewis acid activator (cocatalyst) may be, as described herein, a compound having one to three (C1-C 20 In one embodiment, the Group 13 metal compound includes a tri((C1-C) hydrocarbyl substituent. 20 )hydrocarbyl)substituted aluminum or tri((C1-C 20 In an embodiment, the Group 13 metal compound is a tri(hydrocarbyl)-substituted aluminum, tri((C1-C 20 )hydrocarbyl)-borane compounds, tri((C1-C 10 ) alkyl) aluminum, tri((C6-C 18)aryl)borane compounds and their halogenated (including perhalogenated) derivatives. In further embodiments, the Group 13 metal compound is tris(fluoro-substituted phenyl)borane, tris(pentafluorophenyl)borane. In some embodiments, the activating cocatalyst is tris((C1-C 20 ) hydrocarbyl borate (e.g., trityl tetrafluoroborate) or tri((C 20 )hydrocarbyl)ammonium tetra((C1-C 20 )hydrocarbyl)borane (e.g., bis(octadecyl)methylammonium tetrakis(pentafluorophenyl)borane). As used herein, the term "ammonium" refers to a ((C1-C 20 ) Hydrocarbyl) 4N + , ((C1~C 20 )hydrocarbyl)3N(H) + , ((C1~C 20 )hydrocarbyl)2N(H)2 + , (C1~C 20 ) Hydrocarbyl N(H)3 + , or N(H)4 + Each of the nitrogen cations (C1 to C 20 When two or more hydrocarbyls are present, they may be the same or different.

[0101] As a combination of neutral Lewis acid activators (cocatalysts), tri((C1-C4) alkyl)aluminum and tri((C6-C 18(aryl)borane compounds, particularly tris(pentafluorophenyl)borane. Embodiments include mixtures containing such neutral Lewis acid mixtures in combination with polymeric or oligomeric alumoxanes, and combinations of a single neutral Lewis acid, particularly tris(pentafluorophenyl)borane, with polymeric or oligomeric alumoxanes. The molar ratio of (metal-ligand complex):(tris(pentafluorophenyl)borane):(alumoxane) [e.g., (Group 4 metal-ligand complex):(tris(pentafluorophenyl)borane):(alumoxane)] is 1:1:1 to 1:10:30, and in embodiments, 1:1:1.5 to 1:5:10.

[0102] Catalyst systems comprising the metal-ligand complexes of formula (I) can be activated to form active catalyst compositions by combining 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. Exemplary suitable cocatalysts include modified methylaluminoxane (MMAO), bis(hydrogenated tallow alkyl)methyl, tetrakis(pentafluorophenyl)borate (1 - ) amines, and combinations thereof.

[0103] In some embodiments, one or more of the aforementioned activating cocatalysts are used in combination with one another. Particularly preferred combinations are mixtures of tri((C1-C4)hydrocarbyl)aluminum, tri((C1-C4)hydrocarbyl)borane, or ammonium borate with an oligomeric or polymeric alumoxane compound. The ratio of the total number of moles of the one or more metal-ligand complexes of Formula (I) to the total number of moles of the one or more activating cocatalysts is from 1:10,000 to 100:1. In some embodiments, this 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 alumoxane is used alone as the activating cocatalyst, preferably the number of moles of alumoxane used is at least 100 times the number of moles of the metal-ligand complex of Formula (I). When tris(pentafluorophenyl)borane is used alone as the activating cocatalyst, in some embodiments, the number of moles of tris(pentafluorophenyl)borane used relative to the total number of moles of one or more metal-ligand complexes of Formula (I) is from 0.5:1 to 10:1, from 1:1 to 6:1, or from 1:1 to 5:1. The remaining activating cocatalyst is generally used in a molar amount approximately equal to the total molar amount of one or more metal-ligand complexes of Formula (I).

[0104] Characterization of tetrafunctional long-chain branched polyolefins Depending on the degree of branching, various methods, such as nuclear magnetic resonance (NMR), can determine LCB or identify its influence in polymers. For example, the effect of LCB is observed in shear flow by van Gurp-Palmen analysis, and the increase in shear viscosity at low angular frequencies and the intensity of shear-thinning behavior can be attributed to LCB. In extensional flow, the influence of LCB is usually determined by the degree of stiffening or melt strength and the maximum deformation achieved. Other plots, such as Mark-Hwink-Sakurada plots, extended molecular weight distributions (MWDs), and g' plots, provide additional information about LCB. Achieving high levels of natural LCB in polymers is difficult due to the limited concentration of vinyl-terminated polymers (maximum one per polymer chain) and the need to run high conversions to ensure LCB formation. To ensure high conversions, the ethylene concentration in the reactor is low, thus allowing a large amount of vinyl-terminated polymer to be reinserted into second polymer chains.

[0105] Conventional processes incorporating dienes into polymer synthesis systems suffer from the fundamental drawback of gel formation or reactor fouling at high branching levels. The aforementioned kinetic modeling (International Application Nos. US2019 / 053524 (filed September 27, 2019), US2019 / 053527 (filed September 27, 2019), US2019 / 053529 (filed September 27, 2019), and US2019 / 053537 (filed September 27, 2019)) can provide good predictive results that allow for a better understanding of gel formation. For example, longer polymer chains have proportionally more pendant vinyl, and polymer chains containing more pendant vinyl are more likely to reinsert into the catalyst and form LCBs. Therefore, larger polymer chains preferentially reinsert to form even larger polymer molecules with tetrafunctional branches. When the LCB level reaches a threshold, gel problems or instability result. Weight average molecular weight (M) as a function of conventional tetrafunctional branching w ) and number average molecular weight (M n A simulation of M is shown in Figure 1 for an ethylene-based polymer in a constant pressure semi-batch reactor.n is M w As goes to infinity, it only increases slightly. In this example, M w When the number of ions per mole increases above 200,000 grams per mole (g / mol), the molecular weight distribution (MWD) of the polymer becomes unstable and gel formation begins. The MWD is the weight average molecular weight M w The number average molecular weight M n is defined as dividing by (M w / M n ).

[0106] For the purposes of this disclosure, polymer gels are narrowly defined as phase-separated polymer fractions due to their high branching level and / or high molecular weight. Polymer gels can be observed in solution or in the molten state and tend to interfere with properties such as optical clarity and film and fiber performance. Polyethylene interpolymer gels can be measured by the insolubility of the polymer in hot xylene. Gel content is often correlated with, and therefore estimated from, the GPC polymer recovery percentage. When polymer gels form, they can accumulate in the reactor and cause fouling.

[0107] Effect of molecular weight When two catalysts, e.g., catalyst 1 and catalyst 2, are added to a reactor, a bimodal distribution can occur due to the different MWs of the two catalysts. If one of the catalysts is a dual-chain catalyst, the catalyst can effectively ladder-branch the diene. A dual-chain catalyst is an embodiment of a multi-chain catalyst with only two polymerization sites. Due to the efficiency of the diene reaction at the metal center of the dual-chain catalyst (no vinyl accumulation required), the dual-chain catalyst efficiently joins polymer chains together, while the single-chain catalyst cannot insert enough diene to form significant LCBs or cause fouling problems. Figure 3 shows the MWD of polymers produced by the two catalysts. The dual-chain catalyst produces a small fraction of higher MW polymer, manifesting as a high-MW shoulder. Adding a diene shifts this shoulder further up the MW, while the main peak from the single-chain catalyst remains essentially unaffected.

[0108] Mark Hwink-Sakurada analysis The Mark-Hwink-Sakurada plot describes the power law relationship between intrinsic viscosity [η] and absolute molecular weight M. η=βM α (1)

[0109] Generally, [η] corresponds to the cross-sectional radius of gyration or backbone molecular weight of the polymer. The absolute MW (M) and backbone MW (M) are related in that the absolute MW includes the mass on the side chains but not the backbone MW. b ) Using the absolute molecular weights, a Mark-Hwink-Sakurada plot of log[η] versus logM leads to the following: log(η)=log(β)+αlog(M) (2)

[0110] It should be noted that in this application, the base 10 logarithm is denoted as log.

[0111] For linear polymers, a plot of log[η] versus logM yields a slope α and a vertical offset logβ. The value of α is known to be α=0.73 for polyethylene at 150°C for a typical solvent, trichlorobenzene. In many of the following evaluations, α=0.73.

[0112] When short-chain branches are introduced, deviations from the homopolymer dependence occur. For example, at 10 mol % octene, 23% of the total molecular weight is in the side chains, and M b = 10 / 13M.

[0113]

number

[0114] For α = 0.73 and α log1.3 = 0.083, the Mark-Hwink-Sakurada plot for this polymer is parallel to the homopolymer (no comonomer) but offset by 0.083 on the logarithmic scale. The line is parallel to the homopolymer dependence because the short chain branches are uniformly distributed along the backbone at all molecular weights.

[0115] The effect of long-chain branching on the Mark-Hwink-Sakurada plot is more complex. With significant molecular weight (long-chain branching) in the side chains, the Mark-Hwink-Sakurada dependence also decreases. However, because long-chain branching from conventional diene or high-pressure (LDPE) processes occurs in dendritic or branch-on-branch structures, it is not uniformly distributed, with higher molecular weight species having more long-chain branching. These concepts lead to a Mark-Hwink-Sakurada behavior that deviates more from the linear homopolymer dependence as absolute molecular weight increases (see Figure 4).

[0116] In principle, if the relationship between backbone molecular weight and absolute molecular weight can be determined, a Mark-Hwink-Sakurada plot can be predicted. However, this is too complicated for conventional diene and high-pressure processes. Intrinsic viscosity is calculated as (dW f Note that there is a cutoff at the high MW end when the (logM / dLogM) signal falls below 0.03.

[0117] The term "ladder polymer" refers to a high molecular weight fraction of a polyethylene-based polymer, in which the high molecular weight fraction contains tetrafunctional long-chain branches. Ladder polymers degraded by hydrogenated segments have a defined relationship between the backbone molecular weight and the absolute molecular weight (see Figure 5). In Figure 5, the polymer backbone is shown in black. The dotted lines indicate tetrafunctional branches as shown in Scheme 3. The absolute MW does not exceed two times the backbone MW. As a general rule, the absolute MW should be close to two times the backbone MW, depending on the degree of free chains present in the ladder polymer, which originate from successive hydrogenolysis events on the same polymer chain. The percentage, and therefore the mass, of free chains will be small relative to the molecular weight of the entire polymer. Using an upper limit where the backbone MW is half the absolute MW, the M b =1 / 2M.

[0118]

number

[0119] For α = 0.73 and α log2 = 0.220, the Mark-Hwink-Sakurada plot for this polymer is much lower than for the 10 mol% copolymer. The ladder's Mark-Hwink-Sakurada dependence is even lower than for the 10 mol% octene copolymer, but unlike LDPE and conventional diene branching, it is limited to a range lower than the homopolymer dependence (Figure 4).

[0120] Figure 6 shows the theoretical linear homopolymer power law relationship (Equation 2) and the theoretical ladder limit (Equation 6). Actual data shows the transition from linear to ladder-branched polymers.

[0121] In the case of ladder polymers, considering homopolymers (containing dienes but no octene), the chains are either linear (Equation 2) or long-chain branched (Equation 6). Equation 6 is valid whether there is one LCB (rung) or two or more LCBs. The lowest MW polymer chains contain few LCBs, while the highest MW polymer chains usually contain at least one LCB, with a transition period between them where some chains are linear and some are ladder long-chain branched. This transition period is marked by an inflection point (d 2 [η] / dM 2 = 0, and d 3 [η] / dM 3 >0).

[0122] The single-chain catalyst forms mostly low MW linear polyethylene-based polymers, with MW of S max The bimodal polymers are those in which the MW is below S, and the double chain catalyst forms a slightly high MW ladder long-chain branched polyethylene-based polymer. max (See Figure 7 for an example based on data from Tables 2 to 10.) max (These values ​​are explained in more detail in the following section.) Most low MW linear polyethylene-based polymers follow Equation 2, while a few high MW ladder long-chain branched polyethylene-based polymers follow Equation 6. A large amount of the high MW fraction increases the viscosity, making it difficult to pump out of the reactor. If the amount of high MW fraction can be controlled, the overall viscosity will not reach a point where reactor fouling can occur, and the polymer can be safely removed from the reactor.

[0123] In Figure 6, there is an inflection point between the linear polymers in the low MW fraction and the ladder-branched polymers in the high MW fraction, however, there is also an inflection point for short-chain branching because the bimodal distribution results from two catalysts, each with different comonomer incorporation levels.

[0124] The formula presented above is applicable for the following cases: i) no octene in the low MW fraction and no octene in the ladder polymer; ii) no octene in the low MW fraction and 10 mole % octene in the ladder polymer; iii) 10 mole % octene in the low MW fraction and no octene in the ladder polymer; iv) 10 mole % octene in the low MW fraction and 10 mole % octene in the ladder polymer.

[0125] i) no octene in the low MW fraction and no octene in the ladder polymer: η low =βM α (7) log(η low )=log(β)+α log(M) (8)

[0126]

number

[0127] Equations 8-10, which are the difference between the logarithmic viscosities of the low and high MW regions, respectively, are as follows: log(η low )-log(η high )=αlog(2)=0.220 (11)

[0128] ii) no octene in the low MW fraction and 10 mol% octene in the ladder polymer: log(η low )=log(β)+αlog(M) (8)

[0129]

number

[0130] Equations 8-12, which are the difference between the logarithmic viscosities of the low and high MW regions, respectively, are as follows: log(η low )-log(η high )=αlog(2.6)=0.303 (13)

[0131] iii) 10 mol % octene in the low MW fraction and no octene in the ladder polymer:

[0132]

number

[0133] Equations 15-10, which are the difference between the logarithmic viscosities of the low and high MW regions, respectively, are as follows:

[0134]

number

[0135] iv) 10 mol % octene in the low MW fraction and 10 mol % octene in the ladder polymer: log(η low )=log(β)+αlog(M)-αlog(1.3) (15) log(η high )=log(β)+αlog(M)-αlog(2.6) (12)

[0136] Equations 15-12, which are the difference between the logarithmic viscosities of the low and high MW regions, respectively, are as follows: log(η low )-log(η high )=αlog(2.6)-αlog(1.3)=αlog(2)=0.220 (17)

[0137] For a comparative example of a bimodal distribution with no long chain branching and both polymer fractions having the same octene incorporation (e.g., 0 mol% octene or 5 mol% octene or 10 mol% octene), the difference between the logarithmic viscosities of the low and high MW fractions will be zero. Furthermore, bimodal polymers with differences in comonomer incorporation (no LCB) (i) 10 mol% octene in the low MW fraction and no octene in the high MW fraction, ii) no octene in the low MW fraction and 10 mol% octene in the high MW fraction are as follows:

[0138] i) 10 mole % octene in the low MW fraction and no octene in the high MW fraction: log(η low )=log(β)+αlog(M)-αlog(1.3) (15) log(η high )=log(β)+αlog(M) (18)

[0139] Equations 15-18, which are the difference between the logarithmic viscosities of the low and high MW regions, respectively, are as follows: log(η low )-log(η high )=-αlog(1.3)=-0.083 (19)

[0140] i) no octene in the low MW fraction and 10 mole % octene in the high MW fraction: log(η low )=log(β)+αlog(M) (8) log(η high )=log(β)+αlog(M)-αlog(1.3) (20)

[0141] Equations 8-20, which are the difference between the logarithmic viscosities of the low and high MW regions, respectively, are as follows: log(η low )-log(η high )=αlog(1.3)=0.083 (19)

[0142] The comparative examples provide a theoretical range of logarithmic viscosity differences of -0.083 to +0.083 for the extremes of octene incorporation. For ladder polymers with LCB in the high MW fraction and varying octene incorporation, the range of values ​​was 0.137 to 0.303. These ranges provide both the difference in the Mark-Hwink-Sakurada parameters associated with the two resins, as well as the error bars associated with these experimental measurements.

[0143] The value g' is well defined as the viscosity of a branched polymer divided by the viscosity of a linear polymer of the same absolute MW.

[0144]

number

[0145] There are various ways to average g'. ave , i.e., average g' is the weight average value of g' (BH Zimm, WH Stockmayer, J. Chem. Phys. 1949, 17, 1301). When the entire polymer composition consists of ladder polymers, g' can be determined when the viscosity of the ladder-branched polymer is divided by the viscosity of a linear polymer with the same absolute MW (both polymers have the same comonomer content).

[0146] The viscosity of a linear polymer is given by: log(η linear )=log(β)+αlog(M) (22) η linear =10 {log(β)+αlog(M)} (twenty three)

[0147] The viscosity of the ladder polymer is given by: log(η Ladder )=log(β)+αlog(M)-αlog(2) (24) η Ladder =10 {log(β)+αlog(M)-αlog(2)} (twenty five)

[0148]

number

[0149] The average g' value for LDPE is often less than 0.6. This ladder limit for g' assumes that all polymer chains are ladder-branched. Previous studies (International Application Nos. US2019 / 053524, filed September 27, 2019; US2019 / 053527, filed September 27, 2019; US2019 / 053529, filed September 27, 2019; and US2019 / 053537, filed September 27, 2019) have shown that not all polymer chains are ladder-branched. This study has the majority of polymer chains produced from single-chain catalysts with little or no LCB. In this case, g' ave The values ​​(weighted average g') are much higher than previously achievable, as shown in Table 4.

[0150] Ladder Characteristics (L) As previously mentioned, there is an ongoing problem of balancing the melting properties of a polymer with viscosity or melt index. The ethylene-based polymers of the present disclosure comprise a low molecular weight fraction and a high molecular weight fraction. The high molecular weight fraction comprises a ladder polymer, where the ladder polymer has tetrafunctional long chain branches, as shown in Scheme 3. Without intending to be bound by theory, the uniqueness of the ladder polymer in the high molecular weight fraction and the linear polymer in the low molecular weight fraction enhances melt processing properties without increasing viscosity and decreasing melt index, eliminating viscosity or fouling issues in the reactor.

[0151] A new parameter (L) is introduced to estimate ladder properties. Mark-Hwink-Sakurada plots (log η vs. log M) show a square-law dependence, with the low MW fraction being due to linear polymers and the high MW fraction being due to ladder polymers (Figures 6 and 7). For a given sample, all data points can be fitted to an equation where L is the fraction of ladder polymers and (1-L) is the fraction of linear polymers. log(η)=(1-L)*log(η Linear )+L*log(η Ladder ) (29) log(η Linear )=log(β)+αlog(M) (22) log(η Ladder) =log(β)+αlog(M)-αlog(2) (24) log(η)=log(β)+αlog(M)-L*αlog(2) (30)

[0152] As previously mentioned (International Application Nos. US2019 / 053524, filed September 27, 2019, US2019 / 053527, filed September 27, 2019, US2019 / 053529, filed September 27, 2019, and US2019 / 053537, filed September 27, 2019), S max is the first instance (inflection point) of maximum downward slope on the RHS (high MW side) of the main peak (absolute value of slope) of the scaled MWD. w If one plots the slope of viscosity as a function of viscosity, one can see that there is an initial slope of about 0.73, followed by a transition period, after which there is another slope of about 0.73. During the transition period, the slope decreases, then increases again, before approaching 0.73. In a specific example, Figure 8 illustrates this transition.

[0153] Two slopes are determined for the low and high MW fractions. The slope is interpolated from all 25 data points, with the low MW fraction being the average of the last five slopes and the high MW fraction being the last slope.

[0154] FIG. 9 shows the ladder characteristics of Examples 1 to 11. The ladder is characterized by Smax Below MW it is about zero and then increases to about 1 at the high MW side.

[0155] S max The ladder characteristic (L) can be plotted as a function of log(M) before and after. As can be seen in Figure 10 (left), L is a function of log(M) for all data points in all samples. max When the value is between -0.35 and +0.35, the value is <L<0.35)。S max (See the right of Figure 10) When L exceeds this value, L increases according to Log(M) and reaches the maximum value of L (L max ) is between 0.7 and 1.5 (0.7 <L max <1.5). Two bimodal comparative examples without LCB are also shown in Figure 10. max The prior art examples of single duplex catalysts (not bimodal polymers) show that both definitions are not met for any of the comparative examples (see Figure 11).

[0156] Visual inspection of the "ladder branching" MWD shows a lack of the characteristic high MW tail typically seen in branched polymers. Figure 12 demonstrates how the model predicts the lack of tailing for "ladder branching" polymers. The "ladder branching" MWD data show a characteristic lack of tails in many experiments, but also indicate that tails can form depending on the polymerization conditions and diene / catalyst pairing.

[0157] Polydispersity index (M w / M n , M z / M w ) are known metrics of tailing, but are not preferred due to their sensitivity to low MWD artifacts. Therefore, a more focused version of the polydispersity index is used to develop standards where integration is performed only over the high MW portion of the MWD. w / M n and M z / M w ​The metric successfully distinguishes diene "ladder branches" from conventional branches and is highly sensitive to high MW baseline selection and baseline noise.

[0158] The area under the MWD curve is the MWD dispersity index (M w / M n , M z / M w It is relatively insensitive to baseline problems compared to the higher moments required to calculate the MWD. ​​Therefore, it was decided to develop a metric involving an unweighted integral of the MWD. ​​These MWD area metrics, A HIGH and A TAIL is calculated from the area of ​​the GPC curve for a defined region to the right of the MWD curve. MWD area metric (A HIGH and A TAIL ) is derived from the scaled MWD curve (dW / logM), and the major or highest peak of the MWD is defined as having a value of unity. When two or more peaks have the same height, the highest MW peak is the major peak. The independent variable in the MWD curve is Log(M), which is the logarithm of M to the base 10. Both MWD area metrics depend on the point of maximum slope in the high MW portion of the MWD. ​​The quantities and limits required to evaluate the area metrics are listed below and demonstrated in Figure 12.

[0159] S max = the first case of maximum downward slope on the RHS (higher MW side) of the main peak (absolute value of slope) of the scaled MWD

[0160] H smax = Scaled MWD height at point of maximum gradient

[0161] pt1=S max LogM value of

[0162] pt2=S max LogM value where the tangent intersects the x-axis

[0163] The MWD area metric is defined below, where A HIGH is simply the area of ​​the MWD region after the point of maximum gradient. The second area metric, A TAIL is the small high MW area shown in Figure 12, and A HIGH It is evaluated by subtracting the area of ​​the triangle from

[0164]

number

[0165] In current bimodal polymers, these are bimodal polymers with small amounts of high MW branched material, so A TAIL exceeds the 0.04 value. In this case, A TAIL It is necessary to make it larger than 0.06.

[0166] Ethylene-based polymers produced from the processes of the present disclosure Polymers produced from "ladder branches," as depicted in Scheme 4, are included in the present disclosure.

[0167] In embodiments of the present disclosure, the ethylene-based polymer comprises a low molecular weight polymer fraction and a high molecular weight polymer, both of which contain polymerized units of ethylene, one or more dienes, and optionally one or more C-C 12 The low molecular weight fraction and the high molecular weight fraction are derived from α-olefins. The molecular weight distribution (MWD) curves determined by absolute gel permeation chromatography are shown in S max As mentioned above, S max is the maximum absolute slope on the high molecular weight side of the main peak of the MWD curve, the main peak being the peak of greatest magnitude in the MWD curve.

[0168] In the ethylene-based polymers of the present disclosure, the low molecular weight polymer fraction and the high molecular weight polymer fraction each comprise a ladder profile, L. The ladder profile, L, follows the Mark-Hwink-Sakurada curve, as follows: log[η]=log(β)+αlog(M)−L *It is defined for a given absolute molecular weight (MW) as the fit of the logarithm of the intrinsic viscosity [η] versus the logarithm of the absolute MW (M) using αlog(2), where log(β) is the intercept and α is the slope. The low molecular weight polymer fraction is S max The MW of the polymers is below 0.35, and all L values ​​are between 0.35 and 0.35. The high molecular weight polymer fraction is max It has a MW greater than 0.8 and a maximum L value of 0.8 to 1.5.

[0169] In an embodiment of the present disclosure, the ethylene-based polymer comprises a melt strength (MS) greater than minus 17 times the logarithm of the base 10 of the melt index plus 25 (MS>-17 * log(MI)+25), where MS is the melt strength in cN (Rheotens apparatus, 190°C, 2.4 mm / s 2 , 120mm from die exit to wheel center, extrusion speed 38.2 seconds -1 , a capillary die of 30 mm length, 2 mm diameter, and 180° entry angle), and MI is the melt index in g / 10 min according to ASTM D1238. In some embodiments, the melt strength (MS) is greater than minus 17 times the logarithm of the melt index, plus 30 (MS>-17 * In various embodiments, the melt strength (MS) is greater than minus 17 times the logarithm of the melt index plus 35 (MS>-17 * log(MI)+35). As previously mentioned, generally, as melt strength increases, melt index decreases. As shown by this equation, melt strength can be increased (such that the polymer has a melt strength of 20 cN) and the melt index remains in the normal range (such as 0.1 to 5).

[0170] In an embodiment of the present disclosure, the ethylene-based polymer is a polymer comprising ethylene, a diene, and optionally one or more C-C 12 The ethylene-based polymer contains polymerized units derived from α-olefins. The ethylene-based polymer has a melt viscosity ratio (V) at 190°C of greater than 20. 0.1 / V 100) and an average g' greater than 0.86, where average g' is an intrinsic viscosity ratio determined by gel permeation chromatography using a triple detector. In some embodiments, the ethylene-based polymer has a melt strength greater than 10 cN.

[0171] In an embodiment of the present disclosure, the ethylene-based polymer is a polymer comprising ethylene, a diene, and optionally one or more C-C 12 The ethylene-based polymer comprises polymerized units derived from an α-olefin. The ethylene-based polymer comprises a melt strength greater than 10 cN and an average g' greater than 0.86, where the average g' is an intrinsic viscosity ratio determined by gel permeation chromatography using a triple detector. In one or more embodiments, the ethylene-based polymer has a melt viscosity ratio at 190°C (V 0.1 / V 100 )

[0172] In one or more embodiments, the ethylene-based polymer comprises a low molecular weight polymer fraction and a high molecular weight polymer fraction, wherein the low molecular weight polymer fraction and the high molecular weight polymer fraction each comprise ethylene, a diene, and optionally one or more C3-C6 olefins. 12 Contains polymerized units derived from α-olefins.

[0173] In one or more embodiments, the ethylene-based polymer has an average g' greater than 0.70. In one or more embodiments, the average g' is greater than 0.86, where the average g' is the intrinsic viscosity ratio determined by gel permeation chromatography using a triple detector. In some embodiments, the average g' is greater than 0.88. In various embodiments, the average g' is greater than 0.90.

[0174] In some embodiments, the high molecular weight polymer fraction comprises 0.5 to 30 weight percent (wt%) of polymer, hi other embodiments, the high molecular weight polymer fraction comprises 1 to 15 wt% of polymer.

[0175] In one or more embodiments, all values ​​of L for the low molecular weight polymer fractions are between −0.2 and 0.2, and in some embodiments, the maximum value of L for the high molecular weight polymer fractions is between 0.9 and 1.1.

[0176] In various embodiments, the ethylene-based polymers have an MWD area metric, A TAIL and has a molecular weight tail quantified by A TAIL is greater than 0.06 as determined by gel permeation chromatography using a triple detector. TAIL is greater than 0.08 or A TAIL is greater than 0.10.

[0177] In some embodiments, the ethylene-based polymer has a weight average molecular weight (M) of 250,000 daltons or less, as determined by absolute gel permeation chromatography. w In one or more embodiments, the ethylene-based polymer has a weight average molecular weight (M) of less than, or equal to, 150,000 daltons, or less than, or equal to, 100,000 daltons, as determined by absolute gel permeation chromatography. w )

[0178] In one or more embodiments, the melt index (MI) is greater than 0.1, where MI is the melt index in g / 10 min according to ASTM D1238. In some embodiments, MI is between 0.1 and 5.0, or between 0.3 and 3.0. In various embodiments, MI is greater than 1 or greater than 2. In some embodiments, MI is greater than 3, where MI is the melt index in g / 10 min according to ASTM D1238.

[0179] In various embodiments, the melt strength of the ethylene-based polymer can be greater than 10 cN (Rheotens device, 190° C., 2.4 mm / sec 2 , 120mm from die exit to wheel center, extrusion speed 38.2 seconds -1, 30 mm long, 2 mm diameter, and 180° inlet angle). In one or more embodiments, the MS is greater than 20 cN, greater than 30 cN, or greater than 45 cN. In some embodiments, the MS is greater than 50 cN.

[0180] In various embodiments, the ethylene-based polymer has a melt viscosity ratio (V) at 190° C. greater than 25. 0.1 / V 100 In some embodiments, the melt viscosity ratio at 190°C (V 0.1 / V 100 ) is over 30.

[0181] "Melt strength" has units of centinewtons (cN) and is measured using a Rheotens apparatus at 190°C and 2.4 mm / sec. 2 , 120mm from die exit to wheel center, extrusion speed 38.2 seconds -1 , determined by a capillary die with a length of 30 mm, a diameter of 2 mm, and an inlet angle of 180°.

[0182] "Rheology ratio" and "melt viscosity ratio" are V at 190°C. 0.1 / V 100 is defined by V 0.1 is the viscosity of the ethylene-based polymer at 190°C at an angular frequency of 0.1 rad / sec, and V100 is the viscosity of the ethylene-based polymer at 190°C at an angular frequency of 100 rad / sec.

[0183] The long-chain branching polymerization process described in the preceding section is utilized for the polymerization of olefins, primarily ethylene. In some embodiments, only a single type of olefin, or α-olefin, is present in the polymerization scheme, essentially creating a homopolymer with a small amount of incorporated diene comonomer. However, additional α-olefins may be incorporated into the polymerization procedure. The additional α-olefin comonomer typically 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, 4-methyl-1-pentene, and ethylidene norbornene. For example, 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.

[0184] Long-chain branched polymers, such as homopolymers and / or interpolymers (including copolymers) of ethylene and, optionally, one or more comonomers such as α-olefins, can contain at least 50 mole percent ethylene-derived units. All individual values ​​and subranges encompassed by "at least 50 mole percent" are disclosed herein as separate embodiments; for example, an ethylene-based polymer, a homopolymer and / or interpolymer (including copolymer) of ethylene, and optional one or more comonomers such as α-olefins, can contain at least 60 mole percent ethylene-derived units, at least 70 mole percent ethylene-derived units, at least 80 mole percent ethylene-derived units, or from 50 to 100 mole percent ethylene-derived units, or from 80 to 100 mole percent ethylene-derived units.

[0185] In some embodiments of the ethylene-based polymer, the ethylene-based polymer comprises an additional α-olefin. The amount of additional α-olefin in the ethylene-based polymer is 50 mole percent (mol %) or less, in other embodiments the amount of additional α-olefin is at least 0.01 mol % to 25 mol %, and in further embodiments the amount of additional α-olefin is at least 0.1 mol % to 10 mol %. In some embodiments, the additional α-olefin is 1-octene.

[0186] In some embodiments, the long-chain branched polymer can comprise at least 50 mole percent ethylene-derived units. All individual values ​​and subranges from at least 90 mole percent are included herein and disclosed herein as separate embodiments. For example, the ethylene-based polymer can comprise at least 93 mole percent ethylene-derived units, at least 96 mole percent units, at least 97 mole percent ethylene-derived units, or alternatively, 90 to 100 mole percent ethylene-derived units, 90 to 99.5 mole percent ethylene-derived units, or 97 to 99.5 mole percent ethylene-derived units.

[0187] In some embodiments of the long-chain branched polymer, the amount of additional α-olefin is less than 50%, in other embodiments at least 1 mole percent (mol %) to 20 mol %, and in further embodiments at least 5 mol % to 10 mol %. In some embodiments, the additional α-olefin is 1-octene.

[0188] Any conventional polymerization process may be used to produce the long-chain branched polymer, including, but not limited to, a solution polymerization process, a gas phase polymerization process, a slurry phase polymerization process, and combinations thereof, using one or more conventional reactors, such as loop reactors, isothermal reactors, fluidized bed gas phase reactors, stirred tank reactors, batch reactors, etc., in parallel, in series, or any combination thereof.

[0189] In one embodiment, an ethylene-based polymer can be produced by solution polymerization in a dual 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 catalyst system described herein and, optionally, one or more cocatalysts. In another embodiment, an ethylene-based polymer can be produced by solution polymerization 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 presence of a catalyst system described herein and herein and, optionally, one or more other catalysts. The catalyst system described herein, optionally in combination with one or more other catalysts, can be used in the first reactor or the second reactor. In one embodiment, an ethylene-based polymer can be produced by solution polymerization in a dual reactor system, e.g., a dual loop reactor system, where ethylene and, optionally, one or more α-olefins are polymerized in both reactors in the presence of a catalyst system described herein.

[0190] In another embodiment, long-chain branched polymers can be produced by solution polymerization in a single reactor system, for example a single loop reactor system, where ethylene and optionally one or more α-olefins are polymerized in the presence of a catalyst system described herein and optionally one or more co-catalysts described in the preceding section. In some embodiments, a long-chain branching polymerization process to produce long-chain branched polymers comprises polymerizing ethylene and optionally at least one additional α-olefin in the presence of a catalyst system.

[0191] The long-chain branched polymer 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 ethylene-based polymer may comprise any amount of additives. The ethylene-based polymer may comprise from about 0 to about 10 percent by weight of such additives, based on the weight of the ethylene-based polymer and the one or more additives. The ethylene-based polymer may further comprise a filler, which may include, but is not limited to, organic or inorganic fillers. The long-chain branched polymer may contain from about 0 to about 20 percent by weight of a filler, such as calcium carbonate, talc, or Mg(OH)2, based on the total weight of the ethylene-based polymer and all additives or fillers. The ethylene-based polymer may be further compounded with one or more polymers to form a blend.

[0192] In some embodiments, a polymerization process for producing a long-chain branched polymer can include polymerizing ethylene and at least one additional α-olefin in the presence of a catalyst having two polymer-forming sites. The long-chain branched polymer obtained from such a catalyst system having two polymer-forming sites has a molecular weight of, for example, 0.850 g / cm according to ASTM D792 (which is incorporated herein by reference in its entirety). 3 ~0.960g / cm 3 , 0.880g / cm 3 ~0.920g / cm 3 , 0.880g / cm 3 ~0.910g / cm 3 , or 0.880 g / cm 3 ~0.900g / cm 3 The density may be

[0193] In another embodiment, the long chain branched polymer resulting from the long chain polymerization process has a melt flow ratio (I 10 / I2), where the melt index I2 is measured at 190°C and a load of 2.16 kg according to ASTM D1238 (which is incorporated herein by reference in its entirety), and the melt index I 10 is measured according to ASTM D1238 at 190°C and a load of 10 kg. In other embodiments, the melt flow ratio (I 10 In some, the melt flow ratio is 5-25, and in others, the melt flow ratio is 5-9.

[0194] In some embodiments, the long chain branched polymer obtained from the long chain polymerization process may have a molecular weight distribution (MWD) of 1 to 20, where MWD is the molecular weight distribution of the long chain branched polymer. w / M n is defined as, and M is measured using light scattering. w is the weight average molecular weight, and M n is the number average molecular weight. In another embodiment, the polymer resulting from the catalyst system has an MWD of 1 to 10. Another embodiment includes an MWD of 1 to 3, and another embodiment includes an MWD of 1.5 to 2.5.

[0195] Gel Permeation Chromatography (GPC) (Traditional GPC) The chromatographic system consisted of a PolymerChar GPC-IR (Valencia, Spain) high-temperature GPC chromatograph equipped with an internal IR5 infrared detector (IR5) and a four-capillary viscometer (DV) coupled to a Precision Detectors (now Agilent Technologies) two-angle laser light scattering (LS) detector model 2040. For all absolute light scattering measurements, a 15-degree angle was used. The autosampler oven compartment was set to 160°C, and the column compartment was 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, which contained 200 ppm butylated hydroxytoluene (BHT). The solvent source was nitrogen sparged. The injection volume used was 200 microliters, and the flow rate was 1.0 milliliters / min.

[0196] Calibration of the GPC column set was performed using at least 20 narrow molecular weight distribution polystyrene standards ranging from 580 to 8,400,000, arranged in six "cocktail" mixtures with at least 10 molecular weight intervals between each standard. Standards were purchased from Agilent Technologies. Polystyrene standards were prepared at 0.025 grams in 50 milliliters of solvent for molecular weights above 1,000,000 and 0.05 grams in 50 milliliters of solvent for molecular weights below 1,000,000. The polystyrene standards were dissolved at 80°C for 30 minutes with gentle agitation. The polystyrene standard peak molecular weights were converted to polyethylene molecular weights using Equation 33 (as described in Williams and Ward, J. Polym. Sci., Polym. Let., 6, 621 (1968)). M ポリエチレン =A×(M ポリスチレン ) B (33) where M is the molecular weight, A has a value of 0.4315, and B is equal to 1.0.

[0197] A polynomial between third and fifth order was used to fit each polyethylene-equivalent calibration point. A small adjustment (approximately 0.415 to 0.44) was made to A to correct for column resolution and band broadening effects, such that the NIST standard NBS 1475 is obtained at 52,000 MW.

[0198] Total plate counts for the GPC column set were performed using eicosane (prepared at 0.04 g in 50 milliliters of TCB and dissolved for 20 minutes with gentle agitation). Plate counts (Equation 34) and symmetry (Equation 35) were measured with a 200 microliter injection according to the following equations:

[0199]

number

[0200]

number

[0201] Samples were prepared in a semi-automated fashion using PolymerChar "Instrument Control" software, with a target sample weight of 2 mg / ml, by adding the solvent (containing 200 ppm BHT) via a PolymerChar high-temperature autosampler to a pre-nitrogen-sparged septa-capped vial. Samples were dissolved at 160°C with "slow" shaking for 2 hours.

[0202] M n(GPC) , M w(GPC) , and M z(GPC) The calculation was based on GPC results using the internal IR5 detector (measurement channel) of a PolymerChar GPC-IR chromatograph according to Equations 36-38 using PolymerChar GPCOne™ software, baseline-subtracted IR chromatograms at equally spaced data collection points (i), and polyethylene equivalent molecular weights obtained from a narrow standard calibration curve at point (i).

[0203]

number

[0204] To monitor deviations over time, a flow rate marker (decane) was introduced into each sample via a micropump controlled by the PolymerChar GPC-IR system. This flow rate marker (FM) was used to linearly correct the pump flow rate (flow rate (apparent)) for each sample by aligning the RV of each decane peak in the sample (RV (FM sample)) with that of the decane peak in the narrow standard calibration (RV (FM calibrated)). Any change in the time of the decane marker peak is thus assumed to be related to a linear shift in flow rate (flow rate (effective)) throughout the run. To maximize the accuracy of the RV measurements of the flow rate marker peaks, a least-squares fitting routine was used to fit the peaks in the flow rate marker concentration chromatogram to a quadratic equation. The first derivative of the quadratic equation was then used to determine the true peak position. After calibrating the system based on the flow rate marker peaks, the effective flow rate (relative to the narrow standard calibration) was calculated as shown in Equation 26. Processing of the flow rate marker peaks was performed via PolymerChar GPCOne™ software. The allowable flow correction is to ensure that the effective flow is within + / - 2% of the apparent flow. Flow rate (effective) = Flow rate (apparent) * (RV (FM較正済み) / RV (FM試料) ) (39)

[0205] Triple detector GPC (TDGPC) (absolute GPC) The chromatographic system, analytical conditions, column set, column calibration and calculation and distribution of conventional molecular weight moments were performed according to the methods described in Gel Permeation Chromatography (GPC).

[0206] Regarding the determination of the viscometer and light scattering detector offsets from the IR5 detector, a systematic approach for the determination of multi-detector offsets was performed 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)), which was performed using PolymerChar GPCOne™ software to measure the offsets of broad homopolymer polyethylene standards (M w / M n The triple detector log(MW and IV) results from the narrow standard column calibration curve are optimized to the narrow standard column calibration results from the narrow standard calibration curve.

[0207] Molecular weight data are obtained using PolymerChar GPCOne™ 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 overall injection concentration used in determining molecular weight is 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. Calculated molecular weights (using GPCOne™) are 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 described below. Generally, the mass detector response (IR5) and light scattering constant (determined using GPCOne™) can be determined from linear standards having molecular weights greater than about 50,000 g / mol. Viscometer calibration (determined using GPCOne™) can be achieved using the method described by the manufacturer, or alternatively, using published values ​​of suitable linear standards, such as Standard Reference Material (SRM) 1475a (available from the National Institute of Standards and Technology (NIST)). A viscometer constant (obtained using GPCOne™) is calculated, relating the specific viscosity area (DV) and injected mass for the calibration standard to its intrinsic viscosity. Chromatographic concentrations are assumed to be low enough to preclude addressing second viral coefficient effects (concentration effects on molecular weight).

[0208] Absolute weight average molecular weight (M w(Abs) ) is obtained (using GPCOne™) by dividing the area-integrated light scattering (LS) chromatogram (factored by the light scattering constant) by the mass recovered from the mass constant and mass detector (IR5) area. The molecular weight and intrinsic viscosity responses are linearly extrapolated (using GPCOne™) at the chromatographic end where the signal-to-noise is low. Each of the other moments, M n(Abs) and Mz(Abs) is calculated according to equations 40-41 as follows:

[0209]

number

[0210] Dynamic Mechanical Spectroscopy (or Small Angle Oscillatory Shear) Complex viscosity (η * The elastic modulus (G', G''), tangent delta, and phase angle (δ) are obtained by dynamic oscillatory frequency sweep testing at 190 °C in the frequency range of 0.1 to 100 rad / s. The strain level is set within the linear viscoelastic regime, as determined by strain sweep testing at 100 rad / s and 190 °C. Testing is performed on 25 mm diameter stainless steel parallel plates on a strain-controlled rheometer, ARES-G2, from TA Instruments. Prior to the actual testing, 3.3 mm thick samples are drawn and then trimmed in two steps. In the first step, the sample is melted for 2.5 minutes, drawn to a 3 mm gap, and trimmed. After an additional 2.5 minutes of soaking time at 190 °C, the sample is drawn to a 2 mm gap and excess material is trimmed. This method incorporates an additional 5 minutes of delay to allow the system to reach thermal equilibrium. Testing is performed under a nitrogen atmosphere.

[0211] Batch Reactor Polymerization Procedure Batch reactor polymerization reactions are carried out in a 2 L Parr™ batch reactor. The reactor is heated by an electric heating mantle and cooled by an internal serpentine cooling coil containing cooling water. Both the reactor and the heating / cooling system are controlled and monitored by a Camile™ TG process computer. The bottom of the reactor is fitted with a dump valve that transfers the reactor contents to a stainless steel dump pot. The dump pot is pre-filled with a catalyst deactivation solution (typically 5 mL of an Irgafos / Irganox / toluene mixture). Both the pot and the tank are purged with nitrogen, and the dump pot is vented to a 30-gallon blowdown tank. All solvents used for polymerization or catalyst make-up are passed through a solvent purification column to remove any impurities that may affect the polymerization. 1-Octene and Isopar E are passed through two columns: the first column contains A2 alumina, and the second column contains Q5. Ethylene is passed through two columns, the first containing A204 alumina and 4 Å molecular sieves, the second containing Q5. N2, used for transport, is passed through a single column containing A204 alumina, 4 Å molecular sieves, and Q5.

[0212] The reactor is initially charged from a shot tank, which may contain IsoparE solvent and / or 1-octene, depending on the reactor load. The shot tank is filled to the load setpoint using a lab scale equipped with a shot tank. After the addition of the liquid feed, the reactor is heated to the polymerization temperature setpoint. If ethylene is used, it is added to the reactor at the reaction temperature to maintain the reaction pressure setpoint. The amount of ethylene added is monitored by a Micro Motion flow meter. In some experiments, the standard conditions at 150°C are 25 g ethylene, 22 g 1-octene, and 240 psi hydrogen in 575 g IsoparE; in other experiments, the standard conditions at 150°C are 22 g ethylene, no 1-octene, and 192 psi hydrogen in 602 g IsoparE.

[0213] The procatalyst and activator are mixed with an appropriate amount of purified toluene to obtain a solution of the desired molar concentration. The procatalyst and activator are processed in an inert glovebox, drawn into a syringe, and pressure-transferred into a catalyst shot tank. The syringe is rinsed three times with 5 mL of toluene. Immediately after the catalyst is added, a run timer is started. If ethylene is used, it is added by Camile to maintain the reaction pressure set point in the reactor. The polymerization reaction is run for 10 minutes, then the agitator is stopped, the bottom dump valve is opened, and the reactor contents are transferred to a dump pot. The dump pot contents are poured into a tray and placed in a lab hood, where the solvent is allowed to evaporate overnight. The tray containing the remaining polymer is transferred to a vacuum oven and heated to 140 °C under vacuum to remove any remaining solvent. After the tray cools to ambient temperature, the polymer yield is measured to determine efficiency and the polymer is subjected to polymer testing. [Example]

[0214] Bimodal ladder branching using two catalysts Bimodal polymers were produced using a double-chain catalyst (catalyst 1) {(a) Figueroa, R.; Froese, R.D.; He, Y.; Klosin, J.; Theriault, C.N.; Abboud, K.A. Organometallics 2011, 30, 1695-1709, (b) Froese, R.D.; Jazdzewski, B.A.; Klosin, J.; Kuhlman, R.L.; Theriault, C.N.; Welsh, D.M.; Abboud, K.A. Organometallics 2011, 30, 251-262.} and single-chain catalysts (catalysts 2, 3, and 4). The dienes used were 1,4-pentadiene (pentadiene) and dimethyldivinylsilane (divinylsilane).

[0215] [ka]

[0216] The comparative examples include polymerization reactions involving single double-chain catalyst only experiments, such as Comparative Examples 1-C19, 1-C20, and 1-C21, as well as polymerization reactions excluding dienes (1-C1, 1-C2). Procedures for preparing the comparative examples can be found in International Application Nos. PTCUS 2019 / 053524, 2019 / 053527, 2019 / 053529, 2019 / 053537, 2019 / 053537, all of which are incorporated herein by reference.

[0217] In each example containing a diene, the amount of diene incorporated into the reactor was small compared to the other reactants in the reactor, and therefore the addition of the diene did not affect the amount of comonomer, ethylene, and solvent added to the reactor.

[0218] [Table 2] 0.1 μmol of catalyst 2, 10 μmol of MMAO-3A, ​​25 g of ethylene, T=150°C, activator: methyldi(C 18 H 37 ) Ammonium tetrakis(pentafluorophenyl)borate.

[0219] [Table 3] 10 μmol of MMAO-3A, ​​14 g of ethylene, T = 150 °C, activator: methyldi(C 18 H 37 ) Ammonium tetrakis(pentafluorophenyl)

[0220] [Table 4]

[0221] [Table 5]

[0222] [Table 6] MI estimated from viscosity: MI=10^^{4.7435-0.88267 * Log(V 0.1 )-0.40245 * Log(V 100 )}

[0223] [Table 7] 1 log(η) at log(M) where the polymer weight fraction is 0.03. 2 Average of log(η) measurements for the lowest five weight fractions of polymer above 0.03. 3 The difference between the value in footnote 1 and the standard, log(η) = -3.4 + 0.73 log(M). 4 The difference between the value in footnote 2 and the standard, log(η) = -3.4 + 0.73log(M).

[0224] Comparative Examples 1-C19, 1-C20, and 1-C21 do not have ladder characteristics (L) within the claimed range for the low MW fractions. Non-diene comparative examples (1-C1, 1-C2) do not have ladder characteristics (L) within the claimed values ​​for the high MW fractions.

[0225] [Table 8] 0.1 μmol of catalyst 2, 10 μmol of MMAO-3A, ​​25 g of ethylene, 22 g of octene, 580 g of IsoParE, T=150°C, activator: methyldi(C 18 H 37 ) Ammonium tetrakis(pentafluorophenyl)borate.

[0226] [Table 9]

[0227] [Table 10] MI estimated from viscosity: MI=10^^{4.7435-0.88267 * Log(V 0.1 )-0.40245 * Log(V 100 )}

[0228] Tables 8, 9, and 10 collect examples of bimodal polymers with small amounts of diene present. The run conditions are provided in Table 8, and the MW and comonomer incorporation data are collected in Table 9. Table 10 provides the shear and extensional rheology, including melt strength and melt index values. Melt strength is one of the important values, as this number relates to bubble stability on a blown film line.

[0229] Table 8 provides a design of experiment in which varying the amount of catalyst 1, added hydrogen, and added diene (pentadiene) affect the melt index. One skilled in the art knows how these conditions generally affect MI and MS: i) since catalyst 1 is the high MW fraction, the higher the amount of catalyst 1, the greater the weight fraction of the high MW fraction and therefore the lower the MI; ii) the lower the hydrogen, the lower the total MW and the higher the MI; and iii) the more diene converted, the more LCBs in the ladder fraction and the lower the MI. Because the three parameters are changed, the MI and MS also change, as shown in Table 10.

[0230] A simple linear least-squares fit of the three parameters, amount of catalyst 1 (µmol), hydrogen (psi), and amount of diene added (g), can be used to fit the MS for runs containing pentadiene (Figure 13). MS = 185.3 * catalyst 1 (μmol) - 0.48 * H2 (psi) + 204.4 * pentadiene (g) + 24.48 (42)

[0231] As expected, higher catalyst 1 loadings, lower hydrogen, and higher pentadiene lead to higher melt strengths.

[0232] Table 11 shows the reactor conditions for the polymerization reactions of entries 1-35 and 1-36. For entries 1-35, the polymerization reaction includes catalyst 1, a dual-chain catalyst, and catalyst 3, a single-chain catalyst. For entries 1-36, the polymerization reaction includes catalyst 1, a dual-chain catalyst, and catalyst 4, a single-chain catalyst.

[0233] [Table 11] Activator: Methyldi(C 18 H 37 ) Ammonium tetrakis(pentafluorophenyl)borate, 10 μmol of MMAO-3, diene:pentadiene

[0234] [Table 12]

[0235] [Table 13]

[0236] [Table 14]

[0237] MI estimated from viscosity: MI=10^{4.7435-0.88267 * Log(V 0.1 )-0.40245 * Log(V 100 )}

[0238] Figure 14 shows a plot of MS vs. MI for 15 autoclave and tubular LDPE resins (DOW™ LDPE PG7004, DOW™ LDPE 770G, DOW™ LDPE 6621, DOW™ LDPE 310E, DOW™ LDPE 410E, DOW™ LDPE 450E, DOW™ LDPE 751A, DOW™ LDPE 421E, DOW™ LDPE 7481, DOW™ LDPE 50041, DOW™ LDPE 4005, DOW™ LDPE 722, AGILITY™ EC 7220, AGILITY™ EC 7000, DOW™ LDPE 320E). Generally, these follow a pattern where low MI values ​​result in high melt strength values. The upper melt strength limit is 30 cN. LDPE falls below the line drawn on the curve.

[0239] Figure 15 shows plots of MS vs. MI for ladder polymers and LDPE resins. Bimodal ladder technology can achieve MI / MS relationships that lie above the LDPE limit (line).

[0240] It will be apparent to those skilled in the art that various modifications can be made to the described embodiments without departing from the spirit and scope of the claimed subject matter. Thus, it is intended that this specification cover modifications and variations of the described embodiments provided that such modifications and variations come within the scope of the appended claims and their equivalents. The present invention includes the following aspects. [1] 1. An ethylene-based polymer comprising: Both contain polymerized units of ethylene, one or more dienes, and optionally one or more C 3 ~C 12 a low molecular weight polymer fraction derived from an α-olefin and a high molecular weight polymer; The low molecular weight fraction and the high molecular weight fraction are separated by S on a molecular weight distribution (MWD) curve determined by absolute gel permeation chromatography. max is divided by S max is the maximum absolute slope on the high molecular weight side of the main peak of the MWD curve, the main peak being the peak of greatest magnitude in the MWD curve; The low molecular weight polymer fraction and the high molecular weight polymer fraction each follow the Mark-Hwink-Sakurada curve, log[η]=log(β)+αlog(M)−L * including a ladder characteristic L defined for a given absolute molecular weight (MW) as a curve fit of the log of intrinsic viscosity [η] versus the log of absolute MW (M) using the equation α log(2), where log(β) is the intercept and α is the slope; The low molecular weight polymer fraction is S max All L values ​​are between -0.35 and 0.35. The high molecular weight polymer fraction is S max and a maximum L value of 0.8 to 1.5. [2] 2. The ethylene-based polymer according to claim 1, wherein the diene is non-conjugated. [3] 3. The ethylene-based polymer according to claim 2, wherein the diene is acyclic. [4] 4. The ethylene-based polymer of claim 3, wherein the diene comprises 1,4-pentadiene, 1,5-hexadiene, 1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, 1,10-undecadiene, 1,11-dodecadiene, dimethyldivinylsilane, dimethyldiallylsilane, or dimethylallylvinylsilane. [5] 5. The ethylene-based polymer according to any one of claims 1 to 4, wherein the high-molecular-weight polymer fraction comprises 0.5 to 30% by weight of the polymer. [6] 6. The ethylene-based polymer according to claim 5, wherein the high-molecular-weight polymer fraction comprises 1 to 15% by weight of the polymer. [7] 7. The ethylene-based polymer according to any one of Inventions 1 to 6, wherein all of the low-molecular-weight polymer fractions have an L value of −0.2 to 0.2. [8] 8. The ethylene-based polymer according to any one of Inventions 1 to 7, wherein the high-molecular-weight polymer fraction has a maximum value of L of 0.9 to 1.1. [9] The ethylene-based polymer has an MWD area metric, A TAIL and has a molecular weight tail quantified by A TAIL is greater than 0.06 as determined by gel permeation chromatography using a triple detector.

[10] A TAIL 10. The ethylene-based polymer of claim 9, wherein

[11] A TAIL 11. The ethylene-based polymer according to claim 10, wherein

[12] 12. The ethylene-based polymer of any one of claims 1-11, wherein the ethylene-based polymer has an average g' greater than 0.86, where average g' is the intrinsic viscosity ratio determined by gel permeation chromatography using a triple detector.

[13] 13. The ethylene-based polymer of claim 12, wherein the average g′ is greater than 0.88.

[14] 14. The ethylene-based polymer of claim 13, wherein the average g′ is greater than 0.90.

[15] The ethylene-based polymer has a weight average molecular weight (M) of 250,000 daltons or less as determined by absolute gel permeation chromatography. w 15. The ethylene-based polymer according to any one of Inventions 1 to 14, wherein

[16] The ethylene-based polymer has a weight average molecular weight (M) of 150,000 daltons or less as determined by absolute gel permeation chromatography. w 16. The ethylene-based polymer according to claim 15, wherein

[17] The ethylene-based polymer has a weight average molecular weight (M) of 100,000 daltons or less as determined by absolute gel permeation chromatography. w 17. The ethylene-based polymer according to claim 16, wherein

[18] 18. The ethylene-based polymer of any one of claims 1 to 17, wherein the MI is greater than 0.1, where MI is the melt index in g / 10 min according to ASTM D1238.

[19] 19. The ethylene-based polymer of invention 18, wherein the MI is greater than 1, where MI is melt index in g / 10 min according to ASTM D1238.

[20] 20. The ethylene-based polymer of claim 19, wherein the MI is greater than 2, where MI is melt index in g / 10 min according to ASTM D1238.

Claims

1. 1. An ethylene-based polymer comprising: Both contain polymerized units of ethylene, one or more dienes, and optionally one or more C ３ ~C １２ a low molecular weight polymer fraction derived from an α-olefin and a high molecular weight polymer fraction; The low molecular weight polymer fraction and the high molecular weight polymer fraction are separated by an S on a molecular weight distribution (MWD) curve determined by absolute gel permeation chromatography. ｍａｘ Then, S ｍａｘ is the maximum absolute slope on the high molecular weight side of the main peak of the MWD curve, the main peak being the peak with the largest magnitude in the MWD curve; The low molecular weight polymer fraction and the high molecular weight polymer fraction each follow the Mark-Hwink-Sakurada curve, as expressed by the equation: log[η]=log(β)+αlog(M)−L ＊ including a ladder characteristic L defined for a given absolute molecular weight (MW) as a curve fit of the log of intrinsic viscosity [η] versus the log of absolute MW (M) using the equation α log(2), where log(β) is the intercept and α is the slope; The low molecular weight polymer fraction is S ｍａｘ and all L values ​​are between -0.35 and 0.35; The high molecular weight polymer fraction is S ｍａｘ and a maximum L value of 0.8 to 1.5; An ethylene-based polymer wherein the diene is non-conjugated and acyclic.

2. 2. The ethylene-based polymer of claim 1, wherein the diene comprises 1,4-pentadiene, 1,5-hexadiene, 1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, 1,10-undecadiene, 1,11-dodecadiene, dimethyldivinylsilane, dimethyldiallylsilane, dimethylallylvinylsilane.

3. 3. The ethylene-based polymer of claim 1 or 2, wherein the high molecular weight polymer fraction comprises from 0.5 to 30 weight percent of the polymer.

4. 4. The ethylene-based polymer of claim 3, wherein the high molecular weight polymer fraction comprises 1 to 15 weight percent of the polymer.

5. The ethylene-based polymer of any one of claims 1 to 4, wherein all of the low molecular weight polymer fractions have L values ​​from -0.2 to 0.

2.

6. 6. The ethylene-based polymer of any one of claims 1 to 5, wherein the high molecular weight polymer fraction has a maximum L of from 0.9 to 1.

1.

7. The ethylene-based polymer has a MWD area metric, A ＴＡＩＬ and has a molecular weight tail quantified by A ＴＡＩＬ 7. The ethylene-based polymer of any one of claims 1 to 6, wherein M is greater than 0.06 as determined by gel permeation chromatography using a triple detector.

8. A ＴＡＩＬ 8. The ethylene-based polymer of claim 7, wherein:

9. A ＴＡＩＬ 9. The ethylene-based polymer of claim 8, wherein:

10. 10. The ethylene-based polymer of any one of claims 1-9, wherein the ethylene-based polymer has an average g' greater than 0.86, where average g' is the intrinsic viscosity ratio determined by gel permeation chromatography using a triple detector.

11. 11. The ethylene-based polymer of claim 10, wherein the average g' is greater than 0.

88.

12. 12. The ethylene-based polymer of claim 11, wherein the average g' is greater than 0.

90.

13. The ethylene-based polymer has a weight average molecular weight (M) of 250,000 Daltons or less as determined by absolute gel permeation chromatography. ｗ The ethylene-based polymer of any one of claims 1 to 12, having a

14. The ethylene-based polymer has a weight average molecular weight (M) of 150,000 daltons or less as determined by absolute gel permeation chromatography. ｗ 14. The ethylene-based polymer of claim 13 having

15. The ethylene-based polymer has a weight average molecular weight (M) of 100,000 Daltons or less as determined by absolute gel permeation chromatography. ｗ 15. The ethylene-based polymer of claim 14 having a 16. The ethylene-based polymer of any one of claims 1-15, having a MI greater than 0.1, where MI is melt index in g / 10 min according to ASTM D1238.

17. 17. The ethylene-based polymer of claim 16, wherein the MI is greater than 1, where MI is melt index in g / 10 min according to ASTM D1238.

18. 20. The ethylene-based polymer of claim 17, wherein the MI is greater than 2, where MI is melt index in g / 10 min according to ASTM D1238.

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