Long chain branched ethylene-based polymers

Abstract

Embodiments of the present disclosure relate to ethylene-based polymers. The ethylene-based polymer is a polymerized unit derived from ethylene, diene and optionally one or more C3-C12 alpha olefins. The ethylene-based polymer includes a melt viscosity ratio (V0.1 / V100) greater than 20 at 190°C. V0.1 is the viscosity of ethylene-based polymers at a frequency of 0.1 radians / second at 190°C, and V100 is the viscosity of ethylene-based polymers at a frequency of 100 radians / second at 190°C. In addition, the ethylene-based polymer includes an average g', the average g' is greater than 0.86, wherein the average g' is the intrinsic viscosity ratio determined by gel permeation chromatography using a triple detector.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims priority to U.S. Provisional Patent Application No. 63 / 000,949, filed on March 27, 2020, the entire disclosure of which is hereby incorporated by reference. Technical Field

[0003] Embodiments of the present disclosure are generally directed to polymer compositions having long chain branching and methods of synthesizing ethylene-based polymer compositions. Background Art

[0004] Ethylene-based polymers, such as polyethylene polymers, are produced by various catalyst systems. The selection of such catalyst systems used in the polymerization process of ethylene-based polymers is an important factor that contributes to the characteristics and properties of such ethylene-based polymers.

[0005] Ethylene-based polymers are manufactured for various articles. The polymerization process can be varied in many ways to produce a variety of resulting polymer resins with different physical properties, making various resins suitable for different applications. The effect of branching on the properties of ethylene-based polymers depends on the length and amount of the branches. For example, short chain branching affects the physical properties of the ethylene-based polymer. Short chain branches mainly affect mechanical properties and thermal properties. As the frequency of short chain branching increases, the ability of the polymer to form lamellar crystals decreases, and mechanical properties and thermal properties decrease. A small amount of long chain branching can significantly change the polymer processing properties.

[0006] To form long chain branching (LCB), the vinyl group or terminal double bond of a polymer chain is incorporated into a new polymer chain. Reincorporation of a vinyl terminated polymer and introduction of a diene comonomer are two mechanisms for incorporating a vinyl group on a polymer chain into a second polymer chain. Additionally, long chain branching is caused by free radicals. It is difficult to control the amount of branching in all three mechanisms. When free radicals or dienes are used to initiate long chain branching, the branching may become too much, causing gelation and reactor fouling. The reincorporation mechanism does not produce much branching, and branching can only occur after the polymer chain is created, further limiting the amount of branching that can occur.

[0007] Increased amounts of long chain branching (LCB) provide an increase in melt processing characteristics. Long chain branched materials (e.g., low density polyethylene, LDPE) are added to LLDPE as a processing aid. Typically, LDPE has good processing characteristics, but films made from it have poor physical properties, such as tear or dart strength. Films made from linear low density polyethylene (LLDPE) have good physical properties, such as tear or dart strength, but cannot be processed effectively. A certain amount of LDPE needs to be blended for processing (melt strength, shear thinning), but these reduce the physical properties of LLDPE films. When blending LLDPE and LDPE, researchers balance processability and physical properties, never achieving ideal values ​​for both. Summary of the invention

[0008] There is a need to produce polymer compositions having high melt strength as indicated by melt index and normal to low viscosity, which provides better processability but allows polymer formation in the reactor without fouling. Accordingly, the processes and ethylene-based polymers of the present disclosure seek to form long chain branching without gelling the ethylene-based polymer or fouling the reactor.

[0009] Embodiments of the present disclosure relate to ethylene-based polymers. The ethylene-based polymers are derived from ethylene, a diene, and optionally one or more C3-C 12 The ethylene-based polymer comprises a melt viscosity ratio (V) greater than 20 at 190°C. 0.1 / V 100 ). 0.1 is the viscosity of the ethylene-based polymer at 190°C at a frequency of 0.1 rad / s, and V 100 is the viscosity of the ethylene-based polymer at 190° C. at a frequency of 100 rad / sec. Additionally, the ethylene-based polymer comprises an average g′ greater than 0.86, wherein the average g′ is an intrinsic viscosity ratio as measured by gel permeation chromatography using a triple detector.

[0010] In some embodiments of the present disclosure, the ethylene-based polymer is derived from ethylene, a diene, and one or more C3-C 12 The polymerized units of alpha-olefins. The ethylene-based polymer comprises a melt strength greater than 10 cN (Rheotens device, 190°C, 2.4 mm / s 2 , from die outlet to wheel center is 120mm, extrusion rate is 38.2s -1 , capillary die length of 30 mm, diameter of 2 mm and entry angle of 180°). In addition, the ethylene-based polymer includes an average g' greater than 0.86. Average g' is the intrinsic viscosity ratio determined by gel permeation chromatography using a triple detector. BRIEF DESCRIPTION OF THE DRAWINGS

[0011] Figure 1 It is a graphical depiction of the molecular weight of a polymer as the number of branching methine groups per 1000 carbons increases.

[0012] Figure 2 is a graphical model for the predicted dependence of the molecular weight distribution (MWD) curve on the level of branching.

[0013] Figure 3 The molecular weight distribution (MWD) curves of the dual catalyst bimodal ethylene-based polymer distribution with and without diene.

[0014] Figure 4 It is a conventional long chain branched (FCB) polymer and FDPE, especially DOW TM Mark-Horwin-Sakurada diagram of LDPE 6621.

[0015] Figure 5 is a representation of an ethylene-based ladder polymer in which the polymer backbone is depicted as a solid line and the long chain branches are depicted by dashed lines. This representation provides a visual depiction of the molecular weight differences calculated by conventional standards to the absolute weight average molecular weight (MW) of the long chain branched polymers of the present disclosure.

[0016] Figure 6 is a Mark-Horwin-Sakurada diagram showing the definitions of parameters and variables in a Mark-Horwin-Sakurada diagram that characterizes the long chain branched polymers of the present disclosure.

[0017] Figure 7 is a Mark-Horwin-Sakurada plot for 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.

[0018] Figure 8 is a graph showing a plot of intrinsic viscosity and intrinsic viscosity slope as a function of absolute MW for Examples 3-8.

[0019] Fig. 9 The trapezoidal characteristics L of Examples 3-8 are shown as a function of absolute Mw.

[0020] Fig.10 is a trapezoidal feature of the bimodal embodiment in S 最大 Before (left) and after (right) plots as a function of log(M).

[0021] Fig.11 The trapezoidal characteristics of the comparative example are in S 最大 Before (left) and after (right) plots as a function of log(M).

[0022] Fig.12 is a graph of the absolute molecular weight distribution (MWD) curve showing how the point of maximum slope is used to define the high MWD tail area measure.

[0023] Fig.13 is a graph including a three parameter linear least squares fit of melt strength versus Catalyst 1 loading, hydrogen, and diene.

[0024] Fig.14 is a graph of melt strength versus melt index (MI) for autoclave and tubular LDPE.

[0025] Fig.15 is a plot of melt strength versus melt index (MI) for tetrafunctional long chain branched polymers and comparative LDPE resins. DETAILED DESCRIPTION

[0026] The specific embodiments of the method for synthesizing polymers and the polymers synthesized by the method of the present disclosure will now be described. It should be understood that the method for synthesizing polymers disclosed herein can be embodied in different forms and should not be construed as being limited to the specific embodiments set forth in the present disclosure. On the contrary, embodiments are provided so that the present disclosure will be thorough and complete, and the embodiments will fully convey the scope of the subject matter to those skilled in the art.

[0027] definition

[0028] As used herein, "multimodal" means a composition that can be characterized by having at least two (2) polymer fractions with varying densities and weight-average molecular weights, and optionally can also have different melt index values. In one embodiment, multimodal can be defined by having at least two different peaks in a gel permeation chromatography (GPC) chromatogram showing molecular weight distribution. Specifically, in the present embodiment, GPC measurements are calculated by absolute GPC. In another embodiment, multimodal can be defined by having at least three different peaks in a crystallization elution fractionation (CEF) chromatogram showing short chain branching distribution. Multimodal includes resins with three peaks and resins with more than three peaks.

[0029] The term "bimodal polymer" means a multimodal ethylene-based polymer having two main 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.

[0030] The term "trimodal polymer" means a multimodal ethylene-based polymer having three main fractions: a first ethylene-based polymer fraction, a second ethylene-based polymer fraction and a third ethylene-based polymer fraction.

[0031] The term "polymer" refers to a polymeric compound prepared by polymerizing monomers (whether of the same or different types). Therefore, the general term polymer encompasses the term "homopolymer" commonly used to refer to polymers prepared from only one type of monomer and "copolymer" referring to polymers prepared from two or more different monomers. The term "interpolymer" as used herein refers to a polymer prepared by the polymerization of at least two different types of monomers. Therefore, the general term interpolymer includes copolymers, and polymers prepared from more than two different types of monomers, such as terpolymers. The term "bimodal polymer" refers to two polymers formed, each polymer being formed by different catalysts.

[0032] "Polyethylene" or "ethylene-based polymer" shall mean a polymer comprising greater than 50 mol% of 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, including linear and substantially linear low density resins (m-LLDPE); medium density polyethylene (MDPE); and high density polyethylene (HDPE).

[0033] The term "diene" refers to a monomer or molecule having two olefinic (double bonds).

[0034] Embodiments of the present disclosure include a method of adding ethylene, at least one diene, optionally at least one C3-C4 hydrocarbon in the presence of at least one multi-chain catalyst, at least one single-chain catalyst, and optionally a solvent. 12 A method for synthesizing long chain branched polymers by copolymerizing alpha-olefin comonomers, wherein the multi-chain catalyst comprises a molecule having multiple polymerization sites.

[0035] The method for synthesizing polymers according to the present disclosure is different from conventional long-chain branching. The term "long-chain branching" refers to a branch having more than 100 carbon atoms. "Branch" refers to a part of a polymer extending from a tertiary site or a quaternary site. When a branch extends from a tertiary site, there are two other branches, which can be a polymer chain together, and the branch extends from the polymer chain. Conventionally, long-chain branching (LCB) can occur naturally during polymerization, as shown in Scheme 1. This can occur by the vinyl end-capping of the polymer chain and the reinsertion of the macromolecular vinyl to produce trifunctional long-chain branches. Depending on the degree of branching, a variety of methods can determine LCB (such as nuclear magnetic resonance (NMR)), or distinguish the role of LCB in a polymer. For example, the role of LCB is observed in the shear flow in van Gurp-Palmen analysis, and the shear viscosity also increases at low angular frequencies, and the increase in the degree of shear-thinning behavior can also be attributed to LCB. In extensional flow, the effect of LCB is usually identified in the degree of hardening (strain hardening) or strength of the melt (melt strength) and the maximum deformation achieved. It is difficult to achieve high levels of native LCB in polymers, i.e. polymers with g' values ​​less than 0.5, due to the limited concentration of vinyl terminated polymer (maximum one per polymer chain) and the need to achieve high ethylene conversion to ensure the formation of LCB. In order to enable a larger amount of vinyl terminated polymer to be reinserted into the second polymer chain, the level of ethylene concentration in the reactor is kept low.

[0036] Scheme 1: Naturally occurring long chain branching: chain transfer events leading to vinyl terminated polymers

[0037] In Scheme 1, "Cat" is the catalyst and "P" is the polymer chain.

[0038] Long chain branching is minimal via naturally occurring branching. One way to enhance natural LCBs is by adding α,ω-dienes to the polymerization system, whether in a free radical, heterogeneous, or homogeneous process. Typically, the diene is added to the polymer chain in a similar manner to the α-olefin, but leaves behind pendant vinyl groups that can be inserted again into the polymer chain to form an LCB, as illustrated in Scheme 2. In general, the diene length does not matter as long as it can link two polymer chains together. In principle, the concentration of pendant vinyl groups can be controlled by the amount of diene added to the reactor. Thus, the extent of LCBs can be controlled by the concentration of pendant vinyl groups.

[0039] Scheme 2: Long-chain branching via diene incorporation

[0040]

[0041] In Scheme 2, "Cat" is the catalyst; "P" is the polymer chain; and the diene in this example is 1,5-hexadiene.

[0042] Conventional methods for incorporating dienes into polymer synthesis systems suffer from the fundamental drawbacks of gel formation or reactor fouling. Kinetic modeling, previously described {Guzman-2010 (JD Guzman, DJ Arriola, T. Karjala, J. Gaubert, BWS Kolthammer, Journal of the American Institute of Chemical Engineers (AIChE) 2010, 56, 1325), Application No. PCTUS2019 / 053524 filed on September 27, 2019; Application No. PCTUS2019 / 053527 filed on September 27, 2019; Application No. PCTUS2019 / 053529 filed on September 27, 2019; and Application No. PCTUS2019 / 053537 filed on September 27, 2019} can provide good predictive results for achieving a better understanding of gel formation. For example, longer polymer chains have more inserted olefins, which have more inserted dienes, which have more side vinyl groups, which means that longer polymer chains will be more likely to reinsert into the catalyst to form LCBs. Therefore, longer polymer chains are preferentially reinsert to form tetrafunctional long chain branches, which are even larger polymer molecules and cause gel problems. As shown in Scheme 2, tetrafunctional LCBs have short segments (the number of carbon atoms between the two double bonds of the diene) that bridge two long chains on each side of the short segment. For polyethylene in a semi-batch reactor at constant pressure, the weight average molecular weight (M) that varies with branching w ) and number average molecular weight (M n ) is shown in the simulation Figure 1 In. Figure 1 In, when M w When M becomes infinite, n Only slightly increased. w At amounts greater than 200,000 grams per mole (g / mol), the polymer gels, coagulates, or reactor fouling occurs.

[0043] The term "gel" or "gelled" refers to a solid composed of at least two components: the first is a three-dimensionally crosslinked polymer, and the second is a medium in which the polymer is not completely soluble. When the polymer gels and is not completely soluble, the reactor may be contaminated with the polymer gel.

[0044] The term "ladder-branched" polymer refers to the tetrafunctional long-chain branched polymer disclosed in this application, and the term "ladder-branching mechanism" refers to how the "ladder-branched" polymer is formed.

[0045] In one or more embodiments of the present disclosure, the method for synthesizing long-chain branched polymers achieves long-chain branching and avoids gel formation or reactor fouling. Without being bound by theory, it is believed that reactor fouling is avoided by reacting two olefins of a diene in a consistent manner on two proximal polymer chains. For example and as shown in Scheme 3, an olefin in a diene reacts before a second olefin, and the second olefin reacts before too many ethylene molecules are added to the polymer chain, thereby eliminating the need for the second olefin to be adjacent to the reaction site. Before inserting many ethylene monomers, the reaction of the first olefin in a diene in a polymer and the reaction of the second olefin in the diene with the adjacent polymer chain are referred to as the synergistic addition of the diene to the proximal polymer chain.

[0046] Scheme 3: Description of the incorporation of dienes in a concerted manner (P is the polymer chain), also known as the "ladder branching" mechanism.

[0047]

[0048] A polymer chain is a linear segment of a polymer or more specifically a copolymer, which is optionally connected at the end by a branching connection point. For example, a tetrafunctional branching connection point connects the ends of four polymer chains, as opposed to a trifunctional branching connection point, which connects the ends of three polymer chains as shown in Scheme 1.

[0049] Combinations of multi-chain catalysts and dienes affect the amount and type of branching. Embodiments of the present disclosure relate to controlling polymer properties such as: 1) using multiple diene species, 2) using a multi-chain catalyst and another catalyst species, or 3) a combination of polymerization environments including multiple reactor zones or gradient zones.

[0050] The use of multiple catalysts, including single chain catalysts, can allow for some conventional long chain branching. The use of multiple diene species also includes those dienes that do not produce ladder branches or do not result in "conventional" LCBs. The method of synthesizing polymers according to the present disclosure is different from conventional long chain branching.

[0051] In one or more embodiments, the method for polymerizing a long-chain branched polymer comprises a catalyst having at least two active sites in close proximity (a multi-chain catalyst). In order to make the two active sites in close proximity, the distance between the two active sites can be less than 18.5 angstroms. In some embodiments, the two active sites comprise 2.5 angstroms To 18.5 Angstroms arrive or approximately In various embodiments, the method for polymerizing a long-chain branched polymer comprises a multi-chain catalyst. In one or more embodiments, the multi-chain catalyst may comprise at least one metal center, wherein the two active sites are on the same metal center. In some embodiments, the multi-chain catalyst may comprise a metal-ligand complex, wherein the two active sites (two polymer chains) are on the same metal center.

[0052] In one or more embodiments, the diene is an unconjugated diene, wherein the unconjugated diene is acyclic. In some embodiments, the diene is an α,ω-diene, which means that both double bonds are terminal. In other embodiments, the unconjugated diene includes a branched group, wherein the branched group is a C1-C4 alkyl group. The branched group may occur in sp 2 Hybridized carbon atoms, such as sp in 2-methyl-1,4-pentadiene or diene 3 In various embodiments, the diene is selected from 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.

[0053] According to the X-ray crystal structure (AD Bond, Chem. Comm. 2002, 1664), 1,9-decadiene has The distance between the terminal carbons of . Although there is data that 1,9-decadiene forms a ladder between two polymer chains through a "ladder branching" mechanism, it is believed that α,ω-dienes with more than 10 carbon atoms can also form ladders through a "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 ladders can be determined by the distance between the two polymer chains. For example, when the two polymer chains are located on different metal atoms of the catalyst (e.g., bimetallic, heterogeneous), α,ω-dienes may include additional methylene units (same CC bond length and angle) to extend this structure to 1,15-hexadecadiene. Without intending to be bound by theory, it is speculated that this 16-carbon analogue still has the potential to form ladders through a "ladder branching" mechanism. In this way, dienes, 1,11-dodecene (the distance between the terminal carbons is ), 1,13-tetradecene (the distance between the terminal carbons is ), 1,15-hexadecadiene (the distance between the terminal carbons is ). In some embodiments, when the double-chain catalyst in the "ladder branching" mechanism is a bimetallic catalyst, the diene is less than or equal to

[0054] It is well known that modern computational techniques can reproduce known experimental crystal structures with high accuracy as a means of estimating the distances between the chains of the catalyst. For heterogeneous systems, the surface concentration of the metal can be estimated, usually in M / nm2. 2 ) of metal atoms on the surface. This surface coverage provides an estimate of the metal available on the surface and, if the metal is uniformly dispersed, can be converted to MM distances, which reflect the distances between polymer chains. For extended surfaces, 1 metal / nm 2 The distance between metal atoms is is just within the expected critical value. Under this condition, it can be determined that 0.3 metal / nm 2 The coverage rate below.

[0055] Examples of catalysts having at least two active sites, wherein the active sites are in close proximity, include, but are not limited to, bimetallic transition metal catalysts; heterogeneous catalysts; dianionic activators having two associated active catalysts; transition metal catalysts having more than one attached growing polymer chain; Group IV olefin polymerization catalysts comprising a monoanionic group, a bidentate monoanionic group, a tridentate monoanionic group, or a monodentate, bidentate, or tridentate monoanionic group with an external donor.

[0056] The catalysts in Table 1 are illustrative embodiments of previously described catalyst classes and specific catalysts contemplated. The examples in Table 1 are not intended to be limiting; rather, the examples are merely illustrative and specific examples of previously mentioned catalyst classes.

[0057]

[0058]

[0059] Although not intended to be bound by theory, as explained in this section, the mechanism describes how a multi-chain catalyst can produce a unique bridged molecular architecture when polymerizing a diene comonomer under desired conditions. A graphical description of the kinetics is shown in Scheme 4, where the catalyst center produces two polymer chains. Scheme 4 shows how the combination of diene bridging and chain transfer produces a diene "ladder branched" polymer structure. The term "ladder branched" polymer refers to long chain branching, in which a short chain or ladder containing one to twelve carbon atoms connects two long chains together. As shown, a metal-ligand catalyst with at least two polymer chain sites grows two separate polymer chains. One olefin in the diene is incorporated into one of the sites of the catalyst, and it is believed that due to the close proximity of the growth site, the second olefin of the diene is then rapidly incorporated into the second polymer chain, thereby forming a bridge or ladder. This continuous addition of dienes is referred to as the "cooperative" addition of dienes, which is distinguished from a catalyst without two proximal chains, where the diene addition results in a certain concentration of vinyl-containing polymer in the reactor, which reacts at a subsequent time. The term "ladder" refers to the incorporation of a diene into two separate polymer chains, thereby linking the chains together. The first polymer chain and the second polymer chain continue to grow until the polymer is transferred to another catalyst, the polymer is released from the catalyst, the catalyst mold, or another diene is added.

[0060] Scheme 4: Illustration of the "ladder branching" kinetics including the resulting molecular architecture. Metal-ligand catalysts by LM + Jointly expressed .

[0061]

[0062] 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. Pat. Nos. 5,272,236; 5,278,272; 6,812,289; and WO Publication No. 93 / 08221, which are incorporated herein by reference in their entirety. Details and examples of bis(phenylphenoxy) catalysts are provided in U.S. Pat. Nos. 6,869,904; 7,030,256; 8,101,696; 8,058,373; 9,029,487, which are incorporated herein by reference in their entirety.

[0063] Bis(phenylphenoxy) catalyst is an example of a homogeneous catalyst. Other examples of homogeneous catalysts include constrained geometry catalysts. Examples of heterogeneous catalysts may include heterogeneous Ziegler-Natta catalysts. Examples of such Ziegler-Natta catalysts are catalysts 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. Patents No. 4,314,912 (Lowery, Jr. et al.), No. 4,547,475 (Glass et al.) and No. 4,612,300 (Coleman, III), the teachings of which are incorporated herein by reference.

[0064] Catalyst system

[0065] Specific embodiments of catalyst systems that can be used in one or more embodiments to produce the multimodal ethylene-based copolymer compositions described herein will now be described. It should be understood that the catalyst systems of the present disclosure can be embodied in different forms and should not be construed as limited to the specific embodiments set forth in the present 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.

[0066] The term "independently selected" is used herein to refer to R groups (such as R 1 , R 2 , R 3 , R 4 , and R 5 ) can be the same or different (e.g., R 1 , R 2 , R 3 , R 4 and R 5 can be substituted alkyl, or R 1 and R 2 It may be a substituted alkyl group and R 3 The use of the singular encompasses the use of the plural, and vice versa (e.g., a hexane solvent encompasses a plurality of hexanes). A named R group will generally have an art-recognized structure corresponding to the R group having that name. These definitions are intended to supplement and illustrate, but not to exclude, definitions known to those skilled in the art.

[0067] 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 the procatalyst in a manner that converts the procatalyst into a catalytically active catalyst. As used herein, the terms "procatalyst" and "activator" are interchangeable terms.

[0068] When used to describe certain chemical groups containing carbon atoms, the group having the form "(C x -C y )" means that the unsubstituted form of the chemical group has from x to y carbon atoms, including x and y. For example, (C1-C 40 ) alkyl is an alkyl group having 1 to 40 carbon atoms in unsubstituted form. In some embodiments and general structures, certain chemical groups may be replaced by, for example, R s The parenthetical phrase "(C x -C y )" defined by R S Substituted versions may contain more than y carbon atoms, depending on the number of any group R S For example, “using only one R S Group-substituted (C1-C 40 ) alkyl, wherein R S is phenyl (-C6H5)" may include 7 to 46 carbon atoms. Therefore, generally, when using "(C x -C y )" is inserted into the chemical group defined by one or more carbon-containing substituents R S When substituted, both x and y are added to the substituent R from all carbon atoms. S The combined sum of the number of carbon atoms is used to determine the minimum and maximum total number of carbon atoms in a chemical group.

[0069] The term "substituted" means that at least one hydrogen atom (-H) bonded to a carbon atom or heteroatom in the corresponding unsubstituted compound or functional group is replaced by a substituent (e.g., R S The term "fully substituted" means that each hydrogen atom (H) bonded to a carbon atom or heteroatom in the corresponding unsubstituted compound or functional group is replaced by a substituent (e.g., R s The term "polysubstituted" means that at least two but less than all hydrogen atoms bonded to carbon atoms or heteroatoms in the corresponding unsubstituted compound or functional group are replaced by substituents.

[0070] The term "-H" means a hydrogen or a hydrogen radical covalently bonded to another atom. "Hydrogen" and "-H" are interchangeable and have the same meaning unless expressly specified otherwise.

[0071] The term "(C1-C 40 )hydrocarbyl" means a hydrocarbon group having 1 to 40 carbon atoms, and the term "(C1-C 40)alkylene group" means a hydrocarbon diradical having 1 to 40 carbon atoms, wherein each hydrocarbon group and each hydrocarbon diradical is aromatic or non-aromatic, saturated or unsaturated, straight chain or branched, cyclic (including monocyclic and polycyclic, fused and non-fused polycyclic, including bicyclic; 3 or more carbon atoms) or acyclic, and is unsubstituted or substituted with one or more R S replace.

[0072] In the present disclosure, (C1-C 40 The hydrocarbon group may be 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 aforementioned (C1-C 40 ) Each of the alkyl groups has up to 20 carbon atoms (i.e., (C1-C 20 )hydrocarbyl), and in various embodiments, has up to 12 carbon atoms.

[0073] The term "(C1-C 40 )alkyl" and "(C1-C 18 ) alkyl means a saturated straight or branched hydrocarbon group having 1 to 40 carbon atoms or 1 to 18 carbon atoms, which is unsubstituted or substituted by one or more R S Substituted. Unsubstituted (C1-C 40 Examples of alkyl groups 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. Substituted (C1-C5)alkyl 40 Examples of alkyl groups are substituted (C1-C 20 ) alkyl, substituted (C1-C 10 ) alkyl, trifluoromethyl and [C 45 ] alkyl. The term "[C 45 ] alkyl" (with square brackets) means that there are up to 45 carbon atoms in the group (including substituents) and that, for example, each of the R S , substituted (C 27 -C 40 ) alkyl, the R Sis a (C1-C5)alkyl group. Each (C1-C5)alkyl group may be a methyl group, a trifluoromethyl group, an ethyl group, a 1-propyl group, a 1-methylethyl group or a 1,1-dimethylethyl group.

[0074] The term "(C6-C 40 ) aryl" means an unsubstituted or substituted aryl having 6 to 40 carbon atoms (one or more R S )-substituted monocyclic, bicyclic or tricyclic aromatic hydrocarbon groups, at least 6 to 14 of the carbon atoms of the aromatic hydrocarbon group are aromatic ring carbon atoms, and the monocyclic, bicyclic or tricyclic groups include 1, 2 or 3 rings, respectively; wherein 1 ring is an aromatic ring, and 2 or 3 rings are independently condensed rings or non-condensed rings, and at least one of the 2 or 3 rings is an aromatic ring. Unsubstituted (C6-C 40 Examples of aryl groups are unsubstituted (C6-C 20 )aryl; unsubstituted (C6-C 18 )aryl; 2-(C1-C5)alkyl-phenyl; 2,4-bis(C1-C5)alkyl-phenyl; phenyl; fluorenyl; tetrahydrofluorenyl; dicyclopentadienylphenyl; hexahydrodicyclopentadienylphenyl; indenyl; dihydroindenyl; naphthyl; tetrahydronaphthyl; and phenanthrene. Substituted (C6-C 40 Examples of aryl groups 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.

[0075] The term "(C3-C 40 )Cycloalkyl refers to a cycloalkyl having 3 to 40 carbon atoms which is unsubstituted or substituted with one or more R S Other cycloalkyl groups (e.g., (C x -C y )cycloalkyl) is defined in a similar manner as having x to y carbon atoms and being unsubstituted or substituted with one or more R S Substituted. Unsubstituted (C3-C 40 Examples of cycloalkyl groups are unsubstituted (C3-C 20 )cycloalkyl, unsubstituted (C3-C 10 )cycloalkyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl and cyclodecyl. 40 Examples of cycloalkyl groups are substituted (C3-C 20 )cycloalkyl, substituted (C3-C 10 )cycloalkyl, cyclopentanone-2-yl and 1-fluorocyclohexyl.

[0076] (C1-C 40 Examples of alkylene groups include unsubstituted or substituted (C5-C 40 ) arylene, (C3-C 40 )cycloalkylene and (C1-C 40 ) alkylene (e.g., (C1-C 20 ) alkylene). In some embodiments, the diradicals are located on the same carbon atom (e.g., -CH2-) or on adjacent carbon atoms (i.e., 1,2-diradicals), or are separated by one, two, or more than two intervening carbon atoms (e.g., 1,3-diradicals, 1,4-diradicals, etc.). Some diradicals include α,ω-diradicals. α,ω-diradicals are diradicals with the largest carbon backbone spacing between the radical carbons. (C2-C 20 Some examples of alkylene α,ω-diyl radicals include ethane-1,2-diyl (ie, -CH2CH2-), propane-1,3-diyl (ie, -CH2CH2CH2-), 2-methylpropane-1,3-diyl (ie, -CH2CH(CH3)CH2-). (C6-C 50 Some examples of arylene α,ω-diyl include phenyl 1,4-diyl, naphthalene-2,6-diyl, or naphthalene-3,7-diyl.

[0077] The term "(C1-C 40 ) Alkylene means an unsubstituted or substituted group having 1 to 40 carbon atoms. S Substituted saturated straight or branched chain divalent radical (i.e., the divalent radical is not on a ring atom). Unsubstituted (C1-C 50 Examples of alkylene groups are unsubstituted (C1-C 20 )alkylene, including unsubstituted -CH2CH2-, -(CH2)3-, -(CH2)4-, -(CH2)5-, -(CH2)6-, -(CH2)7-, -(CH2)8-, -CH2C*HCH3 and -(CH2)4C * (H)(CH3), where “C * " represents a carbon atom from which a hydrogen atom is removed to form a secondary or tertiary alkyl group. 50 Examples of alkylene groups are substituted (C1-C 20 )alkylene, -CF2-, -C(O)- and -(CH2) 14 C(CH3)2(CH2)5- (i.e., 6,6-dimethyl-substituted n-1,20-eicosene). As previously mentioned, the two R S Can be combined to form (C1-C 18 ) alkylene, substituted (C1-C 50Examples of the alkylene group 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.

[0078] The term "(C3-C 40 ) Cycloalkylene refers to a cycloalkylene group having 3 to 40 carbon atoms which is unsubstituted or substituted with one or more R S Substituted cyclic diradicals (ie, the radicals are on ring atoms).

[0079] The term "heteroatom" refers to an atom other than hydrogen or carbon. Examples of heteroatoms include O, S, S(O), S(O)2, Si(R c 2. P(R P )、N(R N )、-N=C(R C )2、-Ge(R C )2- or -Si(R C )-, where each R C , each R N and each R P is unsubstituted (C1-C 18 )alkyl or -H. The term "heteroalkyl" refers to a molecule or molecular framework in which one or more carbon atoms are replaced by heteroatoms. 40 )heteroalkyl" means a heteroalkyl group having 1 to 40 carbon atoms, and the term "(C1-C 40 The term "heteroalkylene" means a heteroalkyl diradical having from 1 to 40 carbon atoms, each of which has one or more heteroatoms. The radical of the heteroalkyl group is located on a carbon atom or a heteroatom, and the diradical of the heteroalkyl group can be located on: (1) one or two carbon atoms, (2) one or two heteroatoms, or (3) both carbon atoms and heteroatoms. Each (C1-C 50 ) heteroalkyl and (C1-C 50 ) The heteroalkylene group may be unsubstituted or (substituted by one or more R S ) substituted, aromatic or non-aromatic, saturated or unsaturated, linear or branched, cyclic (including mono- and polycyclic, fused and non-fused polycyclic) or acyclic.

[0080] (C1-C 40 ) heteroalkyl may be unsubstituted or substituted (C1-C 40 )heteroalkyl, (C1-C 40 )alkyl-O-, (C1-C 40 )alkyl-S-, (C1-C 40 )alkyl-S(O)-, (C1-C 40)alkyl-S(O)2-, (C1-C 40 )alkyl-Si(R C )2-、(C1-C 40 )alkyl-N(R N )-、(C1-C 40 )alkyl-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.

[0081] The term "(C4-C 40 ) heteroaryl" means an unsubstituted or substituted (one or more R S ) substituted monocyclic, bicyclic or tricyclic heteroaromatic hydrocarbon groups, and the monocyclic, bicyclic or tricyclic groups include 1, 2 or 3 rings respectively; wherein 2 or 3 rings are independently fused or non-fused, and at least one of the 2 or 3 rings is heteroaromatic. Other heteroaryl groups (for example, usually (C x -C y ) heteroaryl, such as (C4-C 12 ) heteroaryl) is defined in a similar manner as having x to y carbon atoms (e.g. 4 to 12 carbon atoms) and being unsubstituted or substituted with one or more than one R Ssubstituted. The monocyclic heteroaromatic hydrocarbon group 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 groups are pyrrol-1-yl; piperidin-2-yl; furan-3-yl; thien-2-yl; pyrazol-1-yl; isoxazol-2-yl; isothiazol-5-yl; imidazol-2-yl; oxazol-4-yl; thiazol-2-yl; 1,2,4-triazol-1-yl; 1,3,4-oxadiazol-2-yl; 1,3,4-thiadiazol-2-yl; tetrazol-1-yl; tetrazol-2-yl; and tetrazol-5-yl. The 6-membered ring has 6 minus h carbon atoms, where h is the number of heteroatoms and can be 1 or 2, and the heteroatoms can be N or P. Examples of 6-membered ring heteroaromatic hydrocarbon groups are pyridin-2-yl; pyrimidin-2-yl; and pyrazin-2-yl. Bicyclic heteroaromatic hydrocarbon groups can be fused 5,6- or 6,6-ring systems. Examples of fused 5,6-ring system bicyclic heteroaromatic hydrocarbon groups are indol-1-yl; and benzimidazol-1-yl. Examples of fused 6,6-ring system bicyclic heteroaromatic hydrocarbon groups are quinolin-2-yl; and isoquinolin-1-yl. Bicyclic heteroaromatic hydrocarbon groups can be fused 5,6,5-ring systems; 5,6,6-ring systems; 6,5,6-ring systems; or 6,6,6-ring systems. Examples of fused 5,6,5-ring systems are 1,7-dihydropyrrolo[3,2-f]indol-1-yl. Examples of fused 5,6,6-ring systems are 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 acridin-9-yl.

[0082] The aforementioned heteroalkyl group may include (C1-C 50 ) carbon atoms, or less carbon atoms and one or more heteroatoms. Similarly, heteroalkylene can be a saturated straight or branched chain diradical containing 1 to 50 carbon atoms and one or more heteroatoms. The heteroatoms defined above can 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, SR C , S(O) and S(O)2, wherein each of the heteroalkyl and heteroalkylene groups is unsubstituted or substituted with one or more R S replace.

[0083] Unsubstituted (C2-C 40 Examples of heterocycloalkyl groups are unsubstituted (C2-C 20 )heterocycloalkyl, unsubstituted (C2-C 10 ) heterocycloalkyl, aziridine-1-yl, oxetan-2-yl, tetrahydrofuran-3-yl, pyrrolidin-1-yl, tetrahydrothiophene-S,S-dioxide-2-yl, morpholin-4-yl, 1,4-dioxane-2-yl, hexahydroazepin-4-yl, 3-oxa-cyclooctyl, 5-thioxo-cyclononyl and 2-aza-cyclodecyl.

[0084] The term "halogen atom" or "halogen" refers to a free radical of a fluorine atom (F), a chlorine atom (Cl), a bromine atom (Br), or an iodine atom (I). The term "halide" refers to the anionic form of a halogen atom: a fluoride ion (F - ), chloride ion (Cl - ), bromide ion (Br - ) or iodide ion (I - ).

[0085] The term "saturated" means lacking carbon-carbon double bonds, carbon-carbon triple bonds, and (in heteroatom-containing groups) carbon-nitrogen double bonds, carbon-phosphorus double bonds, and carbon-silicon double bonds. S In the case of substitution, one or more double bonds and / or triple bonds may or may not be present in the substituent R S The term "unsaturated" means containing 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, excluding those that may be present in the substituent R S Any such double bonds may be present in a (hetero)aromatic ring (if present).

[0086] According to some embodiments, the single-chain catalyst for use in a method of polymerizing an ethylene-based polymer comprises a metal-ligand complex according to formula (I):

[0087]

[0088] In formula (I), M is a metal selected from titanium, zirconium or hafnium, and the metal is in a formal oxidation state of +2, +3 or +4. n is 0, 1 or 2; when n is 1, X is a monodentate ligand or a bidentate ligand; when n is 2, each X is a monodentate ligand and is the same or different; the metal-ligand complex is electrically neutral as a whole; each Z is independently selected from -O-, -S-, -N(R N )-or-P(R P )-; L is (C1-C 40 )alkylene or (C1-C40 )heteroalkylene, wherein (C1-C 40 ) The alkylene group includes a linker backbone of 1 to 10 carbon atoms connecting the two Z groups (bonded to L) in formula (I), or (C1-C 40 ) The heteroalkylene group includes a linker backbone of 1 to 10 atoms connecting the two Z groups in formula (I), wherein (C1-C 40 ) wherein each of the 1 to 10 atoms of the linker backbone of the 1 to 10 atoms of the heteroalkylene group is independently a carbon atom or a heteroatom, wherein each heteroatom is independently O, S, S(O), S(O)2, Si(R C )2、Ge(R C 2. P(R C ) or N(R C ), where each R C Independently (C1-C 30 ) alkyl or (C1-C 30 ) heteroalkyl; R 1 and R 8 Independently selected from the group consisting of: -H, (C1-C 40 ) hydrocarbon group, (C1-C 40 ) heteroalkyl, -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 group having formula (II), formula (III) or formula (IV):

[0089]

[0090] In formula (II), (III) and (IV), R 31-35 / R 41-48 or R 51-59 Each of which is independently selected from (C1-C 40 ) hydrocarbon group, (C1-C 40 ) heteroalkyl, -Si(R C )3, -Ge(RC )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 At least one of the groups is a group having formula (II), formula (III) or formula (IV).

[0091] In formula (I), R 2-4 , R 5-7 and R 9-16 Each of which is independently selected from (C1-C 40 ) hydrocarbon group, (C1-C 40 ) heteroalkyl, -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.

[0092] An illustrative example of a metal-ligand complex according to formula (I) is catalyst 4:

[0093]

[0094] In one or more embodiments, the single-chain catalyst comprises a metal-ligand complex according to formula (V):

[0095]

[0096] In formula (V), M is hafnium, zirconium, titanium, a Group III or lanthanide metal. A Independently selected from the group consisting of (C1-C 40 ) alkyl; (C1-C 40 ) heteroalkyl, -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 )2NC(O)-, halogen atoms and hydrogen atoms. Optionally, two or more R A The groups can be combined together to form one or more ring structures. B Independently (C1-C 30 ) alkyl or (C1-C 30 ) heteroalkyl.

[0097] In formula (V), Z is [(R D ) n G] m , wherein the subscript m is 1 or 2; each G is independently selected from carbon, silicon, germanium or boron; provided that and when G is carbon, silicon or germanium, n is 2; and when G is boron, n is 1. Each R D Independently (C1-C 30 ) alkyl or (C1-C 30 ) heteroalkyl.

[0098] In formula (V), Y is selected from the group consisting of: -O-, -S-, -NR E -and-PR E -; Each R B , R D or R E Independently (C1-C 30 ) alkyl or (C1-C 30 ) heteroalkyl.

[0099] In formula (V), each X is (C1-C 40 ) hydrocarbons, (C1-C 40 ) heterohydrocarbons, (C1-C40 ) alkyl; (C1-C 40 ) heteroalkyl; 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 )2NC(O)-, halogen atoms and hydrogen atoms. Each R C Independently (C1-C 30 ) alkyl or (C1-C 30 ) heteroalkyl.

[0100] An illustrative example of a metal-ligand complex according to formula (V) is Catalyst 2:

[0101]

[0102] In one or more embodiments, the single-chain catalyst comprises a metal-ligand complex according to formula (VI):

[0103]

[0104] In formula (VI), M is hafnium, zirconium, titanium, a Group III or lanthanide metal. Each X is (C1-C 40 ) hydrocarbons, (C1-C 40 ) heterohydrocarbons, (C1-C 40 ) alkyl; (C1-C 40 ) heteroalkyl; 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)-、(RC )2NC(O)-, halogen atoms and hydrogen atoms. Each R C Independently (C1-C 30 ) alkyl or (C1-C 30 ) heteroalkyl. Each R P Yes (C1-C 30 ) alkyl or (C1-C 30 ) heteroalkyl. (X) n The subscript n is 1 or 2. Cp is a cyclopentadienyl group, which may be unsubstituted or substituted with up to five substituents. Each of the five substituents may be a (C1-C8)alkyl, a (C1-C8)heteroalkyl or a halogen. Optionally, two of the five substituents may be combined together to form a ring.

[0105] In some embodiments, Cp is selected from cyclopentadienyl, indenyl, and fluorenyl.

[0106] In formula (VI), N is nitrogen, P is phosphorus, and each R P Independently (C1-C 30 ) hydrocarbon group.

[0107] An illustrative example of a metal-ligand complex according to formula (VI) is Catalyst 3:

[0108]

[0109] In various embodiments, the multi-chain catalyst comprises a metal-ligand complex according to formula (VII):

[0110]

[0111] In formula (VII), M is hafnium, zirconium, titanium, a Group III or lanthanide metal. Each X is (C1-C 40 ) hydrocarbons, (C1-C 40 ) heterohydrocarbons, (C1-C 40 ) alkyl; (C1-C 40 ) heteroalkyl; 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)-、RC C(O)N(R)-、(R C )2NC(O)-, halogen atoms and hydrogen atoms. Each R C Independently (C1-C 30 ) alkyl or (C1-C 30 ) heteroalkyl.

[0112] In formula (VII), R 71 To R 76 Yes (C1-C 40 ) alkyl; (C1-C 40 ) heteroalkyl.

[0113] An illustrative example of a metal-ligand complex according to formula (VII) is Catalyst 1:

[0114]

[0115] In a catalyst system according to an embodiment of the present disclosure, the molar ratio of the bimetallic activator complex to the Group IV metal-ligand complex can be 1:10,000 to 1000:1, such as, for example, 1:5000 to 100:1, 1:100 to 100:1, 1:10 to 10:1, 1:5 to 1:1, or 1.25:1 to 1:1. The catalyst system can include a combination of one or more bimetallic activator complexes described in the present disclosure.

[0116] Co-catalyst component

[0117] Catalyst systems comprising the metal-ligand complex of formula (I) may be rendered catalytically active by any technique known in the art for activating metal-based catalysts for olefin polymerization reactions. For example, systems comprising the metal-ligand complex of formula (I) may be rendered 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 aluminoxanes (also referred to as aluminoxanes); neutral Lewis acids; and non-polymeric, non-coordinating, ion-forming compounds (including the use of such compounds under oxidizing conditions). A suitable activation technique is bulk electrolysis. Combinations of one or more of the foregoing activating cocatalysts and techniques are also contemplated. The term "alkylaluminum" means a monoalkylaluminum dihydride or monoalkylaluminum dihalide, a dialkylaluminum hydride or dialkylaluminum halide, or a trialkylaluminum. Examples of polymeric or oligomeric aluminoxanes include methylaluminoxane, methylaluminoxane modified with triisobutylaluminum, and isobutylaluminoxane.

[0118] Lewis acid activators (cocatalysts) include those containing 1 to 3 (C1-C 20In one embodiment, the Group 13 metal compound is tri((C1-C 20 ) alkyl) substituted aluminum or tri((C1-C 20 In various embodiments, the Group 13 metal compound is a tri(hydrocarbyl)substituted aluminum, a tri((C1-C 20 )alkyl)-boron compounds, tri((C1-C 10 )alkyl)aluminum, tri((C6-C 18 ) aryl) boron compounds and their halogenated (including perhalogenated) derivatives. In other embodiments, the Group 13 metal compound is tri(fluoro-substituted phenyl) borane, tri(pentafluorophenyl) borane. In some embodiments, the activating cocatalyst is tri((C1-C 20 ) alkyl borate (e.g., trityl tetrafluoroborate) or tris((C1-C 20 )alkyl)ammonium tetra((C1-C 20 )alkyl)borane (e.g., bis(octadecyl)methylammoniumtetra(pentafluorophenyl)borane). As used herein, the term "ammonium" refers to a nitrogen cation, which is ((C1-C 20 )alkyl)4N + 、((C1-C 20 )alkyl)3N(H) + 、((C1-C 20 )alkyl)2N(H)2 + 、(C1-C 20 )Hydrocarbon N(H)3 + or N(H)4 + , where there are two or more (C1-C 20 ) hydrocarbon groups, they may be the same or different.

[0119] The combination of a neutral Lewis acid activator (cocatalyst) includes a tri((C1-C4)alkyl)aluminum and a tri((C6-C 18 In some embodiments, the present invention provides a mixture of a combination of a (pentafluorophenyl)borane and a (pentafluorophenyl)borane. Embodiments are combinations of such neutral Lewis acid mixtures with polymeric or oligomeric aluminoxanes and combinations of a single neutral Lewis acid (especially tris(pentafluorophenyl)borane) with polymeric or oligomeric aluminoxanes. The ratio of the number of moles of (metal-ligand complex):(tris(pentafluoro-phenylborane):(aluminoxane) [e.g., (Group 4 metal-ligand complex):(tris(pentafluoro-phenylborane):(aluminoxane)] is 1:1:1 to 1:10:30, and in other embodiments is 1:1:1.5 to 1:5:10.

[0120] The metal-ligand complex catalyst system comprising formula (I) can be activated to form an active catalyst composition by combining with one or more cocatalysts (e.g., cation-forming cocatalysts, strong Lewis acids, or combinations thereof). Suitable activating cocatalysts include polymeric or oligomeric aluminoxanes (especially methylaluminoxane) and inert, compatible, non-coordinating, ion-forming compounds. Exemplary suitable cocatalysts include, but are not limited to, modified methylaluminoxane (MMAO), bis(hydrogenated tallow alkyl) methyl, tetrakis(pentafluorophenyl)borate (1-)amine, and combinations thereof.

[0121] In some embodiments, one or more of the aforementioned activating co-catalysts are used in combination with each other. A particularly preferred combination is a mixture of tri((C1-C4)hydrocarbyl)aluminum, tri((C1-C4)hydrocarbyl)borane or ammonium borate with an oligomeric or polymeric aluminoxane compound. The ratio of the total number of moles of one or more metal-ligand complexes of formula (I) to the total number of moles of one or more activating co-catalysts in the activating co-catalyst is 1:10,000 to 100:1. In some embodiments, the ratio is at least 1:5000, in some embodiments at least 1:1000; and 10:1 or less, and in some embodiments 1:1 or less. When aluminoxane is used alone as an activating co-catalyst, preferably, the number of moles of aluminoxane employed is at least 100 times the number of moles of the metal-ligand complex of formula (I). In some embodiments, when tri(pentafluorophenyl)borane is used alone as an activating co-catalyst, the ratio of the number of moles of tri(pentafluorophenyl)borane employed to the total number of moles of the one or more metal-ligand complexes of formula (I) is 0.5: 1 to 10: 1, 1: 1 to 6: 1, or 1: 1 to 5: 1. The remaining activating co-catalyst is typically employed in a molar amount approximately equal to the total molar amount of the one or more metal-ligand complexes of formula (I).

[0122] Characterization of tetrafunctional long-chain branched polyolefins

[0123] According to the degree of branching, a variety of methods can determine LCB (such as nuclear magnetic resonance (NMR)), or distinguish the role of LCB in polymer. For example, the role of LCB is observed in the shear flow in the van Gup-Perlman analysis, and the shear viscosity also increases at low angular frequencies, and the intensity of shear thinning behavior can also be attributed to LCB. In extensional flow, the influence of LCB is usually identified in the degree of hardening or melt strength and the maximum deformation achieved. Other figures, such as the Mark-Houwink-Sakurada figure and g' figure of the expanded molecular weight distribution (MWD) provide additional information about LCB. Due to the limited concentration of vinyl-terminated polymers (one at most per polymer chain), and it is necessary to carry out high conversion to ensure the formation of LCB, it is difficult to achieve a high level of natural LCB in polymer. In order to ensure high conversion, the ethylene concentration in the reactor is low, so that a large amount of vinyl-terminated polymers can be reinserted into the second polymer chain.

[0124] Conventional methods for incorporating dienes into polymer synthesis systems suffer from the basic defects of gel formation or reactor fouling at high branching levels.Previously described kinetic modeling (application No. PCTUS2019 / 053524 submitted on September 27, 2019; application No. PCTUS2019 / 053527 submitted on September 27, 2019; application No. PCTUS2019 / 053529 submitted on September 27, 2019; and application No. PCTUS2019 / 053537 submitted on September 27, 2019) provide good prediction results for realizing a better understanding of gel formation.For example, longer polymer chains proportionally have more side vinyl groups and polymer chains comprising more side vinyl groups will be more likely to be reinserted into the catalyst to form LCB.Therefore, larger polymer chains are preferentially reinserted to form tetrafunctional branches as even larger polymer molecules, and gel problems or instability are generated when LCB levels reach threshold values. Weight average molecular weight (M) as a function of conventional tetrafunctional branching for ethylene-based polymers in a semi-batch reactor at constant pressure w ) and number average molecular weight (M n ) is shown in the simulation Figure 1 In. Figure 1 In, when M w When M becomes infinite, n In this example, as M w When the molecular weight increases to a value greater than 200,000 grams per mole (g / mol), the polymer molecular weight distribution (MWD) becomes unstable and gel formation begins. MWD is calculated from the weight average molecular weight M w Divided by the number average molecular weight M n (M w / Mn )definition.

[0125] For the purposes of this disclosure, polymer gel is narrowly defined as a polymer fraction that phase separates due to its high level of branching and / or high molecular weight. Polymer gels can be observed in solution or in the melt, 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 generally related to and therefore estimated by GPC polymer recovery. When polymer gel is formed, the polymer gel may be deposited in the reactor and cause fouling.

[0126] Molecular weight effect

[0127] If two catalysts, such as Catalyst 1 and Catalyst 2, are added to the reactor, a bimodal distribution may exist due to the different MWs of the two catalysts. If one of the catalysts is a double-chain catalyst, then the catalyst can effectively ladder branch the dienes. The double-chain catalyst is an embodiment of a multi-chain catalyst with only two polymerization sites. Due to the efficiency of the diene reaction of the double-chain catalyst at the metal center (no accumulation of vinyl is required), the double-chain catalyst effectively couples the polymer chains together, while the single-chain catalyst may not insert enough dienes to form significant LCBs or create fouling issues. Figure 3 The MWD of polymers produced by the two catalysts is shown, with a small weight integrated higher MW polymer produced by the dual chain catalyst and appearing as a high MW shoulder. After the addition of diene, the MW of this shoulder will be much higher, while the main peak from the single chain catalyst is essentially unaffected.

[0128] Analysis of Mark Horwin-Sakurada

[0129] The Mark-Horwin-Sakurada diagram describes the power law relationship between the intrinsic viscosity [η] and the absolute molecular weight M:

[0130] η=βM α (1)

[0131] Typically, [η] follows the radius of gyration or backbone molecular weight of the polymer. Note that absolute MW (M) is related to backbone MW (M b ) because the absolute MW includes the mass on the side chains, while the backbone MW does not include the mass on the side chains. Using the absolute molecular weight, the Mark-Horwin-Sakurada plot of log[η] versus log M yields:

[0132] log(η)=log(β)+αlog(M) (2)

[0133] Note that in this application, logarithms with a base of ten are represented by log.

[0134] For linear chain polymers, a plot of log [η] versus log M gives a slope of α and a vertical shift of log β. The value of α is known for polyethylene where for a typical solvent of trichlorobenzene α = 0.73 at 150° C. In many of the evaluations below, α = 0.73.

[0135] Deviations from homopolymer dependence occur when one evaluates the introduction of short chain branching. For example, in 10 mol% octene, 23% of the total molecular weight is present in the side chains, which means that M b =10 / 13M:

[0136]

[0137] log(η)=log(β)+αlog(M)-αlog(1.3) (4)

[0138] For α=0.73, αlog 1.3=0.083, the Mark-Horwin-Sakurada plot for this polymer will be parallel to the homopolymer (no comonomer), but shifted below 0.083 on a logarithmic scale. This line is parallel to the homopolymer dependence because the short chain branching is evenly distributed along the backbone at all molecular weights.

[0139] The impact on the Mark-Horwin-Sakurada plot for long chain branching is more complex. The Mark-Horwin-Sakurada dependence is also reduced due to the significant molecular weight on the side chains (long chain branches). However, since the long chain branches formed by conventional diene or high pressure (LDPE) processes grow dendritically or in a branch-on-branch structure, the distribution is not uniform; higher molecular weight species have more long chain branches. These concepts lead to Mark-Horwin-Sakurada behavior, which deviates further from the linear chain homopolymer dependence as the absolute molecular weight becomes larger (see Figure 4 ).

[0140] In principle, if the relationship between backbone molecular weight and absolute molecular weight can be determined, the Mark-Horwin-Sakurada plot can be predicted. However, this is too complex for conventional dienes and high pressure processes. Note that the intrinsic viscosity is cut off at the high MW end once the (dWf / dLogM) signal is less than 0.03.

[0141] The term "ladder polymer" refers to a high molecular weight fraction of a polyethylene-based polymer, wherein the high molecular weight fraction includes tetrafunctional long chain branches. Ladder polymers fragmented by hydrogenolysis segments have a defined relationship between backbone and absolute molecular weight (see Figure 5 ).exist Figure 5In the scheme 3, the polymer backbone is shown in black. The dashed line shows the tetrafunctional branching as shown in Scheme 3. The absolute MW cannot exceed twice the backbone MW. In principle, the absolute MW should be close to double the backbone MW, depending on the extent of free chains present in the ladder polymer; these free chains are caused by successive hydrogenolysis events on the same polymer chain. The percentage (and therefore the mass) of free chains will be small relative to the total molecular weight of the polymer. Using an upper limit value, where the backbone MW is half of the absolute MW, M b =1 / 2M:

[0142]

[0143] log(η)=log(β)+αlog(M)-αlog(2) (6)

[0144] For α=0.73, αlog2=0.220, and the Mark-Horwin-Sakurada plot for this polymer will be more reduced than that of the 10 mol% copolymer. Although the Mark-Horwin-Sakurada dependence is further reduced than that of the 10 mol% octene copolymer, unlike LDPE and conventional diene branching ( Figure 4 ), which is limited to a lesser degree than the homopolymer dependence.

[0145] Figure 6 The theoretical linear homopolymer power law relationship (Equation 2) and the theoretical ladder limit (Equation 6) are plotted. Actual data show the transition from linear polymers to ladder-branched polymers.

[0146] If a homopolymer is considered in the case of a ladder polymer (with diene but no octene), the chain is either linear (Eq. 2) or the chain is long chain branched (Eq. 6). Eq. 6 is valid whether there is one LCB (ladder) or more than one LCB. The lowest MW polymer chains will contain almost no LCBs, while the highest MW polymer chains will generally contain at least one LCB and a transition period in between these where some of the chains are linear and some are ladder long chain branched. This transition period must have a value in Figure 6 The inflection point (d 2 [η] / dM 2 = 0, and d 3 [η] / dM 3 >0).

[0147] The bimodal polymers exhibit the expected Mark-Horwin-Sakurada shift (see Figure 7 , e.g. based on the data in Tables 2-10), where the single chain catalyst produces a large fraction of lower MW linear chain polyethylene-based polymers, resulting in a molecular weight below S 最大, and the dual-chain catalyst produces a small fraction of higher MW ladder-shaped long-chain branched polyethylene-based polymers with MW higher than S 最大 . (S 最大 The values ​​are described in more detail in the previous section). The large fraction of lower MW linear chain polyethylene-based polymers follows Equation 2, while the small fraction of higher MW ladder-shaped long chain branched polyethylene-based polymers follows Equation 6. Large amounts of high MW fractions increase viscosity and thus make it difficult to pump from the reactor. If the amount of high MW fraction can be controlled, the overall viscosity will not reach the point where reactor fouling occurs, and the polymer can be safely removed from the reactor.

[0148] exist Figure 6 In the , there is an inflection point between the linear polymer in the low MW fraction and the ladder-branched polymer in the high MW fraction. However, there will also be an inflection point for the short chain branching because the bimodal distribution comes from two catalysts, each with different comonomer incorporation levels.

[0149] The equations presented previously apply to the cases where there is 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 mol% octene in the ladder polymer; iii) 10 mol% octene in the low MW fraction and no octene in the ladder polymer; iv) 10 mol% octene in the low MW fraction and 10 mol% octene in the ladder polymer.

[0150] i) No octene in the low MW fraction and no octene in the ladder polymer:

[0151] η 低 =βM α (7)

[0152] log(η 低 )=log(β)+αlog(M) (8)

[0153]

[0154] log(η 高 )=log(β)+αlog(M)-αlog(2) (10) In equations 8-10, the differences between the logarithmic viscosities of the low MW region and the high MW region are:

[0155] log(η 低 )-log(η 高 ) = αlog(2) = 0.220 (11) ii) No octene in the low MW fraction and 10 mol% octene in the ladder polymer:

[0156] log(η 低)=log(β)+αlog(M) (8)

[0157]

[0158] log(η 高 )=log(β)+αlog(M)-αlog(2.6) (12)

[0159] In equations 8-12, the differences between the logarithmic viscosities of the low MW region and the high MW region are:

[0160] log(η 低 )-log(η 高 )=αlog(2.6)=0.303 (13)

[0161] iii) 10 mol% octene in the low MW fraction and no octene in the ladder polymer:

[0162]

[0163] log(η 低 )=log(β)+αlog(M)-αlog(1.3) (15)

[0164] log(η 高 )=log(β)+αlog(M)-αlog(2) (10)

[0165] In Equation 15-10, the differences between the logarithmic viscosities of the low MW region and the high MW region are:

[0166]

[0167] iv) 10 mol% octene in the low MW fraction and 10 mol% octene in the ladder polymer:

[0168] log(η 低 )=log(β)+αlog(M)-αlog(1.3) (15)

[0169] log(η 高 )=log(β)+αlog(M)-αlog(2.6) (12)

[0170] In Equation 15-12, the differences between the logarithmic viscosities of the low MW region and the high MW region are:

[0171] log(eta low)-log(eta high)=αlog(2.6)-αlog(1.3)=αlog(2)=0.220(17)

[0172] As a comparative example of a long chain branching-free, bimodal distribution where two polymer fractions have the same octene incorporation (e.g., 0 mol% octene or 5 mol% octene or 10 mol% octene), the difference between the logarithmic viscosity of the low MW fraction and the high MW fraction will be zero. Additionally, for a bimodal polymer with: i) 10 mol% octene in the low MW fraction and no octene in the high MW fraction; ii) octene in the low MW fraction and 10 mol% octene in the high MW fraction, the comonomer incorporation difference (no LCB) will be:

[0173] i) 10 mol% octene in the low MW fraction and no octene in the high MW fraction:

[0174] log(η 低 )=log(β)+αlog(M)-αlog(1.3) (15)

[0175] log(η 高 )-log(β)+αlog(M) (18) In equations 15-18, the differences between the logarithmic viscosities in the low MW region and the high MW region are:

[0176] log(η 低 )-log(η 高 )=-αlog(1.3)=-0.083 (19)

[0177] i) No octene in the low MW fraction and 10 mol% octene in the high MW fraction:

[0178] log(η 低 )=log(β)+αlog(M) (8)

[0179] log(η 高 )-log(β)+αlog(M)-αlog(1.3) (20)

[0180] In Equation 8-20, the differences between the logarithmic viscosities in the low MW region and the high MW region are:

[0181] log(η 低 )-log(η 高 )=αlog(1.3)=0.083 (19)

[0182] The comparative examples provide a theoretical range of log viscosity differences of -0.083 to +0.083 for the extreme values ​​in octene incorporation. For ladder polymers with LCBs in the high MW fraction and variations in octene incorporation, the values ​​range from 0.137-0.303. These ranges provide the differences in the Mark-Horwin-Sakurada parameters associated with the two resins as well as the error bars associated with these experimental measurements.

[0183] The value of g' is explicitly defined as the viscosity of the branched polymer divided by the viscosity of the linear polymer at the same absolute MW:

[0184]

[0185] There are different ways to average g'. ave Or average g' is the weight average of g' (BH Zimm, WH Stockmayer, J. Chem. Phys. 1949, 17, 1301). If the entire polymer composition consists of ladder polymers, g' can be determined because it is the viscosity of the linear polymer with the same absolute MW divided by the viscosity of the ladder-branched polymer (both polymers have the same comonomer content).

[0186] The viscosity of a linear polymer is given by:

[0187] log(η 线性 )=log(β)+αlog(M) (22)

[0188] η 线性 =10 {log(β)+αlog(M)} (twenty three)

[0189] The viscosity of the ladder polymer is given by;

[0190] log(η 梯形 )=log(β)+αlog(M)-αlog(2) (24)

[0191] η 梯形 =10 {log(β)+αlog(M)-αlog(2)} (25)

[0192]

[0193] g′=10 -αlog(2) | 相同M (27)

[0194] g′=0.603, for all M (28)

[0195] The average g' value for LDPE is typically below a value of 0.6. The ladder limit of g' assumes that all polymer chains are ladder-branched. Prior work (Application Nos. PCTUS2019 / 053524, filed September 27, 2019; PCTUS2019 / 053527, filed September 27, 2019; PCTUS2019 / 053529, filed September 27, 2019; and PCTUS2019 / 053537, filed September 27, 2019) has shown that not all polymer chains are ladder-branched. This work has a large fraction of polymer chains produced by single-chain catalysts in which little or no LCBs are present. In this case, g' ave The values ​​(weight average g') are much higher than previously achievable as indicated in Tables 4, 6 and 9.

[0196] Trapezoidal feature (L)

[0197] As previously discussed, there is a balance between the melt properties of a polymer and the 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, wherein the ladder polymer has a tetrafunctional long chain branching, as shown in Scheme 3. Without intending to be bound by theory, it is believed that due to the uniqueness of the ladder polymer of the high molecular weight fraction and the linear polymer of the low molecular weight fraction, the melt processing characteristics are improved without increasing the viscosity and reducing the melt index, thereby without viscosity or fouling problems in the reactor.

[0198] In order to estimate the gradient characteristics, a new parameter (L) is introduced. The Mark-Horwin-Sakurada plot (logη vs. log M) shows two power-law dependencies ( Figure 6 and Figure 7 ), where the low MW fraction is based on linear polymers and the high MW fraction is based on ladder polymers. For a given sample, each data point can be fitted to the equation, where L is the fraction of ladder polymers and (1-L) is the fraction of linear polymers:

[0199] log(η)=(1-L)*log(η 线性 )+L*log(η 梯形 ) (29)

[0200] log(η 线性 )=log(β)+αlog(M) (22)

[0201] log(η 梯形 )=log(β)+αlog(M)-αlog(2) (24)

[0202] log(η) = log(β) + αlog(M) - L*αlog(2) (30)

[0203] As previously described (Application No. PCTUS2019 / 053524 filed on September 27, 2019; Application No. PCTUS2019 / 053527 filed on September 27, 2019; Application No. PCTUS2019 / 053529 filed on September 27, 2019; and Application No. PCTUS2019 / 053537 filed on September 27, 2019), S 最大 is the first instance of the maximum downward slope of the RHS (higher MW side) of the main peak (absolute value of the slope) of the scaled MWD (inflection point). If the slope of the viscosity is plotted as an absolute M w function, it is noted that the initial slope is approximately 0.73, and then there is a transition period before another slope is large 0.73. During the transition period, the slope decreases, then increases again, and then approaches 0.73. For a specific example, Figure 8 depicts this variation.

[0204] Two slopes are determined, namely the slopes of the low MW fraction and the high MW fraction. The slope is interpolated for every 25 data points, where the low MW fraction is the average of the last 5 slopes, and the high MW fraction is the last slope.

[0205] Fig. 9 depicts a trapezoidal feature such as 3 - 8. The trapezoidal feature is approximately zero below S 最大 and then rises to approximately 1 at the high MW end.

[0206] The trapezoidal feature (L) can be plotted as a function of log(M) before and after S 最大 . As can be seen in Fig.10 (left), for all data points in all samples, for log(M) < S 最大 (-0.35 < L < 0.35), L lies between -0.35 and +0.35. Above S 最大 (see Fig.10 , right), L increases with log(M), where the maximum value of L (L 最大 ) lies between 0.7 and 1.5 (0.7 < L 最大 < 1.5). Fig.10 Also shown in are two comparative bimodal examples without LCB, and these two comparative bimodal examples do not conform to the L 最大 criterion. Prior art examples of single - chain catalysts (not bimodal polymers) show that for any of the comparative examples in the comparative examples, neither definition is satisfied (see Fig.11 ).

[0207] Visual inspection of the "ladder branched" MWD shows that there is a lack of the characteristic high MW tail that is typically seen in branched polymers. A tail 12 demonstrates how the model predicts a lack of tailing for a "ladder branched" polymer. The "ladder branched" MWD data shows the characteristic lack of tails for many experiments, but also indicates that some tail formation is possible depending on the polymerization conditions and diene / catalyst pairing. A tail A tail

[0208] Polydispersity index (M w / M n 、M z / M w The polydispersity index (M, etc.) is a known measure of tailing, but is not preferred due to its sensitivity to low MWD artifacts. Therefore, a more focused version of the polydispersity index was used to develop a criterion that performs integration only on the high MW portion of the MWD. w / M n and M z / M w The measurement successfully distinguishes diene "ladder branching" from conventional branching and is very sensitive to high MW baseline selection and baseline noise.

[0209] and calculate the MWD dispersion index (M w / M n 、M z / M w Compared to the higher moments required for MWD, the area under the MWD curve is relatively insensitive to baseline problems. Therefore, it was decided to develop a metric that includes the unweighted integral of the MWD. ​​These MWD area metrics A 高 and A 尾部 It is calculated from the area of ​​the GPC curve defined on the right hand side of the MWD curve. MWD area measurement (A 高 and A 尾部 ) is derived from a scaled MWD curve (dW / logM), where the major or highest peak in the MWD is defined as having unity. If more than one peak has the same height, the highest MW peak is the major peak. The independent variable in the MWD curve is Log(M), which is the base 10 logarithm of M. Both MWD area measures depend on the point of maximum slope of the high MW portion of the MWD. ​​The quantities and restrictions required to evaluate the area measures are listed below and are shown in Fig.12 middle.

[0210] S 最大 = First example of maximum downward slope of the RHS (higher MW side) of the main peak (absolute value of the slope) of the scaled MWD

[0211] H smax = Height of scaled MWD at the point of maximum slope

[0212] pt1=S最大 LogM value

[0213] pt2 = LogM value, where S 最大 Tangent intersects x-axis

[0214] The MWD area measure is defined below, where A 高 It is simply the area of ​​the MWD region that falls after the point of maximum slope. The second area measure A 尾部 is depicted in Fig.12 The small high MW area in the 高 Evaluate by subtracting the area of ​​the triangle.

[0215]

[0216] A 尾部 =A 高 -1 / 2(H smax ) 2 / S 最大 (32)

[0217] Using current bimodal polymers, A 尾部 The value 0.04 will be exceeded because these are bimodal polymers with a small amount of high MW branched material. In this case, A is required 尾部 Greater than 0.06.

[0218] Ethylene-based polymers produced by the process of the present disclosure

[0219] As described in Scheme 4, polymers produced by "ladder branching" are encompassed by the present disclosure.

[0220] In an embodiment of the present disclosure, the ethylene-based polymer comprises a low molecular weight polymer fraction and a high molecular weight polymer, both of which are derived from ethylene, one or more dienes, and optionally one or more C3-C 12 The low molecular weight fraction and the high molecular weight fraction are determined by the S on the molecular weight distribution (MWD) curve determined by absolute gel permeation chromatography. 最大 As presented previously, S 最大 It is the maximum absolute slope on the higher molecular weight side of the main peak of the MWD curve, where the main peak is the peak with the largest amplitude in the MWD curve.

[0221] In the ethylene-based polymers of the present disclosure, the low molecular weight polymer fraction and the high molecular weight polymer fraction each include a trapezoidal characteristic L. The trapezoidal characteristic L is defined as the fit of the logarithm of the intrinsic viscosity [η] to the logarithm of the absolute MW (M) curve for a given absolute molecular weight (MW) using the expression log[η]=log(β)+αlog(M)-L*αlog(2) according to the Mark-Horwin-Sakurada curve, where log(β) is the intercept and α is the slope. The low molecular weight polymer fraction has a molecular weight lower than S. 最大 MW, and all L values ​​are between -0.35 and 0.35; and the high molecular weight polymer fraction has a value higher than S 最大 MW, and the maximum value of L is between 0.8 and 1.5.

[0222] In an embodiment of the present disclosure, the ethylene-based polymer comprises a melt strength (MS) greater than negative 17 multiplied by the logarithm base 10 of the melt index plus 25 (MS>-17*log(MI)+25). In this equation, MS is the melt strength in cN (Rheotens device, 190°C, 2.4 mm / s 2 , from die outlet to wheel center is 120mm, extrusion rate is 38.2s -1 , capillary die length is 30mm, diameter is 2mm and entrance angle is 180°), and MI is the melt index in grams / 10 minutes according to ASTM D1238. In some embodiments, the melt strength (MS) greater than minus 17 multiplied by the logarithm of the melt index plus 30 (MS>-17*log(MI)+30). In various embodiments, the melt strength (MS) greater than minus 17 multiplied by the logarithm of the melt index plus 35 (MS>-17*log(MI)+35). As previously described, generally, when melt strength increases, melt index decreases. As shown in this equation, melt strength can be increased (so that the polymer has a melt strength of 20cN) and the melt index remains within a normal range (such as 0.1 to 5).

[0223] In an embodiment of the present disclosure, the ethylene-based polymer comprises a monomer derived from ethylene, a diene, and optionally one or more C3-C 12 The ethylene-based polymers include melt viscosity ratios (V 0.1 / V 100 ), the melt viscosity ratio is greater than 20 at 190°C and an average g', the average g' is greater than 0.86, wherein average g' is the 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.

[0224] In an embodiment of the present disclosure, the ethylene-based polymer comprises a monomer derived from ethylene, a diene, and optionally one or more C3-C 12 The ethylene-based polymer comprises a melt strength greater than 10 cN; and an average g' greater than 0.86, wherein the average g' is an intrinsic viscosity ratio as measured by gel permeation chromatography using a triple detector. In one or more embodiments, the ethylene-based polymer has a melt viscosity ratio (V 0.1 / V 100 ), the melt viscosity ratio is greater than 20 at 190°C.

[0225] 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 a olefin derived from ethylene, a diene, and optionally one or more C3-C 12 Polymerization units of α-olefins.

[0226] In one or more embodiments, the average g' is greater than 0.860, wherein 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 0.880. In one or more embodiments, the ethylene-based polymer has an average g' greater than 0.700. In various embodiments, the average g' is greater than 0.900.

[0227] In some embodiments, the high molecular weight polymer fraction comprises 0.5% to 30% by weight (by wt.%) of the polymer. In other embodiments, the high molecular weight polymer fraction comprises between 1% and 15% by weight of the polymer.

[0228] In one or more embodiments, all values ​​of L for the low molecular weight polymer fraction are between -0.2 and 0.2. In some embodiments, the maximum value of L for the high molecular weight polymer fraction is between 0.9 and 1.1.

[0229] In various embodiments, the ethylene-based polymer has a molecular weight tail as measured by the MWD area measure A. 尾部 quantified and the A was determined by gel permeation chromatography using triple detection 尾部 Greater than 0.06. In one or more embodiments, A 尾部 Greater than 0.08 or A 尾部 Greater than 0.10.

[0230] In some embodiments, the ethylene-based polymer has a weight average molecular weight (M) of less than or equal to 250,000 Daltons as determined by absolute gel permeation chromatography. wIn 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 ).

[0231] In one or more embodiments, the melt index (MI) is greater than 0.1, wherein MI is a melt index in grams per 10 minutes according to ASTM D1238. In some embodiments, MI is from 0.1 to 5.0 or from 0.3 to 3.0. In various embodiments, MI is greater than 1 or greater than 2. In some embodiments, MI is greater than 3, wherein MI is a melt index in grams per 10 minutes according to ASTM D1238.

[0232] In some embodiments, the melt strength of the ethylene-based polymer is greater than 10 cN (Rheotens apparatus, 190° C., 2.4 mm / s 2 , from die outlet to wheel center is 120mm, extrusion rate is 38.2s -1 , capillary die length is 30 mm, diameter is 2 mm and entry angle is 180°).

[0233] 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.

[0234] In various embodiments, the ethylene-based polymer comprises a melt viscosity ratio (V 0.1 / V 100 ) is greater than 25 at 190°C. In some embodiments, the melt viscosity at 190°C is greater than (V 0.1 / V 100 ) is greater than 30.

[0235] The unit of "melt strength" is centinewton (cN) and is determined by: Rheotens apparatus, 190°C, 2.4 mm / s 2 , from die outlet to wheel center is 120mm, extrusion rate is 38.2s -1 , the capillary die length is 30 mm, the diameter is 2 mm and the entry angle is 180°.

[0236] The “rheological ratio” and “melt viscosity ratio” are given by V at 190°C. 0.1 / V 100 Definition, where V 0.1 is the viscosity of the ethylene-based polymer at 190°C at an angular frequency of 0.1 rad / s, and V 100 It is the viscosity of an ethylene-based polymer at 190°C at an angular frequency of 100 rad / s.

[0237] The long-chain branched polymerization method described in the preceding paragraph is used to polymerize olefins, mainly ethylene. In some embodiments, there is only a single type of olefin or α-olefin in the polymerization scheme, thereby producing a homopolymer that is essentially a diene comonomer with a small amount of incorporation. However, additional α-olefins can be incorporated into the polymerization procedure. Additional α-olefin comonomers generally have no more than 20 carbon atoms. For example, α-olefin comonomers 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-l-pentene and ethylidene norbornene. For example, one or more α-olefin comonomers can be selected from the group consisting of propylene, 1-butene, 1-hexene and 1-octene; or alternatively, selected from the group consisting of 1-hexene and 1-octene.

[0238] Long chain branched polymers, such as homopolymers and / or interpolymers (including copolymers) of ethylene and optionally one or more comonomers such as α-olefins, may include at least 50 mole percent of units derived from ethylene. All individual values ​​and subranges encompassed by "at least 50 mole %" are disclosed herein as separate embodiments; for example, ethylene-based polymers, homopolymers and / or interpolymers (including copolymers) of ethylene and optionally one or more comonomers such as α-olefins may include: at least 60 mole percent of units derived from ethylene; at least 70 mole percent of units derived from ethylene; at least 80 mole percent of units derived from ethylene; or 50 mole percent to 100 mole percent of units derived from ethylene; or 80 mole percent to 100 mole percent of units derived from ethylene.

[0239] In some embodiments of ethylene-based polymers, the ethylene-based polymers include additional α-olefins. The amount of additional α-olefins in the ethylene-based polymer is less than or equal to 50 mole percent (mol%); in other embodiments, the amount of additional α-olefins includes at least 0.01 mol% to 25 mol%; and in other embodiments, the amount of additional α-olefins includes at least 0.1 mol% to 10 mol%. In some embodiments, the additional α-olefin is 1-octene.

[0240] In some embodiments, the long chain branched polymer may include at least 50 mole percent of units derived from ethylene. All individual values ​​and subranges from at least 90 mole percent are included herein and disclosed as separate embodiments herein. For example, an ethylene-based polymer may include at least 93 mole percent of units derived from ethylene; at least 96 mole percent of units; at least 97 mole percent of units derived from ethylene; or in an alternative, 90 mole percent to 100 mole percent of units derived from ethylene; 90 mole percent to 99.5 mole percent of units derived from ethylene; or 97 mole percent to 99.5 mole percent of units derived from ethylene.

[0241] In some embodiments of the long chain branched polymer, the amount of additional α-olefin is less than 50%; other embodiments include at least 1 mole percent (mol%) to 20 mol%; and in other embodiments, the amount of additional α-olefin includes at least 5 mol% to 10 mol%. In some embodiments, the additional α-olefin is 1-octene.

[0242] Any conventional polymerization method can be used to produce long chain branched polymers. Such conventional polymerization methods include, but are not limited to, solution polymerization, gas phase polymerization, slurry phase polymerization, and combinations thereof, for example, using one or more conventional reactors, such as loop reactors, isothermal reactors, fluidized bed gas phase reactors, stirred tank reactors, batch reactors in parallel or in series, or any combination thereof.

[0243] In one embodiment, ethylene-based polymers may be produced by solution polymerization in a dual reactor system, for example, a single loop reactor system, wherein ethylene and optionally one or more alpha-olefins are polymerized in the presence of a catalyst system as described herein and optionally one or more cocatalysts. In another embodiment, ethylene-based polymers may be produced by solution polymerization in a dual reactor system, for example, a dual loop reactor system, wherein ethylene and optionally one or more alpha-olefins are polymerized in the presence of a catalyst system in the present disclosure and as described herein and optionally one or more other catalysts. The catalyst system as described herein may be optionally used in the first reactor or the second reactor in combination with one or more other catalysts. In one embodiment, ethylene-based polymers may be produced via solution polymerization in a dual reactor system, for example, a dual loop reactor system, wherein ethylene and optionally one or more alpha-olefins are polymerized in the two reactors in the presence of a catalyst system as described herein.

[0244] In another embodiment, the long chain branched polymers can be produced via solution polymerization in a single reactor system, such as a single loop reactor system, wherein ethylene and optionally one or more α-olefins are polymerized in the presence of a catalyst system as described within the present disclosure and optionally one or more cocatalysts as described in the preceding paragraphs. In some embodiments, the long chain branched polymerization process for producing the long chain branched polymer comprises polymerizing ethylene and optionally at least one additional α-olefin in the presence of a catalyst system.

[0245] 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. Ethylene polymers may contain any amount of additives. According to the weight of the ethylene-based polymer and one or more additives, the ethylene-based polymer may comprise about 0 percent to about 10 percent of the total weight of such additives. The ethylene-based polymer may further comprise a filler, which may include, but is not limited to, an organic or inorganic filler. According to the combined weight of the ethylene-based polymer and all additives or fillers, the long-chain branched polymer may contain about 0 percent by weight to about 20 percent by weight of filler, such as calcium carbonate, talcum powder, or Mg(OH) 2. The ethylene-based polymer may further be blended with one or more polymers to form a blend.

[0246] In some embodiments, a polymerization process for producing a long chain branched polymer may include polymerizing ethylene and at least one additional α-olefin in the presence of a catalyst having two polymer production sites. The long chain branched polymer produced by this catalyst having two polymer production sites may have a molecular weight according to ASTM D792 (incorporated herein by reference in its entirety), for example, 0.850 g / cm 3 To 0.960g / cm 3 、0.880g / cm 3 To 0.920g / cm 3 、0.880g / cm 3 To 0.910g / cm 3 or 0.880g / cm 3 To 0.900g / cm 3 density.

[0247] In another embodiment, the long chain branched polymer produced by the long chain polymerization process may have a melt flow ratio (MFR) of 5 to 100. 10 / I2), wherein the melt index I2 is measured at 190°C and 2.16 kg load according to ASTM D1238 (incorporated herein by reference in its entirety), and the melt index I is measured at 190°C and 10 kg load according to ASTM D1238 10 In other embodiments, the melt flow ratio (I 10 / I2) is from 5 to 50, and in other embodiments, the melt flow ratio is from 5 to 25, and in other embodiments, the melt flow ratio is from 5 to 9.

[0248] In some embodiments, the long chain branched polymer produced by the long chain polymerization process has a molecular weight distribution (MWD) of 1 to 20, wherein MWD is defined as M w / M n , M w is the weight average molecular weight and M n is the number average molecular weight using light scattering. In other embodiments, the polymer obtained from the catalyst system has an MWD of 1 to 10. Another embodiment includes an MWD of 1 to 3; and other embodiments include an MWD of 1.5 to 2.5.

[0249] Gel Permeation Chromatography (GPC) (Conventional GPC)

[0250] The chromatographic system consisted of a PolymerChar GPC-IR (Valencia, Spain) high temperature GPC chromatograph equipped with an internal IR5 infrared detector (IR5) and 4 capillary viscometers (DV) connected to a Precision Detectors (now Agilent Technologies) 2-angle laser scattering (LS) detector model 2040. For all absolute light scattering measurements, a 15 degree angle was used for measurement. The autosampler oven chamber was set to 160 degrees Celsius, and the column chamber was set to 150 degrees Celsius. The columns used were 4 Agilent "MixedA" 30 cm 20 micron linear mixed bed columns. The chromatographic solvent used was 1,2,4 trichlorobenzene and contained 200 ppm of butylated hydroxytoluene (BHT). The solvent source was nitrogen sparged. The injection volume used was 200 microliters, and the flow rate was 1.0 ml / min.

[0251] The calibration of the GPC column set was performed with at least 20 narrow molecular weight distribution polystyrene standards with a molecular weight range of 580 to 8,400,000, and arranged in 6 "cocktail" mixtures with at least ten times of interval between each molecular weight. Standards were purchased from Agilent Technologies. For molecular weights equal to or greater than 1,000,000, 0.025 grams of polystyrene standards were prepared in 50 milliliters of solvent, and for molecular weights less than 1,000,000, 0.05 grams of polystyrene standards were prepared in 50 milliliters of solvent. The polystyrene standards were dissolved and gently stirred for 30 minutes at 80 degrees Celsius. Equation 33 was used to convert the polystyrene standard peak molecular weight to polyethylene molecular weight (as described in Williams and Ward, Journal of Polymer Science (J.Polym.Sci.), Polym.Let., Vol. 6, p. 621 (1968)):

[0252] M 聚乙烯 =A×(M 聚苯乙烯 ) B (33)

[0253] Where M is the molecular weight, A has a value of 0.4315, and B equals 1.0.

[0254] A polynomial between the 3rd and 5th order was used to fit the corresponding polyethylene equivalent calibration points. A small adjustment was made to A (from approximately 0.415 to 0.44) to correct for column resolution and band broadening effects so that the NIST standard NBS 1475 was obtained at 52,000 Mw.

[0255] Plate counts for the GPC column set were performed with eicosane (prepared as 0.04 g in 50 mL TCB and dissolved for 20 minutes under slow stirring). Plate counts (Equation 34) and symmetry (Equation 35) were measured for a 200 μL injection volume according to the following equations:

[0256]

[0257] where RV is the retention volume in milliliters, peak width is in milliliters, peak maximum is the maximum height of the peak, and 1 / 2 height is 1 / 2 the height of the peak maximum.

[0258]

[0259] Where RV is the retention volume in milliliters, and peak width is in milliliters, peak maximum is the maximum position of the peak, tenth height is 1 / 10 of the height of the peak maximum, and where post-peak refers to the tail of the peak with a retention volume later than the peak maximum, and where pre-peak refers to the front of the peak with a retention volume earlier than the peak maximum. The plate count of the chromatographic system should be greater than 24,000, and the symmetry should be between 0.98 and 1.22.

[0260] The samples were prepared semi-automatically using the PolymerChar "Instrument Control" software, where the target weight of the sample was set to 2 mg / ml and the solvent (containing 200 ppm BHT) was added to a septum-capped vial previously sparged with nitrogen by the PolymerChar high temperature autosampler. The samples were dissolved at 160°C for 2 hours under "slow" shaking.

[0261] Based on the GPC results using the internal IR5 detector (measurement channel) of the PolymerChar GPC-IR spectrometer according to Equations 36-38, the TM M was determined using the software, the baseline-subtracted IR chromatogram at each equally spaced data collection point (i), and the polyethylene equivalent molecular weight obtained from the narrow standard calibration curve at point (i). n(GPC) 、M w(GPC) and M z(GPC) Calculation.

[0262]

[0263] 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 (nominal)) for each sample by comparing the RV of the corresponding decane peak in the sample (RV (FM sample)) with the RV of the alkane peak in the narrow standard calibration (RV (FM calibrated)). It was then assumed that any changes in the decane marker peak time were related to linear changes in the flow rate (flow rate (effective)) throughout the run. In order to facilitate the highest accuracy measured for the RV of the flow marker peak, a least squares fitting procedure was used to fit the peak of the flow marker concentration chromatogram to a quadratic equation. The first derivative of the quadratic equation was then used to solve for the true peak position. After calibrating the system based on the flow marker peak, the effective flow rate (relative to the narrow standard calibration) was calculated as Equation 26. By PolymerCharGPCOne TMThe software completes the processing of the flow marker peaks. An acceptable flow rate correction is such that the effective flow rate should be within + / - 2% of the nominal flow rate.

[0264] Flow rate (effective) = flow rate (nominal) * (RV (FM calibrated) / RV (FM sample)) (39)

[0265] Triple Detector GPC (TDGPC) (Absolute GPC)

[0266] The chromatography system, running conditions, column setup, column calibration and calculation of conventional molecular weight moments and distributions were performed according to the methods described in Gel Permeation Chromatography (GPC).

[0267] To determine the offset of the viscometer and light scattering detectors relative to the IR5 detector, a systematic method for determining the multi-detector offset was performed in a manner consistent with that published by Balke, Mourey et al. (Mourey and Balke, Chromatography Polym. Chapter 12, (1992)) (Balke, Thitiratsakul, Lew, Cheung, Mourey, Chromatography Polym. Chapter 13 (1992)) using the PolymerChar GPCOne TM The software optimizes the results from a broad homopolymer polyethylene standard (M w / M n >3) with triple detector log (MW and IV) results from narrow standards column calibration curves.

[0268] Absolute molecular weight data using PolymerChar GPCOne TM The software was obtained in a manner consistent with that published by Zimm (Zimm, BH, Journal of Physical Chemistry, 16, 1099 (1948)) and Kratochvil (Kratochvil, P., Classical Light Scattering from Polymer Solutions, Elsevier, Oxford, NY (1987)). The total injected concentration used to determine the molecular weight is obtained from the mass detector area and the mass detector constant, which is derived from a suitable linear polyethylene homopolymer or one of the polyethylene standards of known weight average molecular weight. The calculated molecular weight (using GPCOne TM) are obtained using the light scattering constant from one or more polyethylene standards mentioned below and the refractive index concentration coefficient dn / dc 0.104. Typically, the mass detector response (IR5) and the light scattering constant (using GPCOne TM Viscometer calibration (using GPCOne TM The viscometer constant (determined using GPCOne TM The specific viscosity area (DV) and injected mass of the calibration standards are related to their intrinsic viscosity. The chromatographic concentrations are assumed to be low enough to eliminate the effects of the 2nd viral coefficient (the effect of concentration on molecular weight).

[0269] Absolute weight average molecular weight (M W(Abs) )Yes (Using GPCOne TM ) is obtained by dividing the area of ​​the light scattering (LS) integrated chromatogram (calculated from the light scattering constant) by the mass recovered from the mass constant and the mass detector (IR5) area. Molecular weight and intrinsic viscosity responses are at the end of the chromatogram where the signal-to-noise ratio becomes low (using GPCOne TM ) linear extrapolation. According to equations 40-41, the other corresponding moments M are calculated as follows n(Abs) and M z(Abs) :

[0270]

[0271] Dynamic mechanical spectroscopy (or small angle oscillatory shear)

[0272] Complex viscosity (η *), modulus (G', G"), tanδ and phase angle (δ) were obtained by dynamic oscillation frequency sweep testing at 190°C in the frequency range of 0.1 rad / s to 100 rad / s. The strain level was set in the linear viscoelastic range, as identified by strain sweep testing at 190°C at 100 rad / s. The tests were performed on a strain controlled rheometer ARES-G2 from TA Instruments using stainless steel parallel plates with a diameter of 25 mm. 3.3 mm thick samples were extruded and then trimmed in two steps before the actual test. In the first step, the sample was melted for 2.5 minutes, extruded to a 3 mm gap and trimmed. After an additional soaking at 190°C for 2.5 minutes, the sample was extruded to a 2 mm gap and the excess material was trimmed. The method has an additional built-in five minute delay to allow the system to reach thermal equilibrium. The tests were performed under a nitrogen atmosphere.

[0273] Batch Reactor Polymerization Procedure

[0274] Batch reactor polymerization was carried out in a 2L Parr TM The reactor is heated by an electric heating mantle and cooled by an internal winding cooling coil containing cooling water. TM The TG process computer controls and monitors the reactor and heating / cooling system. A dump valve is installed at the bottom of the reactor to drain the contents of the reactor into a stainless steel dump pot. The dump pot is pre-filled with a catalyst kill solution (typically 5 mL of an Irgafos / Irganox / toluene mixture). The dump pot is discharged into a 30-gallon blowdown tank, and both the tank and the tank are purged with nitrogen. All solvents used in the polymerization or catalyst composition are passed through solvent purification columns to remove any impurities that may affect the polymerization. 1-Octene and Isopar E are passed through two columns, the first column containing A2 alumina and the second column containing Q5. Ethylene is passed through two columns, the first column containing A204 alumina and molecular sieves, and the second column contains the Q5 reactant. The N2 used for the transfer is passed through a column containing A204 alumina, Single column of mol-sieve and Q5.

[0275] According to the reactor load, first the reactor is loaded from a spray tank that may contain IsoparE solvent and / or 1-octene. The spray tank is filled to the load set point by using a laboratory scale equipped with a spray tank. After adding the liquid feed, the reactor is heated to the polymerization temperature set point. If ethylene is used, it is added to the reactor when ethylene is at the reaction temperature to maintain the reaction pressure set point. The addition of ethylene is monitored by a micro-motion flow meter (Micro Motion). For some experiments, the standard condition at 150°C is 575gIsoparE containing 25g ethylene, 22g 1-octene, 240psi hydrogen, and in other experiments, the standard condition at 150°C is 602gIsoparE containing 22g ethylene, not containing 1-octene, 192psi hydrogen.

[0276] The primary catalyst and activator are mixed with an appropriate amount of purified toluene to obtain the desired molar concentration solution. The primary catalyst and activator are handled in an inert glove box, extracted into a syringe and transferred to a catalyst injection tank under pressure. The syringe is rinsed three times with 5mL of toluene. After the catalyst is added, the run timer starts immediately. If ethylene is used, it is added by Camile to maintain the reaction pressure set point in the reactor. The polymerization reaction runs for 10 minutes, then the agitator is stopped and the bottom discharge valve is opened to discharge the reactor contents to the pouring pot. The contents of the pouring pot are poured into a tray and placed in a laboratory fume hood, where the solvent is evaporated overnight. The tray containing the remaining polymer is transferred to a vacuum oven, where it is heated to 140°C under vacuum to remove any residual solvent. After the tray cools to ambient temperature, the yield of the polymer is weighed to measure the efficiency and submitted for polymer testing.

[0277] Example

[0278] Bimodal gradient branching using two catalysts

[0279] Bimodal polymers were produced using a dual-chain catalyst (catalyst 1) {(a) Figueroa, R.; Froese, RD; He, Y.; Klosin, J.; Theriault, CN; Abboud, KA Organometallics 2011, 30, 1695-1709, (b) Froese, RD; Jazdzewski, BA; Klosin, J.; Kuhlman, RL; Theriault, CN; Welsh, DM; Abboud, KA 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).

[0280]

[0281] In addition to the polymerization reactions that only include single and double chain catalyst runs, that is, comparison 3-C12, 3-C13, 3-C14, the comparative examples include polymerization reactions that do not include dienes (3-C1, 3-C2). The procedures for making comparisons can be found in application No. PCTUS2019 / 053524 filed on September 27, 2019; application No. PCTUS2019 / 053527 filed on September 27, 2019; application No. PCTUS2019 / 053529 filed on September 27, 2019; and application No. PCTUS2019 / 053537 filed on September 27, 2019, which are incorporated herein by reference.

[0282] In each example containing diene, the amount of diene introduced into the reactor was small compared to the other reactants in the reactor. Therefore, the addition of diene did not affect the amount of comonomer, ethylene and solvent added to the reactor.

[0283] Table 2: Batch Reactor Conditions for Polymerization with Catalyst 1 and Catalyst 2 .

[0284] Catalyst 1 Activator hydrogen Octene Isopar E Diene Diene entry μmol μmol Δpsi g g g 3-C1 0.25 0.42 193 0 605 none 3-C2 0.25 0.42 191 0 595 none 3-3 0.25 0.42 193 0 602 Pentadiene 0.2 3-4 0.25 0.42 212 0 600 Pentadiene 0.2 3-5 0.3 0.48 155 22 578 Divinylsilane 0.2 3-6 0.2 0.36 192 0 602 Divinylsilane 0.15 3-7 0.2 0.36 191 0 596 Divinylsilane 0.25 3-8 0.2 0.36 153 22 574 Divinylsilane 0.25 3-9 0.2 0.36 106 22 579 Divinylsilane 0.2 3-10 0.3 0.48 104 22 577 Pentadiene 0.3 3-11 0.2 0.36 192 0 596 Divinylsilane 0.2

[0285] 0.1 μmol catalyst 2, 10, 10 μmol MMAO-3A, ​​25 g ethylene, T = 150 ° C, activator: methyl di (C 18 H 37 )ammonium tetrakis(pentafluorophenyl)borate.

[0286] Table 3: Previously compared batch reactor conditions (examples from application number PCTUS2019 / 053524) .

[0287] Catalyst 1 Activator hydrogen Octene Isopar E Diene Diene entry μmol μmol Δpsi g g g 3-C12 0.3 0.36 200 45 555 Decadiene 0.3 3-C13 0.3 0.36 200 45 555 Decadiene 0.25 3-C14 0.4 0.48 240 0 600 Decadiene 0.20

[0288] 10 μmol MMAO-3A, ​​14 g ethylene, T = 150 ° C, activator: methyl di(C 18 H 37 )Tetrakis(pentafluorophenyl)ammonium

[0289] Table 4: Molecular weight and octene incorporation data for samples from Tables 2 and 3

[0290]

[0291]

[0292] Table 5: Trapezoidal characteristics and Mark-Horwin slopes of samples in Tables 2 and 3 .

[0293]

[0294] Table 6: Shear and extensional rheological properties of samples from Tables 2 and 3 .

[0295]

[0296]

[0297] MI estimated from viscosity: MI = 10^{4.7435-0.88267*Log(V 0.1 )-0.40245*Log(V 100 )}

[0298] Table 7: Mark-Horwin-Sakurada fitting parameters for samples in Tables 2 and 3 .

[0299] Fraction wt% <![CDATA[Log(η) 1 ]]> <![CDATA[Log(η) 2 ]]> <![CDATA[ΔLog(η) 3 ]]> <![CDATA[ΔLog(η) 4 ]]> High MW entry Components 3-C1 0.890 0.873 0.042 0.018 10 3-C2 0.853 0.845 0.039 0.015 9 3-3 1.205 1.194 0.279 0.277 17 3-4 1.150 1.138 0.247 0.242 18 3-5 1.044 1.037 0.219 0.218 28 3-6 1.057 1.045 0.175 0.173 18 3-7 1.130 1.114 0.191 0.189 24 3-8 1.020 1.009 0.217 0.215 21 3-9 1.084 1.072 0.215 0.215 18 3-10 1.219 1.211 0.292 0.295 19 3-11 1.095 1.082 0.207 0.207 28 3-C12 0.964 0.939 0.284 0.286 0 3-C13 0.924 0.904 0.244 0.243 0 3-C14 1.403 1.389 0.632 0.631 0

[0300] 1 log(η) at log(η) where the weight fraction of the polymer is 0.03. 2 For the five lowest weight fractions of polymer above 0.03, the log(η) measurements are averaged. 3 The difference between the value in footnote 1 and the standard, log(η) = -3.4

[0301] +0.73log(M). 4 The difference between the value in footnote 2 and the standard, log(η)=-3.4+0.73log(M).

[0302] Comparative Example 3-C2 has an average g' of 1.0, but a melt viscosity ratio of 3.4, indicating a linear polymer structure. Comparative Examples 3-C12, 3-C13, and 3-C14 have g' values ​​less than 0.86. In contrast, Inventive Examples 3-5 to 3-9 have melt viscosity ratios greater than 20 and average g' values ​​greater than 0.860.

[0303] Table 8: Batch Reactor Conditions for Polymerization with Catalyst 1 and Catalyst 2 .

[0304] Catalyst 1 Activator hydrogen Diene Diene entry μmol μmol Δpsi g 3-15 0.4 0.6 84 Pentadiene 0.3 3-16 0.2 0.36 107 Pentadiene 0.2 3-17 0.3 0.48 107 Pentadiene 0.1 3-18 0.2 0.36 103 Divinylsilane 0.2 3-19 0.2 0.36 106 Pentadiene 0.4 3-20 0.3 0.48 103 Pentadiene 0.2 3-21 0.3 0.48 104 Pentadiene 0.3 3-22 0.3 0.48 154 Pentadiene 0.3 3-23 0.2 0.36 105 Pentadiene 0.3 3-24 0.3 0.48 152 Pentadiene 0.2 3-25 0.2 0.36 154 Pentadiene 0.3 3-26 0.3 0.48 154 Pentadiene 0.1 3-27 0.1 0.24 58 Divinylsilane 0.3

[0305] 0.1 μmol catalyst 2, 10 μmol MMAO-3A, ​​25 g ethylene, 22 g octene, 580 g IsoParE, T = 150 ° C, activator: methyl di(C 18 H 37 )ammonium tetrakis(pentafluorophenyl)borate.

[0306] Table 9: Molecular weight, octene incorporation and melting point data for samples in Table 8 .

[0307]

[0308] Table 10: Shear and extensional rheology of samples in Table 8 .

[0309] <![CDATA[V 0.1 ]]> <![CDATA[V1]]> <![CDATA[V 100 ]]> RR MI MS Ext entry Pas Pas Pas g / 10 min cN mm / s 3-15 104,000 1,150 90.0 0.1 120 40 3-16 8,519 2,490 442 19.3 1.6 29 47 3-17 15,885 5,010 780 20.4 0.7 24 51 3-18 27,358 7,645 1,063 25.7 0.4 36 66 3-19 10,010 455 22.0 1.4 79 47 3-20 18,772 819 22.9 0.6 57 38 3-21 36,608 11,695 826 44.3 0.3 57 39 3-22 5,473 329 16.6 2.7 29 45 3-23 13,077 637 20.5 1.0 41 72 3-24 21,695 515 42.1 0.7 18 51 3-25 10,070 390 25.8 1.5 23 72 3-26 7,060 465 15.2 1.9 8 165 3-27 33,392 2,404 13.9 0.2 63 50

[0310] MI estimated from viscosity: MI = 10^{4.7435-0.88267*Log(V 0.1 )-0.40245*Log(V 100 )}

[0311] Examples of bimodal polymers with small amounts of diene present are collected in Tables 8, 9, and 10. The run conditions are provided in Table 8, while the MW and comonomer incorporation data are collected in Table 9. Shear and extensional rheology including melt strength and melt index values ​​are provided in Table 10. Melt strength is one of the key values ​​as this number relates to bubble stability on the blown film line.

[0312] Table 8 provides the design of the experiment, where changes in Catalyst 1 loading, added hydrogen, and added diene (pentadiene) affect the melt index. One skilled in the art will know how changes in these conditions generally affect MI and MS: i) Catalyst 1 is the higher MW fraction, so the greater the amount of Catalyst 1, the greater the weight fraction of the higher MW fraction, and thus the lower the MI; ii) the more hydrogen, the lower the total MW, the higher the MI; iii) the more diene added, the more LCB in the ladder fraction, the lower the MI. As the three parameters change, the MI and MS also change, as shown in Table 10.

[0313] The MS ( Fig.13 ): MS = 185.3*catalyst 1 (μmol) 0.48*H2 (psi) + 204.4*pentadiene (g) + 24.48 (42)

[0314] As expected, higher Catalyst 1 loading, lower hydrogen, and more pentadiene resulted in higher melt strength.

[0315] In Table 11, the reactor conditions for the polymerization reactions of entries 3-28 and 3-29. For entry 3-28, the polymerization reaction included a double-chain catalyst, i.e., Catalyst 1, and a single-chain catalyst, i.e., Catalyst 3. For entry 3-29, the polymerization reaction included a double-chain catalyst, i.e., Catalyst 1, and a single-chain catalyst, i.e., Catalyst 4.

[0316] Table 11: Batch Reactor Conditions for Polymerization with Catalyst 1, Catalyst 3, and Catalyst 4 .

[0317] Cat 1 Cat 3 Cat 4 Activator hydrogen Ethylene Octene Isopar E Temp Diene entry μmol μmol μmol μmol Δpsi g g g ℃ g 3-28 0.3 0.05 0 0.42 13 25 34 570 150 0.3 3-29 0.3 0 0.1 0.48 210 20 20 580 160 0.4

[0318] Activator: Methyl di(C 18 H 37 )Tetrakis(pentafluorophenyl)ammonium borate, 10 μmol MMAO-3A, ​​diene:pentadiene

[0319] Table 12: Molecular weight and octene incorporation data for samples in Table 11 .

[0320]

[0321] Table 13: Trapezoidal characteristics and Mark-Horwin slopes of samples in Table 11 .

[0322]

[0323] Table 14: Shear and extensional rheology of samples in Table 11 .

[0324]

[0325] MI estimated from viscosity: MI = 10^{4.7435-0.88267*Log(V 0.1 )-0.40245*Log(V 100 )}

[0326] Fig.14 Plots of MS versus MI for 15 autoclave and tubular LDPE resins (DOW TM LDPE PG7004, DOW TM LDPE 770G, DOW TM LDPE 6621, DOW TM LDPE 310E, DOW TM LDPE 410E, DOW TM LDPE 450E, DOW TM LDPE 751A, DOW TM LDPE 421E, DOW TM LDPE 7481, DOWTM LDPE 50041, DOW TM LDPE 4005, DOW TM LDPE 722, AGILITY TM EC 7220、AGILITY TM EC 7000、DOW TM LDPE 320E). Generally, these follow a pattern where lower MI values ​​lead to higher melt strength values. The upper limit of melt strength is 30 cN. LDPE is below the line drawn on the curve.

[0327] Fig.15 MS versus MI is plotted for ladder polymers as well as LDPE resins. The bimodal ladder technique allows for a MI / MS relationship that is above the LDPE limit (line).

[0328] It should be apparent to those skilled in the art that various modifications may be made to the described embodiments without departing from the spirit and scope of the claimed subject matter. Therefore, this specification is intended to cover modifications and variations of the described embodiments as long as these modifications and variations are within the scope of the appended claims and their equivalents.

Claims

1. An ethylene-based polymer comprising a polyolefin derived from ethylene, a diene and one or more C3-C 12 A polymerization unit for the polymerization of alpha-olefins in the presence of a catalyst system, wherein the ethylene-based polymer comprises: Melt viscosity ratio (V 0.1 / V 100 ), the melt viscosity ratio is greater than 20 at 190°C, wherein V 0.1 is the viscosity of the ethylene-based polymer at 190°C at a frequency of 0.1 rad / sec, and V 100 is the viscosity of the ethylene-based polymer at 190°C at a frequency of 100 rad / sec; and an average g' greater than 0.860, wherein the average g' is an intrinsic viscosity ratio as measured by gel permeation chromatography using a triple detector; 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; wherein the C3-C 12 The α-olefin is selected from propylene, 1-butene, 1-hexene, and 1-octene; and wherein the catalyst system comprises a double-chain catalyst and a single-chain catalyst.

2. An ethylene-based polymer comprising a polyolefin derived from ethylene, a diene and optionally one or more C3-C 12 A polymerization unit for the polymerization of alpha-olefins in the presence of a catalyst system, wherein the ethylene-based polymer comprises: Melt strength, the melt strength is greater than 10 cN, measured as follows: using a Rheotens device, 190°C, 2.4 mm / s 2 , from die outlet to wheel center is 120mm, extrusion rate is 38.2s -1 , the capillary die has a length of 30 mm, a diameter of 2 mm and an entry angle of 180°; and an average g' greater than 0.860, wherein the average g' is an intrinsic viscosity ratio as measured by gel permeation chromatography using a triple detector; 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; wherein the C3-C 12 The α-olefin is selected from propylene, 1-butene, 1-hexene, and 1-octene; and wherein the catalyst system comprises a double-chain catalyst and a single-chain catalyst.

3. The ethylene-based polymer of claim 1, wherein the ethylene-based polymer has a melt strength greater than 10 cN as measured using a Rheotens apparatus at 190°C, 2.4 mm / s 2 , from die outlet to wheel center is 120mm, extrusion rate is 38.2s -1 , the capillary die length is 30 mm, the diameter is 2 mm and the entry angle is 180°.

4. The ethylene-based polymer of any one of claims 1 to 3, wherein the ethylene-based polymer comprises: a first ethylene-based polymer fraction, which is a low molecular weight polymer fraction, and a second ethylene-based polymer fraction, which is a high molecular weight polymer fraction, wherein the low molecular weight polymer fraction and the high molecular weight polymer fraction each comprise a hydrocarbon derived from ethylene, a diene, and one or more C3-C 12 Polymerization units of α-olefins.

5. The ethylene-based polymer of any one of claims 1 to 3, wherein the second molecular weight polymer fraction comprises from 0.5 wt% to 30 wt% of the polymer.

6. The ethylene-based polymer of claim 5, wherein the second molecular weight polymer fraction comprises between 1 wt% and 15 wt% of the polymer.

7. The ethylene-based polymer of any one of claims 1 to 3, wherein the MI is greater than 0.1, wherein MI is the melt index in grams / 10 minutes according to ASTM D1238.

8. The ethylene-based polymer of any one of claims 1 to 3, wherein MI is greater than 1, wherein MI is the melt index in grams / 10 minutes according to ASTM D1238.

9. The ethylene-based polymer of any one of claims 1 to 3, wherein the average g' is greater than 0.

88.

10. The ethylene-based polymer of any one of claims 1 to 3, wherein the melt strength is greater than 20 cN, measured as follows: using a Rheotens apparatus, 190°C, 2.4 mm / s 2 , from die outlet to wheel center is 120mm, extrusion rate is 38.2s -1 , the capillary die length is 30 mm, the diameter is 2 mm and the entry angle is 180°.

11. The ethylene-based polymer of any one of claims 1 to 3, wherein the melt viscosity ratio (V 0.1 / V 100 ) is greater than 25 at 190°C, where V 0.1 is the viscosity of the ethylene-based polymer at 190°C at a frequency of 0.1 rad / sec, and V 100 is the viscosity of the ethylene-based polymer at 190°C at a frequency of 100 rad / sec.

12. The ethylene-based polymer of any one of claims 1 to 3, wherein the ethylene-based polymer has a weight average molecular weight (MW) of less than or equal to 250,000 Daltons as determined by absolute gel permeation chromatography. w ).

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