Trifunctional long-chain branched polyolefin

Abstract

To provide polymers comprising tri-functional long-chain branches.SOLUTION: Embodiments of this disclosure include polymers comprising a polymerized product of ethylene, at least one diene comonomer, and optionally at least one C3-C14 comonomer. The polymer comprises tri-functional long-chain branches resulting from the diene that occur at a frequency of at least 0.03 per 1000 carbon atoms of the polymer. The diene has a structure according to a formula (I), where X represents CR2, SiR2, or GeR2, and each R independently represents C1-C12 hydrocarbyl or -H.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application is a continuation of U.S. Provisional Patent Application No. 62 / 826,27, filed March 29, 2019. No. 4, the entire disclosure of which is incorporated herein by reference.

[0002] Embodiments of the present disclosure generally relate to polymer compositions having trifunctional long chain branches, and The present invention relates to a process by which polymer compositions are synthesized. [Background technology]

[0003] Olefin polymers such as polyethylene are produced through a variety of catalyst systems. The selection of such catalyst systems used in the polymerization process of olefinic polymers is dependent on the It is an important factor that contributes to the characteristics and properties of olefin-based polymers.

[0004] Polyethylene and polypropylene are manufactured for a wide variety of products. The ethylene and polypropylene polymerization process makes a variety of resins suitable for different applications. A wide variety of resulting polyethylene resins with different physical properties make The amount of long chain branching in the polyolefin can be varied in many ways to produce The effect of branching on the properties of polyethylene The branching depends on the length and amount of branching. Short branches mainly affect the mechanical and thermal properties. As the branch length increases, the branches can form layered crystals, which are mechanically and Thermal properties are reduced. Small amounts of long chain branching can significantly alter the processing properties of a polymer. Summary of the Invention [Problem to be solved by the invention]

[0005] To form long chain branches, the vinyl or terminal double bonds of the polymer chain are linked to the new polymer. Reincorporation of vinyl-terminated polymers and introduction of diene comonomers The insertion occurs when a vinyl group on one polymer strand is incorporated into a second polymer strand. In addition, long-chain branching is induced via radicals. All three mechanisms It is difficult to control the amount of branching in the polymers. If branching begins, there will be too much branching, which will lead to gelation and reactor fouling. The reintegration mechanism does not generate many branches, and the branches are can only occur after a land has been generated, thereby further limiting the amount of branching that can occur. will be done.

[0006] An embodiment of the present disclosure is a polymerizable copolymer comprising the polymerization product of ethylene, at least one diene comonomer, and optionally at least one of C3 to C 14 Includes polymers containing comonomers. The polymer occurs at a frequency of at least 0.03 per 1000 carbon atoms in the polymer Contains trifunctional long chain branches arising from dienes.

[0007] The diene has a structure according to formula (I). [ka]

[0008] In formula (I), X is CR2, SiR2, or GeR2, and each R is independently: C1~C 12 In some embodiments, in formula (I), X is -C(R)2-, and each R is -H. In another embodiment, X in formula (I) is -Si(R)2-, and each R is C1 to C 12 It is alkyl.

[0009] Various embodiments of the process may be carried out in a solution polymerization reactor, or in a slurry reactor or gas phase. Particle formation occurs in polymerization reactors such as reactors, and molecular or solid supported catalysts are delivered to the reaction medium. The reaction medium is reached or developed in the reactor system, which may be batch, continuous, or cell. The reactor residence time distribution is similar to that of a non-backmixed reactor. These reactors can be narrow, such as backmixed reactors, and series and recycle reactors. [Brief explanation of the drawings]

[0010] [Figure 1] FIG. 1 is a graphical depiction of polymer molecular weight with the number of branched methines per 1000 carbons. [Figure 2A] FIG. 2A is a plot of molecular weight increase versus diene incorporation. [Figure 2B] FIG. 2B is a plot of polydispersity versus diene linkages. [Figure 3] FIG. 3 is a graphical depiction of the predicted dependence of molecular weight distribution (MWD) curves on trifunctional diene branching level. [Figure 4] FIG. 4 is a graphical depiction of the predicted dependence of relative peak molecular weight (MW) on trifunctional diene branching level. [Figure 5] FIG. 5 is a graphical depiction of the MWD curve showing how the point of maximum slope is used to define the high MWD tail area metric. [Figure 6] Figure 6 is a conventional (RI) GPC of dimethyldivinylsilane samples (Examples 1.C and 1.1-1.7) with increasing amounts of diene. [Figure 7]FIG. 7 is a global carbon NMR spectrum of dimethyldivinylsilane branched polyethylene (Example 12.1). [Figure 8] Figure 8 is the Si(Me)2 region of the carbon NMR spectrum of dimethyldivinylsilane branched polyethylene (Example 12.1). Trifunctional LCB carbon = 0.17 Me / 1000C and tetrafunctional LCB carbon = 0.12 Me / 1000C. [Figure 9] Figure 9 shows the methine region of the carbon NMR spectrum of dimethyldivinylsilane-branched polyethylene (Example 12.1). Trifunctional LCB = 0.09 CH / 1000C, tetrafunctional LCB = 0.16 CH / 1000C. [Figure 10] FIG. 10. Conventional (RI) and absolute (LS) GPC of linear PE (Example 12.C) and dimethyldivinylsilane branched PE (Example 12.1). [Figure 11] Figure 11 shows the extensional viscosity fixture (EVF) of dimethyldivinylsilane branched PE (Example 12.1). [Figure 12] FIG. 12 is a melt strength plot of dimethyldivinylsilane branched polyethylene (Example 12.1). [Figure 13] Figure 13. DMS of dimethyldivinylsilane branched polyethylene (Example 12.1) at 190°C. [Figure 14A] FIG. 14A is a graph of absolute molecular weight distributions of comparative conventional branched polymer samples with varying amounts of diene. [Figure 14B] FIG. 14B is a graph of conventional molecular weight distributions of comparative conventional branched polymer samples with varying amounts of diene. DETAILED DESCRIPTION OF THE INVENTION

[0011] Processes for synthesizing polymers and polymers synthesized by the processes of the present disclosure Specific embodiments of the polymers are described herein. The process may be embodied in different forms and is limited to the specific embodiments described in this disclosure. It should be understood that the embodiments are not to be construed as limiting the present disclosure to any specific embodiments. This disclosure is provided so that it will be comprehensive and complete, and will fully convey the scope of the subject matter to those skilled in the art.

[0012] definition The term "polymer" refers to a group of monomers, whether of the same or different types. It refers to a polymer compound prepared by polymerizing The generic term is usually used to refer to polymers prepared from only one type of monomer The term "homopolymer" refers to a polymer prepared from two or more different monomers. As used herein, the term "interpolymer" encompasses "copolymers." refers to a polymer prepared by polymerization of at least two different types of monomers. Therefore, the general term interpolymer includes copolymers and polymers with three or more units, such as terpolymers. and polymers prepared from different types of monomers.

[0013] "Polyethylene" or "ethylene-based polymer" refers to a polymer derived from the monomer ethylene. % of units. This is intended to mean a polymer containing more than 0 mole % of polyethylene homopoly It includes a mer or copolymer (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 (UL DPE), very low density polyethylene (VLDPE), linear and substantially linear low density Resin containing both single-site catalyzed linear low-density polyethylene (m-LLDPE), High density polyethylene (MDPE) and high density polyethylene (HDPE) .

[0014] "Ethylene-diene polymer" means a polymer containing more than 50 mol% of ethylene monomer. It means a polymer containing a small amount of diene. The polymer optionally comprises one or more (C3 to C 12 ) Units derived from α-olefins may include:

[0015] An embodiment of the present disclosure is a polymerizable copolymer comprising the polymerization product of ethylene, at least one diene comonomer, and optionally at least one of C3 to C 14 Includes polymers containing comonomers. The polymer occurs at a frequency of at least 0.03 per 1000 carbon atoms in the polymer Contains trifunctional long chain branches arising from dienes.

[0016] The diene has a structure according to formula (I). [ka]

[0017] In formula (I), X is CR2, SiR2, or GeR2, and each R is independently: C1~C 12 In some embodiments, in formula (I), X is -C(R)2-, and each R is -H. In another embodiment, X in formula (I) is -Si(R)2-, and each R is C1 to C 12 One or more embodiments In one embodiment, the diene is dimethyldivinylsilane.

[0018] In some embodiments, R in formula (I) is C1-C 12 If alkyl, C1 ~C 12Alkyl is methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2- Butyl, 2-methylpropyl, 1,1-dimethylethyl, 1-pentyl, 1-hexyl, 1-heptyl, n-octyl, tert-octyl, nonyl, decyl, undecyl, or is dodecyl. C1~C 12 The term "alkyl" refers to a saturated alkyl group of 1 to 12 carbon atoms. means a linear or branched hydrocarbon radical.

[0019] In various embodiments, the polymer has at least one trifunctional long chain branch per 1000 carbon atoms. In one or more embodiments, the trifunctional long chain of the polymer occurs with a frequency of at least 0.05. The branches occur at a frequency of at least 0.1 per 1000 carbon atoms. In this case, the trifunctional long chain branches of the polymer should have a frequency of at least 0.2 per 1000 carbon atoms. Occurs at a rate of

[0020] The polymers of the present disclosure are produced via a process for synthesizing long-chain branched polymers. In one or more embodiments, the process includes one or more of C2 to C 14 Alkene monomers, at least a multi-chain catalyst in the presence of a diene, optionally a solvent, and optionally hydrogen; together, wherein the multi-chain catalyst comprises a plurality of polymerization sites, and the diene is a compound represented by the formula ( I) C2~C 14 At least two polymer chains of alkene monomers are produced, and each polymer chain polymerizes at one of the polymerization sites. Polymers are synthesized by linking two polymer chains with a diene. The linking or joining of chains is carried out in a concerted manner during polymerization. Long chain branching polymers are It has a ratio of trifunctional to tetrafunctional long chain branches of 5:1 to 100:0. In embodiments, the ratio of trifunctional to tetrafunctional long chain branches is If the target ratio for chain branching is deviated from, it is adjusted. The ratio is C2 to C 14 Alkenes By varying the amount of monomer feed, the amount of hydrogen feed, or a combination thereof, is adjusted accordingly.

[0021] In various embodiments, the long chain branched polymer has a trifunctionality of 0.05:1 to 100:0. ratio to tetrafunctional long chain branches.

[0022] In one or more embodiments, the trifunctional long chain branches are produced from dienes and The branches occur at a frequency of at least 0.03 per 1000 carbon atoms.

[0023] The term "link" in the context of "linking two polymer chains" is used in a broad sense to mean This means that the polymer chains are covalently bonded.

[0024] In one or more embodiments, the ratio of trifunctional to tetrafunctional long chain branches is The ratio is adjusted if the ratio deviates from the target ratio of tetrafunctional long chain branches to C2 ~C 14 Amount of alkene monomer feed, amount of hydrogen feed, C2 to C 14 Alkene Monomers by changing the ratio of feed to hydrogen, or a combination thereof. do.

[0025] In some embodiments, C2 to C 14 Molar Alkene Monomer Feed to Hydrogen The feed ratio is from 100:0 to 1:1. In one or more embodiments, the feed ratio is from 80: In various embodiments, the feed ratio is 70:1 to 30:1, 60:2 ~10:1, or 50:1 to 25.1.

[0026] Processes for synthesizing polymers according to the present disclosure are disclosed in US Pat. No. 6,399,425, filed Sep. 27, 2019. Application No. PCTUS2019, filed on Oct. 1, 2019, and incorporated herein by reference in its entirety. No. / 053524, No. PCTUS2019 / 053527, No. PCTUS2019 / 0 No. 53529 and PCTUS2019 / 053537 It is different from chain branching or the earlier "ladder" branching. The term "long chain branching" refers to "Branch" refers to a branch having more than 1 carbon atom in a polymer extending from a tertiary carbon atom. If a branch extends from a tertiary carbon atom, two other branches are present and may collectively be polymer strands from which branches extend. In the present disclosure, branches are Defined as trifunctional long chain branching in that the point has three polymer chains emanating from it Conventionally, long-chain branching (LCB) is achieved by polymerization processes, as shown in Scheme 1. Naturally occurring LCBs are formed by vinyl termination of the polymer chain and This can occur through vinyl reinsertion to create trifunctional long chain branches. Depending on the degree of branching, Various methods, such as nuclear magnetic resonance (NMR), determine the LCB or L in a polymer. For example, the effect of LCB can be distinguished from that of van Gurp-Palmen. It is observed in the shear flow of the sintered body, and the increase in shear viscosity at low angular frequencies and the shear The strength of the thinning behavior can be attributed to the LCB. In extensional flow, the effect of the LCB is usually dominated by strain hardening. The degree or melt strength and maximum deformation achieved are distinguished by the degree of To ensure a limited concentration of mers (maximum one per polymer chain) and the formation of LCBs, High levels of natural LCBs in polymers due to the need to achieve high ethylene conversions for To ensure high conversion, the ethylene concentration in the reactor must be low. Therefore, a large amount of vinyl-terminated polymer can be reinserted into a second polymer chain. Scheme 1: Spontaneous long-chain branching: Chain transfer events leading to vinyl-terminated polymers [ka]

[0027] In Scheme 1, "Cat" is the catalyst and "P" is the polymer chain.

[0028] There is minimal long chain branching formed by naturally occurring branching. One approach to this is to use a radical, heterogeneous, or homogeneous process. This is due to the addition of α,ω-diene to the polymerization system. Generally, dienes are As shown, they are added to the polymer chain in a similar manner to α-olefins, but they are also added to the polymer chain. This leaves pendant vinyl groups that can be inserted once to create LCBs. Generally, the diene length is It is not essential that the polymer chain be bonded together, only that it be possible to bond two polymer chains together. The concentration of pendant vinyl can be controlled by the amount of diene added to the reactor. Thus, the degree of LCB can be controlled by the concentration of pendant vinyl. Scheme 2: Long-chain branching via diene incorporation [ka] In Scheme 2, "Cat" is the catalyst and "P" is the polymer chain. The diene is 1,5-hexadiene.

[0029] Conventional processes for incorporating dienes into polymer synthesis systems can lead to problems such as gel formation or reactor fouling. Kinetic modeling, discussed in a later section, is fundamentally flawed. For example, longer polymer chains can provide better prediction results that allow for a better understanding of , the more inserted olefins and therefore the more inserted dienes, Thus, longer polymer chains with more pendant vinyl are reinserted into the catalyst. This means that the longer polymer chains are more likely to form LCBs. The polymer molecules are then reinserted to form larger tetrafunctional branches, which form the gel. As shown in Scheme 2, tetrafunctional LCBs are produced by combining short segments (diene (number of carbon atoms between the two double bonds) and it consists of two long chains on either side of a short segment. The weight average molecular weight (M w ) and number average molecular weight (M n )of Simulations were performed for polyethylene in a constant pressure semi-batch reactor, as shown in Figure 1. In Figure 1, M n is M w As goes to infinity, it only increases slightly. w When the number increases to more than 200,000 grams per mole (g / mol), a polymer gel, Gelling occurs or there is reactor fouling.

[0030] The term "gel" or "gelling" refers to a solid composed of at least two components. The first refers to a three-dimensionally cross-linked polymer, and the second refers to a medium in which the polymer is not completely soluble. If the polymer gels and does not dissolve completely, the reactor will be fouled with polymer gel. It is possible.

[0031] The term "ladder branching" polymer refers to a polymer formed from a "ladder branching mechanism" As shown in Scheme 2, the polymer has a tetrafunctional long-chain branching structure. In addition, the terms "ladder branching" polymer and "ladder branching mechanism" refer to the It also refers to the polymerization process that produces polymers and trifunctional long chain branched polymers.

[0032] The process for synthesizing tetrafunctional long-chain branched polymers achieves long-chain branching and prevents gel formation or Without being bound by theory, it is believed that the reaction of two alkenes with a diene Reactor fouling is avoided by reacting in a concerted manner across two proximal polymer chains For example, as shown in Scheme 3, one alkene of a diene , reacts before the second alkene, and the second alkene reacts because too many ethylene molecules are added to the reacts before being added to the monomer strand, thereby introducing a second alkene into the reaction site. Remove the adjacent ethylene monomers. the reaction of one alkene to a polymer of the other, and the reaction of the diene to a second alkene to a neighboring polymer of the other. The reaction towards the proximal polymer chain is referred to as the concerted addition of the diene to the proximal polymer chain. Scheme 3: Incorporating dienes in a concerted fashion, also known as the tetrafunctional "ladder branching" mechanism (P is the polymer chain.) [ka]

[0033] Depending on the catalyst or diene, different intermediates can result from the diene reaction. showed the formation of tetrafunctional LCBs by the addition of dienes to double-chain catalysts (Scheme 3 ), the formation of trifunctional long-chain branches is also possible (Scheme 4). Scheme 4: Depiction of trifunctional long-chain branch formation from the reaction of dienes. [ka]

[0034] A polymer strand is a linear segment of a polymer, or more specifically, a copolymer. The hydroxyl groups are optionally joined at their termini by branched junctions. For example, the hydroxyl groups shown in Scheme 1 In contrast to trifunctional branched junctions, which join the ends of three polymer strands, as shown in In turn, a tetrafunctional branched junction joins the ends of four polymer strands.

[0035] Without wishing to be bound by theory, it is believed that the mechanisms described in this section How the double-chain catalyst produces a unique trifunctional crosslinking molecule when the dimer is polymerized under the desired conditions The term "diene" refers to a compound that has two alkenes. The mechanism is illustrated in Scheme 5, where the catalyst The center generates two polyolefin chains. Scheme 5 shows the diene crosslinking and chain transfer. How does the combination create a diene "ladder-branched" trifunctional polymer structure? The term "ladder-branched" polymers of dienes refers to long chain branching, and In a branch, a short chain or rung containing 1 to 12 carbon atoms joins two polymer chains together. As shown, metal-ligand catalysts with at least two polymer chain moieties , growing two separate polymer chains. One alkene of the diene is attached to one of the catalytic sites. Due to the proximity of the propagation sites, the second alkene of the diene is then incorporated into the second It is believed that they are rapidly incorporated into the polymer chain, thereby forming bridges or rungs. This sequential addition of dienes is called the "concerted" addition of dienes, and the two proximal chains Diene addition is distinguished from catalysts that do not have a vinyl-containing polymer that reacts later in the reactor. The term "langue" refers to the fact that the diene is once split into two separate polymers. Refers to a diene that, when incorporated into a strand, thereby bonds the strands together The first and second polymer strands are formed when the polymer is transferred to another catalyst or when the polymer The reaction continues until the diene is released from the catalyst, the catalyst dies, or another diene is added. continue. Scheme 5. Diagram of the trifunctional "ladder branching" mechanism, including the resulting molecular structure. -ligand catalyst, LM + are collectively expressed as [ka]

[0036] As shown in Scheme 5, trifunctional ladder branching can occur upon introduction of hydrogen gas. The introduction of hydrogen gas causes the polymer chain to terminate at one of the polymerization sites of the multi-chain catalyst. Upon termination, the polymer chain is scission to produce a trifunctional polymer. The mer contains trifunctional long chain branches arising from the diene of formula (I).

[0037] In one or more embodiments, the ratio of trifunctional to tetrafunctional branches is It is controlled through adjusting other reactor conditions such as the oxygen / hydrogen ratio or temperature. In some embodiments, the ratio of trifunctional to tetrafunctional long chain branches is from greater than 0.1:1 to about 1. It's 00:0.

[0038] Without wishing to be bound by theory, the molecular weight distributions associated with these proposed kinetics However, when diene crosslinking reactions are the only source of branching, they are inherently stable at high branching levels. The molecular weight distribution (MWD) is defined as the weight average molecular weight divided by the number average molecular weight. (M w / M n The inherent stability of MWD is determined by the weight average molecular weight (M w ) but with high branching levels This means that the M w and M w / M n However, the four senses are moderate. This is in contrast to conventional diene comonomer branching technology, where the level of potential branching is infinite.

[0039] The combination of multi-chain catalyst and diene affects the amount and type of branching. The illustrated embodiments are directed to polymer properties such as: 1) the use of multiple diene species; 2) multiple multi-chain polymers; the use of catalytic species; 3) combinations of polymerization environments, including multiple reactor zones or zone gradients. or 4) different types of long chain branching, e.g., controlled trifunctional and tetrafunctional long chain branching. and combinations thereof.

[0040] Nevertheless, by using multiple catalysts, including single-chain catalysts, traditional branching The use of multiple diene species also creates no branching or "conventional" Also included are those dienes that tend to result in LCB. The process is different from conventional long-chain branching. The term "long-chain branching" refers to a chain of more than 100 carbon atoms. The term "branched" refers to a polymer that extends from a tertiary carbon atom. If a branch extends from a tertiary carbon atom, two other branches are present and These can collectively be branched polymer chains. Long chain branching (LCB) is represented by the scheme This can occur naturally in the polymerization process, as shown in Figure 1. This can occur by termination and reinsertion of polymeric vinyl to create trifunctional long chain branches.

[0041] In one or more embodiments, the process for polymerizing the long chain branched polymer comprises This includes catalysts with at least two active sites (multi-chain catalysts). Distances of less than 1000 Å (Å), less than 6 Å, or about 5 Å are included.

[0042] Modern computational techniques allow for a good comparison of known experimental structures as a method for estimating the distance between catalytic chains. It is well known that the method can be reproduced with high accuracy. or -Ge(R)-, where each R is independently hydrogen or a hydrocarbyl group; The diene structure according to formula (I) allows the size of the diene to be estimated. The end-to-end distance of the diene according to formula (I) where X is -Ge(R)2-, the diene is about 7 Therefore, the polymerization site for multiple chains is 8 Å or 2 Å for bimetallic catalysts. The two metals are within 8 Å.

[0043] In the case of heterogeneous systems, the surface concentration of the metal can be estimated, which is often on the order of nanometers. Metal atoms per square (M / nm 2 ) This surface coating is uniformly distributed. In the case of accessible surfaces, this can be converted into M-M distances, which reflect the distance between polymer chains. For extended surfaces, it provides an estimate of the metal concentration. 2 is the 10 Å gap between metal atoms. At 8 Å, the distance is 1.5 metals / nm 2 The coverage of can be determined.

[0044] Examples of catalysts with at least two active sites in close proximity include bimetallic catalysts. transition metal catalysts, heterogeneous catalysts, dianionic activators with two related active catalysts, Ligation of growing polymer chains with transition metal catalysts, monoanionic groups, bidentate monoanionic groups anionic groups, tridentate monoanionic groups, or monodentate, bidentate, or tridentate monoanionic groups with external donors. These include, but are not limited to, Group IV olefin polymerization catalysts containing anionic groups.

[0045] The catalysts in Table 1 are exemplary examples of the aforementioned catalyst classes and specific catalysts contemplated. The examples in Table 1 are not intended to be limiting, but rather They are merely illustrative and specific examples of the aforementioned classes of catalysts. [Table 1]

[0046] Without wishing to be bound by theory, it is believed that the mechanisms described in this section How the double-chain catalyst produces a unique trifunctional crosslinking molecule when the dimer is polymerized under the desired conditions The term "diene" refers to a compound that has two alkenes. The mechanism is illustrated in Scheme 5, where the catalyst The center generates two polyolefin chains. Scheme 5 shows the diene crosslinking and chain transfer. How does the combination create a diene "ladder-branched" trifunctional polymer structure? The term "ladder-branched" polymers of dienes refers to long chain branching, and In a branch, a short chain or rung joins two polymer chains together. A metal-ligand catalyst with at least two polymer chain sites will produce two separate polymer chains. One alkene of the diene is incorporated into one of the catalytic sites and is then propagated near the propagation site. Due to the bonding, the second alkene of the diene is then rapidly incorporated into the second polymer chain. This succession of dienes is believed to form bridges or rungs. This addition is called a "concerted" diene addition and is distinct from catalysts that do not have two proximal chains. This results in the addition of dienes and the subsequent concentration of vinyl-containing polymers in the reactor. The term "diene" refers to the fact that once the diene is incorporated into two separate polymer strands, , thereby referring to the diene that bonds the strands together. Strands can occur when the polymer transfers to another catalyst, the polymer is released from the catalyst, or the polymer is released from the catalyst. Growth continues until the catalyst dies or another diene is added.

[0047] In one or more embodiments, the polymers of the present disclosure contain at least 50 mole % ethylene. In this disclosure, "ethylene-based polymer" refers to an ethylene-based copolymer comprising ethylene. homopolymers, and / or ethylene and optionally one or more α-olefins, Refers to interpolymers (including copolymers) with comonomers, and is a monomer derived from ethylene The unit may comprise at least 50 mole percent (mol %). All individual values ​​and subranges encompassed by "from 100 percent" are considered separate embodiments. Disclosed herein are, for example, ethylene-based polymers, homopolymers of ethylene and / or or an interpolymer of ethylene and optionally one or more comonomers such as α-olefins The polymer (including copolymer) contains at least 60 mole percent ethylene-derived monomer units. at least 70 mole percent of monomer units derived from ethylene; At least 80 mole percent of monomer units and 50 to 100 mole percent of monomer units derived from ethylene 00 mole percent, or 80 to 100 mole percent of ethylene-derived monomer units may include:

[0048] kinetics Mathematical models have previously been derived for tetrafunctional "ladder" long-chain branches, Each was filed on September 27, 2019, application number PCTUS2019 / 05352 No. 4, No. PCTUS2019 / 053527, No. PCTUS2019 / 053529 and PCTUS2019 / 053537, in which trifunctional A model is derived for "ladder branching" long chain branching. The mathematical model is The mathematics of the branching structures described in this disclosure are also used to establish the metrics and ranges of A mathematical model can be derived from the kinetic description of the proposed branching mechanism. Although some assumptions are made to promote simplicity, these assumptions are within the scope of this disclosure. The assumption is not intended to limit the scope of the non-living addition of copolymers. The resulting product is subject to typical industrial applications, as well as additional assumptions specific to the hypothesized diene branching mechanism. The general assumptions made are: (1) propagation is much faster than chain transfer, and therefore the average chain length (2) only a single pure catalytic species is active. (3) The catalytic center makes many chains during its lifetime, and therefore the lifetime of a chain is (4) copolymerization is a process in which composition drift is minimal; In some cases, the polymeric model can be approximated by a homopolymerization model.

[0049] Kinetics for the trifunctional "ladder branching" theory of dienes. Model derivation. The first step in deriving a model of the system is to express the kinetics in symbolic form. Describe and indicate the effect of each reaction on the molecular attributes of the target. It is standard practice to use an index to indicate the number of repeat units associated with a polymer chain. Furthermore, if the homopolymer rate constant is considered to be the effective complex copolymerization rate constant, The molecular structure of addition copolymers is accurately described by the kinetics and models of homopolymers. It is also recognized that it is possible to olymer 1991,32(14),2641).

[0050] P n,m Dual-site catalysts in which the active catalytic center grows two polymer molecules The kinetics of a simple addition polymerization using The molecule on the right has m repeat units. The formation of tetrafunctional branches from diene bridges across the mer molecule was investigated. The following kinetics , a diene bridge across two growing molecules to trifunctional (b3) branches or bifunctional bonds (b 2) Consider the diene bridge that is assumed to be created. The reaction is considered unproductive and is ignored in the kinetic scheme.

[0051] Kinetics of diene trifunctional and difunctional ladder branching theory. [Table 2]

[0052] The kinetics are described for each of the two polymer molecules growing on the catalyst, left and right. The result of growth is identified as the left side (P n+1,m ) or right side (P n,m+1 ) Regardless of the molecular size, the molecular size increases stepwise by one repeat unit. The chain is separated from the catalyst and the left (D n ) or Right (D m ) to remove dead polymer molecules from Additional simple chain transfer type reactions such as hydrogenation or beta hydride elimination can occur. Do not add complexity to the model.

[0053] k for diene crosslinking reaction d is written for each catalyst side, and each rate is the rate of the diene (D) Use a factor of 2 due to the two reactive groups. Both (two) aspects are described, Since the diene (D) has two reactive groups, the diene crosslinking reaction k g is 4 at that speed Thus, the diene consumption kinetics is calculated on a group basis rather than a molecular basis. The rate constant is defined in terms of the base.

[0054] Reinitiation of polymer chains occurs very rapidly and relatively infrequently relative to growth. It is standard practice to assume that by assuming instantaneous restart, the species P n,0 , P 0,m , and P 0,0is essentially excluded from consideration in the polymer population.

[0055] Population balance and rates. The kinetic scheme shows how each reaction affects the molecular structure. These can be rendered into a series of balancing equations that describe how In describing the balance, it is convenient to use an abbreviated nomenclature to represent the rate of each reaction. These velocity groups are defined below. The translation terms, e.g., Ω=k tra A+k trh H2+ k b Only by expanding the definition of trh )oh and beta hydride desorption (k b ) can be included.

[0056] The kinetic velocity group is Ω=k tra AΨ=k d DП=k g DΦ=k p It is defined as M.

[0057] Growth polymer (P n,m ) molecules and dead polymer molecules (D n ) discrete population The kinetic balance is calculated using the kinetic group defined above for n ≥ 1 and m ≥ 1 molecular systems. These balances determine the rate of change in molecular population versus size. Define and add an additional convection term if the balance applies to a particular reactor environment or type. can be modified to include δ k terms in these discrete balances, and the term k=0 Specifies that the element is included only if

[0058]

number

number

[0059] Another important population balance is the left side (L n ) and right side (R n ) growth point Distribution of Rimer subspecies and convolution distribution (V n ) can be derived from the above. The symmetry imposed in defining the scheme allows for the separation of left- and right-hand growing polymer variants. The fabric is equal.

[0060]

number

number

[0061] ξ as the total active catalyst concentration 0,0 Using

number

[0062] The first step in rendering a usable model is to determine the speed of the relevant polymer variants. degree

number

[0063] Method of moments for prediction of MWD mean Models that describe the moments of the chain length distribution of polymer species are often based on kinetic theory. Moment-based models can be derived from population balances obtained from the , are useful for predicting molecular weight averages and polydispersity indices, but generally, bimodality, Peak MW and smaller nuances in MWD such as tailing are discussed. The method of moments provides chain length distribution models for various polymer subspecies, such as: The bulk polymer moment (λ i ) reflects bulk polymer properties The solution of the bulk moment model is generally a function of the various living polymer moments. Needs a solution.

[0064] Living Polymer Moment:

number

[0065] Bulk polymer MWD moment:

number

[0066] Considering that the rate of change of live species is assumed to be zero, the bulk moment The rate of change of the polymer is easily derived from the population balance of the dead polymer.

number

[0067] Any experienced polymer reaction engineer can calculate the It would be expected that a moment model could be derived. The rates of change of the moments (λ0, λ1, λ2) are given below, and the kinetic chain is After imposing the assumption that Φ>>Ω, Φ>>Ψ, and Φ>>Ο are long, negligible terms are be removed.

number

[0068] The evaluation of the rates of change of these bulk moments is based on the analysis of a number of living polymer subpopulations. These live polymer moments are due to the "steady state assumption." is an algebraic quantity given below. Higher bulk moments such as λ are predicted. If so, additional live moments are required.

number

[0069] Evaluation of moment velocities After algebraic simplification, the instantaneous number-averaged and weight-averaged chain lengths (DP n , DP w ) are provided below. Of course, the average molecular weight (M n , M w ) is the average chain length It is equal to the length multiplied by the apparent monomer repeat unit weight (g / mol).

number

number

[0070] Branch Metrics The model expression is the diene-free average linear kinetic chain length DP, which is equal to Φ / Ω. no The model is further simplified by some substitutions such as F, the fraction of ene conjugates b By expressing it in terms of a dimensionless instantaneous branching metric, This can be further simplified by: When the diene level is varied, F b is almost constant can be expected, but will certainly vary with catalyst choice and possibly with reaction conditions. Therefore, F as a metric b The use of is reasonable.

[0071] Fraction of bifunctional diene conjugates

number

[0072] Additional metrics are needed to describe the relative levels of divergence, and here we consider two options: One preferred option is to use a diene bond to the original polymer molecule. R is the ratio c The solution is to use R c One advantage of this is that it is simply a diene bond. This is a scaling factor for the case, and is expected to increase proportionally with the diene. k c The drawback of this approach is that the original kinetic chain length or concentration generally falls within a series containing zero diene branching levels. The problem is that the data are only directly available if they are measured.

[0073] Diene junctions per original kinetic chain

number

[0074] Metric R n is the branch metric R kc is an alternative to R n is a diene-linked poly The ratio of the α-to-β-mer molecules is shown in Figure 1. R was used to analyze the data.n The use of number average molecular weight G This is facilitated by the possibility of measuring chain length or concentration by PC measurement. Since the number of polymer molecules is affected by the junctions, R n is not simply proportional to the diene. Bifunctional Coupling (F b =0), the two metrics R kc and R n teeth, are identical.

[0075] Diene conjugations per polymer molecule

number

[0076] The average chain length and molecular weight are listed below along with the polydispersity, and the diene-free polydispersity is The dispersity index is 2 due to the simplicity of the kinetics and the assumption of ideality.

number

number

number

[0077] F b , R kc , and R n Rendering as a function of physically meaningful parameters such as Once the model is applied, some simple conclusions can be drawn from the above model. The weight average chain length (DP w ) or molecular weight (M w ) but up to twice as much when dienes are incorporated Any bifunctional bond can only increase the DP n or M n Low It is expected to bring down the DP w or M w mitigates any increase in. 2 zero diene maybe Starting from polydispersity, polydispersity (Z) at high trifunctional branching levels p ) is a maximum of 4 and can be set to any This is alleviated by the appearance of arbitrary bifunctional bonds.

[0078] Figure 2 shows the relationship between diene-grafted functional groups (F) and the molecular weight and polydispersity of the polymer. b ) effect The model demonstrates that pure trifunctional diene bridges exert a restraint on molecular weight and polydispersity. It has a limited double potential effect and R kc Incremental effect at high diene levels such as >3 Furthermore, it is clearly shown that F b = 5% or 10% moderately bifunctional diene If the diene junction level is expected, experimental data will be w Even the positive correlation between It may not be possible to prove it.

[0079] Complete MWD curve model Sometimes it is possible to solve the population balance of the molecular weight distribution curve. A practical algebraic solution is usually based on the assumption that the reaction rate does not have spatial or temporal variations, as is assumed in this case. Of particular interest is the bulk MWD moment The polymer distribution function D, previously used to render the model equation for n Yes Similarly, the instantaneous bulk polymer chain length distribution, X n can be expressed as follows:

[0080] Instantaneous bulk chain length distribution:

number

[0081] The long chain assumption ensures that the distribution of all species (X n , D n , L n , V n etc.) into discrete functions The population of the steady-state polymer species can be treated as if it were a continuous function rather than a constant. The ration balance is a function of the differential equation in a continuous variable n when the difference terms are replaced by derivatives. For example, L n The steady-state population balance of The difference term L can be replaced by the derivative as shown n ~L n-1 Contains:

[0082]

number

[0083] Similar substitutions lead to the following set of ordinary differential equations (ODEs), Integrate to obtain the chain length distributions for various defined live subspecies distributions L(n) and V(n). The model is summarized below as an initial value problem, where the chain length distribution function is The lower bound of n=0 on the distribution function is chosen only for mathematical simplicity. Finally, if high molecular weight polymers are formed, this does not significantly affect the model predictions. stomach.

number

number

[0084] Analytical solutions exist for the continuous distribution functions L(n) and V(n), and these functions are used to can be used to render a function of the continuous bulk polymer chain length distribution (X(n)). do.

number

[0085] The solution for X(n) is a little complicated, but can be simply expressed as follows:

number

number

number

number

[0086] Alternative assignments of X(n) functional terms have been previously applied to instantaneous average chain length and molecular weight models. The branch metric (F b , R kc , R n ) can be rendered using the following X Item (n) is F b and R kc is written as a function of R kc =R n / (1- F b R n ) by applying R n can be converted to use α=1+R kc +1 / 2F b R kc

number

number

number

[0087] The integral of X(n) can be used to express the number and weight average chain lengths as well as the polydispersity. can.

number

[0088] As expected, integrating the distribution equation X(n) gives the average degree of polymerization and average molecular weight The results are in exact agreement with the instantaneous moment model presented previously. The model does not provide additional or contradictory predictions of MWD mean and polydispersity. Using this full chain length distribution model, we can determine how the MWD nuances are affected by diene addition. In particular, the model allows us to understand how diene incorporation levels are affected. Modality, steepness, and thickness of MWD as a function of the bell and embedded modes It is possible to predict the

[0089] Limiting cases of MWD models There are two limiting cases for the chain length distribution model. The trivial case is F b =1, and the polymer is completely linear and has the most probable MWD. The average chain length of the most probable MWD decreases with the diene crosslink level, which is b =1 Therefore, it is completely bifunctional.

[0090] A more interesting limiting case is when there is no bifunctional bond (F b =0), and branching Trick R kc and R n Each diene bond is a trifunctional branch point. Therefore, a specific nomenclature for branched polymers can be used.

[0091] F b If =0, B n = branch points per polymer molecule = R kc =R n

[0092] F b If =0, B c = Branch points per linear segment = (1 + B n ) / B n

[0093] This pure trifunctional branch chain length distribution is B n and B c is shown below for

number

number

[0094] By integrating the above distribution function, F b The MWD average for =0 can be obtained, and this is The number average molecular weight of this trifunctional branched system is determined by the number of polymer molecules in the system as the branching reaction proceeds. does not change with increasing diene incorporation.

number

number

number

[0095] Polydispersity (M w / M n The above relationship to the trifunctional branching level of Most surprisingly, at high branching levels, The prediction is that the dispersion will level off at 4. Naturally, this prediction is unreasonable. Ideal copolymerization and symmetric catalyst systems, whereas non-ideal ones increase polydispersity. It is expected that this will happen.

[0096] The chain length distribution function can again be used to construct a predicted MWD curve. Functional Branching (B c or B n A series of simulated SEC songs with varying levels of The independent variable in Figure 3 is the starting molecular weight, which is the plot universal and dependent on the starting molecular weight. The zero point in Figure 3 is scaled by the linear molecular weight or chain length. The branched case is the well-known "most probable" MWD, a linear chain reaction carried out under ideal uniform conditions. Figure 4 shows a plot of the relative peak MW of trifunctional diene branches. , MWD peak is 0.2 n <0.9 or 0.17 c Approximate range of <0.5 This demonstrates that the most sensitive branching level is at the mid-branch level within the nucleus.

[0097] Traditional branching model The purpose of this section is to investigate the various conventional diene branched and random polymer couples. The main point to be made here is to compare the "ladder branch" model. In contrast, the inherent instability of traditional diene branching and random polymer coupling is realized. The molecular structure resulting from diene "ladder branching" is (a) a conventional diene continuous stirred tank process. (b) conventional diene semi-batch branching model; (c) poly What are the (a) polymer-CSTR coupling model and (b) polymer-batch coupling model? different. ​​

[0098] a) Conventional diene CSTR branching model, Ver Strate-1980 (G.V. r Strate, C. Cozewith, WW Graessley, J. App. Polym.Sci.1980,25,59), Guzman-2010(JDGu zman, DJ Arriola, T. Karjala, J. Gaubert, BW .S.Kolthammer,AIChE 2010,56,1325):

number

[0099] b) Traditional diene semi-batch branching model, Cozewith-1979 (C. Coz ewith,WWGraessley,G.Ver Strate,Chem.En g.Sci.1979,34,245), and d) polymer batch coupling model , Cozewith-1979, Flory-1953(PJFlory,Prin ciples of Polymer Chemistry,Cornell Univ. ersity Press,1953), Tobita-1995(H. Tobita, J.Polym.Sci.B 1995,33,1191):

number

number

[0100] c) Polymer CSTR coupling model:

number

[0101] Characterization of trifunctional long-chain branched polyolefins. Depending on the degree of branching, various methods, such as nuclear magnetic resonance (NMR), can determine the LCB. or can distinguish the effect of LCB in the polymer. The effect of is observed in shear flows in van Gurp-Palmen analysis and low The increase in shear viscosity at high angular frequencies and the intensity of shear thinning behavior can be attributed to the LCB. In extensional flow, the effect of LCB is usually determined by the degree of strain hardening or the strength of the melt and the Identified at maximum deformation. Other plots, e.g., Mark-Houwink plots g, broadened molecular weight distribution (MWD), and g' vis The plot provides additional information about the LCB. Limited concentration of vinyl-terminated polymers (maximum one per polymer chain), and Due to the need to achieve high ethylene conversion to ensure the formation of LCB, Achieving high levels of natural LCB in the cellulose is difficult. The ethylene concentration in the reactor is low, and therefore a large amount of vinyl-terminated polymer is produced in the second polymer. The mer strand can be reinserted.

[0102] NMR analysis is best used to distinguish between trifunctional and tetrafunctional long chain branches. The dienes in this group allow for diagnostics of tri- and tetrafunctional long chain branching. Scheme 6 This mechanism shows the difference between the formation of trifunctional and tetrafunctional long chain branches. In this case, the branching ratio The rate can be controlled by the ratio of ethylene to hydrogen in the reactor. In this particular example Dimethyldivinylsilane has a diagnostic methyl group on the silicon atom, which can be used to Trifunctional or tetrafunctional long-chain branches can be determined (Scheme 6 and Figure 7). 9). The carbon on the silicon of the tetrafunctional branched polymer is The carbon atoms are shifted upfield relative to the carbon atoms on the nucleus (see Figure 8). An example is a trifunctional tetrafunctional long chain molecule. This shows that it is possible to control the ratio of branching. Scheme 6: Depiction of trifunctional long-chain branch formation from the reaction of dienes. [ka]

[0103] In addition to hydrogenolysis, termination events such as β-hydride elimination also lead to trifunctional long-chain branches. If β-hydride elimination is the key mechanism, then, for example, the vinylene group in Scheme 7 There is unsaturation as shown. Scheme 7: Trifunctional long-chain branch formation from the reaction of dienes followed by β-hydride elimination Description of. [ka]

[0104] Conventional processes for incorporating dienes into polymer synthesis systems result in high branching levels leading to gel formation or The kinetic modeling discussed in the previous section suffers from the fundamental drawback of reactor fouling. It may provide better predictive results that allow for a better understanding of gel formation. For example, longer The polymer chains have proportionally more pendant vinyls, The polymer chains containing the hydroxyl groups are likely to be reinserted into the catalyst to form LCBs. Thus, larger polymer chains are preferentially reinserted to form even larger polymer molecules. When the LCB level reaches a threshold, gel problems or instability may occur. Weight average molecular weight (M) as a function of conventional tetrafunctional branching w ) and number average molecular Amount (M n ) was simulated in a constant pressure semi-batch reactor for the production of ethylene-based polymers. This is shown in Figure 1. In Figure 1, M n is M w As goes to infinity, it increases slightly In this example, M w But 200,000 grams per mole (g / mol) When the number increases above 100, the molecular weight distribution (MWD) of the polymer becomes unstable and gel formation begins. MWD is the weight average molecular weight M w The number average molecular weight M n is defined as dividing by (M w / M n ).

[0105] A polymer gel, for purposes of this disclosure, is defined as a polymeric gel having a high branching level and / or a high molecular weight. A polymer gel is defined in the narrow sense as a phase-separated polymer fraction due to the These properties can be observed in the molten or melt and affect optical clarity and film and fiber performance. The polyethylene interpolymer gel tends to interfere with the properties of the polymer. The gel content can be measured by the degree of insolubility of the polymer. The percentage of polymer gel formed is correlated with the recovery percentage of the polymer gel and can therefore be estimated from it. If so, they can accumulate in the reactor and cause fouling.

[0106] To describe the high molecular weight tailing effect when dienes are added to the polymerization, the following measures are used: previously disclosed (Application No. PCTUS2019 / 0100222, each filed September 27, 2019). No. 019 / 053524, No. PCTUS2019 / 053527, No. PCTUS201 (described in PCTUS Nos. 9 / 053529 and PCTUS No. 2019 / 053537) Tetrafunctional "ladder branched" polymers do not exhibit this tailing effect. High MW polymers A series of metrics quantifying the amount of A HIGH , and A TAIL has been previously disclosed (see Figure 5). The terms "high molecular weight tail" or "high molecular weight tail" are used to describe the Depending on the catalyst and diene pairing and experimental conditions, , "ladder branch" system has some conventional branching, whereby the shape metric One might expect values ​​to be higher than would be expected for a pure "ladder branch".

[0107] A HIGH or A TAIL The value defined by increases as the conventional branching level increases. However, the "ladder branching" model (tetrafunctional or trifunctional ) high MW area metric (A HIGH or A TAIL ) is the "ladder branch" level Most probable MWD A HIGH and A TAIL of The values ​​are approximately 0.07 and 0.015, respectively. Exemplary MWD data are for diene-containing Linear polymers that do not form due to non-ideal polymerization behavior are HIGH and A TAI L The exemplary data demonstrate that the most probable MWD tends to have slightly higher values ​​of A variety of highly branched "ladder" molecules with essentially no high MW tail beyond what would be expected. High MW area metrics, when accompanied by some degree of conventional branching, also indicate "branched" polymers. It is also diagnostic of the slight levels of high MW tail formation that "under-branched" polymers can exhibit. Rick A TAIL is A HIGH It is less affected by linear MWD non-idealities than However, theoretically, A HIGH and A TAIL Metrics are high MW tail formation are shown equivalently.

[0108] Trifunctional long-chain branched polyolefin As depicted in Scheme 4, the polymer generated from the "ladder branch" Included in the disclosure.

[0109] In some embodiments, the polymers of the present disclosure have a 0.1 per 1000 carbon atoms In some embodiments, the polymers of the present disclosure have a level of trifunctional long chain branching greater than or equal to 100%. , greater than 0.2 per 1000 carbon atoms, greater than 0.3 per 1000 carbon atoms , more than 0.4 per 1000 carbon atoms or less than 0.5 per 1000 carbon atoms has a level of trifunctional long chain branching in excess of

[0110] In embodiments, the ethylene-based polymers of the present disclosure have a melting point of at least 10°C. Melt viscosity ratio or rheology ratio (V 0.1 / V 100 ), including V 0.1 is 0.1 radians is the viscosity of the ethylene polymer at 190 °C at an angular frequency of 1 / sec, and V 100 is 100 Viscosity of ethylene-based polymers at 190°C at an angular frequency in radians / second. In embodiments, the melt viscosity ratio is at least 14, at least 20, at least 25, or In some embodiments, the melt viscosity ratio is greater than 50 and at least 6. 0 or greater than 100. In some embodiments, the melt viscosity ratio is 14 to 200. do.

[0111] "Rheology ratio" and "melt viscosity ratio" are V at 190°C. 0.1 / V 100 By Defined, V 0.1 is the temperature of an ethylene polymer at 190°C with an angular frequency of 0.1 rad / s. is the viscosity of 100 is the ethylene system at 190°C with an angular frequency of 100 rad / s. is the viscosity of the polymer.

[0112] In one or more embodiments, the ethylene-based polymers of the present disclosure have an average g' of less than 0.86. and the average g' is determined by gel permeation chromatography using a triple detector. In some embodiments, the ethylene-based polymers of the present disclosure have an intrinsic viscosity ratio of 0.5 The average g' is between 0.55 and 0.86. Values ​​and fractional ranges are disclosed herein as separate embodiments and are not intended to be limiting unless otherwise specified, for example, to the extent that the ethylene-based polyolefins are not specifically limited. The mean g' of Rimmer was 0.64-0.75, 0.58-0.79, or 0.65-0. In one or more embodiments, the average g' may range from 0.55 to 0.84, 0 .59 to 0.82, or 0.66 to 0.80.

[0113] In one or more embodiments, the melt viscosity ratio of the ethylene-based polymers of the present disclosure is The melt viscosity ratio (V 0.1 / V 100 ) is V 0.1 , 0.1 radians / Viscosity of ethylene-based polymers at 190 °C at an angular frequency of s, and V 100 , 100 radians The elastic modulus is determined by the viscosity of an ethylene polymer at 190°C at an angular frequency of 1000 kJ / sec. m is [((tan(δ 0.1 )-tan(δ 100 ))*1000) / (0.1-10 0))] and tan(δ 0.1 ) is the tangent of the phase angle in 0.1 radians / second, tan(δ 100 ) is the tangent of the phase angle in 100 radians / second.

[0114] In one or more embodiments, the ethylene-based polymer has a viscosity of 19 sec / radian or less. The elastic modulus at 0°C may be m, where m is [((tan(δ 0.1 )-tan(δ 100 )) *1000) / (0.1-100)). In another embodiment, the ethylene-based polymer may have a modulus of elasticity m at 190° C. that is 4 seconds / radian or less.

[0115] In various embodiments, the melt strength of the ethylene-based polymers of the present disclosure may be greater than 6 cN. (Rheotens device, 190°C, 2.4 mm / s) 2 , from the die exit to the wheel 120mm to center, extrusion speed 38.2 seconds -1 , 30 mm long, 2 mm diameter, and inflow In some embodiments, the melt of the ethylene-based polymer is The strength can be greater than 10 cN.

[0116] In an embodiment, the ethylene-based polymer has an MWD area metric A TAIL Determined by may have a quantified molecular weight tail, A TAIL is 0.04 or less. All individual values ​​and subranges encompassed by the above are herein disclosed as separate embodiments. For example, in some embodiments, the A of the ethylene-based polymers of the present disclosure TAIL is determined by gel permeation chromatography using a triple detector. exceeding and less than or equal to 0.03.

[0117] In one or more embodiments, the polymers of the present disclosure are used in gel permeation chromatography using triple detectors. A molecular weight average of less than 800,000 daltons as determined by chromatography. Amount (M w In various embodiments, the polymer may be subjected to gel immersion using a triple detector. less than 400,000 daltons, 200 ,000 Daltons or less, or a weight average molecular weight (M w )of It is possible.

[0118] In one or more embodiments, the polymers of the present disclosure are used in gel permeation chromatography using triple detectors. M less than or equal to 6, as determined by w / M n (Weight average molecular weight / number In various embodiments, the polymer may be analyzed by gel immersion using a triple detector. M less than 5, or less than 4, as determined by permeation chromatography w / M n of In some embodiments, the MWD of the long-chain branched polymer is 1 to 3, and the other Embodiments include an MWD of 1.5 to 2.5.

[0119] Each M w0 and M p0 As previously discussed, diene was added to the reactor during polymerization. is not a polymer resin metric. Each subsequent addition of diene increases the metric M w or M p The amount of diene introduced into the reactor is used to produce a polymer resin from which the reaction mass can be determined. Therefore, the addition of diene is less than the amount of comonomers in the reactor. The total amount of ethylene and solvent is not affected.

[0120] In various embodiments, the ethylene-based polymer has a gpcBR branching index from 0.1 to 3.0. All individual values ​​and subranges encompassed by "0.10 to 3.00" are separate. As disclosed herein in certain embodiments, for example, the ethylene-based polymer may have a molecular weight of 0.10 to 2 .00, 0.10-1.00, 0.15-0.65, 0.20-0.75, or 0.1 It may include a gpcBR branching index of 0 to 0.95.

[0121] The long-chain branching polymerization process described in the preceding paragraph is a process for polymerizing olefins, primarily ethylene and propane. In some embodiments, a single type of olefin is used in the polymerization scheme. Only olefins or α-olefins are present, with small amounts of incorporated diene comonomers. However, if additional α-olefins are added to the polymerization procedure, Additional α-olefin comonomers may be incorporated. Typically, the additional α-olefin comonomers are 20 carbon atoms or less. For example, α-olefin comonomers have 3 to 10 carbon atoms, or 3 Exemplary α-olefin comonomers include propylene and propylene copolymers. , 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene , 1-decene, 4-methyl-l-pentene, and ethylidene norbornene For example, but not limited to, the one or more α-olefin comonomers may be propylene. from the group consisting of 1-butene, 1-hexene, and 1-octene, or alternatively 1 1-hexene and 1-octene.

[0122] Long chain branched polymers, for example, homopolymers of ethylene and / or ethylene and optionally Optionally, interpolymers (copolymers) with one or more comonomers such as α-olefins The copolymer (including the copolymer) may contain at least 50 weight percent of units derived from ethylene. All individual values ​​and subranges encompassed by "at least 50 weight percent" are separate. Disclosed herein in certain embodiments are, for example, ethylene-based polymers, ethylene homopolymers, polymers, and / or ethylene and optionally one or more com- pounds such as α-olefins Interpolymers (including copolymers) with monomers of at least 60 weight percent Units derived from ethylene, at least 70 percent by weight of units derived from ethylene, At least 80 weight percent of units derived from ethylene, or 50 to 100 weight percent 80 to 100 weight percent ethylene-derived units or It may contain units such as

[0123] In some embodiments of the ethylene-based polymer, the ethylene-based polymer comprises an additional α- The amount of additional α-olefin in the ethylene-based polymer is 50 mole percent or more. In other embodiments, the amount of additional α-olefin is at least In a further embodiment, the additional α-olefin comprises 0.01 mol % to 25 mol % of the α-olefin. In some embodiments, the amount of at least 0.1 mol % to 10 mol % of The α-olefin is 1-octene.

[0124] In some embodiments, the long chain branched polymer is at least 50 mole percent ethylenediamine. At least 90 mole percent of all individual units may be derived from ethylene. All values ​​and subranges are included herein and disclosed herein as separate embodiments. For example, the ethylene-based polymer may contain at least 93 mole percent units derived from ethylene, at least 96 mole percent ethylene-derived units, at least 97 mole percent Ethylene-derived units, or alternatively, 90 to 100 mole percent ethylene-derived units 90 to 99.5 mole percent of units derived from ethylene, 97 to 99.5 mole percent It may contain units derived from ethylene.

[0125] In some embodiments of the long chain branched polymer, the amount of additional α-olefin is 50% and other embodiments include at least 1 mole percent (mol %) to 20 mole %. In a further embodiment, the amount of additional α-olefin is at least 5 mol % to 10 mol %. In some embodiments, the additional α-olefin is 1-octene.

[0126] Any conventional polymerization process may be used to produce the long-chain branched polymer. Conventional polymerization processes involve the use of one or more conventional reactors, e.g., loop reactors, isothermal reactors, , fluidized bed gas phase reactors, stirred tank reactors, batch reactors, etc., in parallel, in series, or in any combination thereof. Solution polymerization process, gas phase polymerization process, slurry phase polymerization process, any combination thereof These include, but are not limited to, any of the above processes, and any combination thereof.

[0127] In one embodiment, the ethylene-based polymer is produced in a dual reactor system, e.g., a single loop reactor system. can be produced via solution polymerization of ethylene and optionally one or more α-olefins The olefins are polymerized in the presence of the catalyst system described herein and optionally one or more cocatalysts. In another embodiment, the ethylene-based polymer is produced in a dual reactor system, e.g., a dual loop. In a reactor system, ethylene and optionally one or more The α-olefin is produced by the catalyst system described herein and optionally one or more The catalyst systems described herein are optionally polymerized in the presence of one or more other catalysts. It can be used in combination with other catalysts in the first reactor or the second reactor. In one embodiment, the ethylene-based polymer is produced in a dual reactor system, e.g., a dual loop reactor system. can be produced via solution polymerization of ethylene and optionally one or more α-olefins The olefins are polymerized in both reactors in the presence of the catalyst system described herein.

[0128] In another embodiment, the long chain branched polymers can be prepared in a single reactor system, e.g., a single loop reactor system. can be produced via solution polymerization of ethylene and optionally one or more α-olefins The olefins may be prepared by reacting a catalyst system as described herein with one or more of the cocatalysts described in the preceding paragraph. In some embodiments, the long chain branching step is carried out in the presence of a long chain branching agent to produce a long chain branched polymer. The chain branching polymerization process comprises the step of reacting ethylene and at least one additional α- It involves polymerizing olefins.

[0129] The long-chain branched polymer may further comprise one or more additives. antistatic agents, color enhancers, dyes, lubricants, pigments, primary antioxidants, secondary antioxidants, additives processing aids, UV stabilizers, and combinations thereof. The ethylene-based polymer may contain any amount of additives. Based on the weight of the ethylene-based polymer and one or more additives, the total weight of such additives The ethylene-based polymer may further comprise a filler in an amount of from about 0 to about 10 percent. The filler may include, but is not limited to, organic or inorganic fillers. Long-chain branched polymers are not suitable for use with ethylene-based polymers and any additives or fillers. Fillers such as calcium carbonate, talc, or Mg(OH)2, based on total weight The ethylene-based polymer may contain from about 0 to about 20 weight percent of a polymer. The composition may be further blended with a polyisoprene to form a blend.

[0130] In some embodiments, the long chain polymerization process to produce the long chain branched polymer comprises: In the presence of a catalyst having two polymer-forming sites, ethylene and at least one additional Such a polymer may include polymerizing an α-olefin having two polymer-forming sites. Long-chain branched polymers resulting from such catalyst systems are prepared according to ASTM D792 (the entire contents of which are incorporated herein by reference). In accordance with the specification, for example, 0.850 g / cm 3 ~0.960g / cm 3 , 0.880g / cm 3 ~0.920g / cm 3 , 0.880g / cm 3 ~0.910 g / cm 3 , or 0.880 g / cm 3 ~0.900g / cm 3 The density may be

[0131] In another embodiment, the long chain branched polymer resulting from the long chain polymerization process has 5 to 100 Melt flow ratio (I 10 / I2), where the melt index I2 is determined by ASTM D1 238 (which is incorporated herein by reference in its entirety), Measured under a load of 0.16 kg, melt index I 10 conforms to ASTM D1238 In another embodiment, the melt flow ratio is (I 10 / I2) is 5 to 50, in others the melt flow ratio is 5 to 25, in others In this case, the melt flow ratio is 5 to 9.

[0132] Gel Permeation Chromatography (GPC) (Traditional GPC) The chromatographic system was a Polymer chromatograph equipped with an internal IR5 infrared detector (IR5). rChar GPC-IR (Valencia, Spain) High-Temperature GPC Chromatograph , and Precision Detectors (now Agilent Tech A 4-key laser coupled to a (Nologies) two-angle laser light scattering (LS) detector model 2040 was used. For all absolute light scattering measurements, a 15 degree angle is measured. The autosampler oven compartment is set to 160 degrees Celsius and the column compartment is The temperature was set at 150°C. The columns used were four Agilent "Mixed A" 3 The column was a 0 cm, 20 micron linear mixed bed column. Chromatography solvents used is 1,2,4-trichlorobenzene and 200 ppm butylated hydroxytoluene The solvent source was nitrogen sparged. The injection volume used was 2 The volume was 1.00 microliters and the flow rate was 1.0 milliliters / minute.

[0133] Calibration of the GPC column set has molecular weights ranging from 580 to 8,400,000 Run with at least 20 narrow molecular weight distribution polystyrene standards and measure the individual molecular weights. The standards were placed in six "cocktail" mixtures with at least 10 intervals between them. , purchased from Agilent Technologies. Over 1,000,000 The molecular weight is 0.025 grams in 50 milliliters of solvent and 1,000,000 For molecular weights less than 0, use 0.05 g polystyrene standards in 50 ml solvent. The polystyrene standards were dissolved at 80°C for 30 minutes with gentle agitation. The peak molecular weights of the polystyrene standards were converted to polyethylene molecular weights using Equation 48. (Williams and Ward, J. Polym. Sci., Pol ym. Lett., 6, 621 (1968). M ポリエチレン =A×(M ポリスチレン ) B (48) where M is the molecular weight, A has a value of 0.4315, and B is equal to 1.0.

[0134] A polynomial between third and fifth order was used to fit each polyethylene equivalent calibration point. As NIST standard NBS1475 is obtained at 52,000 MW, A is adjusted slightly (approximately 0.415 to 0.44) to minimize column resolution and band broadening effects. Corrected.

[0135] The total plate count for the GPC column set is 100 ml of eicosane (50 ml of T (prepared at 0.04 g in CB and dissolved for 20 min with gentle stirring) Plate count (Equation 49) and symmetry (Equation 50) were calculated according to the following equations: Measurements were performed by injecting 200 microliters.

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[0136] The sample was analyzed using PolymerChar's "Instrument Control" software. The samples were prepared in a semi-automated fashion using Poly Septa caps pre-sparged with nitrogen were placed through a MerChar high-temperature autosampler. A solvent (containing 200 ppm BHT) was added to the vial. The sample was shaken slowly. The mixture was melted at 160 degrees Celsius for 2 hours.

[0137] M n(GPC) , M w(GPC) , and Mz(GPC) The calculation is Polymer Char GPCOne™ software, based on each equally spaced data collection point (i). The baseline-subtracted IR chromatogram and the narrow standard at point (i) from Equation 1 Po according to Equations 51-53 using the polyethylene equivalent molecular weight obtained from the calibration curve Internal IR5 detector (measurement channel) of the lymerChar GPC-IR chromatograph Based on the GPC results using

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[0138] To monitor deviations over time, a PolymerChar GPC-IR system was used. A flow rate marker (decane) was introduced into each sample via a controlled micropump. The mass marker (FM) narrowly aligned each decane peak in the sample (RV (FM sample)). The peaks of each sample were determined by matching the decane peak in the semi-calibration (RV (FM calibrated)). The decane marker was then used to linearly calibrate the flow rate (apparent flow rate). Any change in the time of the peak is associated with a linear shift in flow rate (effective flow rate). To facilitate the highest accuracy of RV measurements of flow marker peaks, a minimum of two A quadratic fitting routine was used to fit the peaks in the flow marker concentration chromatogram to quadratic values. Then, use the first derivative of the quadratic equation to find the true peak position. After calibrating the system based on the peak of the flow marker (for narrow standard calibration), ) Effective flow is calculated as in Equation 7. The processing of flow marker peaks is performed using Polym Flow compensation was performed via the erChar GPCOne™ software. Positive means that the effective flow rate should be within + / - 2% of the apparent flow rate. Flow rate (effective) = Flow rate (apparent) * (RV (FM calibrated) / RV (FM sample)) (54 )

[0139] Triple detector GPC (TDGPC) (absolute GPC) Chromatography system, run conditions, column set, column calibration, and conventional molecular The calculation and distribution of molecular moments was performed using gel permeation chromatography (GPC). This was carried out according to the method described.

[0140] Multiplex detection for determining viscometer and light scattering detector offsets from the IR5 detector A systematic approach for determining the instrument offset is described by Balke, Mourey, et. al. ( Mourey and Balke,Chromatography Polym.Ch pt 12,(1992))(Balke,Thitiratsakul,Lew,Ch eung,Mourey,Chromatography Polym.Chpt 13 ,(1992)) which is based on the Polym Using erChar GPCOne™ software, a wide range of homopolymer and polyester polymers were analyzed. Styrene standard (M w / M n >3) triple detector log(MW and IV) results Optimize for narrow standard column calibration results from narrow standard calibration curve.

[0141] Absolute molecular weight data was obtained using PolymerChar GPCOne™ software. Using Zimm (Zimm, BH, J. Chem. Phys., 16, 109 9 (1948)) and Kratochvil (Kratochvil, P., Clas sical Light Scattering from Polymer Solu tions, Elsevier, Oxford, NY (1987) The overall injection concentration used in the molecular weight determination is Suitable linear polyethylene homopolymers or polyethylene standards of known weight average molecular weights is obtained from the mass detector area and mass detector constant, which are derived from one of the quasi-quantum quantities. (G Molecular weights calculated using PCOne™ are based on the polyethylene standards set forth below. and a refractive index concentration coefficient, dn / , of 0.104, derived from one or more of Generally, the mass (determined using GPCOne™) The detector response (IR5) and light scattering constant are consistent with those with molecular weights above about 50,000 g / mol. Viscometer calibration (determined using GPCOne™) can be determined from linear standards. (as determined) using the method described by the manufacturer, or alternatively, Materials (SRM) 1475a (available from the National Institute of Standards and Technology (NIST)) This can be achieved using published values ​​of suitable linear standards. The viscosity area (DV) and injected mass are related to the intrinsic viscosity (GPCOne ( Calculate the viscometer constant (obtained using the chromatographic concentration) using the second Assume low enough to eliminate the effect of viral coefficient (concentration effect on molecular weight) will be done.

[0142] Absolute weight average molecular weight (M w(Abs) ) is photochemically analyzed (using GPCOne™) The area-integrated chromatogram of the scattering (LS) (factored by the light scattering constant) was calculated using the mass constant and The molecular weight and specificity are calculated by dividing the area of ​​the mass detector (IR5) by the mass recovered. The viscosity response is linearly extrapolated at the chromatographic end where the signal-to-noise is low (GP COne™). Each of the other moments, M n(Abs) and M z (Abs) is calculated according to equations 55-56 as follows:

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[0143] Dynamic Mechanical Spectroscopy (or Small Angle Oscillatory Shear) The complex viscosity (η*), elastic modulus (G', G''), tan delta, and phase angle (δ) are Dynamic oscillation frequency sweep test at 190°C in the frequency range of 0.1 to 100 rad / s The strain level is determined by strain sweep testing at 100 rad / sec at 190°C. The test was performed by TA Instruments. The strain-controlled rheometer ARES-G2 was used with stainless steel parallel plates of 25 mm diameter. Before the actual test, a 3.3 mm thick sample is squeezed and then subjected to two steps. In the first step, the sample was melted for 2.5 minutes and squeezed to a 3 mm gap. After a further 2.5 minutes at 190°C, the sample is placed in a 2 mm gap. This method allows the system to reach thermal equilibrium. An additional 5 minute delay is incorporated to allow for the testing to proceed under nitrogen atmosphere.

[0144] gpcBR branching index by triple detector GPC (TDGPC) The gpcBR branching index can be calculated by first calibrating the light scattering, viscosity, and concentration detectors described above. The baseline was then determined from light scattering, viscometer, and concentration chromatograms. The refractive index chromatogram was then subtracted to show the presence of detectable polymer. The full integral of the low molecular weight retention volume range in the light scattering and viscometer chromatograms was confirmed. An integration window was then set to ensure the accuracy of the linear polyethylene standard. The Mark-Houwink constants for polyethylene and polystyrene were established using the constants Then, using the two values, we can obtain the following equations (57) and (58): , 2 for polyethylene molecular weight and polyethylene intrinsic viscosity as a function of elution volume Two linear reference conventional calibrations were constructed.

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[0145] The gpcBR branching index is based on Yau, Wallace W., “Examples of Using 3D-GPC-TREF for Poly-olefin Chara cterization,”Macromol.Symp.,2007,257,29- 45, this is a robust method for characterizing long chain branching. The conventional method used in determining g' and calculating branching frequencies is to use the entire detector area. Avoid the "slice-by-slice" TDGPC calculations. The method was used to measure the sample bulk absolute weight average molecular weight (M w , abs) can be obtained. This method uses the light scattering detection required for traditional g' determination. Avoid the "slice-by-slice" ratio of the detector signal to the concentration detector signal. The intrinsic viscosity of the sample was also obtained independently using equation (63). As the actual sample area, the baseline and integration are determined by the detector noise and TDGPC settings. It provides greater accuracy because it is less sensitive to variations caused by the temperature limit. More importantly, the peak area calculation was not affected by the detector volume offset. Similarly, the high-precision intrinsic viscosity (IV) of the sample was calculated by the area method in equation (59): Got it.

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[0146] In equation (59), DPi represents the differential pressure signal monitored directly from the online viscometer. To determine the gpcBR branching index, the light scattering elution area of ​​the sample polymer was used. The molecular weight of the sample was determined. The viscosity detector elution area of ​​the sample polymer was used to determine the intrinsic viscosity of the sample. (IV or [η]) was determined. First, the molecular weight and intrinsic viscosity as a function of elution volume were determined. SRM1475a or equivalent, using conventional calibration ("cc") for both degrees The molecular weights and intrinsic viscosities of linear polyethylene standards such as

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[0147] All statistics with a "cc" or "conv" subscript are The elution volume of the analyte is determined using the corresponding conventional calibration as described above, and the concentration (Ci). Values ​​without a letter are measurements based on mass detector, LALLS, and viscometer area. .K PE The value of is iteratively adjusted until the linear reference sample has a gpcBR measurement of zero. For example, in this particular case, α and Log K for determining gpcBR The final values ​​were 0.725 and -3.355 for polyethylene and 0.725 and -3.355 for polystyrene, respectively. are 0.722 and -3.993, respectively. Once the K and α values ​​are determined.

[0148] The procedure was repeated using the previously branched sample. The final "cc" value was taken as the best calibration value. Branched samples were analyzed using the typical Mark-Houwink constants.

[0149] The interpretation of gpcBR is simple: for linear polymers, the LS and viscometers The gpcBR is close to zero because the values ​​measured are close to the traditional calibration standards. If -, the measured polymer molecular weight is calculated M w,cc higher than RuIV cc is higher than the measured polymer IV, especially at high levels of long chain branching, g The pcBR becomes greater than zero. In fact, the gpcBR value increases as a result of polymer branching. The gpcBR value of 0.5 or 2.0 represents the fractional IV change due to the molecular size shrinkage effect. are at levels of 50% and 200%, respectively, relative to an equivalent weight of linear polymer molecules. In these particular cases, the traditional "g' index" The advantage of using gpcBR compared to branch frequency calculations is the higher accuracy of gpcBR. All parameters used in determining the gpcBR index were determined with good precision. and is adversely affected by the low TDGPC detector response at high molecular weights from the concentration detector. Errors in detector volume alignment also do not affect the accuracy of the gpcBR index determination.

[0150] NMR analysis Sample preparation. The raw polymer sample must be cleaned prior to NMR measurement of unsaturation and branching. The polymer contained solvent and catalyst residues that must be removed. Dissolved in tetrachloroethane (TCE) at 5°C, then 3-propanol (IPA) The polymer was precipitated using a centrifuge and cooled to room temperature. The polymer was isolated by centrifugation. This process of washing the polymer was repeated at least three times. It was dried in a vacuum oven at 100°C.

[0151] Approximately 70 mg of the washed and dried polymer was placed in a 10 mm N The sample was placed in an MR tube. The sample was then purified by bubbling house nitrogen through the sample for 15 minutes. The purged sample was then placed in an aluminum heating block at 125°C. .

[0152] For bifurcation analysis, a single pulse of the sample 13 C NMR spectra were obtained using a 10 mm 13 600MHz Bruker Avan equipped with C / 1H DUL CryoProbe Acquired at 120 °C using a CE III HD spectrometer with 90 pulses and a 10 s total time. 1400-5000 scans were collected with relaxation delay (AQ+D1).

[0153] Tetrafunctional and Single pulse of sample for quantification of trifunctional long chain branches 13 1 C NMR spectrum 600MHz Bruk equipped with a 0mm 13C / 1H DUL CryoProbe Acquired at 120°C using an Avance III HD spectrometer, with 90 pulses and 960-5000 scans were collected with a total relaxation delay (AQ+D1) of 12 seconds. QA-RINEPT spectrum (J. Hou, Y. He, X. Qiu, Mac romolecules 2017,50,2407-2414) with a 7-second relaxation delay. The parameter QA-RINEPT is the total methyl group of QA-RINEPT. The ratio to carbon was chosen to match the single pulse data.

[0154] Data processing and assignment methods. All NMR data were obtained from the proton spectra. Mnova for 0.5Hz line broadening in the case of NMR spectra and 3Hz line broadening in the case of carbon spectra. The proton data were processed using the NMR spectroscopy. The proton data were referenced to the TCE solvent resonance at 5.99 ppm. The carbon spectrum was referenced to the predominant CH2 of the polymer at 29.99 ppm.

[0155] Trifunctional LCB (-3.36 ppm) and tetrafunctional LCB silylmethyl (-4.0 ppm) A virtual assignment for the 1000 keV peak at 6 ppm was obtained using the ACD CNMR predictor, and the observed coherence These assignments were found to be in close agreement with the branched methine resonances (24 0.9 ppm for tetrafunctional and 25.7 ppm for trifunctional) and CH2 carbon to Y-branch silicon This was confirmed using a quantitative relationship between the alpha resonance (approximately 15.3 ppm).

[0156] Batch Reactor Polymerization Procedure Batch reactor polymerization reactions are carried out in a 2 L Parr™ batch reactor. The reactor is heated by an electric heating mantle and cooled by an internal serpentine cooling coil containing cooling water. Both the reactor and the heating / cooling system were equipped with Camile™ TG processors. The reactor is controlled and monitored by a process computer. At the bottom of the reactor, a A dump valve is fitted to a stainless steel dump pot. Catalyst deactivation solution (typically 5 mL of Irgafos / Irganox / toluene mixture) Both the pot and the tank are purged with nitrogen and the dump pot is The mixture was vented to a 30 gallon blowdown tank. All solvents are passed through a solvent purification column to remove any impurities that may affect the polymerization. 1-Octene and Isopar E were separated in the first column, Q, containing A2 alumina. The ethylene is passed through two columns, the second column containing A204 alumina and

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[0157] The reactor is charged with IsoparE solvent and / or 1-octene depending on the reactor load. The shot tank is loaded first, which may contain the Fill to the load set point using the attached lab scale. After adding the liquid feed, Heat the reactor to the polymerization temperature set point. If ethylene is used, maintain the reaction pressure set point. Ethylene is added to the reactor at a reaction temperature to achieve the desired reaction temperature. The flow rate is monitored by a Micro Motion flow meter. In experiments, the standard conditions at 150°C were 13g ethylene in 585g IsoparE, 1 The standard conditions are 5g of 1-octene, 240 psi of hydrogen, and 150°C. 15g ethylene, 45g 1-octene, 200 psi hydrogen in IsoparE do.

[0158] The procatalyst and activator are mixed with an appropriate amount of purified toluene to form a solution of the desired molar concentration. The procatalyst and activator are handled in an inert glove box and syringed together to obtain The syringe is then filled with 5 mL of toluene and transferred under pressure into the catalyst shot tank. Rinse 3 times. Start the run timer immediately after adding the catalyst. If using ethylene , which is added by Camile to maintain the reaction pressure set point in the reactor. The reaction was carried out for 10 minutes, then the agitator was stopped and the bottom dump valve was opened to allow the contents of the reactor to cool. Transfer contents to a dump pot. Pour contents of the dump pot into a tray and place in a lab hood. The tray containing the remaining polymer is then placed in a vacuum oven where the solvent is allowed to evaporate overnight. The mixture is transferred to a tray and heated to 140°C under vacuum to remove any remaining solvent. After the tube was cooled to ambient temperature, the polymer yield was measured to determine the efficiency, and the polymer were subjected to the Mar test. Example from a batch reactor [ka]

[0159] In Table 2, the polymer characteristics of the comparative linear polymer sample (1.C) are shown from the batch reactor. The polymerization reaction consisted of 585 g of ISOPAR-E™, 15 g of of octene and 240 psi hydrogen pressure (ΔH2) at a temperature of 150 °C. 14 g of ethylene was charged, and the pressure was adjusted to 0.3 μmol of catalyst 1, 0.36 μmol of co-catalyst Catalytic A (methyldi(tetradecyl)ammonium tetrakis(pentafluorophenyl)boron) The cells were maintained in the presence of 10 μM MMAO-3A (Table 1). Benzenedimethyldivinylsilane was added. [Table 3] [Table 4]

[0160] Table 2 collects data for Comparative Example 1.C and other diene Examples 1.1-1.7. NMR data show both tri- and tetrafunctional LCBs and LCBs with increasing diene functionality. and demonstrate increased levels of

[0161] FIG. 6 shows the conventional molecular weight distributions of examples using different amounts of diene.

[0162] Batch Reactor Example 2 In Table 3, the polymer characteristics of the comparative linear polymer sample (2.C) are shown from the batch reactor. The polymerization reaction consisted of 585 g of ISOPAR-E™, 15 g of of octene and 240 psi hydrogen pressure (ΔH2) at a temperature of 150 °C. 15 g of ethylene was charged, and the pressure was adjusted to 0.3 μmol of catalyst 1, 0.36 μmol of co-catalyst Catalytic A (methyldi(tetradecyl)ammonium tetrakis(pentafluorophenyl)boron) The cells were maintained in the presence of 10 μM MMAO-3A (Table 1). Benzenedimethyldivinylsilane was added. [Table 5] [Table 6]

[0163] Table 3 collects data for Comparative Example 2.C and diene Example 2.1. NMR Data The ratio of trifunctional LCB to tetrafunctional LCB was 1.4:1 (0.15 LCB / 10 Both tetrafunctional (0.10LCB / 1000C) and tetrafunctional (0.10LCB / 1000C) are demonstrated. The dynamic mechanical spectrum of branched Example 2.1 was measured and the results are recorded in Table 3. The viscosity at 1 rad / s was determined to be 609,361 Pa s and at 100 rad / s The viscosity of the solution was measured to be 2,453 Pa s, with a rheological ratio (V 0.1 / V1 00 ) was provided.

[0164] Batch Reactor Example 3 In Table 4, the polymer characteristics of the comparative linear polymer sample (3.C) are shown from the batch reactor. The polymerization reaction consisted of 585 g of ISOPAR-E™, 15 g of of octene and 240 psi hydrogen pressure (ΔH2) at a temperature of 140 °C. 10 g of ethylene was charged, and the pressure was adjusted to 0.3 μmol of catalyst 1, 0.36 μmol of co-catalyst Catalytic A (methyldi(tetradecyl)ammonium tetrakis(pentafluorophenyl)boron) The cells were maintained in the presence of 10 μM MMAO-3A (Table 1). Benzenedimethyldivinylsilane was added. [Table 7] [Table 8]

[0165] Table 4 collects the NMR data for Comparative Example 3.C and Diene Example 1.1. The ratio of trifunctional LCB to tetrafunctional LCB was 1.8:1 (0.23 LCB / 10 Both tetrafunctional (0.13LCB / 1000C) and tetrafunctional (0.13LCB / 1000C) are demonstrated.

[0166] The dynamic mechanical spectrum of branched Example 3.1 was measured and the results are recorded in Table 4. The viscosity at .1 rad / s was determined to be 515,022 Pa s and at 100 rad / s The viscosity at 2140 Pa s was measured, with a rheological ratio (V 0.1 / V 100 ) was provided.

[0167] Batch Reactor Example 4 In Table 5, the polymer characteristics of the comparative linear polymer sample (4.C) are shown from the batch reactor. The polymerization reaction consisted of 585 g of ISOPAR-E™, 15 g of of octene and 160 psi hydrogen pressure (ΔH2) at a temperature of 150 °C. 15 g of ethylene was charged, and the pressure was adjusted to 0.4 μmol of catalyst 1, 0.48 μmol of co-catalyst Catalytic A (methyldi(tetradecyl)ammonium tetrakis(pentafluorophenyl)boron) The cells were maintained in the presence of 10 μM MMAO-3A at 100 μM RT (rate), and 10 μM MMAO-3A. Dienedimethyldivinylsilane was added. [Table 9] [Table 10]

[0168] Table 5 collects data for Comparative Example 4.C and diene Example 4.1. NMR Data The ratio of trifunctional LCB to tetrafunctional LCB was 1.03:1. Both tetrafunctional (0.30LCB / 1000C) and tetrafunctional (0.30LCB / 1000C) are demonstrated.

[0169] The dynamic mechanical spectrum of branched Example 4.1 was measured and the results are recorded in Table 5. The viscosity at 1 rad / s was determined to be 867,379 Pa s and at 100 rad / s The viscosity at 2818 Pa s was measured, with a rheological ratio (V 0.1 / V 100 ) was provided.

[0170] Batch Reactor Example 5 In Table 6, the polymer characteristics of the comparative linear polymer sample (5.C) are shown from the batch reactor. The polymerization reaction consisted of 585 g of ISOPAR-E™, 15 g of of octene and 80 psi hydrogen pressure (ΔH2) at a temperature of 160 °C. 15 g of ethylene was charged, and the pressure was adjusted to 0.4 μmol of catalyst 1 and 0.48 μmol of cocatalyst. A (methyldi(tetradecyl)ammonium tetrakis(pentafluorophenyl)borate The cells were maintained in the presence of 10 μM of diene (diester) and 10 μM of MMAO-3A. Dimethyldivinylsilane was added. [Table 11] [Table 12]

[0171] Table 6 collects data for Comparative Example 5.C and diene Example 5.1. NMR Data The ratio of trifunctional LCB to tetrafunctional LCB was 0.8:1 (0.25 LCB / 10 Both tetrafunctional (0.30LCB / 1000C) and tetrafunctional (0.30LCB / 1000C) are demonstrated.

[0172] The dynamic mechanical spectrum of branched Example 5.1 was measured and the results are recorded in Table 6. The viscosity at .1 rad / s was determined to be 813,746 Pa s and at 100 rad / s The viscosity at 2742 Pa s was measured, with a rheological ratio (V 0.1 / V 100 ) was provided.

[0173] Batch Reactor Example 6 In Table 7, the polymerization reaction of Example 6.1 consisted of 585 g of ISOPAR-E™, At 15 g of octene and 240 psi hydrogen pressure (ΔH), at a temperature of 150 °C 13 g of ethylene was charged, and the pressure was adjusted to 0.3 μmol of catalyst 1, 0.36 μmol of Cocatalyst A (methyldi(tetradecyl)ammonium tetrakis(pentafluorophenyl) The samples were maintained in the presence of 10 μmol of MMAO-3A (as shown in Table 1). Dienedimethyldivinylsilane was added to the polymerization reaction of Example 6.2. The mixture was prepared by adding 600g of ISOPAR-E™, zero octene, and 240 psi of hydrogen. The reaction mixture was generated at a temperature of 160°C under a pressure (ΔH2). 13 g of ethylene was charged and the pressure was , 0.4 μmol of catalyst 1, 0.48 μmol of cocatalyst A (methyldi(tetradecyl)ammonium) ammonium tetrakis(pentafluorophenyl)borate), and 10 μmol of MMAO The mixture was maintained in the presence of -3A. Dienedimethyldivinylsilane was added as shown in the table. In Table 7, the polymerization reaction of Example 6.3 was carried out using 600 g of ISOPAR-E™, Zeolite, At 240 psi hydrogen pressure (ΔH2), octene is generated at a temperature of 160°C. 13 g of ethylene was charged, and the pressure was adjusted to 0.4 μmol of catalyst 2, 0.48 μmol of catalyst 3, and Catalyst A (methyldi(tetradecyl)ammonium tetrakis(pentafluorophenyl) The cells were maintained in the presence of 10 μmol of MMAO-3A (borate) and 10 μmol of MMAO-3A. Dienedimethyldivinylsilane was added. [Table 13] [Table 14]

[0174] Table 7 collects data for diene Examples 6.1, 6.2, and 6.3. Example 6 6.2 and 6.3 show that different catalysts produce different amounts of trifunctional LCB and different ratios of trifunctional For example, under the same conditions, catalyst 1 (actual Example 6.2) and Catalyst 2 (Example 6.3) were 0.26LCB / 1000C and 0. Trifunctional LCB levels of 07LCB / 1000C and trifunctional LCB levels of 2.2:1 and 0.4:1 The amount of trifunctional LCB and the ratio of trifunctional LCB were: The proportion of tetrafunctional LCB is highly dependent on the catalyst.

[0175] Examples 6.1 and 6.2 show that polymerizations are carried out under comparable conditions, but The main difference is that Example 6.1 contains octene and Example 6.2 does not contain octene. The amount of trifunctional LCB and the ratio of trifunctional to tetrafunctional LCB were varied for the two runs. are very similar in

[0176] The dynamic mechanical spectrum of Example 6.1 was measured and the results are recorded in Table 7. The viscosity in Angstroms / second was determined to be 306,441 Pa s, and the viscosity at 100 radians / second was determined to be 306,441 Pa s. was measured to be 1,754 Pa s, with a rheological ratio (V 0.1 / V 100 ) was provided.

[0177] Batch Reactor Example 7 In Table 8, the polymer characteristics of the comparative linear polymer sample (7.C) are shown from the batch reactor. The polymerization reaction consisted of 580 g of ISOPAR-E™, 20 g of of octene and zero hydrogen at a temperature of 160°C. 11 g of ethylene The pressure was adjusted to 0.7 μmol of catalyst 1, 0.84 μmol of cocatalyst A (methyldi(tet)), tetrakis(pentafluorophenyl)borate), and 10 The mixture was maintained in the presence of 1 μmol of MMAO-3A. Silane was added. [Table 15] [Table 16]

[0178] Table 8 collects data for Comparative Example 7.C and Diene Example 7.1. NMR Data demonstrated that trifunctionality is not present in this example where hydrogen is not present. CB is present (0.14LCB / 1000C) and the trifunctional:tetrafunctional ratio is zero. be.

[0179] The dynamic mechanical spectrum of Example 7.1 was measured and the results are recorded in Table 8. The viscosity in Angstroms / second was determined to be 475,848 Pa s, and the viscosity at 100 radians / second was determined to be 475,848 Pa s. was measured to be 1,982 Pa s, with a rheological ratio (V 0.1 / V 100 ) was provided.

[0180] Batch Reactor Example 8 In Table 9, the polymer characteristics of the comparative linear polymer sample (8.C) are shown from the batch reactor. The polymerization reaction consisted of 580 g of ISOPAR-E™, 20 g of of octene and 28 psi hydrogen pressure (ΔH2) at a temperature of 160 °C. 13 g of ethylene was charged, the pressure was adjusted, 0.7 μmol of catalyst 1, 0.84 μmol of cocatalyst A (methyldi(tetradecyl)ammonium tetrakis(pentafluorophenyl)borate The cells were maintained in the presence of 10 μM of diene (diester) and 10 μM of MMAO-3A. Dimethyldivinylsilane was added. [Table 17] [Table 18]

[0181] Table 9 collects data for Comparative Example 8.C and diene Example 8.1. NMR Data The ratio of trifunctional LCB to tetrafunctional LCB was 0.8:1 (0.09 LCB / 10 Both tetrafunctional (0.11LCB / 1000C) and tetrafunctional (0.11LCB / 1000C) are demonstrated.

[0182] The dynamic mechanical spectrum of Example 8.1 was measured and the results are recorded in Table 9. The viscosity in Angstroms / second was determined to be 721,022 Pa s, and the viscosity at 100 radians / second was determined to be 721,022 Pa s. was measured to be 2,297 Pa s, with a rheological ratio (V 0.1 / V 100 ) was provided.

[0183] Batch Reactor Example 9 Table 10 lists the polymer characteristics of the comparative linear polymer sample (9.C) from a batch reactor. The polymerization reaction was carried out using 580 g of ISOPAR-E™, 20 g of octene and 46 psi of hydrogen pressure (ΔH2) at a temperature of 160 °C. 13 g of ethylene was charged, and the pressure was adjusted to 0.7 μmol of catalyst 1, 0.84 μmol of co-catalyst Catalytic A (methyldi(tetradecyl)ammonium tetrakis(pentafluorophenyl)boron) The cells were maintained in the presence of 10 μM MMAO-3A (Table 1). Benzenedimethyldivinylsilane was added. [Table 19] [Table 20]

[0184] Table 10 collects data for Comparative Example 9.C and diene Example 9.1. NMR Data The tetrafunctional LCB was mixed with trifunctional (0.09 LCB / 1) in a ratio of 0.9:1 (trifunctional:tetrafunctional LCB). Both tetrafunctional (0.10LCB / 1000C) and tetrafunctional (0.10LCB / 1000C) are demonstrated.

[0185] The dynamic mechanical spectrum of Example 9.1 was measured and the results are recorded in Table 10. The viscosity at 100 radians / second was determined to be 697,565 Pa s, and the viscosity at 100 radians / second was determined to be 697,565 Pa s. The viscosity was measured to be 2,782 Pa s, with a rheological ratio (V) of 250.7. 0.1 / V 100 ) was provided.

[0186] Batch Reactor Example 10 In Table 11, the polymer characteristics of the comparative linear polymer sample (10.C) are shown for the batch reactor. The polymerization reaction was carried out using 575 g of ISOPAR-E™, 2 Generated at 160°C with 5g of octene and 83 psi hydrogen pressure (ΔH2) 14 g of ethylene was charged, and the pressure was adjusted to 0.6 μmol of catalyst 1, 0.72 μmol of catalyst 2, and Catalyst A (methyldi(tetradecyl)ammonium tetrakis(pentafluorophenyl) The cells were maintained in the presence of 10 μmol of MMAO-3A (borate) and 10 μmol of MMAO-3A. Dienedimethyldivinylsilane was added. [Table 21] [Table 22]

[0187] Table 11 collects NMR data for Comparative Example 10.C and diene Example 10.1. Data are for a trifunctional (0.07 LCB) in a 0.7:1 (trifunctional:tetrafunctional LCB) ratio. Both tetrafunctional (0.10LCB / 1000C) and tetrafunctional (0.10LCB / 1000C) are demonstrated.

[0188] The dynamic mechanical spectrum of Example 10.1 was measured and the results are recorded in Table 11. The viscosity in radians / second was determined to be 240,894 Pa s, and the viscosity at 100 radians / second The viscosity was measured to be 1,642 Pa s, with a rheological ratio (V 0.1 / V 10 0) was provided.

[0189] Batch Reactor Example 11 In Table 12, the polymer characteristics of the comparative linear polymer sample (11.C) are shown for the batch reactor. The polymerization reaction was carried out using 575 g of ISOPAR-E™, 2 At 5 g of octene and 160 psi of hydrogen pressure (ΔH2), the 14 g of ethylene was charged, and the pressure was adjusted to 0.4 μmol of catalyst 1, 0.48 μmol of Cocatalyst A (methyldi(tetradecyl)ammonium tetrakis(pentafluorophenyl) ) borate), and 10 μmol of MMAO-3A. , dienedimethyldivinylsilane was added. [Table 23] [Table 24]

[0190] Table 12 collects NMR data for Comparative Example 11.C and diene Example 11.1. Data are for a 1.5:1 (trifunctional:tetrafunctional LCB) ratio of trifunctional (0.09 LCB) Both tetrafunctional (0.06LCB / 1000C) and tetrafunctional (0.06LCB / 1000C) are demonstrated.

[0191] The dynamic mechanical spectrum of Example 11.1 was measured and the results are recorded in Table 12. The viscosity in radians / second was determined to be 203,979 Pa s, and the viscosity at 100 radians / second The viscosity was measured to be 1,523 Pa s, with a rheological ratio (V 0.1 / V 10 0) was provided.

[0192] The measured melt strength of the polymer of Example 11.1 was 18 cm at an elongation of 32 mm / sec. It was N.

[0193] Batch Reactor Example 12 In Table 13, the polymer characteristics of the comparative linear polymer sample (12.C) are shown for the batch reactor. The polymerization reaction was carried out using 570 g of ISOPAR-E™, 3 At 0 g of octene and 240 psi of hydrogen pressure (ΔH2), the 20 g of ethylene was charged, and the pressure was adjusted to 0.3 μmol of catalyst 1, 0.36 μmol of Cocatalyst A (methyldi(tetradecyl)ammonium tetrakis(pentafluorophenyl) ) borate), and 10 μmol of MMAO-3A. , dienedimethyldivinylsilane was added. [Table 25] [Table 26]

[0194] Table 13 collects NMR data for Comparative Example 12.C and diene Example 12.1. Data are for a 1.3:1 (trifunctional:tetrafunctional LCB) ratio of trifunctional (0.08 LCB) Both tetrafunctional (0.06LCB / 1000C) and tetrafunctional (0.06LCB / 1000C) are demonstrated (Figure 7 ~See Figure 9).

[0195] The conventional and absolute molecular weights of Examples 12.C and 12.1 are plotted in Figure 10. To do.

[0196] The extensional viscosity fixture (EVF) for Example 12.1 is shown in FIG.

[0197] The measured melt strength of the polymer of Example 12.1 was 19 cm at an elongation of 32 mm / sec. N (see Figure 12).

[0198] The dynamic mechanical spectrum of Example 12.1 was measured and the results are recorded in Table 13. The viscosity in radians / second was determined to be 395,948 Pa s, and the viscosity at 100 radians / second The viscosity was measured to be 2,075 Pa s, with a rheological ratio (V) of 190.8. 0.1 / V 10 0) was provided (see Figure 13).

[0199] Batch Reactor Example 13 In Table 14, the polymer characteristics of the comparative linear polymer sample (13.C) are shown for the batch reactor. The polymerization reaction was carried out using 585 g of ISOPAR-E™, 1 At 5 g of octene and 240 psi hydrogen pressure (ΔH2), the 11 g of ethylene was charged, and the pressure was adjusted to 0.4 μmol of catalyst 1, 0.48 μmol of Cocatalyst A (methyldi(tetradecyl)ammonium tetrakis(pentafluorophenyl) ) borate), and 10 μmol of MMAO-3A. , dienedimethyldivinylsilane was added. [Table 27] [Table 28]

[0200] Table 14 collects NMR data for Comparative Example 13.C and diene Example 13.1. Data are for a 1.7:1 (trifunctional:tetrafunctional LCB) ratio of trifunctional (0.12 LCB) Both tetrafunctional (0.07LCB / 1000C) and tetrafunctional (0.07LCB / 1000C) are demonstrated.

[0201] The dynamic mechanical spectrum of Example 13.1 was measured and the results are recorded in Table 14. The viscosity at radians / second was determined to be 53,390 Pa s, and the viscosity at 100 radians / second was The viscosity was measured to be 887 Pa s, with a rheological ratio (V) of 60.2. 0.1 / V 100 ) is proposed was served.

[0202] The measured melt strength of the polymer of Example 13.1 was 10 cm at an elongation of 65 mm / sec. It was N.

[0203] Examples 7 (Table 8) to 13 (Table 14) show the results for given catalysts and equivalent conditions. The control of the ratio of trifunctional to tetrafunctional LCBs is essential to the conversion of hydrogen to ethylene in the reactor. This shows that the mechanism in Scheme 6 can be supported by controlling the ratio.

[0204] Examples 7 (Table 8) to 13 (Table 14) show the ratio of trifunctional to tetrafunctional LCBs. As the rate increases, M w / M w0 shows that M w is a diene is the weight average molecular weight of the sample, M w0 is the weight average molecular weight of the unbranched comparison sample The higher the ratio of trifunctional branches, the higher the M w The present specification includes an increase or decrease in The trifunctional kinetic model in the, and each application was filed on September 28, 2018 U.S. Provisional Patent Applications Nos. 62 / 738,606, 62 / 738,612, and 62 / 738 ,621, and previously derived tetrafunctional moieties described in 62 / 738,633. Support Dell.

[0205] Guzman-2010 is a stoichiometric CSTR derived from conventional diene branching. The MWD and physical properties of the catalysts were demonstrated and analyzed. In a very well mixed one gallon reactor system, ethylene, 1-octene, and 1 ,9-decadiene was copolymerized. The specific CG used by Guzman (2010) For the C catalyst, see U.S. Pat. No. 5,965,756 (Structure IX) and U.S. Pat. 553,917 (Example 3). The catalyst was designed to grow a single chain from the catalytic center. The data showed that the CSTR was operated at a pressure of 525 psig and a temperature of 155°C over a range of diene feed concentrations. The data were collected at steady state while operating over a wide range of conditions. The various steady-state polymer samples collected contained measurable levels of gel or insoluble material. However, at the highest diene feed levels, some internal reaction occurred. Reactor fouling was observed, and higher levels of diene feed resulted in gel formation or reactor MWD failure. It was expected to bring stability.

[0206] Guzman-2010 uses a selected set of data to quantify diene feed-level speciation. The reactor conditions were fixed throughout the series. The feed concentrations of 1-octene and 1-octene were set at 13.8 wt% and 3.6 wt%, respectively. The catalyst feed rate was adjusted to maintain a constant ethylene conversion of 79% throughout the series. The temperature was continuously adjusted to give a fixed polymer production rate of 2.2 kg / h. The polymer density, a measure of polymer composition, remained constant at about 0.922 g / cc.

[0207] According to the data from Guzman-2010, I2 and I 10 is reflected by As mentioned above, changes in the level of conventional diene branching affect the average molecular weight and polydispersity as well as viscosity. It has been demonstrated how the molecular weight of conventional diene branching affects properties. The effect of both absolute and conventional MWD measurement techniques is shown. Absolute MWD measurements are the preferred method for branched polymers, but are not always available. Therefore, the Guzman-2010 was measured using conventional techniques using a refractive index detector. The results in Table 33 show that, by both measurement techniques, the diene feed As the weight average molecular weight (M w ) will increase substantially Demonstrate the following.

[0208] Although not reported in Guzman-2010, absolute GPC measurement techniques and conventional For the GPC measurement technique, the MWD curves are found in Figure 14A and Figure 14B, respectively; The MWD curve data in Figure 14 show the expected high yields resulting from conventional diene branching. I M w This demonstrates that tail formation occurred. The significant increase in peak MW with increasing diene branching The lack of movement is also evident from the MWD curves.

[0209] The molecular weight distribution data in Figures 14A and 14B show that more diene monomers are present in the CST A simple metric that describes the evolution of the position and shape of the MWD curve as it is fed into R The data are based on the absolute MWD measurements of polymer samples in Guzman-2010 and These MWD metrics are shown for both conventional and absolute MWD measurements. The data shows that the 1,9-decadiene feed ranges from 0 to 923 ppm, resulting in a maximum molecular weight of It was shown that the increase was 87%. p The peak molecular weight change, as shown by Neither measure of quantity varied significantly, and the results were consistent with those for the "ladder-branched" polymer. The shape factors are summarized in Table 34 (Guzman-2010) and Supply levels and M w As G increases 79 / 29 and A TAIL Both values ​​of As increases, their shape factors are not consistent with "ladder bifurcations."

[0210] It will be apparent to those skilled in the art that various modifications can be made to the described embodiments without departing from the spirit and scope of the claimed subject matter. Thus, it is intended that this specification cover modifications and variations of the described embodiments provided that such modifications and variations come within the scope of the appended claims and their equivalents. The present invention includes the following aspects. Section 1. Ethylene, at least one diene comonomer, and optionally at least one C-C 14 1. A polymer comprising the polymerization product of a comonomer, the diene has a structure according to formula (I): [ka] wherein X is CR2, SiR2, or GeR2, and each R is independently C1 to C 12 is hydrocarbyl or -H, A polymer wherein said polymer comprises trifunctional long chain branches arising from said diene occurring at a frequency of at least 0.03 per 1000 carbon atoms in said polymer. Section 2. Item 3. The polymer according to item 1, wherein X in formula (I) is -C(R)2- and each R is -H. Section 3. In formula (I), X is -Si(R)2-, and each R is C1 to C 12 Item 1. The polymer according to item 1, wherein the alkyl is alkyl. Section 4. Item 4. The polymer according to item 3, wherein the diene is dimethyldivinylsilane. Section 5. Item 5. The polymer according to any one of items 1 to 4, wherein the polymer is an ethylene-based copolymer containing at least 50 mol% ethylene. Section 6. The polymer has a molecular weight distribution (MWD) area metric, A TAIL A is defined by a molecular weight tail quantified by TAIL is 0.04 or less as determined by gel permeation chromatography using a triple detector. Section 7. Item 7. The polymer according to any one of items 1 to 6, wherein the polymer has an average g' of 0.55 to 0.86, the average g' being an intrinsic viscosity ratio determined by gel permeation chromatography using a triple detector. Section 8. The polymer has a melt viscosity ratio (V) at 190°C of at least 20. 0.1 / V 100 ), wherein V 0.1 is the viscosity of the polymer at 190°C at a shear rate of 0.1 rad / sec, and V 100 Item 8. The polymer according to any one of Items 1 to 7, wherein is the viscosity of the ethylene-based polymer at 190°C and a shear rate of 100 rad / sec. Section 9. The melt viscosity ratio (V 0.1 / V 100 Item 9. The polymer according to item 8, wherein the .times. ... Section 10. Item 10. The polymer according to any one of items 1 to 9, wherein the trifunctional long chain branches occur at a frequency of at least 0.05 per 1000 carbon atoms. Section 11. Item 11. The polymer according to any one of items 1 to 10, wherein the trifunctional long chain branches occur at a frequency of at least 0.1 per 1000 carbon atoms. Section 12. Item 12. The polymer according to any one of items 1 to 11, wherein the polymer has a melt strength of more than 6 cN. Section 13. The polymer has a weight average molecular weight (M) of 800,000 daltons or less as determined by gel permeation chromatography using a triple detector. w Item 13. The polymer according to any one of items 1 to 12, having a structure comprising: Section 14. The polymer has a weight average molecular weight (M) of 400,000 daltons or less as determined by gel permeation chromatography using a triple detector. w Item 14. The polymer according to any one of items 1 to 13, having a structure comprising: Section 15. The polymer has a weight average molecular weight (M) of 200,000 daltons or less as determined by gel permeation chromatography using a triple detector. w Item 15. The polymer according to any one of items 1 to 14, having a structure comprising: Section 16. The polymer has a weight average molecular weight (M) of less than 150,000 daltons as determined by gel permeation chromatography using a triple detector. w Item 16. The polymer according to any one of items 1 to 15, having a structure comprising: Section 17. The polymer has a weight average molecular weight / number average molecular weight, M, of less than 4, as determined by gel permeation chromatography using a triple detector. w / M n Item 17. The polymer according to any one of items 1 to 16, having the following structure:

Claims

1. Ethylene, at least one diene comonomer, and optionally at least one C ３ ~C １４ 1. A polymer comprising the polymerization product of a comonomer, the diene has a structure according to formula (I): 【Chemical 1】 wherein X is CR 2 and each R is independently C １ ~C １２ is hydrocarbyl or —H, A polymer wherein said polymer comprises trifunctional long chain branches originating from said diene occurring at a frequency of at least 0.03 per 1000 carbon atoms of said polymer.

2. X in formula (I) is -C(R) ２ 2. The polymer of claim 1, wherein: - and each R is -H.

3. 3. The polymer of claim 1 or 2, wherein the polymer is an ethylene-based copolymer comprising at least 50 mole percent ethylene.

4. The polymer has a molecular weight distribution (MWD) area metric, A ＴＡＩＬ and the molecular weight tail is quantified by A ＴＡＩＬ 4. The polymer of claim 1, wherein the .DELTA..times ...

5. 5. The polymer of any one of claims 1 to 4, wherein the polymer has an average g' of 0.55 to 0.86, wherein the average g' is an intrinsic viscosity ratio determined by gel permeation chromatography using a triple detector.

6. The polymer has a melt viscosity ratio at 190°C (V ０．１ / V １００ ), wherein V ０．１ is the viscosity of the polymer at 190°C at a shear rate of 0.1 rad / sec, and V １００ 6. The polymer of any one of claims 1 to 5, wherein V is the viscosity of the polymer at 190°C at a shear rate of 100 rad / sec.

7. The melt viscosity ratio at 190 ° C. (V ０．１ / V １００ 7. The polymer of claim 6, wherein .gtoreq..times ...

8. 8. The polymer of any one of claims 1 to 7, wherein the trifunctional long chain branches occur at a frequency of at least 0.05 per 1000 carbon atoms.

9. 9. The polymer of any one of claims 1 to 8, wherein the trifunctional long chain branches occur at a frequency of at least 0.1 per 1000 carbon atoms.

10. The polymer of any one of claims 1 to 9, wherein the polymer has a melt strength greater than 6 cN.

11. The polymer has a weight average molecular weight (M) of 800,000 Daltons or less as determined by gel permeation chromatography using a triple detector. ｗ 11. The polymer of claim 1, wherein

12. The polymer has a weight average molecular weight (M) of 400,000 Daltons or less as determined by gel permeation chromatography using a triple detector. ｗ 12. The polymer of claim 1, wherein

13. The polymer has a weight average molecular weight (M) of 200,000 Daltons or less as determined by gel permeation chromatography using a triple detector. ｗ 13. The polymer of claim 1, wherein

14. The polymer has a weight average molecular weight (M) of less than 150,000 Daltons as determined by gel permeation chromatography using a triple detector. ｗ 14. The polymer of claim 1, wherein

15. The polymer has a weight average molecular weight / number average molecular weight, M, of less than 4, as determined by gel permeation chromatography using a triple detector. ｗ / M ｎ The polymer of any one of claims 1 to 14, having

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