CN121420002A

CN121420002A - Catalysts and polymerization for improved polyolefins

Info

Publication number: CN121420002A
Application number: CN202480043413.XA
Authority: CN
Inventors: M·W·赫尔特卡姆; K·A·史蒂文斯; 李东明; L·G·麦卡洛; C·J·哈兰
Original assignee: ExxonMobil Technology and Engineering Co
Current assignee: ExxonMobil Technology and Engineering Co
Priority date: 2023-05-23
Filing date: 2024-05-14
Publication date: 2026-01-27
Also published as: WO2024242936A1

Abstract

本公开涉及聚乙烯聚合物和由其制造的膜。在一些实施方案中，聚乙烯共聚物包含90重量%或更多的乙烯单元和剩余余量的C₃ ₃‑C₂₀ ₂₀共聚单体单元。聚乙烯共聚物具有双峰组成分布，0.914 g/cm³ ³至0.925 g/cm³ ³的密度，0.1 g/10min至1 g/10min的熔体指数，21 g/10 min至70 g/10 min的高负荷熔体指数(HLMI)，40至65的熔体指数比率(MIR)，和4至7的分子量分布(MWD)。This disclosure relates to polyethylene polymers and films made therefrom. In some embodiments, the polyethylene copolymer comprises 90% by weight or more ethylene units and the balance _C33 _- _C2020 comonomer units. The polyethylene copolymer has a bimodal composition distribution, _a density of ^0.914 g/ ^cm3 to ^0.925 g/ ^cm3 , a melt index of 0.1 g/10min to 1 g/10min, a high-load melt index (HLMI) of 21 g/10min to 70 g/10min, a melt index ratio (MIR) of 40 to 65, and a molecular weight distribution (MWD) of 4 to 7.

Description

Catalyst and polymerization for improved polyolefins

Cross Reference to Related Applications

The application claims the benefit of U.S. provisional application 63/503845 filed on month 5 of 2023 and entitled "Polyethylenes Having Improved Processability and Films Thereof [ polyethylene with improved processability and film thereof ]", the entire contents of which are incorporated herein by reference.

Technical Field

The present disclosure relates to polyethylene polymers and films made therefrom.

Background

Linear Low Density Polyethylene (LLDPE) is a substantially linear polymer composed of ethylene monomer units and alpha-olefin comonomer units. The usual comonomer units used are derived from 1-butene, 1-hexene, or 1-octene. LLDPE can be distinguished from conventional Low Density Polyethylene (LDPE) in several ways, including different methods of manufacture thereof. Furthermore, LLDPE has little or no detectable Long Chain Branching (LCB)/1,000 carbon atoms, whereas conventional LDPE contains a relatively high degree of long chain branching. Long chain branching provides reduced necking (neg-in) and increased tensile stability during the extrusion process. Furthermore, LLDPE generally has a narrower Molecular Weight Distribution (MWD) relative to LDPE, especially metallocene-catalyzed LLDPE ("mLLDPE"). LLDPE also has different rheological and mechanical properties, such as tear properties, compared to LDPE.

While mLLDPE typically provides mechanical properties in films and other articles made therefrom that are superior to existing LDPEs, they are generally more difficult to process than LDPEs, e.g., they have lower melt strength (which can not only affect bubble stability in a variety of film forming processes, but can also result in melt fracture-surface roughness or similar irregularities in films produced at typical commercial extrusion rates).

Thus, various levels of LDPE have been blended with mLLDPE to increase melt strength, increase shear sensitivity, e.g., increase flow in an extruder at commercial shear rates, and reduce the propensity for melt fracture. However, such blending typically has a negative impact on the mechanical properties of films made from the polymers. Indeed, improving mLLDPE processability without sacrificing physical properties has been challenging.

Comparing LLDPEs to each other, LLDPEs with higher melt index are better for processing, and the combination of higher melt index and lower density is particularly good for cast film applications. However, less long chain branching may result in reduced film properties (e.g., tear properties in films/articles made therefrom). Indeed, it is challenging to find a LLDPE that has a combination of density and melt index while still being commercially processable.

Some references that may be of interest in this regard include U.S. Pat. Nos. 6,479,424, 7,601,666, 9,068,033, 10,633,471 and 11,352,386, WIPO publication WO 2021/257264, US 2021/0395404, US 2022/0185916, US 2022/0315680 and Foster et al, journal of Organometallic Chemistry,571 (1998) 171.

In general, there is a need for new LLDPE's that have a combination of desirable properties (such as density, melt index properties, long chain branching) while providing commercially desirable LLDPE polymerization and extrusion.

Disclosure of Invention

In some embodiments, the polyethylene copolymer comprises about 90 wt.% or more ethylene units and the balance C ₃-C₂₀ comonomer units. The polyethylene copolymer has a bimodal composition distribution, a density of about 0.914 g/cm ³ to about 0.925 g/cm ³, a melt index of about 0.1 g/10min to about 1 g/min, a High Load Melt Index (HLMI) of about 21 g/10min to about 70 g/10min, a Melt Index Ratio (MIR) of about 40 to about 65, and a Molecular Weight Distribution (MWD) of about 4 to about 7.

In some embodiments, the polyethylene copolymer comprises about 90 wt.% or more ethylene units and the balance C ₃-C₂₀ comonomer units. The polyethylene copolymer has a bimodal composition distribution, a density of about 0.92 g/cm ³ to about 0.925 g/cm ³, a melt index of about 0.4 g/10min to about 0.5 g/min, a High Load Melt Index (HLMI) of about 24 g/10min to about 29 g/10min, a Melt Index Ratio (MIR) of about 50 to about 65, and a Molecular Weight Distribution (MWD) of about 4 to about 7.

In some embodiments, the polyethylene copolymer comprises about 90 wt.% or more ethylene units and the balance C ₃-C₂₀ comonomer units. The polyethylene copolymer has a bimodal composition distribution, a density of about 0.92 g/cm ³ to about 0.925 g/cm ³, a melt index of about 0.9 g/10min to about 1 g/min, a High Load Melt Index (HLMI) of about 50 g/10min to about 60 g/10min, a Melt Index Ratio (MIR) of about 55 to about 65, and a Molecular Weight Distribution (MWD) of about 6 to about 7.

In some embodiments, the film comprises the polyethylene copolymer of the present disclosure.

Drawings

So that the manner in which the above recited features of the present invention can be understood in detail, a more particular description of the invention, briefly summarized above, may be had by reference to embodiments, some of which are illustrated in the appended drawings. It is to be noted, however, that the appended drawings illustrate only typical embodiments of this invention and are therefore not to be considered limiting of its scope, for the invention may admit to other equally effective embodiments.

Fig. 1 is a graph showing a 4D GPC (population of polymer chains) or mass as a function of logarithm of molecular weight (LogM) trace of polyethylene copolymers prepared using a base catalyst and/or a base catalyst plus a conditioning catalyst according to various embodiments described herein. The y-axis value of the population or mass of polymer chains may be labeled d (wt fraction)/d (log) or equivalently MWD (IR) to reflect that the y-axis value is a molecular weight population or distribution, but it should be noted that in this context MWD does not mean Mw/Mn as in other contexts herein. FIG. 1 also shows on its y-axis the g' _{vis ave} values for polyethylene copolymers prepared using a base catalyst and/or a base catalyst plus a conditioning catalyst according to various embodiments described herein.

Fig. 2 is a graph showing 4D GPC (population or mass of polymer chains as a function of logarithm of molecular weight (LogM)) traces of polyethylene copolymers prepared using a base catalyst and/or a base catalyst plus a conditioning catalyst according to various embodiments described herein. The y-axis value of the population or mass of polymer chains may be labeled d (wt fraction)/d (log) or equivalently MWD (IR) to reflect that the y-axis value is a molecular weight population or distribution, but it should be noted that in this context MWD does not mean Mw/Mn as in other contexts herein. Fig. 2 also shows on its y-axis the g' _{vis ave} values for polyethylene copolymers prepared using a base catalyst and/or a base catalyst plus a conditioning catalyst according to various embodiments described herein.

FIG. 3 is a graph showing the TREFIR superposition of a polyethylene copolymer prepared using a single catalyst and a polyethylene copolymer prepared using a base catalyst plus a conditioning catalyst according to various embodiments described herein.

FIG. 4 is a graph showing the TREFIR superposition of a polyethylene copolymer prepared using a single catalyst and a polyethylene copolymer prepared using a base catalyst plus a conditioning catalyst according to various embodiments described herein.

Detailed Description

Various embodiments, variations of the disclosed compounds, methods, and articles of manufacture will now be described, including the specific embodiments and definitions employed herein. While the following detailed description gives specific embodiments, those skilled in the art will appreciate that these embodiments are exemplary only, and that embodiments of the present disclosure may be practiced in other ways. Any reference to an embodiment may refer to one or more, but not necessarily all, of the compounds, methods, or articles of manufacture defined by the claims. The headings are used for convenience only and do not limit the scope of the disclosure.

The present disclosure relates to polyethylene polymers and films made therefrom. Polyethylene polymers are copolymers formed from dual catalyst systems, particularly such systems that are provided to polymerization reactors using a "tuning" process, and have a combination of low density, low melt index, high melt index ratio, and controlled long chain branching (introduced by the tuning process), while also providing polymerization and extrusion of commercially desirable polyethylene copolymers.

The polyethylene copolymers of the present disclosure increase long chain branching (also referred to as "LCB") in the copolymer, as compared to conventional LLDPE, thereby providing reduced neck-in and increased stretch stability. The polyethylene copolymers of the present disclosure may exhibit lower zero shear viscosity, resulting in lower motor torque during extrusion and lower melt pressure and melt temperature, thereby providing increased output of the extruded polyethylene copolymer product. Furthermore, since the LCB is controlled (adjustable, e.g., by an adjustment method), the advantageous tear properties can likewise be controlled (adjustable) for the desired polymer end use (e.g., shrink wrap film). For example, a decrease in motor torque and melt pressure can be observed during cast film fabrication due to the increased polymer LCB. LCB can be demonstrated by, for example, the ratio of high melt index ratios and/or rheological characteristics (e.g., η _0.01/η₁₀₀ (complex viscosity recorded at shear rates of 0.01 and 100 rad/s, respectively) shown by Small Angle Oscillation Shear (SAOS) experiments, and in the Van Gurp Palmen plot of phase angle versus complex modulus (which tracks the viscosity response of the polymer to applied shear).

In addition, it has been found that the polyethylene copolymers of the present disclosure can provide excellent shear thinning characteristics and, in addition, can be used to produce blown films having excellent bubble stability and/or little or no melt fracture. The polyethylene copolymers of the present disclosure may further provide films formed with reduced motor load and melt pressure (which increases throughput) due to improved flow behavior compared to conventional LLDPE. For example, a reduction in melt pressure and a reduction in melt temperature may be provided during blown film manufacture. The films of the present disclosure may be particularly useful as shrink wrap films (improved by the presence of LCB in the polyethylene copolymers of the present disclosure).

In fact, the catalysts (e.g., for the tuning process) and methods of the present disclosure may tune (e.g., adjust online) the LCB-promoting catalyst onto the supported catalyst, for example, to control (adjust) the melt index ratio of the polyethylene copolymer formed in the reactor. The catalyst used for the adjustment may provide a different molecular weight capability than, for example, an in-line supported catalyst. The different molecular weight capabilities of the catalyst provide a bimodal composition distribution of the polyethylene copolymer formed in the reactor.

Definition of the definition

As used herein, an "olefin," alternatively referred to as an "olefin," is a linear, branched, or cyclic compound of carbon and hydrogen having at least one double bond. For the purposes of this specification and the appended claims, when a polymer or copolymer is referred to as "comprising" an olefin, the olefin present in such polymer or copolymer is the polymerized form of the olefin. For example, when a copolymer is described as having an "ethylene" content of 35 to 55 weight percent, it is understood that the monomer units in the copolymer are derived from ethylene in the polymerization reaction, and that the derived units are present at 35 to 55 weight percent based on the weight of the copolymer.

As used herein, the terms "polyethylene polymer", "polyethylene copolymer", "polyethylene", "ethylene polymer", "ethylene copolymer" and "ethylene-based polymer" mean a polymer or copolymer comprising at least 50 mol% ethylene units, or at least 70 mol% ethylene units, or at least 80 mol% ethylene units, or at least 90 mol% ethylene units, or at least 95 mol% ethylene units, or 100 mol% ethylene units (in the case of homopolymers).

As used herein, "polymer" may refer to homopolymers, copolymers, interpolymers, terpolymers, etc. "Polymer" has two or more monomer units that are the same or different. "homopolymer" is a polymer having the same monomer units. A "copolymer" is a polymer having two or more monomer units that are different from each other. "terpolymer" is a polymer having three monomer units that differ from one another. The term "different" as used to refer to monomer units indicates that the monomer units differ from each other by at least one atom or are isomerically different. Thus, as used herein, the definition of copolymer includes terpolymers, etc. Likewise, as used herein, the definition of polymer includes copolymers and the like.

As used herein, ethylene polymers having a density of greater than 0.860 to less than 0.910 g/cm ³ are referred to as ethylene plastomers or plastomers, ethylene polymers having a density of 0.910 to 0.925 g/cm ³ are referred to as "linear low density polyethylene" (LLDPE) when substantially linear (with little or no long chain branching), as is typical for ziegler-natta or metallocene-catalyzed PEs, or as "branched low density polyethylene" (LDPE) when significantly branched (with a high degree of long chain branching), as is typical for free-radical polymerized PEs, 0.925 to 0.940 g/cm ³ are referred to as "medium density polyethylene" (MDPE), and ethylene polymers having a density of greater than 0.940 g/cm ³ are referred to as "high density polyethylene" (HDPE). The density was determined according to ASTM D792. Samples were prepared according to ASTM D4703-appendix 1 procedure C, then conditioned according to ASTM D618-procedure a, and then tested.

As used herein and unless otherwise indicated, the term "hydrocarbon" means a class of compounds containing hydrogen bound to carbon and includes (i) saturated hydrocarbon compounds, (ii) unsaturated hydrocarbon compounds, and (iii) mixtures of hydrocarbon compounds (saturated or unsaturated), including mixtures of hydrocarbon compounds having different n values.

As used herein, a composition or film that is "free of" a component refers to a composition/film that is substantially free of the component, or that contains a component in an amount of less than about 0.01 weight percent of the total composition by weight.

As used herein, the term "polymerization conditions" refers to conditions that favor the reaction of one or more olefin monomers to produce a polyolefin polymer upon contact with an activated olefin polymerization catalyst, including the choice of temperature, pressure, reactant concentration, optional solvents/diluents, reactant mixing/addition parameters, and other conditions within at least one polymerization reactor by the skilled artisan.

For brevity, only certain ranges are explicitly disclosed herein. However, a range from any lower limit may be combined with any upper limit to list a range not explicitly recited, and a range from any lower limit may be combined with any other lower limit to list a range not explicitly recited, in the same manner, a range from any upper limit may be combined with any other upper limit to list a range not explicitly recited. Furthermore, "in a range" or "in a range (WITHIN A RANGE)" includes every point or single value between its endpoints, even if not explicitly recited, and includes the endpoints themselves. Thus, each point or individual value may be combined as its own lower or upper limit with any other point or individual value or any other lower or upper limit to list ranges not explicitly recited.

For the purposes of this disclosure, numbering schemes of the periodic table groups as described in CHEMICAL AND ENGINEERING NEWS, 63 (5), page 27 (1985) are used.

The abbreviations Me is methyl, et is ethyl, ph is phenyl, tBu is t-butyl, PDI is polydispersity index, MAO is methylaluminoxane, SMAO is supported methylaluminoxane, NMR is nuclear magnetic resonance, ppm is parts per million, THF is tetrahydrofuran.

As used herein, one or more olefin polymerization catalysts refers to any catalyst, such as an organometallic complex or compound capable of coordination polymerization addition in which a continuous monomer is added in a monomer chain at an organometallic active center.

The terms "substituent", "group" and "moiety" may be used interchangeably.

The term "linear alpha-olefin" refers to an olefin having a terminal carbon-carbon double bond in its structure ((R ^"R^''')-C=CH₂, where R ^" and R ^''' may independently be hydrogen or any hydrocarbyl group; such as R ^" is hydrogen and R ^''' is alkyl), "linear alpha-olefin" is an alpha-olefin as defined in this paragraph, where R ^" is hydrogen and R ^''' is hydrogen or linear alkyl).

For purposes of this disclosure, ethylene should be considered an alpha-olefin.

As used herein, and unless otherwise indicated, the term "C _n" means hydrocarbon(s) having n carbon atom(s) per molecule, where n is a positive integer. The term "hydrocarbon" means a class of compounds containing hydrogen bonded to carbon and includes (i) saturated hydrocarbon compounds, (ii) unsaturated hydrocarbon compounds, and (iii) mixtures of hydrocarbon compounds (saturated and or unsaturated), including mixtures of hydrocarbon compounds having different n values. Likewise, a "C _m-C_y" group or compound refers to a group or compound comprising a total number of carbon atoms from m to y. Thus, a C ₁-C₅₀ alkyl group refers to an alkyl group containing a total number of carbon atoms from about 1 to about 50.

Unless otherwise indicated (e.g., definition of "substituted hydrocarbyl", "substituted aromatic compound", etc.), the term "substituted" means that at least one hydrogen atom has been replaced by at least one non-hydrogen group, such as a hydrocarbyl, heteroatom, or heteroatom-containing group, such as a halo group (such as Br, cl, F, or I) or at least one functional group (such as -NR*₂、-OR*、-SeR*、-TeR*、-PR*₂、-AsR*₂、-SbR*₂、-SR*、-BR*₂、-SiR*₃、-GeR*₃、-SnR*₃、-PbR*₃, where each R is independently hydrocarbyl or halogenated hydrocarbyl (halocarbyl), and two or more R's may join together to form a substituted or unsubstituted fully saturated, partially unsaturated, or aromatic ring or polycyclic structure), or where at least one heteroatom has been inserted into the hydrocarbyl ring.

The term "substituted hydrocarbyl" means a hydrocarbyl in which at least one hydrogen atom of the hydrocarbyl has been replaced by at least one heteroatom (such as halo, e.g., br, cl, F, or I) or heteroatom-containing group (such as a functional group, e.g., ,-NR*₂、-OR*、-SeR*、-TeR*、-PR*₂、-AsR*₂、-SbR*₂、-SR*、-BR*₂、-SiR*₃、-GeR*₃、-SnR*₃、-PbR*₃, etc., in which each R is independently a hydrocarbyl or halocarbyl group, and two or more R may join together to form a substituted or unsubstituted fully saturated, partially unsaturated, or aromatic ring or polycyclic structure), or in which at least one heteroatom has been inserted into the hydrocarbyl ring.

The term "substituted aromatic compound" means an aromatic group in which one or more hydrogen groups are replaced with a hydrocarbyl, substituted hydrocarbyl, heteroatom, or heteroatom-containing group.

The terms "hydrocarbyl (hydrocarbyl radical)", "hydrocarbyl (hydrocarbyl group)", or "hydrocarbyl (hydrocarbyl)" may be used interchangeably and are defined to mean groups containing only hydrogen and carbon atoms. For example, the hydrocarbyl group may be a C ₁-C₁₀₀ group, which may be linear, branched, or cyclic, and when cyclic, is aromatic or non-aromatic. Examples of such groups may include, but are not limited to, alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, hexyl, octyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, and aryl groups such as phenyl, benzyl, naphthyl.

The term "alkoxy" or "alkoxy" means an alkyl or aryl group bound to an oxygen atom, such as an alkyl ether or aryl ether group (group/functional) attached to an oxygen atom, and may include those wherein the aryl/alkyl group is a C ₁ to C ₁₀ hydrocarbon group. The alkyl groups may be linear, branched, or cyclic. The alkyl groups may be saturated or unsaturated. Examples of suitable alkoxy groups may include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, phenoxy.

The term "alkenyl" means a linear, branched, or cyclic hydrocarbon group having one or more double bonds. These alkenyl groups may be optionally substituted. Examples of suitable alkenyl groups may include ethenyl, propenyl, allyl, 1, 4-butadienyl, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cyclooctenyl, including substituted analogs thereof.

The terms "alkyl (ALKYL RADICAL)", "alkyl group" and "alkyl" are used interchangeably throughout this disclosure. For the purposes of this disclosure, "alkyl" is defined as a C ₁-C₁₀₀ alkyl group that may be linear, branched, or cyclic. Examples of such groups may include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, hexyl, octyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, including substituted analogs thereof. Some examples of alkyl groups may include 1-methylethyl, 1-methylpropyl, 1-methylbutyl, 1-ethylbutyl, 1, 3-dimethylbutyl, 1-methyl-1-ethylbutyl, 1-diethylbutyl, 1-propylpentyl, 1-phenylethyl, isopropyl, 2-butyl, sec-pentyl, sec-hexyl, and the like.

The term "aryl (aryl)" or "aryl (aryl group)" means aromatic rings and substituted variants thereof, such as phenyl, 2-methyl-phenyl, xylyl, 4-bromo-xylyl. Likewise, "heteroaryl" means an aryl group in which a ring carbon atom (or two or three ring carbon atoms) has been replaced by a heteroatom such as N, O, or S. As used herein, the term "aromatic" also refers to a pseudo-aromatic heterocycle, which is a heterocyclic substituent having similar properties and structure (nearly planar) as an aromatic heterocycle ligand, but is by definition not an aromatic compound, and as such, the term aromatic compound also refers to a substituted aromatic compound.

Where an isomer of a named alkyl, alkenyl, alkoxy, or aryl group is present (e.g., n-butyl, isobutyl, sec-butyl, and tert-butyl), references to the alkyl, alkenyl, alkoxy, or aryl group without specifying the particular isomer (e.g., butyl) expressly disclose all isomers (e.g., n-butyl, isobutyl, sec-butyl, and tert-butyl).

The term "ring atom" means an atom that is part of a cyclic ring structure. For this definition, benzyl has six ring atoms and tetrahydrofuran has five ring atoms.

A heterocycle is a ring having a heteroatom in the ring structure, as opposed to a ring in which a hydrogen on a ring atom is replaced by a heteroatom. For example, tetrahydrofuran is a heterocyclic ring, while 4-N, N-dimethylamino-phenyl is a heteroatom-substituted ring. Other examples of heterocycles may include pyridine, imidazole, and thiazole.

As used herein, mn is the number average molecular weight, mw is the weight average molecular weight, and Mz is the z average molecular weight, wt% is the weight percent, and mol% is the mole percent. Molecular Weight Distribution (MWD), also known as Polydispersity (PDI), is defined as Mw divided by Mn. Unless otherwise indicated, all molecular weight units (e.g., mw, mn, mz) are g/mol.

The terms "catalyst compound", "catalyst complex", "transition metal compound", "precatalyst compound" and "precatalyst complex" are used interchangeably.

A "catalyst system" is a combination of at least one catalyst compound, optionally at least one activator, optionally a co-activator, and optionally a support material. When "catalyst system" is used to describe such pairing prior to activation, it means that the unactivated catalyst complex (pre-catalyst) is together with the activator and optionally the co-activator. When it is used to describe such pairing after activation, it means an activated complex and an activator or other charge balancing moiety. The catalyst compound may be neutral as in the precatalyst or a charged species with a counter ion as in the activated catalyst system. For purposes of this disclosure and the claims thereto, when a catalyst system is described as comprising components in neutral stable form, it will be well understood by those of ordinary skill in the art that the ionic form of the components is the form that reacts with the monomer to produce the polymer. The polymerization catalyst system is a catalyst system that can polymerize monomers into polymers. Furthermore, the catalyst compounds and activators represented by the formulae herein are intended to include both neutral and ionic forms of the catalyst compounds and activators.

An "anionic ligand" is a negatively charged ligand that provides one or more pairs of electrons to a metal ion. A "lewis base" or "neutral donor ligand" is an uncharged ligand that provides one or more pairs of electrons to a metal ion. Examples of lewis bases include diethyl ether, trimethylamine, pyridine, tetrahydrofuran, dimethyl sulfide, and triphenylphosphine. The term "heterocyclic lewis base" refers to lewis bases that are also heterocyclic. Examples of heterocyclic lewis bases include pyridine, imidazole, thiazole, and furan.

Scavengers are compounds that can be added to promote polymerization by scavenging impurities. Some scavengers may also act as activators and may be referred to as co-activators. Co-activators other than scavengers may also be used in combination with the activator to form an active catalyst. In at least one embodiment, the coactivator may be premixed with the transition metal compound to form the alkylated transition metal compound.

The term "continuous" means a system that does not interrupt or stop operation for an extended period of time. For example, a continuous process for producing a polymer would be one in which reactants are continuously introduced into one or more reactors and polymer product is continuously withdrawn.

Solution polymerization means a polymerization process in which the polymer is dissolved in a liquid polymerization medium, such as an inert diluent or one or more monomers or blends thereof. Solution polymerization may be homogeneous. Homogeneous polymerization is a polymerization in which the polymer product is dissolved in the polymerization medium. Suitable systems may not be cloudy, as described in J. Vladimir Oliveira, C. Dariva and J.C. Pinto, ind. Eng. Chem. Res., 2000, volume 29, page 4627.

Bulk polymerization means a polymerization process in which the polymerized monomers and/or comonomers are used as solvents or diluents, with little or no inert solvents as solvents or diluents. A small fraction of inert solvent/diluent may be used as a carrier for the catalyst and scavenger. The bulk polymerization system contains less than 25 wt% of an inert solvent or diluent, such as less than 10 wt%, such as less than 1 wt%, such as 0 wt%.

The term "single catalyst compound" refers to a catalyst compound corresponding to a single structural formula, although such catalyst compound may comprise and be used as a mixture of isomers (e.g., stereoisomers).

By a catalyst system utilizing a single catalyst compound is meant a catalyst system prepared using only a single catalyst compound in the preparation of the catalyst system. Thus, such catalyst systems are distinguished from, for example, "dual" catalyst systems (which are prepared using two catalyst compounds having different structural formulas), e.g., the connectivity between atoms, the number of atoms, and/or the type of atoms in the two catalyst compounds are different. Thus, one catalyst compound is considered to be different from another if it differs in the number, type, or connectivity of at least one atom. For example, bis-indenyl zirconium dichloride is different from (indenyl) (2-methylindenyl) zirconium dichloride, which is different from (indenyl) (2-methylindenyl) hafnium dichloride. The only difference is that the catalyst compounds which are stereoisomers of each other are not considered to be different catalyst compounds. For example, rac-dimethylsilylbis (2-methyl-4-phenyl) hafnium dimethyl and meso-dimethylsilylbis (2-methyl-4-phenyl) hafnium dimethyl are not considered to be different.

The terms "cocatalyst" and "activator" are used interchangeably herein and are defined as any compound that can activate any of the catalyst compounds described above by converting a neutral catalyst compound to a catalytically active catalyst compound cation.

Polymerization process

The polymerization process may include gas phase polymerization, and in particular fluidized bed gas phase polymerization. Generally, in a fluidized gas bed process for producing polymers, a gaseous stream containing one or more monomers is continuously circulated through a fluidized bed in the presence of a catalyst under reactive conditions. In some embodiments, the reaction medium includes a condensing agent, which is typically a non-coordinating inert liquid that is converted to a gas in the polymerization process, such as isopentane, isohexane, or isobutane. The gaseous stream is withdrawn from the fluidized bed and recycled back to the reactor. At the same time, the polymer product is withdrawn from the reactor and fresh monomer is added to replace the polymerized monomer. (see, e.g., U.S. Pat. Nos. 4,543,399;4,588,790;5,028,670;5,317,036;5,352,749;5,405,922;5,436,304;5,453,471;5,462,999;5,616,661; and 5,668,228; incorporated herein by reference in their entirety.) gas phase polymerization may be carried out in any suitable reactor system (e.g., a stirred or paddle reactor system). For a discussion of suitable gas phase fluidized bed polymerization systems, see U.S. Pat. Nos. 7,915,357;8,129,484;7,202,313;6,833,417;6,841,630;6,989,344;7,504,463;7,563,851; and 8,101,691, which are incorporated herein by reference.

In such polymerization processes, the gas phase fluidized bed process is carried out by continuously passing a stream containing ethylene and olefin comonomer through a fluidized bed reactor under reaction conditions and in the presence of a catalyst composition at a velocity sufficient to maintain a bed of solid particles in suspension. A stream containing unreacted ethylene and olefin comonomer (which may be referred to as a "recycle gas" stream) is continuously withdrawn from the reactor, compressed, cooled, optionally partially or fully condensed, and recycled back to the reactor. The prepared polyethylene copolymer is withdrawn from the reactor and replacement ethylene and olefin comonomer are added to the recycle stream. In some embodiments, a gas inert to the catalyst composition and reactants is present in the gas stream.

The recycle gas may include an Induced Condensing Agent (ICA). ICA is one or more non-reactive alkanes that are condensable in the polymerization process for removing the heat of reaction. In some embodiments, the non-reactive alkane is selected from the group consisting of C ₁-C₆ alkanes, such as, for example, propane, butane, isobutane, pentane, isopentane, hexane, and one or more of its isomers and derivatives thereof. In some cases, mixtures of two or more such ICAs may be particularly useful (e.g., propane and pentane, propane and butane, butane and pentane, etc.).

The reactor pressure during polymerization may be from about 100 psig (680 kPag) to about 500 psig (3448 kPag), such as from about 200 psig (1379 kPag) to about 400 psig (2759 kPag), such as from about 250 psig (1724 kPag) to about 350 psig (2414 kPag). In some embodiments, the reactor is operated at a temperature of about 60 ℃ to about 120 ℃, such as about 60 ℃ to about 115 ℃, such as about 70 ℃ to about 110 ℃, such as about 70 ℃ to about 95 ℃, such as about 80 ℃ to about 90 ℃. The ratio of hydrogen to ethylene may be from about 10 to about 30 ppm/mol%, such as from about 15 to about 25 ppm/mol%, such as from about 16 to about 20 ppm/mol%.

The mole percent of ethylene (based on total monomer) may be from about 25 to about 90 mole percent, such as from about 50 to about 90 mole percent, or from about 70 to about 85 mole percent, and the ethylene partial pressure (in the reactor) may be from about 75 psia (517 kPa) to about 300 psia (2069 kPa), or from about 100 psia to about 275 psia (689-1894 kPa), or from about 150 psia to about 265 psia (1034-1826 kPa), or from about 180 psia to about 200 psia. The ethylene concentration in the reactor may also be in the range of from about 35 mol% to about 95 mol%, such as a low value of 35 mol%, 40 mol%, 45 mol%, 50 mol%, or 55 mol% to a high value of 70 mol%, 75 mol%, 80 mol%, 85 mol%, 90 mol%, or 95 mol%, and further wherein the ethylene mol% is based on the total moles of gases in the reactor (including ethylene and/or comonomer gases and inert gases, if present, such as one or more of nitrogen, isopentane, or one or more other ICAs, etc.), as in the case of vol-ppm hydrogen, which measurement may be made in the recycle gas outlet rather than in the reactor itself, for convenience. The comonomer concentration may be from a low value of about 0.2 mol% to about 1 mol%, such as 0.2 mol%, 0.3 mol%, 0.4 mol%, or 0.5 mol% to a high value of 0.65 mol%, 0.70 mol%, 0.75 mol%, 0.80 mol%, 0.85 mol%, 0.90 mol%, 0.95 mol%, or 1.0 mol%.

Polymerization using adjustment

The polymerization process of the present disclosure may be performed using a "tuning" process. The adjustment method is described, for example, in U.S. patent publication No. 2021/0395404, particularly in connection with fig. 1 therein and at paragraphs [0113] - [0124] therein, which descriptions are incorporated herein by reference. An overview of such methods, particularly for the present disclosure, is also provided below.

For delivering the catalyst slurry to the reactor, the high solids concentration of the slurry generally increases the slurry viscosity. The high solids concentration also increases the amount of froth typically generated in the catalyst slurry vessel. High slurry viscosity and foaming can lead to handling problems, storage problems, and reactor injection problems. A low viscosity diluent may be added to the slurry to reduce the viscosity. However, the reduced viscosity promotes settling of the slurry in solution, which can lead to plugging of reactor components and accumulation of solids on the walls of the catalyst slurry vessel.

The second catalyst solution may be added to (i.e., "conditioned") the slurry to adjust one or more properties of the polymer formed in the reactor "in situ". Such "tuning" methods are very economical because they do not require polymerization to be stopped in order to adjust the polymer properties in the event that the catalyst system does not behave in the desired manner. However, the second catalyst is typically delivered into the slurry as a low viscosity solution, which can promote settling of the slurry solution and subsequent gelation and/or plugging of reactor components.

Thus, a method for polymerizing one or more olefins may include using a dual catalyst system (e.g., by loading a second catalyst in situ). In particular, the method includes combining (to "tailor") the catalyst component slurry with the catalyst component solution to form a third catalyst composition, and introducing the third composition into a polymerization reactor (e.g., a gas phase reactor).

In some embodiments, the method includes contacting the first composition with the second composition in a line to the reactor to form a third composition. The first composition comprises a first catalyst (or catalyst compound), a support, and a diluent. The first catalyst or catalyst compound may be referred to herein as the "primary catalyst" or "base catalyst". The second composition comprises a second catalyst (or catalyst compound) and a second diluent. The second catalyst or catalyst compound may be referred to as a "tuning catalyst", particularly within the scope of the methods described herein, the tuning method preferably being used to tune the ratio of the first catalyst to the second catalyst by increasing or decreasing the relative amounts of tuning catalyst to the primary catalyst. The method includes introducing a third composition from a line into a gas phase fluidized bed reactor, and exposing the third composition to polymerization conditions. The process comprises obtaining a polyolefin.

The method may include adjusting reactor conditions, such as the amount of a second catalyst fed to the reactor (via a line leading to the reactor), to control one or more polymer properties of the polyolefin obtained from the reactor.

By using the metallocene catalysts of the present disclosure as a second catalyst that is on-line tuned to the slurry feeding the first catalyst in various ratios, and vice versa, as well as different reactor conditions (including temperature, reaction mixture component concentrations, etc.), beneficial polyolefin products can be formed.

Furthermore, it is also contemplated that for the different catalysts selected, some of the second catalyst may initially be co-deposited with the first catalyst on a common support and the remaining amount of the first catalyst or second catalyst added as a modifier.

The catalyst system may include a catalyst compound in a slurry and an added solution catalyst component added to the slurry. Typically, depending on the solubility, the first catalyst and/or the second catalyst will be supported in the initial slurry. However, in at least one embodiment, the initial catalyst component slurry may not have a catalyst. In this case, two or more solution catalysts may be added as "modifiers" to the slurry so that each is supported.

Furthermore, while the distinction between "primary catalyst" or "base catalyst" and "trim catalyst" is as noted above, it is contemplated that the roles of the primary catalyst described herein can be readily exchanged with the trim catalyst to achieve a similar effect (i.e., in various embodiments, any of the "primary catalyst" described herein can be used as the "second catalyst" in the process just described, and any of the "trim catalyst" can be used as the "first catalyst" in the process just described).

The slurry may include one or more activators and a support, and one or more catalyst compounds. For example, the slurry may include two or more activators (such as aluminoxane and modified aluminoxane) and a catalyst compound, or the slurry may include a supported activator and more than one catalyst compound. In at least one embodiment, the slurry comprises a support, an activator, and two catalyst compounds. In another embodiment, the slurry comprises a support, an activator, and two different catalyst compounds, which may be added to the slurry separately or in combination. The slurry containing the silica and the aluminoxane may be contacted with a catalyst compound to effect a reaction, and thereafter the slurry is contacted with another catalyst compound (e.g., as a "trim").

One or more diluents may be used to facilitate the combination of any two or more components of the catalyst system in the slurry or in the trim catalyst solution. For example, a single site catalyst compound and an activator may be combined together in the presence of toluene or another non-reactive hydrocarbon or hydrocarbon mixture to provide a catalyst mixture. In addition to toluene, other suitable diluents may include, but are not limited to, ethylbenzene, xylenes, pentanes, hexanes, heptanes, octanes, other hydrocarbons, or any combination thereof. The support, dried or mixed with toluene, may then be added to the catalyst mixture, or the catalyst/activator mixture may be added to the support.

The diluent may be or include mineral oil. According to ASTM D4052, the mineral oil may have a density of about 0.85 g/cm ³ to about 0.9 g/cm ³, such as about 0.86 g/cm ³ to about 0.88 g/cm ³, at 25 ℃. According to ASTM D341, mineral oils may have a kinematic viscosity at 25 ℃ of about 150 cSt to about 200 cSt, such as about 160 cSt to about 190 cSt, such as about 170 cSt. According to ASTM D2502, the mineral oil may have an average molecular weight of about 400 g/mol to about 600 g/mol, such as about 450 g/mol to about 550 g/mol, such as about 500 g/mol. In at least one embodiment, the mineral oil is HYDROBRITE ^® 380,380, 380 PO White Mineral Oil ("HB 380") from Sonneborn, LLC.

The diluent may additionally include a wax, which may provide increased viscosity to the slurry (such as a mineral oil slurry). Waxes are food grade petrolatum, also known as petroleum petrolatum (petrolatum). The wax may be paraffin wax. Paraffin waxes include SONO JELL ^® paraffin waxes such as SONO JELL ^® and SONO JELL ^® 9 from Sonneborn, LLC. In at least one embodiment, the slurry has 5 wt% or more, such as 10 wt% or more, such as 25 wt% or more, such as 40 wt% or more, such as 50 wt% or more, such as 60 wt% or more, such as 70 wt% or more of wax. For example, the mineral oil slurry may have about 70 wt% mineral oil, about 10 wt% wax, and about 20 wt% of one or more supported catalysts (e.g., supported dual catalysts). The increased viscosity provided by the wax in the slurry, such as a mineral oil slurry, provides reduced settling of the one or more supported catalysts in the trim vessel or catalyst tank (for introducing the supported catalyst into the line) while the trim efficiency can be suitably maintained. In at least one embodiment, the wax has a density of about 0.7 g/cm ³ (at 100 ℃) to about 0.95 g/cm ³ (at 100 ℃) such as about 0.75 g/cm ³ (at 100 ℃) to about 0.87 g/cm ³ (at 100 ℃). The wax may have a kinematic viscosity of about 5mm ²/s (at 100 ℃) to about 30 mm ²/s (at 100 ℃). The wax may have a boiling point of about 200 ℃ or greater, such as about 225 ℃ or greater, such as about 250 ℃ or greater. The wax may have a melting point of about 25 ℃ to about 100 ℃, such as about 35 ℃ to about 80 ℃.

The catalyst component solution (referred to as a "conditioning" solution) may contain only one or more catalyst compounds or may contain an activator. In at least one embodiment, one or more catalyst compounds in the catalyst component solution are unsupported. The catalyst solution used in the conditioning process may be prepared by dissolving the catalyst compound and optionally the activator in a liquid diluent. The liquid diluent may be an alkane, such as a C ₅ to C ₃₀ alkane, or a C ₅ to C ₁₀ alkane. Cyclic alkanes such as cyclohexane and aromatic compounds such as toluene may also be used. Mineral oil is used as a diluent in place of or in addition to other alkanes such as C ₅ to C ₃₀ alkanes. According to ASTM D4052, the mineral oil may have a density of about 0.85 g/cm ³ to about 0.9 g/cm ³, such as about 0.86 g/cm ³ to about 0.88 g/cm ³, at 25 ℃. According to ASTM D341, mineral oils may have a kinematic viscosity at 25 ℃ of about 150 cSt to about 200 cSt, such as about 160 cSt to about 190 cSt, such as about 170 cSt. According to ASTM D2502, the mineral oil may have an average molecular weight of about 400 g/mol to about 600 g/mol, such as about 450 g/mol to about 550 g/mol, such as about 500 g/mol. In at least one embodiment, the mineral oil is HYDROBRITE ^® 380,380, 380 PO White Mineral Oil ("HB 380") from Sonneborn, LLC.

The solution used should be liquid and relatively inert under the polymerization conditions. In at least one embodiment, the liquid utilized in the catalyst compound solution is different from the diluent used in the catalyst component slurry. In another embodiment, the liquid utilized in the catalyst compound solution is the same as the diluent used in the catalyst component solution.

In alternative embodiments, the catalyst is not limited to a slurry arrangement, as the mixed catalyst system may be prepared on a support and dried. The dried catalyst system may then be fed to the reactor through a dry feed system.

In gas phase polyethylene production processes, it may be desirable to use one or more static control agents to help regulate the static level in the reactor. As used herein, a static control agent is a chemical composition that, when introduced into a fluidized bed reactor, can affect or drive the static charge (negative, positive, or zero charge) in the fluidized bed. The particular static control agent used may depend on the nature of the static charge, and the choice of static control agent may vary depending on the polymer produced and the single site catalyst compound used.

Control agents such as aluminum stearate may be used. The static control agent used may be selected for its ability to receive static charge in the fluidized bed without adversely affecting productivity. Other suitable static control agents may also include aluminum distearate, ethoxylated amines, and antistatic compositions.

Primary catalyst

The catalyst employed in the polymerization of the present disclosure may be a metallocene catalyst. Metallocene catalysts are well described, for example, in US 2021/0395404 at paragraphs [0066] - [0083], which description is incorporated herein by reference. Any metallocene catalyst according to this description may be suitable as the primary catalyst in the systems and methods described herein. Of particular interest are metallocene catalysts having a cyclopentadienyl (Cp) and/or indenyl (In) ligand, bridged or unbridged, bound to at least one group 3 to 12 metal atom (preferably Zn, hf, or Ti), and one or more (preferably two) leaving groups bound to the at least one metal atom (preferably wherein each leaving group is independently a C ₁ to C ₄ alkyl group such as methyl, or a halo group such as Cl).

More particularly, the primary catalyst according to various embodiments may comprise a non-bridged hafnocene or zirconocene, such as the hafnocene described in U.S. Pat. No. 7,078,467 at column 3, line 62 to column 4, line 51, which description is incorporated herein by reference, and zirconocene analogs thereof, and/or the catalyst described in U.S. Pat. No. 6,936,675 at column 4, line 22 to column 7, line 36, which description is also incorporated herein by reference. For example, suitable primary catalysts may include non-bridged bis-indenyl hafnocenes or zirconocenes, such as one or more of the following:

bis (n-ethylcyclopentadienyl) Zr (CH ₃)₂,

Bis (n-ethylcyclopentadienyl) ZrCl ₂,

Bis (n-ethylcyclopentadienyl) Hf (CH ₃)₂,

Bis (n-ethylcyclopentadienyl) HfCl ₂,

(N-ethylcyclopentadienyl, pentamethylcyclopentadienyl) ZrCl ₂,

(N-ethylcyclopentadienyl, pentamethylcyclopentadienyl) Zr (CH ₃)₂,

(N-ethylcyclopentadienyl, pentamethylcyclopentadienyl) HfCl ₂,

(N-ethylcyclopentadienyl, pentamethylcyclopentadienyl) Hf (CH ₃)₂,

Bis (n-propylcyclopentadienyl) Zr (CH ₃)₂,

Bis (n-propylcyclopentadienyl) ZrCl ₂,

Bis (n-propylcyclopentadienyl) Hf (CH ₃)₂,

Bis (n-propylcyclopentadienyl) HfCl ₂,

(N-propylcyclopentadienyl, pentamethylcyclopentadienyl) ZrCl ₂,

(N-propylcyclopentadienyl, pentamethylcyclopentadienyl) Zr (CH ₃)₂,

(N-propylcyclopentadienyl, pentamethylcyclopentadienyl) HfCl ₂,

(N-propylcyclopentadienyl, pentamethylcyclopentadienyl) Hf (CH ₃)₂,

Bis (n-butylcyclopentadienyl) Zr (CH ₃)₂,

Bis (n-butylcyclopentadienyl) ZrCl ₂,

Bis (n-butylcyclopentadienyl) Hf (CH ₃)₂,

Bis (n-butylcyclopentadienyl) HfCl ₂,

(N-butylcyclopentadienyl, pentamethylcyclopentadienyl) ZrCl ₂,

(N-butylcyclopentadienyl, pentamethylcyclopentadienyl) Zr (CH ₃)₂,

(N-butylcyclopentadienyl, pentamethylcyclopentadienyl) HfCl ₂,

(N-butylcyclopentadienyl, pentamethylcyclopentadienyl) Hf (CH ₃)₂,

Or a combination thereof.

In yet other embodiments, the primary catalyst may be a bridged metallocene catalyst, such as those described in one or more of US 5,314,973;US 6,255,426 (especially where column 2, line 61 to column 3, line 17, the description being incorporated herein by reference) and US 5,763,543 (especially column 2, line 42 to column 4, line 22, the description being incorporated herein by reference). Specific examples include bridged bis-indenyl catalysts, such as bridged bis-indenyl zirconocenes or bridged bis-indenyl hafnocenes, particularly those in which each indenyl ligand is unsubstituted (e.g., is a tetrahydroindenyl ligand), and wherein the bridge is a C ₁ - C₁₀ alkyl or R ₁R₂ Si, wherein R ₁ and R ₂ are each independently selected from methyl, ethyl, propyl, butyl and pentyl. Examples of such bridged bis-indenyl hafnocenes and zirconocenes may include (CH ₃)₂ Si (4, 5,6, 7-tetrahydroindenyl) ₂Zr(CH₃)₂、(CH₃)₂ Si (4, 5,6, 7-tetrahydroindenyl) ₂ZrCl₂、(CH₂CH₃)₂ Si (4, 5,6, 7-tetrahydroindenyl) ₂Zr(CH₃)₂、(CH₂CH₃)₂ Si (4, 5,6, 7-tetrahydroindenyl) ₂ZrCl₂、((CH₃)₂Si)₂ (4, 5,6, 7-tetrahydroindenyl) ₂Zr(CH₃)₂、((CH₃)₂Si)₂ (4, 5,6, 7-tetrahydroindenyl) ₂ZrCl₂、(CH₃)₂ Si (4, 5,6, 7-tetrahydroindenyl) ₂Hf(CH₃)₂、(CH₃)₂ Si (4, 5,6, 7-tetrahydroindenyl) ₂HfCl₂、(CH₂CH₃)₂ Si (4, 5,6, 7-tetrahydroindenyl) ₂Hf(CH₃)₂、(CH₂CH₃)₂ Si (4, 5,6, 7-tetrahydroindenyl) ₂HfCl₂、((CH₃)₂Si)₂ (4, 5,6, 7-tetrahydroindenyl) ₂Hf(CH₃)₂、((CH₃)₂Si)₂ (4, 5,6, 7-tetrahydroindenyl) ₂HfCl₂, Or a combination thereof.

Although the catalyst compound may be written or shown attached to the central metal with a methyl-, chloro-or phenyl-leaving group, it is understood that these groups may be different. For example, each of these ligands may independently be a benzyl (Bn), methyl (Me), chloro (Cl), fluoro (F), or any number of other groups, including organic groups, or heteroatom groups. Furthermore, these ligands will change during the reaction, as the pre-catalyst is converted to an active catalyst to carry out the reaction.

Second catalyst (e.g., a "trim" catalyst)

The second catalyst of the present disclosure includes a second catalyst supported on a support along with the first catalyst to form a dual catalyst system. The second catalyst may be supported and the dual catalyst system may be separated. Alternatively, the second catalyst may be supported on-line as a "trim" catalyst to the supported first catalyst on its way to the reactor. A dual catalyst system (e.g., also with an activator) is introduced into a reactor (e.g., a gas phase reactor).

In some embodiments, the second catalyst is represented by formula (III):

(III)

Wherein:

m is a group 4 metal, such as titanium (Ti), zirconium (Zr), or hafnium (Hf);

Optionally, one or more pairs of R ⁵ and R ⁶、R⁷ and R ⁸、R⁸ and R ⁹ and R ⁹ and R ¹⁰ may be joined to form a substituted or unsubstituted fully saturated ring or a substituted or unsubstituted aromatic ring, and further at least one pair of R ⁵ and R ⁶ is independently a substituted or unsubstituted aryl or a substituted or unsubstituted heteroaryl;

T represents formula R ^a ₂J、(R^a)₄J₂, or (R ^a)₆J₃, wherein each J is independently C, si, or Ge, and each R ^a is independently hydrogen, halo, substituted or unsubstituted C ₁ to C ₄₀ hydrocarbyl, and wherein two R ^a optionally may join to form a substituted or unsubstituted cyclic structure comprising a substituted or unsubstituted fully saturated ring, or a substituted or unsubstituted partially saturated ring (preferably such ring structure has 2-10 carbon atoms in addition to J atoms, and the ring structure is preferably saturated), and

Each X is independently halo, substituted or unsubstituted hydrocarbyl, hydrogen, amino, substituted or unsubstituted alkoxy, thio, phosphorus, or a combination thereof, or two X are joined together to form a substituted or unsubstituted metallocycle ring, or two X are joined to form a chelating ligand, diene ligand, or alkylene;

Wherein at least one of R ⁵ or R ⁶ is independently a substituted or unsubstituted aryl or a substituted or unsubstituted heteroaryl.

In some embodiments, at least one of R ⁵ or R ⁶ is hydrogen and the other of R ⁵ or R ⁶ is independently substituted or unsubstituted aryl or substituted or unsubstituted heteroaryl. Aryl or heteroaryl groups may be represented by the formula:

Wherein each of R ¹¹、R¹²、R¹³、R¹⁴ and R ¹⁵ is independently hydrogen, a hydrocarbyl group, a heteroatom, or a heteroatom-containing group, or one or more pairs of R ¹¹ and R ¹²、R¹² and R ¹³、R¹³ and R ¹⁴, and R ¹⁴ and R ¹⁵ join to form a fully saturated, partially saturated, or aromatic ring. In some embodiments, each of R ¹¹、R¹²、R¹³、R¹⁴ and R ¹⁵ is independently hydrogen or C ₁-C₁₀ alkyl (such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, or decyl). In some embodiments, each of R ¹¹、R¹²、R¹³、R¹⁴ and R ¹⁵ is hydrogen.

In some embodiments, each of R ¹、R²、R³ and R ⁴ of formula (III) is independently hydrogen or C ₁-C₁₀ alkyl (such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, or decyl). In some embodiments, each of R ¹、R²、R³ and R ⁴ is independently methyl, ethyl, or propyl. In some embodiments, each of R ¹、R²、R³ and R ⁴ is methyl.

In some embodiments, each of R ⁷、R⁸、R⁹ and R ¹⁰ of formula (III) is independently hydrogen or C ₁-C₁₀ alkyl (such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, or decyl). In some embodiments, each of R ⁷、R⁸、R⁹ and R ¹⁰ is hydrogen.

In some embodiments of formula (III), T is represented by formula R ^a ₂J、(R^a)₄J₂, or (R ^a)₆J₃), wherein J is C, si, or Ge, and each R ^a is independently hydrogen or a C ₁ to C ₂₀ hydrocarbyl group, in some embodiments, two R ^a may form a cyclic structure, in some embodiments, T is selected from CH₂、CH₂CH₂、C(CH₃)₂、CPh₂、SiMe₂、SiEt₂、SiMeEt、SiPr₂、SiBu₂、SiPh₂、SiMePh、Si(CH₂)₃、Si(CH₂)₄、 or Si (CH ₂)₅. In some embodiments, T is SiMe ₂、SiEt₂、SiPr₂、SiBu₂, or, more preferably, T is a ring structure such as Si (CH ₂)₃ (silacyclobutyl), si (CH ₂)₄ (silacyclopentyl), or Si (CH ₂)₅ (silacyclohexyl)).

In some embodiments, each of R ¹、R²、R³、R⁴、R⁵、R⁶、R⁷、R⁸、R⁹ and R ¹⁰ (and R ¹¹、R¹²、R¹³、R¹⁴ and R ¹⁵) of formula (III) is independently hydrogen, hydrocarbyl, silylhydrocarbyl (silylcarbyl), alkoxy, halo, or siloxy.

In some embodiments of formula (III), M is a group 4 metal, such as titanium (Ti), zirconium (Zr), or hafnium (Hf). In some embodiments, M is Zr or Hf. In some embodiments, each X is independently halo, such as chloro. In still other embodiments, each X is independently a C ₁-C₄ alkyl group, such as methyl. In some embodiments, each X is independently selected from substituted or unsubstituted hydrocarbyl, heteroatom, or substituted or unsubstituted heteroatom-containing group, such as methyl, benzyl, trimethylsilyl, methyl (trimethylsilyl), neopentyl, ethyl, propyl, butyl, phenyl, hydrogen (hydro), chloro, fluoro, bromo, iodo, trifluoromethylsulfonate, dimethylamino (dimethylamido), diethylamino (diethylamido), dipropylamino (dipropylamido), and diisopropylamino (diisopropylamido).

In some embodiments of formula (III), (1) M is Zr or Hf, (2) X is C ₁-C₅ alkyl, (3) T is Si (CH ₂)₃、Si(CH₂)₄, or Si (CH ₂)₅,(4) R⁵、R⁷、R⁸、R⁹ and R ¹⁰ are independently hydrogen or substituted or unsubstituted C ₁-C₁₀ alkyl, (5) R ¹、R²、R³ and R ⁴ are independently methyl, ethyl, or propyl, and (6) R ⁶ is substituted or unsubstituted aryl or substituted or unsubstituted heteroaryl.

In some embodiments of formula (III), the catalyst is selected from:

In some embodiments, the second catalyst is represented by formula (IV):

(IV)

Wherein:

m is a group 4 metal, such as titanium (Ti), zirconium (Zr), or hafnium (Hf);

Each of R ¹、R²、R³、R⁴、R⁵、R⁶、R⁷、R⁸、R⁹ and R ¹⁰ is independently hydrogen, a substituted or unsubstituted hydrocarbyl group, a substituted or unsubstituted heteroatom, or a substituted or unsubstituted heteroatom-containing group, or one or more pairs of R ⁵ and R ⁶、R⁷ and R ⁸、R⁸ and R ⁹, and R ⁹ and R ¹⁰ join to form a substituted or unsubstituted fully saturated ring or a substituted or unsubstituted aromatic ring;

T represents formula R ^a ₂J、(R^a)₄J₂, or (R ^a)₆J₃, wherein each J is independently C, si, or Ge, and each R ^a is independently hydrogen, halo, substituted or unsubstituted C ₁ to C ₄₀ hydrocarbyl, or two R ^a may form a substituted or unsubstituted cyclic structure including a substituted or unsubstituted fully saturated ring, a substituted or unsubstituted partially saturated ring, or a substituted or unsubstituted aromatic ring, and

Wherein at least one pair of (1) R ⁷ and R ⁸、(2) R⁸ and R ⁹, or (3) R ⁹ and R ¹⁰, join to form a substituted or unsubstituted fully saturated ring fused to an indenyl ring shown in formula (IV).

In some embodiments, each of R ⁷、R⁸、R⁹ and R ¹⁰ of formula (IV) is independently hydrogen or C ₁-C₁₀ alkyl (such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, or decyl), wherein at least one pair of (1) R ⁷ and R ⁸、(2) R⁸ and R ⁹, or (3) R ⁹ and R ¹⁰, join to form a substituted or unsubstituted fully saturated ring fused to an indenyl ring shown in formula (IV).

In some embodiments, at least one pair of (1) R ⁷ and R ⁸、(2) R⁸ and R ⁹, or (3) R ⁹ and R ¹⁰, join to form a substituted or unsubstituted fully saturated ring fused to an indenyl ring shown in formula (IV). In some embodiments, R ⁷ and R ⁸ join to form a substituted or unsubstituted saturated C ₄ ring, a substituted or unsubstituted saturated C ₅ ring, A substituted or unsubstituted saturated C ₆ ring, or a substituted or unsubstituted saturated C ₇ ring, wherein the C ₄ ring, C ₅ ring, the C ₆ ring, or the C ₇ ring is fused to the indenyl ring shown in formula (IV). In some embodiments, R ⁸ and R ⁹ join to form a substituted or unsubstituted saturated C ₄ ring, a substituted or unsubstituted saturated C ₅ ring, A substituted or unsubstituted saturated C ₆ ring, or a substituted or unsubstituted saturated C ₇ ring, wherein the C ₄ ring, C ₅ ring, the C ₆ ring, or the C ₇ ring is fused to the indenyl ring shown in formula (IV). In some embodiments, R ⁹ and R ¹⁰ join to form a substituted or unsubstituted saturated C ₄ ring, a substituted or unsubstituted saturated C ₅ ring, A substituted or unsubstituted saturated C ₆ ring, or a substituted or unsubstituted saturated C ₇ ring, wherein the C ₄ ring, C ₅ ring, the C ₆ ring, or the C ₇ ring is fused to the indenyl ring shown in formula (IV).

In some embodiments, each of R ¹、R²、R³ and R ⁴ of formula (IV) is independently hydrogen or C ₁-C₁₀ alkyl (such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, or decyl). In some embodiments, each of R ¹、R²、R³ and R ⁴ is independently methyl, ethyl, or propyl. In some embodiments, each of R ¹、R²、R³ and R ⁴ is methyl.

In some embodiments of formula (IV), T is represented by formula R ^a ₂J、(R^a)₄J₂, or (R ^a)₆J₃) wherein J is C, si, or Ge, and each R ^a is independently hydrogen or a C ₁ to C ₂₀ hydrocarbyl group, in some embodiments, two R ^a may form a cyclic structure, in some embodiments, T is selected from CH₂、CH₂CH₂、C(CH₃)₂、CPh₂、SiMe₂、SiEt₂、SiPh₂、SiMePh、SiEtPh、SiMeEt、Si(CH₂)₃、Si(CH₂)₄、 or Si (CH ₂)₅. In some embodiments, T is SiMe ₂、SiEt₂, or SiMeEt.

In some embodiments, one or more of R ¹、R²、R³、R⁴、R⁵、R⁶、R⁷、R⁸、R⁹ and R ¹⁰ of formula (IV) are independently hydrogen, hydrocarbyl, silylhydrocarbyl, alkoxy, halo, or siloxy.

In some embodiments of formula (IV), M is a group 4 metal, such as titanium (Ti), zirconium (Zr), or hafnium (Hf). In some embodiments, M is Zr or Hf. In some embodiments, each X is independently halo, such as chloro. In still other embodiments, each X is independently a C ₁-C₄ alkyl group, such as methyl. In some embodiments, each X is independently selected from substituted or unsubstituted hydrocarbyl, heteroatom, or substituted or unsubstituted heteroatom-containing group, such as methyl, benzyl, trimethylsilyl, methyl (trimethylsilyl), neopentyl, ethyl, propyl, butyl, phenyl, hydrogen, chloro, fluoro, bromo, iodo, triflate, dimethylamino, diethylamino, dipropylamino, and diisopropylamino.

In some embodiments of formula (IV), (1) M is Zr or Hf, (2) X is C ₁-C₅ alkyl, (3) T is Si (CH ₂)₃、Si(CH₂)₄, or Si (CH ₂)₅,(4) R⁵、R⁶、R⁷、R⁸、R⁹ and R ¹⁰ are independently hydrogen or substituted or unsubstituted C ₁-C₁₀ alkyl, (5) at least one pair of R ⁷ and R ⁸、R⁸ and R ⁹, or R ⁹ and R ¹⁰ are joined to form a substituted or unsubstituted fully saturated ring fused to an indenyl ring shown in formula (IV), and (6) R ¹、R²、R³ and R ⁴ are independently methyl, ethyl, or propyl.

In some embodiments of formula (IV), the catalyst is selected from:

Activating agent

The terms "cocatalyst" and "activator" are used interchangeably herein.

The catalyst systems described herein may include one or more catalyst compounds and an activator such as an alumoxane or a non-coordinating anion as described above, and may be formed by combining the catalyst compounds described herein with the activator in any manner known from the literature, including combining them with a support such as silica. The catalyst system may also be added to or formed in solution or bulk polymerization (in monomers). The catalyst systems of the present disclosure may have one or more activators and one, two, or more catalyst components. An activator is defined as any compound that can activate any of the catalyst compounds described above by converting a neutral metal compound to a catalytically active metal compound cation. Non-limiting activators may include, for example, aluminoxanes, aluminum alkyls, ionizing activators, which may be neutral or ionic, and cocatalysts of conventional type. Suitable activators can include aluminoxane compounds, modified aluminoxane compounds, and ionizing, anionic precursor compounds that abstract reactive sigma-binding metal ligands, render the metal compounds cationic and provide charge-balancing non-coordinating or weakly-coordinating anions, e.g., non-coordinating anions.

In at least one embodiment, the catalyst system comprises an activator, a catalyst compound of formula (I), formula (II), formula (III), and/or formula (IV), and a support.

Aluminoxane activator

An alumoxane activator is utilized as the activator in the catalyst systems described herein. Aluminoxanes are generally oligomeric compounds containing-Al (R ^a''') -O-subunits, where R ^a''' is an alkyl group. Examples of alumoxanes include Methylalumoxane (MAO), modified Methylalumoxane (MMAO), ethylalumoxane, and isobutylalumoxane. Alkylaluminoxane and modified alkylaluminoxane are suitable as catalyst activators, such as when the grippable ligand is an alkyl, halo, alkoxy or amino (amide). Mixtures of different aluminoxanes and modified aluminoxanes can also be used. It may be appropriate to use visually clear methylaluminoxane. The cloudy or gelled aluminoxane can be filtered to produce a clear solution or the clear aluminoxane can be decanted from the cloudy solution. Useful alumoxanes are Modified Methylalumoxane (MMAO) co-catalyst type 3A (commercially available under the trade name Modified Methylalumoxane type a (modified methylalumoxane type 3A) from Akzo Chemicals, inc., as described in U.S. Pat. No. 5,041,584, which is incorporated herein by reference). Another useful alumoxane is solid polymethylalumoxane as described in U.S. patent No. 9,340,630, US 8,404,880, and US 8,975,209, which are incorporated herein by reference.

When the activator is an alumoxane (modified or unmodified), and in at least one embodiment, the activator may be used in an amount up to 5,000-fold molar excess of Al/M relative to the catalyst compound (as metal catalytic sites). The minimum activator to catalyst compound may be a 1:1 molar ratio. Alternative ranges may include about 1:1 to about 500:1, alternatively about 1:1 to about 200:1, alternatively about 1:1 to about 100:1, or alternatively about 1:1 to about 50:1.

In alternative embodiments, little or no aluminoxane is used in the polymerization process described herein. For example, the aluminoxane may be present in zero mole percent, alternatively the aluminoxane may be present in a molar ratio of aluminum to the transition metal of the catalyst compound of less than 500:1, such as less than 300:1, such as less than 100:1, such as less than 1:1.

Ionizing/non-coordinating anion activators

The term "non-coordinating anion" (NCA) means an anion that does not coordinate to a cation or only weakly coordinates to a cation so as to remain sufficiently labile to be displaced by a lewis base. "compatible" non-coordinating anions are those that do not degrade to neutrality when the initially formed complex decomposes. In addition, the anion will not transfer an anionic substituent or fragment to the cation, thereby allowing it to form a neutral transition metal compound and neutral byproducts from the anion. The non-coordinating anions useful in accordance with the present disclosure are those that are compatible, stabilize the transition metal cation in the sense of balancing its ionic charge at +1, and yet remain sufficiently labile to allow displacement during polymerization. Suitable ionizing activators may include NCAs, such as compatible NCAs.

It is within the scope of the present disclosure to use a neutral or ionic ionizing activator. It is also within the scope of the present disclosure to use a neutral or ionic activator alone or in combination with an alumoxane or modified alumoxane activator. For some suitable activators and activator combinations, as well as the relative amounts of activator and catalyst compound, and descriptions of optional chain transfer agents for use in combination with these catalyst compounds, see U.S. 8,658,556 and U.S. 6,211,105 (incorporated herein by reference), and U.S. patent publication No. 2021/0179650, and in particular paragraphs [0084] - [0135] of WIPO patent publication No. WO2021/257264, which descriptions are incorporated herein by reference (including the various descriptions incorporated herein by reference, such as page 72 [00119] to page 81 [00151] and page 72 [00177] to page 74 [00178] of WO 2004/046214).

In addition, the catalyst system of the present disclosure may include a metal hydrocarbenyl (hydrocarbenyl) chain transfer agent represented by the following formula:

Al(R')_3-v(R'')_v

Wherein each R ' may independently be a C ₁-C₃₀ hydrocarbon group, and or each R ' ' may independently be a C ₄-C₂₀ hydrocarbon alkenyl group (hydrocarbenyl) having a terminal vinyl group, and v may be 0.1 to 3.

Carrier material

In embodiments herein, the catalyst system may include an inert support material. The support material may be a porous support material, for example, talc and inorganic oxides. Other support materials include zeolite, clay, organoclay, or another organic or inorganic support material, or mixtures thereof.

The support material may be an inorganic oxide. The inorganic oxide may be in finely divided form. Suitable inorganic oxide materials for use in the catalyst systems herein may include group 2, 4, 13, and 14 metal oxides, such as silica, alumina, and mixtures thereof. Other inorganic oxides that may be employed, alone or in combination with silica or alumina, may be magnesia, titania, zirconia. However, other suitable support materials may be employed, for example, finely divided functionalized polyolefins, such as finely divided polyethylene. Examples of suitable carriers may include magnesia, titania, zirconia, montmorillonite, phyllosilicate, zeolite, talc, clay. In addition, combinations of these support materials may be used, for example, silica-chromium, silica-alumina, silica-titania. In at least one embodiment, the support material is selected from Al₂O₃、ZrO₂、SiO₂、SiO₂/Al₂O₃、SiO₂/TiO₂、 silica clay, silica/clay, or mixtures thereof.

The support material, such as an inorganic oxide, may have a surface area of about 10m ²/g to about 700 m ²/g, a pore volume of about 0.1 cm ³/g to about 4.0 cm ³/g, and an average particle size of about 5 μm to about 500 μm. The surface area of the support material may be from about 50m ²/g to about 500m ²/g, from about 0.5 cm ³/g to about 3.5 cm ³/g pore volume, and an average particle size of from about 10 μm to about 200 μm. For example, the surface area of the support material may be from about 100m ²/g to about 400 m ²/g, from about 0.8 cm ³/g to about 3.0 cm ³/g pore volume and the average particle size may be from about 5 μm to about 100 μm. The average pore size of the carrier materials useful in the present disclosure may be from about 10a to about 1000 a, such as from about 50 a to about 500 a, and such as from about 75 a to about 350 a. In at least one embodiment, the support material is high surface area amorphous silica (surface area = 300m ²/gm;1.65 cm³/gm pore volume). For example, a suitable silica may be silica sold under the trade names DavisonTM 952 or DavisonTM 955 by Davison Chemical Division of w.r. Grace and Company. In other embodiments DAVISONTM 948 is used. Alternatively, the silica may be, for example, ES-70 (TM) silica (PQ Corporation, malvern, pennsylvania) that has been calcined (such as at 875 ℃).

The carrier material should be dry, i.e., free or substantially free of absorbed water. Drying of the support material may be achieved by heating or calcining at about 100 ℃ to about 1000 ℃, such as at least about 600 ℃. When the support material is silica, it is heated to at least 200 ℃, such as from about 200 ℃ to about 850 ℃, and such as at about 600 ℃, and for a period of from about 1 minute to about 100 hours, from about 12 hours to about 72 hours, or from about 24 hours to about 60 hours. The calcined support material must have at least some reactive hydroxyl groups (OH) to produce the supported catalyst system of the present disclosure. The calcined support material is then contacted with at least one polymerization catalyst comprising at least one catalyst compound and an activator.

A support material having reactive surface groups such as hydroxyl groups is slurried in a non-polar diluent and the resulting slurry is contacted with a solution of a catalyst compound and an activator. In at least one embodiment, the slurry of support material is first contacted with the activator for a period of time from about 0.5 h to about 24h, from about 2 h to about 16 h, or from about 4h to about 8 h. The solution of catalyst compound is then contacted with the separated support/activator. In at least one embodiment, the supported catalyst system is generated in situ. In alternative embodiments, the slurry of support material is first contacted with the catalyst compound for a period of time from about 0.5 h to about 24h, from about 2 h to about 16 h, or from about 4h to about 8 h. The slurry of supported catalyst compound is then contacted with an activator solution.

The mixture of one or more catalysts, one or more activators, and support is heated at about 0 ℃ to about 70 ℃, such as about 23 ℃ to about 60 ℃, such as at room temperature. The contact time may be about 0.5 hours to about 24 hours, such as about 2 hours to about 16 hours, or about 4 hours to about 8 hours.

Suitable non-polar diluents are materials in which all of the reactants used herein (e.g., activators and catalyst compounds) are at least partially soluble and liquid at the polymerization temperature. The nonpolar diluent may be an alkane such as isopentane, hexane, n-heptane, octane, nonane, and decane, but a variety of other materials may be employed including cycloalkanes such as cyclohexane, aromatics such as benzene, toluene, and ethylbenzene.

In at least one embodiment, the support material is a Supported Methylaluminoxane (SMAO), which is a MAO activator treated with silica (e.g. ES-70-875 silica).

Polyethylene copolymer

The present disclosure provides polyethylene copolymers having a combination of low density, high melt index, long chain branching, and bimodal composition distribution. In addition, the polyethylene copolymers and films thereof may be formed by polymerization and extrusion of commercially desirable polyethylene copolymers.

Accordingly, the polyethylene copolymers of the various embodiments herein may exhibit one or more of the following properties:

A density of about 0.914 to about 0.925 g/cm ³, such as from a low value of any of 0.914, 0.915, 0.916, 0.917, 0.918, 0.919, or 0.92 g/cm ³ to a high value of any of 0.925, 0.924, 0.923, 0.922, 0.921, 0.920, or 0.919 g/cm ³, such as from about 0.915 g/cm ³ to about 0.920 g/cm ³, alternatively from about 0.918 g/cm ³ to about 0.922 g/cm ³, wherein any combination of low values to any high values is contemplated (provided that the high end is greater than the low end), e.g., from about 0.916 to about 0.921 g/cm ³.

About 0.1 g/10 min or greater (MI, also referred to as I ₂ or I _2.16, per the 2.16 kg load used in the test) (ASTM D1238,190 ℃,2.16 kg), such as a low value from any of 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.1, 1.2, 1.3, 1.4, or 1.5 g/10 min to a high value of any of 0.5、0.6、0.7、0.8、0.9、1、1.1、1.2、1.3、1.4、1.5、1.6、1.7、1.8、1.9、2、2.1、2.2、2.3、2.4、2.5、2.6、2.7、2.8、2.9、3、4、 or 5 g/10 min, wherein any low end to any high end range is contemplated herein (provided that the high end is greater than the low end), such as from about 0.1 to about 1 g/10 min, such as about 0.3 to about 0.8 g/10 min, such as about 0.4 to about 0.6 g/10 min.

The polyethylene copolymer may be the polymerization product of ethylene monomer and one or more olefin comonomers, such as alpha-olefin comonomers. The alpha-olefin comonomer may have 3 to 12 carbon atoms, or 4 to 10 carbon atoms, or 4 to 8 carbon atoms. The olefin comonomer may be selected from the group consisting of propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 4-methylpent-1-ene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-hexadecene, and the like, and any combination thereof, such as 1-butene, 1-hexene, and/or 1-octene. In some embodiments, polyenes are used as comonomers. In some embodiments, the polyene is selected from the group consisting of 1, 3-hexadiene, 1, 4-hexadiene, cyclopentadiene, dicyclopentadiene, 4-vinylcyclohex-1-ene, methyl octadiene, 1-methyl-1, 6-octadiene, 7-methyl-1, 6-octadiene, 1, 5-cyclooctadiene, norbornadiene, ethylidene norbornene, 5-vinylidene-2-norbornene, 5-vinyl-2-norbornene, and olefins formed in situ in the polymerization medium. In some embodiments, the comonomer is selected from the group consisting of isoprene, styrene, butadiene, isobutylene, chloroprene, acrylonitrile, and cyclic olefins. In some embodiments, a combination of olefin comonomers is utilized. In some embodiments, the olefin comonomer is selected from the group consisting of 1-butene and 1-hexene. The olefin comonomer content of the polyethylene copolymer may range from a low value of about 0.1 wt%, 5wt%, 5.5 wt%, 6 wt%, 6.5 wt%, 7 wt%, 7.5 wt%, 8 wt%, or 8.5 wt% to a high value of about 20 wt%, 15 wt%, 13 wt%, 12.5 wt%, 12 wt%, 11.5 wt%, 11 wt%, 10.5 wt%, 10 wt%, 9.5 wt%, or 9 wt%, based on the total weight of monomers in the polyethylene copolymer. The balance of the polyethylene comonomer consists of units derived from ethylene (e.g., low values of about 80 wt%, 85 wt%, 88 wt%, 90 wt%, 91 wt%, 92 wt%, 92.5 wt%, 93 wt%, 93.5 wt%, or 94 wt% to high values of about 90 wt%, 91 wt%, 92 wt%, 92.5 wt%, 93 wt%, 93.5 wt%, 94 wt%, 94.5 wt%, 95 wt%, 95.5 wt%, 96 wt%, 97 wt%, 99 wt%, or 99.9 wt%. Any of the foregoing low values to any of the foregoing high values (e.g., about 88 wt% to about 93 wt%, such as about 91 wt% to about 93 wt% ethylene derived units and the balance olefin comonomer derived content) are contemplated herein.

The polyethylene copolymer may also have a High Load Melt Index (HLMI) in the range of from a low value of about 15, 20, 25, 30, 35, 40, 45, 50, or 55 g/10 min to a high value of about 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, or 25 g/10 min (also referred to as I ₂₁ or I _21.6 as per the 21.6 kg load used in the test), wherein any of the foregoing low value to any of the foregoing high value ranges are contemplated herein (e.g., about 45 to about 70 g/10 min, such as about 50 to about 60 g/10 min, alternatively about 20 to about 30 g/10 min). The term "high load melt index" ("HLMI") is the number of grams extruded in 10 minutes under standard load (21.6 kg) and is a reverse measure of viscosity. As provided herein, HLMI (I ₂₁) is determined according to ASTM D1238 (190 ℃ C./21.6 kg), and is also sometimes referred to as I ₂₁ or I _21.6.

The polyethylene copolymer may also have a melt index ratio (MIR, defined as the ratio of I _21.6/I_2.16) ranging from a low value of any of about 20, 25, 30, 35, 40, 45, 50, or 55 to a high value of any of about 70, 65, 60, 55, 50, 45, or 40, wherein any of the foregoing low values to any of the foregoing high values are contemplated herein (e.g., about 40 to about 50, alternatively about 50 to about 60).

The polyethylene copolymer may also have a Molecular Weight Distribution (MWD) of about 2 to about 10. The MWD may be a low value of about 2, 2.5, 3, 3.5, 4, 4.2, 4.4, 4.5, 4.6, 4.8, 5, 5.1, 5.2, 5.3, 5.4, 5.5, or 6 to a high value of about 3.5, 4, 4.5, 5, 5.1, 5.2, 5.3, 5.4, 5.5, 5.6, 5.7, 5.8, 5.9, 6, 6.5, 7, 7.1, 7.2, 7.3, 7.4, 7.5, 8.0, 8.5, 9.0, 9.5, or 10.0, with the proviso that the high end of the range is greater than the low end. MWD is defined as weight average molecular weight (Mw) divided by number average molecular weight (Mn) and may be referred to as polydispersity index (PDI).

The weight average molecular weight (Mw) of the polyethylene copolymers of various embodiments may be in the range of about 70,000 to about 200,000 g/mol, such as about 75,000 to about 150,000 g/mol, such as about 90,000 to about 130,000 g/mol, such as about 100,000 to about 120,000 g/mol, with any of the foregoing low to any of the foregoing high end ranges contemplated.

The number average molecular weight (Mn) of the polyethylene copolymers of various embodiments may be in the range of about 10,000 to about 40,000 g/mol, such as about 10,000 to about 30,000 g/mol, such as about 15,000 to about 25,000 g/mol, with any of the foregoing low end to any of the foregoing high end ranges contemplated.

The Z-average molecular weight (Mz) of the polyethylene copolymers of various embodiments may be in the range of about 150,000 to about 400,000 g/mol, such as about 200,000 to about 350,000 g/mol, or about 200,000 to about 275,000 g/mol, such as about 220,000 to about 260,000 g/mol, with any of the foregoing low end to any of the foregoing high end ranges contemplated.

The polyethylene copolymers of the various embodiments may also exhibit long chain branching. As indicated previously, this can be demonstrated by, for example, SAOS viscosity data (especially η _0.01/η₁₀₀) and/or MIR. Furthermore, the LCB or branching index (referred to herein as g '_{vis ave} or alternatively g' _vis) may be less than 1, such as in the range of a low value of about 0.65、0.66、0.67、0.68、0.69、0.70、0.71、0.72、0.73、0.74、0.75、0.76、0.77、0.78、0.79、0.80、0.81、0.82、0.83、0.84、0.85、 or 0.86 to a high value of any of about 0.80, 0.85, 0.86, 0.87,0.88,0.89, 0.90, 0.91, 0.92, 0.93, or 0.94, with the proviso that the high end is greater than the low end (e.g., 0.65 to 0.87, or 0.90, or 0.95, such as 0.72 to 0.87, or 0.82 to 0.92, or 0.86 to 0.92, or 0.72 to 0.92, or 0.70 to 0.87,0.88,0.89, or 0.90, etc.).

The distribution and moment of molecular weight (Mw, mn, mw/Mn, etc.) and branching index (g' vis) were determined by high temperature gel permeation chromatography (Polymer Char GPC-IR) using an infrared detector IR5 equipped with a multichannel band pass filter based, an 18-angle WYATT DAWN Heleos light scattering detector and a 4-capillary viscometer with a Wheatstone bridge configuration. Three AGILENT PLGEL 10- μm Mixed-B LS columns were used to provide polymer separation. Aldrich reagent grade 1,2, 4-Trichlorobenzene (TCB) with 300 ppm antioxidant Butylated Hydroxytoluene (BHT) was used as mobile phase. The TCB mixture was filtered through a 0.1- μm Teflon (Teflon) filter and degassed with an in-line degasser before entering the GPC apparatus. The nominal flow rate was 1.0 ml/min and the nominal sample volume was 200 μl. The entire system, including the transfer line, column and viscometer detector, is contained in a furnace maintained at 145 ℃. The polymer samples were weighed and sealed in standard vials with 80- μl flow marker (heptane) added. After the vials were filled into the autosampler, the polymer was automatically dissolved in the instrument by adding 8 ml TCB solvent. The polymer was dissolved under continuous shaking at 160 ℃ for about 2 hours. The concentration (c) at each point in the chromatogram is calculated from the baseline subtracted IR5 broadband signal intensity (I) using the following equation c=βi, where β is the mass constant. Mass recovery is calculated from the ratio of the integrated area of concentration chromatography within the elution volume to the sample mass equal to the predetermined concentration times the sample loop volume. Conventional molecular weights (IR MW) were determined by combining a generic calibration relationship with column calibration with a series of monodisperse Polystyrene (PS) standards ranging from 700 to 1 million g/mol. MW at each elution volume was calculated using the following equation:

Wherein the variable with the subscript "PS" represents polystyrene and the variable without the subscript is the test sample. In this method, α _PS =0.67 and K _PS = 0.000175, whereas α and K are calculated from empirical equations (Sun, t. Et al Macromolecules 2001, 34, 6812) for ethylene-hexene copolymers, where a=0.695 and k= 0.000579 (1-0.75 Wt), where Wt is the weight fraction of hexene comonomer. It should be noted that the comonomer composition is determined by the ratio of the IR5 detector intensities corresponding to the CH ₂ and CH ₃ channels, calibrated with a series of PE and ethylene-hexene homo/copolymer standards whose nominal values are predetermined by NMR or FTIR. Here the concentration is expressed in g/cm ³, the molecular weight in g/mol and the intrinsic viscosity (hence K in the Mark-Hok equation) in dL/g.

LS molecular weight (M) at each point in the chromatogram is determined by analyzing LS output using Zimm model for static light scattering

。

Here, Δr (θ) is the excess rayleigh scattering intensity measured at the scattering angle θ, c is the polymer concentration determined by IR5 analysis, a ₂ is the second in-plane coefficient, P (θ) is the form factor of the monodisperse random coil, and Ko is the optical constant of the system:

Where N _A is the Avwhereabouts and (dn/dc) is the refractive index increment of the system. At 145 ℃ and λ=665 nm, the refractive index n=1.500 of TCB. For the purposes of the present disclosure and claims thereof, (dn/dc) = 0.1048 for ethylene-hexene copolymers.

Unless otherwise stated, when molecular weight values are referred to herein, it should be assumed that they are determined via Light Scattering (LS) techniques.

Viscosity average molecular weight (M _V) the specific viscosity was determined using a high temperature Polymer Char viscometer with four capillaries arranged in a Wheatstone bridge configuration and two pressure sensors. One sensor measures the total pressure drop across the detector, while the other sensor, located between the two sides of the bridge, measures the pressure difference. From their outputs, the specific viscosity etas of the solution flowing through the viscometer is calculated. The intrinsic viscosity [ eta ] at each point in the chromatogram is calculated from the equation [ eta ] = etas/c, where c is the concentration and is determined from the IR5 broadband channel output. The viscosity MW at each point was calculated asWherein αps is 0.67 and Kps is 0.000175. The average intrinsic viscosity [ eta ] _avg of the sample was calculated by:

wherein the sum is taken from chromatographic slices i between the integration limits.

The branching index (g' _vis) can be calculated using the output of the GPC-IR5-LS-VIS method as follows. First, it should be noted that g ' or g ' _vis can generally be regarded as the ratio of the intrinsic viscosity of a polymer to the intrinsic viscosity of a linear polymer of the same molecular weight and composition, g ' = [ η _Polymer] / [η_{Reference to} ], where [ η _Polymer ] is the intrinsic viscosity of the polymer under investigation and [ η _{Reference to} ] is the intrinsic viscosity of a linear resin of the same molecular weight and of the same composition. Thus, the relative intrinsic viscosity (g') of a polymer is a measure of how much a polymer enhances the viscosity of its solution under the same temperature and pressure conditions relative to a linear polymer having the same molecular weight and composition.

Following this principle, the [ η _Polymer ] value in the above simplified relationship can be regarded as the weight average intrinsic viscosity of the sample [ η ] _avg, which is calculated by:

Where the sum is taken from all chromatographic slices i between the integration limits. The branching index g' _vis is defined relative to a linear reference as Wherein Mv is a viscosity average molecular weight based on the molecular weight determined by LS analysis and K and alpha are for a reference linear polymer, and for the purposes of this disclosure, alpha and K are the same as described above for the linear polyethylene polymer.

The branching index g ' _vis may be equivalently referred to as g ' _{vis ave} to reflect that it is the average of g ' determined at each of a plurality of discrete concentration slices. For example, referring to FIG. 1, it can be seen that the g 'of various polyethylene copolymers is plotted as a function of LogM (log of molecular weight), meaning that the g' value for a given molecular weight population of polymer chains in the polyethylene copolymer composition can be calculated. The above calculations provide g '_{vis ave} as a weighted average of these multiple g' values, and when comparing such values between two different copolymer compositions, g '_{vis ave} may be regarded as a good relative indicator of the presence of long chain branching, with lower g' _{vis ave} indicating greater long chain branching.

Wide orthogonal composition distribution

"BOCD" refers to a broad orthogonal composition distribution in which the comonomer of the copolymer is incorporated predominantly into the high molecular weight chain or mass of the polyolefin polymer or composition. For example, the distribution of non-short chain branches can be measured using Temperature Rising Elution Fractionation (TREF) in combination with a Light Scattering (LS) detector to determine the weight average molecular weight of molecules eluting from a TREF column at a given temperature. The combination of TREF and LS (TREF-LS) gives information about the breadth of the composition distribution and whether the comonomer content increases, decreases or is uniform over the chain of different molecular weights of the polymer chain. BOCD has been described, for example, in U.S. patent No. 8,378,043, column 3, line 34, to column 4, line 19, and 8,476,392, line 43, to column 16, line 54.

The BOCD properties of the polyethylene copolymers of the invention can be quantified in terms of the Composition Distribution Breadth Index (CDBI). For example, the polyethylene copolymers described herein may have a low value composition distribution breadth index (CBDI), wherein the polyethylene copolymer may have a CBDI ranging from a low value of any of about 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, or 80% to a high value of any of about 99%, 95%, 90%, 85%, 80%, 75%, 70%, 65%, or 60%, wherein any of the foregoing low values to any of the foregoing high values are contemplated herein (e.g., from about 50% to about 85%, such as from about 55% to about 75%, alternatively from about 70% to about 85%, alternatively from about 75% to about 85%). In some embodiments, the polyethylene copolymers described herein may have a low value composition distribution breadth index (CBDI), where the polyethylene copolymer may have a CBDI in the range of a low value of any of about 30%, 35%, 40%, 45%, 50%, or 55% to a high value of any of about 70%, 65%, 60%, 55%, 50%, or 45%, where any of the foregoing low to any of the foregoing high values ranges are contemplated herein (e.g., about 35% to about 65%, such as about 40% to about 50%, alternatively about 50% to about 65%, such as about 50% to about 60%).

CDBI is defined as the weight percent of copolymer molecules having a comonomer content within +/-50% of the median comonomer mol% value, as described in WO 1993/003093 at pages 18-19 in conjunction with FIG. 17 therein. This means that for copolymers having a median comonomer mol% value of 8 mol% comonomer on the polymer chain (Cmed), CDBI is the weight% of copolymer chains having from (0.5 x Cmed) to (1.5 x Cmed) comonomer mol%. In this example, the CDBI is the weight percent of copolymer chains having a comonomer content of (0.5 x 8) to (1.5 x 8) mole percent or 4 mol% to 12 mol%. WO 1993/003093 also describes a method for determining the weight fraction of a polymer relative to the composition curve (i.e. composition profile) and the median comonomer composition Cmed therefrom using chromatography and C ¹³ NMR, reference being made to figures 16 and 17 of this publication. The CDBI of the copolymer is readily determined using techniques for separating individual fractions of a sample of the copolymer. One such technique is the use of Temperature Rising Elution Fractionation (TREF) to generate a solubility profile as described in WO 1993003093 (which in turn refers to Wild, et al, j. Poly. Sci., poly. Phys. Ed., volume 20, page 441 (1982) and U.S. Pat. No. 5,008,204). All three of the foregoing publications are incorporated herein by reference.

The solubility profile of the copolymer may first be generated using data obtained from the TREF technique (as described, for example, in the publications just referenced). The solubility profile is a plot of the weight fraction of copolymer dissolved as a function of temperature. This can be converted into a weight fraction versus composition profile. Weight fractions less than 15,000 may be omitted for the purpose of simplifying the dependence of composition on elution temperature. These low weight fractions generally represent a trivial portion of the ethylene-based polymers disclosed herein.

Alternatively or additionally, the composition distribution may be characterized by a T ₇₅- T₂₅ value, where T ₂₅ is the temperature at which 25% of the eluted polymer is obtained and T ₇₅ is the temperature at which 75% of the eluted polymer is obtained, both in a TREF experiment (and plot of eluted polymer molecular weight versus elution temperature) as described in US 2019/019413 (especially in paragraphs [0055] - [0058] thereof, which description is incorporated herein by reference). The narrow component distribution is reflected in the relatively small difference in T ₇₅ - T₂₅ values, while the broad distribution is reflected in the relatively larger difference in T ₇₅ – T₂₅ values (meaning the larger difference in crystallinity between the fractions of the polymer composition). It should also be noted that in case there is a difference between the actual TREF procedure as described in US 2019/019413 with respect to the TREF procedure as described in WO 1993003093, US 5,382,630, and/or US 5,008,204, the TREF procedure as described in US 2019/019413 should be used. (it should be further noted that the TREF program assists in generating the profile-the solubility profile of the CDBI and the elution molecular weight of T ₇₅ – T₂₅ versus elution temperature, which may have appropriate differences in the generation and analysis of CDBI and T ₇₅ – T₂₅.) finally, the generated TREF profile (eluted polymer molecular weight versus elution temperature) in combination with the measurement of T ₇₅-T₂₅ may be further processed as follows:

1. The solvent-only response of the instrument can be generated and subtracted from the TREF curve of the sample. The solvent-only response can be generated by running the same process prior to running the process for the polymer sample, but without adding any polymer to the sample vial, using the same solvent reservoir as for the polymer sample and without replenishing fresh solvent, and within a reasonable time from the running of the polymer sample.

2. The temperature axis of the TREF curve can be shifted appropriately to correct for the delay in the IR signal caused by the column to detector volume. This volume can be obtained by first filling the injection valve loop with 1-mg/ml of HDPE resin solution, then loading the loop volume at the same location within the column that was loaded with the sample for TREF analysis, then flowing the hot solution directly to the detector using isothermal methods at a constant flow rate of 1 ml/min, and then measuring the time that the HDPE probe peak appears in the IR signal after injection. Thus, the delay volume (ml) is equal to the time (min).

3. The curve may be baseline corrected and an appropriate integration limit may be selected, and the curve may be normalized such that the area of the curve is 100 wt%.

As in some embodiments of the polyethylene copolymers of the invention, the narrow distribution is reflected in a relatively small difference in T ₇₅ - T₂₅ values of less than 15 ℃, such as in a range of low values of any of 1 ℃,2 ℃,3 ℃,4 ℃, 5 ℃,6 ℃, 7 ℃, 8 ℃, or 9 ℃ to high values of any of 10 ℃, 11 ℃, 12 ℃, 13 ℃, 14 ℃, or 15 ℃, wherein any of the foregoing low values to any of the foregoing high values are contemplated (e.g., about 1 ℃ to about 10 ℃, such as about 5 ℃ to about 8 ℃, alternatively about 7 ℃ to about 11 ℃). In yet other embodiments, the polyethylene copolymers of the present disclosure may exhibit a bimodal composition distribution, such as BOCD (wide orthogonal composition distribution meaning that the comonomer preferentially incorporates onto a longer polymer chain than a shorter chain), and have a relatively high T ₇₅ - T₂₅ value, such as 15 ℃ or greater, such as a range of low values from any of 15 ℃, 16 ℃, 17 ℃, or 18 ℃ to high values of any of 21 ℃, 22 ℃, 23 ℃, 24 ℃, 25 ℃, 26 ℃, 27 ℃, 28 ℃, 29 ℃,30 ℃, or 35 ℃, wherein any of the foregoing low values to any of the foregoing high values ranges are contemplated (e.g., from about 15 ℃ to about 30 ℃, such as from 18 ℃ to 28 ℃, alternatively from about 18 ℃ to about 25 ℃, such as from about 19 ℃ to about 22 ℃, or 23 ℃).

Blends and additives

In some embodiments, the polyethylene copolymer may be formulated (e.g., blended) with one or more other polymer components. In some embodiments, those other polymer components are alpha-olefin polymers, such as polypropylene or polyethylene homo-and copolymer compositions. In some embodiments, those other polyethylene polymers are selected from the group consisting of linear low density polyethylene, high density polyethylene, medium density polyethylene, low density polyethylene, and other differentiated polyethylenes.

In some embodiments, the formulated blend may contain additives, which are determined based on the end use of the formulated blend. In some embodiments, the additive is selected from the group consisting of fillers, antioxidants, phosphites, anti-blocking additives, tackifiers, uv stabilizers, heat stabilizers, anti-blocking agents, mold release agents, antistatic agents, pigments, colorants, dyes, waxes, silica, processing aids, neutralizers, lubricants, surfactants, and nucleating agents. In some embodiments, the additive is present in an amount of about 0.1 ppm to about 5 wt%.

The polyethylene copolymers of the present disclosure may optionally be blended with one or more processing aids to form a polyethylene blend. Due to the improved properties of the polyethylene copolymers of the present disclosure, such processing aids may advantageously be omitted even in blown films (e.g., films of some embodiments and particularly blown films may be free or substantially free of polymeric processing aids, and particularly polymeric processing aids comprising fluorine; where "substantially free" means free of any intentionally added components, but allowing up to 100 ppm of one or more such components as impurities).

Article of manufacture

The polyethylene copolymers of the present disclosure may be particularly useful in the manufacture of end-use articles such as films (e.g., as may be formed by lamination, extrusion, coextrusion, casting, and/or blow molding), as well as other articles as may be formed, for example, by rotational molding or injection molding. The polyethylene copolymer may be formed into articles by cast film extrusion, blown film extrusion, rotational molding or injection molding processes. In some embodiments, the polyethylene copolymer may be used in a blend.

It has been found that the polyethylene copolymers of the present disclosure can provide excellent shear thinning characteristics with little or no melt fracture of the extrudate at high die shear rates. Furthermore, due to the improved flow behaviour, the polyethylene copolymers of the present disclosure may provide films formed with reduced motor load and melt pressure compared to other LLDPE.

The polyethylene copolymers of the present disclosure (or blends thereof) may be used in such forming operations as film, sheet and fiber extrusion and coextrusion, as well as blow molding, injection molding and rotational molding. Films include blown or cast films formed by coextrusion or lamination that are useful as shrink films, cling films, stretch films, sealing films, oriented films, snack packaging, heavy duty bags, grocery bags, baked and frozen food packaging, medical packaging, industrial liners, films, and the like in food-contact and non-food contact applications. For example, due to the long chain branching properties, the polyethylene copolymers of the present disclosure provide improved shrink packaging capability. Fibers include melt spinning, solution spinning, and melt blowing fiber operations for making filters, diaper fabrics, medical garments, geotextiles, and the like in woven or nonwoven form. Extruded articles include medical tubing, wire and cable jackets, tubing, geomembranes, and pond liners. Molded articles include single and multi-layer constructions in the form of bottles, cans, large hollow articles, rigid food containers, toys and the like.

The polyethylene copolymer (or blends thereof) may be formed into a monolayer or multilayer film. These films may be formed by any conventional technique including extrusion, coextrusion, extrusion coating, lamination, blow molding, and casting. The film may be obtained by a flat film or tubular process, which may then be oriented in a uniaxial direction or in two mutually perpendicular directions in the plane of the film. One or more of these layers of the film may be oriented to the same or different extents in the transverse and/or longitudinal directions. This orientation may be performed before or after bringing the individual layers together. For example, a layer of polyethylene copolymer (or blend thereof) may be extrusion coated or laminated to an oriented polypropylene layer, or the polyethylene copolymer (or blend thereof) and polypropylene may be co-extruded together into a film and then oriented. Likewise, the oriented polypropylene may be laminated to the oriented polyethylene copolymer (or blend thereof), or the oriented polyethylene copolymer (or blend thereof) may be coated onto the polypropylene, and then optionally the combination may be oriented even further.

The film comprises a single layer film or a multilayer film. Specific end use films include, for example, blown films, cast films, stretch/cast films, stretch cling films, stretch hand wrap films, machine stretch wrap, shrink films, shrink wrap films, greenhouse films, laminates, and laminated films. Exemplary films are prepared by any conventional technique known to those skilled in the art, such as, for example, techniques for preparing blown, extruded, and/or cast stretched and/or shrink films, including layer-by-layer shrink (shrnk-on-shrnk) applications.

In at least one embodiment, the multilayer film (multilayer films) (multilayer film (multiple-LAYER FILMS)) can be formed by any suitable method. The total thickness of the multilayer film may vary depending on the desired application. Total film thicknesses of 5-100 μm, such as 10-50 μm, are suitable for most applications. Those skilled in the art will appreciate that the thickness of the individual layers of the multilayer film may be adjusted based on the desired end use properties, the polymer or polymers employed, the equipment capabilities, and other factors. The materials forming each layer may be co-extruded through a co-extrusion feed block and die assembly to give a film having two or more layers adhered together but differing in composition. Coextrusion can be adapted for use in both cast film or blown film processes. Exemplary multilayer films have at least two, at least three, or at least four layers. In one embodiment, the multilayer film consists of five to ten layers.

In at least one embodiment, the films of the present disclosure have an average 1% secant modulus (M) of from about 30,000 psi to about 40,000 psi, such as from about 31,000 psi to about 40,000 psi, such as from about 33,000 to about 38,000 psi, such as from about 34,000 psi to about 36,000 psi, at 23 ℃ according to ASTM D882-18.

The films of the present disclosure may have an elmendorf tear value according to ASTM D-1922. In at least one embodiment, the film has an elmendorf tear (MD) of at least 30 g/mil, such as at least 50 g/mil, such as from about 60 g/mil to about 100 g/mil, such as from about 80 g/mil to about 100 g/mil.

The films of the present disclosure may have Dart impact (or impact failure or Dart F50 or Dart Impact Strength (DIS)) reported in grams (g) or grams per mil (g/mil) according to ASTM D-1709 method a. The films of the present disclosure may have dart impact of about 5 g/mil to about 600 g/mil. In at least one embodiment, the film has a dart impact of at least about 100 g/mil, such as at least about 120 g/mil, such as at least about 130 g/mil. For example, the dart impact may be about 100 g/mil to about 200 g/mil, such as about 120 g/mil to about 170 g/mil, such as about 130 g/mil to about 160 g/mil.

Shrinkage of the film (reported as a percentage) can be measured by cutting round specimens from the film using a 100 mm die. The samples may be marked in their respective directions, dusted with talc, and placed on pre-heated talc-covered tiles. The sample may then be heated using a heat gun (e.g., HG-501A type) for about 10 to 45 seconds, or until any dimensional change ceases. The value is the average of three samples. Negative shrinkage values indicate expansion of the dimensions after heating when compared to their pre-heating dimensions. The films of the present disclosure may have a% shrinkage (machine direction) of from about 40% to about 90%, such as from about 60% to about 80%, such as from about 65% to about 75%. The films of the present disclosure may have a% shrinkage (cross direction) of from about 0% to about 5%, such as from about 0.5% to about 4%, such as from about 1% to about 3%.

In certain embodiments, the film can have a break puncture energy (also referred to as puncture break energy) of at least about 25 in-lbs/mil, such as at least about 30 in-lbs/mil, such as at least about 35 in-lbs/mil, such as about 25 in-lbs/mil to about 40 in-lbs/mil, such as about 30 in-lbs/mil to about 40 in-lbs/mil, such as about 30 in-lbs/mil to about 35 in-lbs/mil, according to modified ASTM D5748 (using an ASTM probe with two 0.25 mil HDPE slides).

In at least one embodiment, the films of the present disclosure have a haze value of about 45% or less, about 40% or less, about 35% or less, about 30% or less, about 25% or less, about 20% or less, about 15% or less, or about 10% or less, as determined by ASTM D-1003.

In at least one embodiment, the films of the present disclosure have a transparency (defined as conventional transmitted light that deviates from the axis of incident light passing through the film sample block by less than 0.1) of about 80% or greater, about 85% or greater, about 90% or greater, about 95% or greater, about 97% or greater, as determined by ASTM D1746.

In at least one embodiment, the films of the present disclosure have a gloss of about 30% or greater, about 35% or greater, about 40% or greater, about 45% or greater, about 50% or greater, as determined by ASTM D-2457, wherein a light source is illuminated onto the film surface at a 45 ° angle and the amount of reflected light is measured.

Shrink film

The compositions of the present disclosure may be used to prepare shrink films. Shrink films, also known as heat shrinkable films, are widely used in both industrial and retail strapping and packaging applications. Such films are capable of shrinking upon application of heat to relieve stress imparted to the film during or after extrusion. Shrinkage may occur in one direction or in both the longitudinal and transverse directions. Conventional shrink films are described, for example, in U.S. patent No. 7,235,607, incorporated herein by reference.

Industrial shrink films may be used to bundle articles on pallets. Typical industrial shrink films are formed in a single bubble blow extrusion process to a thickness of about 80 to 200 μm and provide shrinkage in both directions.

The retail film may be used to package and/or bundle articles for consumer use, such as, for example, in supermarket goods. Such films are typically formed in a single bubble blow extrusion process to a thickness of about 35 μm to about 80 μm.

Films can be used in "layer-by-layer shrink" applications. As used herein, "layer-by-layer shrink" refers to a method of applying an outer shrink wrap layer around one or more articles that have been shrink wrapped individually (herein, the "inner layer" of the package). In these methods, it may be desirable for the film used to package the individual articles to have a higher melting point (or shrink point) than the film used for the outer layer. When such a configuration is used, a desired level of shrinkage may be achieved in the outer layer while preventing the inner layer from melting, further shrinking, or otherwise deforming during shrinkage of the outer layer. Some of the films described herein may have sharp shrink points when subjected to heat from a heat gun in a high heat environment, indicating that they may be particularly useful as inner layers in a variety of layer-by-layer shrink applications.

Experiment

General considerations and reagents unless otherwise indicated, all procedures were carried out under an inert atmosphere using glove box techniques. Toluene and pentane were purchased from SIGMA ALDRICH and degassed and dried over 3a molecular sieves overnight prior to use. Methylaluminoxane was purchased from Grace and used as received.

And (3) synthesis:

general considerations and reagents. Unless otherwise indicated, all operations were performed under an inert atmosphere using glove box techniques. Ether and dichloromethane (SIGMA ALDRICH) were degassed and dried over 3a molecular sieve overnight prior to use. ZrCl ₄ was purchased from STREM CHEMICALS, inc.

Synthesis of catalyst 2 and catalyst 1:

1-chloro-1- (2, 3,4, 5-tetramethylcyclopent-2, 4-dien-1-yl) silacyclobutane

To a colorless solution of 1, 1-dichlorosilacyclobutane (11.00 g,78.0 mmol,2.00 eq.) in tetrahydrofuran (50 mL) at-35 ℃ was added (tetramethylcyclopentadienyl) lithium (5.00 g,39.0 mmol,1.00 eq.) to give a cloudy white mixture that slowly became clear over one hour. The reaction was stirred for 3 hours and then evaporated under vacuum to give a thick white mixture. The mixture was extracted with pentane (50 mL, then 4 x 5 mL) and the extract was filtered to give a colorless solution. The solution was evaporated in vacuo to give an amber oil. Yield 8.79 g（99%）.¹H NMR (C₆D₆) δ 3.11 (br s, 1H), 1.98 (br m, 1H), 1.90 (s, 6H), 1.68-1.79 ( overlapping multiple and single peaks, 7H), 1.21-1.40 (m, 4H).

(3-Phenylindene) lithium

To a colorless solution of 3-phenylindene (26.20 g,136 mmol,1.00 eq.) in pentane (250 mL) was added 2.73. 2.73M butyllithium (50.0 mL,136 mmol,1.00 eq.) to give a cloudy yellow solution. The reaction was stirred for 69 hours to give a cloudy yellow mixture. The mixture was then filtered to give a pale yellow solid. The solid was washed with pentane (100 mL) and dried under vacuum. Yield is good 25.71 g（95%）.¹H NMR (THF-d8) δ 7.72 (dm, 1H), 7.55 (dm, 2H), 7.19 (dm, 1H), 7.02 (tm, 2H), 6.86 (d, 1H), 6.51 (tm, 1H), 6.47 (tm, 1H), 6.37 (tm, 1H), 5.93 (dd, 1H).

1- (3-Phenyl-1H-inden-1-yl) -1- (2, 3,4, 5-tetramethylcyclopent-2, 4-dien-1-yl) silacyclobutane

To an amber solution of 1-chloro-1- (2, 3,4, 5-tetramethylcyclopent-2, 4-dien-1-yl) silacyclobutane (5.14 g,22.7 mmol,1.00 eq.) in ether (25 mL) was added (3-phenylindene) lithium (4.81 g,24.3 mmol,1.07 eq.) at-35 ℃ to give a cloudy yellow-orange mixture. The reaction was allowed to warm to room temperature and stirred for 24 hours to give a cloudy, green-white mixture. The reaction was then evaporated under vacuum leaving a green semi-solid. The residue was extracted with pentane (3×30 mL, then 3×5 mL) and the extract was filtered to give a yellow solution. The solution was evaporated under vacuum leaving a manila solid. Yield is good 8.41 g（97%）.¹H NMR (C₆D₆) δ 7.73 (m, 1H), 7.66 (m, 1H), 7.64. (m, 1H), 7.46 (m, 1H), 7.27 (m, 2H), 7.22 (m, 2H), 7.17 (m, 2H), 6.49 (d, 1H), 3.36 (d, 1H), 2.98 (br s, 1H), 1.95 (m, 1H), 1.91 (s, 3H), 1.88 (s, 3H), 1.78 (s, 3H), 1.75 (s, 6H), 1.54 (m, 1H), 1.13-1.26 (m, 2H), 1.02 (m, 1H), 0.81 (m, 1H).

[ Tetramethyl cyclopentadienyl silacyclobutyl (3-phenylindenyl) ] (diethyl ether) dilithium

To a cloudy amber solution of 1- (3-phenyl-1H-inden-1-yl) -1- (2, 3,4, 5-tetramethylcyclopent-2, 4-dien-1-yl) silacyclobutane (8.27 g,21.6 mmol,1.00 eq.) in ether (40 mL) was added 2.74M butyllithium in hexane (16.4 mL,44.9 mmol,2.08 eq.) at-35 ℃ to give a cloudy yellow mixture. The reaction was allowed to warm to room temperature and stirred for 17 hours. Pentane (40 mL) was added to the reaction and the mixture was filtered to give a yellow solid. The solid was washed with pentane and dried under vacuum. Yield 9.11 g (90%) yellow powder .¹H NMR (THF-d8) δ 7.71 (d, 1H), 7.61 (d, 1H), 7.57 (dd, 2H), 7.18 (s, 1H), 7.02 (t, 1H), 6.55 (t, 1H), 6.50 (t, 1H), 6.41 (t, 1H), 3.40 (q, 4H), 2.27 (br m, 2H), 2.19 (s, 6H), 1.95 (s, 6H), 1.46 (br m, 4H), 1.13 (t, 6H).

[ Tetramethyl cyclopentadienyl silacyclobutyl (3-phenylindenyl) ] zirconium dichloride, catalyst 2

To a vigorously stirred white suspension of zirconium bis (etherate) (3.25 g,8.54 mmol,1.00 eq) in ether (50 mL) was added [ tetramethylcyclopentadienyl silacyclobutyl (3-phenylindene) ] (diethyl ether) dilithium (4.00 g,8.54 mmol,1.00 eq) at-35 ℃ to give a cloudy yellow mixture. The reaction was allowed to warm to room temperature and stirred for 18 hours. The cloudy, bright yellow mixture was then evaporated under vacuum leaving a yellow solid. The solid was extracted with dichloromethane (50 ml, then 4×5 mL) and the extract was filtered to give a yellow solution. The solution was evaporated under vacuum leaving a yellow solid. The solid was washed with pentane and dried under vacuum to give a bright yellow powder. Yield is good 4.26 g（92%）.H NMR (CD₂Cl₂) δ 7.91 (dt, 1H), 7.61 (m, 1H), 7.59 (m, 1H), 7.47-7.52 (m, 3H) 7.39-7.41 (m, 1H) 7.34-7.38 (m, 1H), 7.06-7.10 (m, 1H), 6.01 (s, 1H), 2.64-2.81 (m, 2H), 2.04-2.18 (m, 2H), 1.93-1.99 (m, 2H), 1.95 (s, 3H), 1.91 (s, 3H), 1.90 (s, 3H), 1.85 (s, 3H).

[ Tetramethyl cyclopentadienyl silacyclobutyl (3-phenylindenyl) ] zirconium dimethyl, (catalyst 1)

Catalyst 1 was obtained by continuous synthesis by adding 3.28M methyl magnesium bromide in ether (2.35 mL,7.71 mmol,2.09 eq) to a bright yellow suspension of [ tetramethyl cyclopentadienyl silacyclobutyl (3-phenylindenyl) ] zirconium dichloride (2.00 g,3.69 mmol,1.00 eq) in toluene (20 mL) at-35 ℃ to give a cloudy yellow mixture. The reaction was allowed to warm to room temperature and stirred for 18 hours. The cloudy dark amber solution was then evaporated under vacuum leaving a yellowish-brown solid. The solid was extracted with toluene (30 mL, then 3×5 mL) and the extract was filtered to give a yellow solution. The solution was evaporated under vacuum leaving a yellow solid. Yield 1.77 g（96%）.¹H NMR (C₆D₆) δ 8.07 (dt, 1H), 7.69 (m, 2H), 7.28-7.35 (m, 3H), 7.21 (m, 1H), 7.13-7.18 ( overlapping multiple peaks , 3H), 6.86 (m, 1H), 5.93 (s, 1H), 2.40-2.57 (m, 2H), 1.80 (s, 3H), 1.77 (s, 3H), 1.74 (s, 3H), 1.64-1.72 (m, 2H), 1.58 (m, 2H), 1.55 (s,3H), -0.46 (s, 3H), -1.25 (s, 3H).

Preparation 2 synthesis further catalyst 2:

to a vigorously stirred white suspension of zirconium bis (etherate) tetrachloride (2.00 g,5.25 mmol,1.00 eq) in ether (30 mL) was added [ tetramethylcyclopentadienyl) silacyclobutyl (3-phenylindene) ] (diethyl ether) dilithium (2.46 g,5.25 mmol,1.00 eq) at-35 ℃ to give a cold, cloudy, pale yellow mixture. After stirring for 20 minutes, the reaction turned cloudy bright yellow. The reaction was stirred for 18 hours and then evaporated under vacuum leaving a bright yellow solid. The solid was extracted with dichloromethane (30 mL, then 3 x 5 mL) and the extract was filtered to give a bright yellow solution and a dark yellow solid. The solution was evaporated under vacuum leaving a yellow solid. The solid was washed with pentane (20 mL) and dried under vacuum. Yield was 2.61 g (92%) as bright yellow powder .1H NMR (CD₂Cl₂) δ 7.91 (dt, 1H), 7.60-7.58 (m, 2H), 7.53-7.47 (m, 3H), 7.43-7.34 (m, 2H), 7.10-7.06 (m, 1H), 6.01 (s, 1H), 2.80-2.65 (m, 2H), 2.15-2.06 (m, 2H), 1.97-1.93 (m, 1H), 1.94 (s, 3H), 1.92, (s, 3H), 1.90 (s, 3H), 1.85 (s, 3H).

Preparation 2 synthesis further catalyst 1:

To a yellow suspension of [ tetramethyl cyclopentadienyl silacyclobutyl (3-phenylindenyl) ] zirconium dichloride (5806) (catalyst 2) (2.00 g,3.69 mmol,1.00 eq.) in toluene (20 mL) was added 3.28M methyl magnesium bromide in ether (2.35 mL,7.71 mmol,2.09 eq.) at-35 ℃ to give a cold cloudy yellow mixture. After stirring for 30 minutes, the reaction turned a cloudy amber-yellow color. The reaction was stirred for 18 hours to give a cloudy dark amber-yellow mixture. The reaction was evaporated under vacuum leaving a yellowish-brown solid. The solid was extracted with toluene (30 mL, then 3 x 5 mL) and the extract was filtered to give a yellow solution and a brown solid. The solution was evaporated under vacuum leaving a yellow solid. The yield is 1.77 g（96%）.1H NMR (CD₂Cl₂) δ 8.07 (dt, 1H), 7.70-7.68 (m, 2H), 7.35-7.28 (m, 3H), 7.23-7.13 (m, 2H), 6.89-6.84 (m, 1H), 5.93 (s, 1H), 2.53-2.42 (m, 2H), 1.80 (s, 3H), 1.77 (s, 3H), 1.75-1.66 (m, 2H), 1.74 (s, 3H), 1.61-1.56 (m, 2H), 1.55 (s, 3H), -0.46 (s, 3H), -1.25 (s, 3H).

Synthesis of catalyst 13 and catalyst 14:

Dimethyl (2, 3,4, 5-tetramethylcyclopent-2, 4-dien-1-yl) silyl triflate

To a pale amber solution of chlorodimethyl (2, 3,4, 5-tetramethylcyclopent-2, 4-dien-1-yl) silane (30.00 g,140 mmol,1.00 eq.) in toluene (100 mL) was added silver triflate (38.00 g,148 mmol,1.06 eq.) to give a warm, cloudy white mixture that slowly turned grey-purple. The reaction was stirred for 4 hours and then evaporated under vacuum leaving a dark mixture. The mixture was extracted with pentane (100 mL, then 3×20 mL) and the extract was filtered to give a yellow solution. The solution was evaporated under vacuum leaving a yellow liquid. Yield is good 44.56 g（97%）.¹H NMR (C₆D₆) δ 2.77 (br s, 1H), 1.74 (s, 6H), 1.60 (s, 6H), 0.042 (s, 6H).

Tetrahydroindacene lithium

To a yellow solution of 1,2,3, 5-tetrahydro-s-indacene (12.70 g,81.3 mmol,1.00 eq.) in ether (100 mL) at-35 ℃ was added 2.71M butyllithium (30.0 mL,81.3 mmol,1.00 eq.) to give a cloudy manila-colored mixture. The reaction was allowed to warm to room temperature and stirred for 30 minutes. Pentane (80 mL) was added to the reaction and the mixture was filtered to give a manila-colored solid. The solid was washed with pentane (40 mL) and dried under vacuum. Yield is good 13.05 g（99%）.¹H NMR (THF-d8) δ 7.16 (d, 2H), 6.42 (t, 1H), 5.81 (m, 2H), 2.84 (m, 4H), 1.97 (m, 2H).

Dimethyl (1, 5,6, 7-tetrahydro-s-indacen-1-yl) (2, 3,4, 5-tetramethylcyclopent-2, 4-dien-1-yl) silane

To a pale yellow solution of dimethyl (2, 3,4, 5-tetramethylcyclopent-2, 4-dien-1-yl) silyl triflate (5.00 g,15.2 mmol,1.00 eq.) in ether (20 mL) was added lithium tetrahydroindacene (2.65 g,16.2 mmol,1.07 eq.) at-35 ℃ to give a cloudy amber-orange mixture. The reaction was allowed to warm to room temperature and stirred for 16 hours to give a clear orange solution. The reaction was then evaporated under vacuum leaving an orange solid. The solid was extracted with pentane (50 mL, then 3 x 20 mL) and the extract was filtered to give an amber solution. The solution was evaporated in vacuo leaving an orange oil. Yield is good 5.04 g（99%）.¹H NMR (C₆D₆) δ 7.40 (s, 1H), 7.34 (s, 1H), 6.91 (dm, 1H), 6.50 (dd, 1H), 3.64 (s, 1H), 2.97 (br s, 1H), 2.85 (q, 4H), 1.90-1.96 (m, 8H), 1.83 (d, 6H), -0.09 (s, 3H), -0.35 (s, 3H).

[ Tetramethylcyclopentadienyl dimethylsilyl (tetrahydroindacene) ] (diethyl ether) dilithium

To an amber solution of dimethyl (1, 5,6, 7-tetrahydro-s-indacen-1-yl) (2, 3,4, 5-tetramethylcyclopent-2, 4-dien-1-yl) silane (5.00 g,14.9 mmol,1.00 eq.) in ether (20 mL) was added 2.74M butyllithium in hexane (11.3 mL,31.0 mmol,2.07 eq.) at-35 ℃ to give a cloudy manila-orange mixture. The reaction was allowed to warm to room temperature and stirred for 24 hours. Pentane (20 mL) was added to the reaction and the mixture was filtered to give a manila-colored solid. The solid was washed with pentane and dried under vacuum. Yield is good 5.86 g（93%）.¹H NMR (THF-d8) δ 7.46 (s, 1H), 7.16 (s, 1H), 6.65 (d, 1H), 5.91 (d, 1H), 3.40 (q, 4H), 2.82 (m, 4H), 2.10 (s, 6H), 1.95 (m, 2H), 1.87 (s, 6H), 1.13 (t, 6H), 0.59 (br s, 6H).

[ Tetramethyl cyclopentadienyl dimethylsilyl (tetrahydroindacenyl) ] zirconium dichloride (catalyst 14)

To a vigorously stirred white suspension of zirconium bis (etherate) tetrachloride (2.00 g,5.25 mmol,1.00 eq) in ether (30 mL) at-35 ℃ was added [ tetramethylcyclopentadienyl dimethylsilyl (tetrahydroindacene) ] (diethyl ether) dilithium (2.21 g,5.25 mmol,1.00 eq) to give a cloudy manila-colored mixture. The reaction was allowed to warm to room temperature and stirred for 18 hours. The cloudy, bright yellow mixture was then evaporated under vacuum leaving a yellow solid. The solid was extracted with dichloromethane (30 ml, then 4×5 mL) and the extract was filtered to give an orange solution. The solution was evaporated under vacuum leaving a yellow solid. The solid was washed with pentane and dried under vacuum to give a bright yellow powder. Yield is good 2.22 g（86%）.¹H NMR (CD₂Cl₂) δ 7.47 (d, 1H), 7.30 (s, 1H), 7.07 (m, 1H), 5.87 (d, 1H), 2.90-3.10 (dm, 2H), 2.83 (m, 2H), 2.05 (m, 2H), 1.924 (s, 3H), 1.920 (s, 3H), 1.895 (s, 3H), 1.888 (s,3H), 1.15 (s, 3H), 0.94 (s, 3H).

[ Tetramethyl cyclopentadienyl dimethylsilyl (tetrahydroindacenyl) ] zirconium dimethyl (catalyst 13)

To a bright yellow suspension of [ tetramethylcyclopentadienyl dimethylsilyl (tetrahydroindacenyl) ] zirconium dichloride (catalyst 14) (1.00 g,2.02 mmol,1.00 eq.) in toluene (10 mL) at-35 ℃ was added 3.28M methyl magnesium bromide in ether (1.30 mL,4.26 mmol,2.11 eq.) to give a cloudy yellow mixture. The reaction was allowed to warm to room temperature and stirred for 18 hours. The cloudy brown mixture was then evaporated under vacuum leaving a tan solid. The solid was extracted with toluene (25 mL, then 3 x 5 mL) and the extract was filtered to give a yellow solution. The solution was evaporated under vacuum leaving a yellow solid. Yield 0.95 g（103%）.¹H NMR (C₆D₆) δ 7.47 (s, 1H), 7.25 (s, 1H), 7.04 (d, 1H), 5.55 (d, 1H), 2.89 (m, 1H), 2.78 (m, 1H), 2.70 (t, 2H), 1.87 ( overlapping multiple and single peaks, 8H), 1.79 (s, 3H), 1.65 (s, 3H), 0.73 (s, 3H), 0.52 (s, 3H), 0.14 (s, 3H), 1.34 (s, 3H).

Adjustment on base catalyst B1

The basic or main catalyst B1 (dimethylsilylbis (tetrahydroindenyl) dimethylzirconocene) to be conditioned is then synthesized by methylation with 2 equivalents of methylmagnesium bromide as described in U.S. Pat. No. 3,5,314,973.

Adjustment procedure for catalyst 1:

the iC6 conditioning solution was prepared by adding pure catalyst 1 (0.04 wt%) to an empty tank and then filling the tank with iC6 diluent at the required total mass (6 kg).

Adjustment procedure for catalyst 13:

The iC6 conditioning solution was prepared by adding pure catalyst 13 (0.04 wt%) to an empty tank and then filling the tank with iC6 solvent/diluent at the required total mass (6 kg).

Polymerization

Gas phase fluidized bed polymerization was performed using the same reactor conditions (bed temperature to 185°f, pressure to 290 psig, the same ethylene, hydrogen, and hexene comonomer flow ratio, and using 10 to mol% iC5 as the induction condensing agent, with 25 to mol% N ₂ present) except that catalyst B1 without adjustment (example 1) and catalyst 13 in iC6 solution adjusted to a supported catalyst B1 slurry in increased relative amounts (examples 2 and 3) were used, as shown in table 1, with MI, HLMI, MIR and density of each PE produced also shown in table 1. As shown in table 2 below, polymerization under the same conditions was repeated again for base catalyst B1 (example 4) and using catalyst 13 (example 5) in an iC6 solution adjusted to a supported base catalyst B1 slurry in a similar relative amount as example 3.

Table 3 below lists the molecular weight and g' data obtained from GPC of examples 1-5, which are also shown in FIG. 1 (for examples 1-3) and FIG. 2 (for examples 4-5). Table 3 and figures 1 and 2 show that the PE copolymer shows lower g' values (indicating greater and greater degrees of long chain branching) with increasing relative amounts of trim catalyst, and some very slight flattening and broadening of the molecular weight distribution with the use of relatively more trim catalyst. This generally indicates that copolymers prepared using the trim catalyst will be expected to exhibit improved processability (as shown by reduced g' and broadened molecular weight distribution).

Table 4 lists the CDBI and T75-T25 values (derived from the TREF-IR5 distribution) for the PE copolymers, where the TREF-IR5 distribution is also shown in FIG. 3 (showing the TREF-IR5 distribution for examples 4 and 5) and FIG. 4 (showing the TREF-IR5 distribution for examples 1-3). As can be seen in table 4, with the catalyst 13 adjusted, the CDBI T75-T25 values remain substantially similar to examples 1 (without adjustment) to examples 2-3 (with the catalyst 13 adjusted), indicating that the catalyst pair increases long chain branching while maintaining similar comonomer distribution between different length polymer chains.

On the other hand, in the case of catalyst 1, we see from Table 4 and FIG. 3 that a certain Broad Orthogonal Composition Distribution (BOCD) is obtained, with a suitable decrease in CDBI consistent with a more heterogeneous distribution of comonomer between polymer chains of different lengths, and an increase in T75-T25 values derived from TREF-IR 5. Consistently, fig. 3 shows the apparent bimodal crystallinity in example 5 PE (as shown by the two distinct peaks of the TREF trace of example 5) compared to the PE copolymer of example 4 prepared without adjustment. This can be explained by the different distribution of comonomer over the different length polymer chains, resulting in different regions of higher and lower crystallinity respectively in the PE copolymer. Furthermore, the greater T75-T25 value of example 5 indicates that the comonomer distribution of the PE has BOCD properties, meaning that the comonomer preferentially incorporates on longer polymer chains, and this is generally associated with excellent processability without sacrificing strength properties in films made from such polyethylene.

TABLE 1 base catalyst B1 example polymerization

TABLE 2 additional base catalyst B1 example polymerization

Table 3 gpc data, processability improvement as measured by g' using catalyst with a modified metallocene catalyst 13 and catalyst 1 along with base catalyst B1.

Gel permeation chromatography via 4D GPC

TABLE 4 TREF data

Production of films Using examples 1-5

The copolymer resins of examples 1-3 and 5 PE were compounded with stabilizers into pellet resins by simple melt blending on a laboratory scale twin screw extruder (such as Coperion W & P57) under typical PE compounding conditions. Prior to melt mixing, the polyethylene resin in pellet form was dry blended in a drum mixer with the following additives, irganox-1076, 500 ppm, irgafosTM at 1,000 ppm and DYNAMARTM FX5920A at 600 ppm.

The pellets of examples 1-3 and 5 obtained above plus commercially available Enable 2005HH (commercial C1) were converted into monolayer films on a 2.5 "Battenfeld Gloucester production line with 30:1 l:d equipped with a 6" swinging die (oscillating die) and a Future Design wind ring (air ring). The die gap was 60 mil die gap and the blow-up ratio (BUR) was 2.5. Table 5 shows the film properties (and repetitions of MI, HLMI and MIR of the base polymer used therein).

TABLE 5 Membrane data for polymers obtained using base catalyst B1

In general, catalysts, catalyst systems, polyethylene polymers, and polymerization processes for making such polyethylene copolymers can provide polyethylene polymers formed by "tailored" processes, and which can have a combination of low density, low melt index, high melt index ratio, and controlled long chain branching (introduced by tailored processes), while also providing polymerization and extrusion of commercially desirable polyethylene copolymers.

Certain embodiments and features have been described using a set of upper numerical limits and a set of lower numerical limits. It should be understood that ranges including any two values (e.g., any lower value combined with any upper value, any combination of two lower values, and/or any combination of two upper values) are contemplated unless otherwise indicated. Certain lower limits, upper limits, and ranges appear in one or more of the following claims. All numerical values are indicative of "about" or "approximately" and take into account experimental errors and deviations that would be expected by one of ordinary skill in the art.

All priority documents are fully incorporated by reference herein for all purposes and for all jurisdictions in which such incorporation is permitted, and to the extent such description is consistent with this disclosure. Moreover, to the extent that all jurisdictions that allow such incorporation are permitted, and to the extent such descriptions are consistent with this disclosure, all documents and references cited herein, including test procedures, publications, patents, journal articles, and the like, are fully incorporated by reference.

Likewise, whenever a composition, element, or group of elements is preceded by the transitional phrase "comprising," it is understood that we also contemplate the same composition or group of elements having the transitional phrase "consisting essentially of (consisting essentially of)", "consisting of (consisting of)", "selected from the group consisting of (selected from the group of consisting of)", or "is)", and vice versa, prior to the recitation of the composition, element or elements. Unless otherwise indicated, the phrases "consisting essentially of (consists essentially of)" and "consisting essentially of (consisting essentially of)" do not exclude the presence of other steps, elements, or materials, whether or not such steps, elements, or materials are specifically mentioned in the present specification, so long as such steps, elements, or materials do not affect the essential and novel features of the claimed invention, and additionally, the phrases do not exclude impurities and differences that are normally associated with the elements and materials used.

While the claimed invention has been described with reference to various embodiments and examples, those skilled in the art, having benefit of this disclosure, will appreciate that other embodiments can be devised which do not depart from the scope and spirit of the present disclosure.

Claims

1. A polyethylene copolymer comprising:

About 90% by weight or more of ethylene units, and

The balance of C ₃-C₂₀ comonomer units,

The polyethylene copolymer has:

A bimodal composition distribution,

A density of about 0.914 g/cm ³ to about 0.925 g/cm ³,

A Melt Index (MI) of about 0.1 g/10min to about 1 g/min,

A High Load Melt Index (HLMI) of about 21 g/10 min to about 70 g/10 min,

A Melt Index Ratio (MIR) of about 40 to about 65, and

A Molecular Weight Distribution (MWD) of about 4 to about 7.

2. The polyethylene copolymer of claim 1, wherein the polyethylene copolymer has a C ₃-C₂₀ comonomer content of from about 5 wt% to about 10 wt%.

3. The polyethylene copolymer of claim 1 or 2, wherein the High Load Melt Index (HLMI) is from about 45 g/10 min to about 70 g/10 min.

4. The polyethylene copolymer of any one of claims 1 or 3, wherein the polyethylene copolymer has a melt index of from about 0.3 g/10min to about 0.8 g/10 min.

5. The polyethylene copolymer according to any one of claims 1 to 4, wherein the polyethylene copolymer has a g' vis value of from about 0.8 to about 0.95 or from about 0.82 to about 0.92.

6. A film comprising the polyethylene copolymer of claim 1.

7. The film of claim 6, wherein the polyethylene copolymer has a C ₃-C₂₀ comonomer content of about 5 wt% to about 10 wt%.

8. The film of claim 6 or 7, wherein the polyethylene copolymer has a melt index of about 0.3 g/10 min to about 0.8 g/10 min.

9. The film of any one of claims 6 to 8, wherein the polyethylene copolymer has a g' vis value of about 0.8 to about 0.95, or about 0.82 to about 0.92.

10. The film according to any one of claims 6 to 9, wherein the film has:

an average 1% secant modulus (M) at 23C of from about 30000 psi to about 40000 psi,

An elmendorf tear value (MD) of about 30 g/mil to about 75 g/mil,

Dart impact of about 150 g/mil to about 600 g/mil, and

Breaking puncture energy of about 25 in-lbs/mil to about 40 in-lbs/mil.

11. The film according to any one of claims 6 to 10, wherein the film has:

A haze value of about 35% or less, and

A transparency of about 85% or greater.

12. A polyethylene copolymer comprising:

About 90% by weight or more of ethylene units, and

The balance of C ₃-C₂₀ comonomer units,

The polyethylene copolymer has:

A bimodal composition distribution,

A density of about 0.92 g/cm ³ to about 0.925 g/cm ³,

A Melt Index (MI) of about 0.4 g/10min to about 0.5 g/min,

A High Load Melt Index (HLMI) of about 24 g/10 min to about 29 g/10 min,

A Melt Index Ratio (MIR) of about 50 to about 65, and

A Molecular Weight Distribution (MWD) of about 4 to about 7.

13. The polyethylene copolymer according to claim 12, wherein the polyethylene copolymer has a C ₃-C₂₀ comonomer content of from about 5 wt% to about 10 wt%.

14. The polyethylene copolymer of claim 12 or 13, wherein the polyethylene copolymer has a melt index of from about 0.46 g/10min to about 0.48 g/10 min.

15. The polyethylene copolymer according to any one of claims 12 to 14, wherein the polyethylene copolymer has a g' vis value of from about 0.86 to about 0.92.

16. The polyethylene copolymer according to any one of claims 12 to 15, wherein the polyethylene copolymer has a z-average molecular weight (Mz) from about 250000 g/mol to about 350000 g/mol.

17. A film comprising the polyethylene copolymer according to any one of claims 12 to 16.

18. A polyethylene copolymer comprising:

About 90% by weight or more of ethylene units, and

The balance of C ₃-C₂₀ comonomer units,

The polyethylene copolymer has:

A bimodal composition distribution,

A density of about 0.92 g/cm ³ to about 0.925 g/cm ³,

A melt index of about 0.9 g/10min to about 1 g/min,

A High Load Melt Index (HLMI) of about 50 g/10 min to about 60 g/10 min,

A Melt Index Ratio (MIR) of about 55 to about 65, and

A Molecular Weight Distribution (MWD) of about 6 to about 7.

19. The polyethylene copolymer according to claim 18, wherein the polyethylene copolymer has a C ₃-C₂₀ comonomer content of from about 5 wt% to about 10 wt%.

20. The polyethylene copolymer of claim 18 or 19, wherein the polyethylene copolymer has a melt index of from about 0.9 g/10min to about 0.95 g/10 min.

21. The polyethylene copolymer according to any one of claims 18 to 20, wherein the polyethylene copolymer has a g' vis value of from about 0.8 to about 0.85.

22. The polyethylene copolymer according to any one of claims 18 to 21, wherein the polyethylene copolymer has a z-average molecular weight (Mz) of from about 260000 g/mol to about 300000 g/mol.

23. A film comprising the polyethylene copolymer of any one of claims 18 to 22.