CN121420001A

CN121420001A - Polyethylene, catalysts used for their polymerization, and their membranes

Info

Publication number: CN121420001A
Application number: CN202480042913.1A
Authority: CN
Inventors: M·W·赫尔特卡姆; 李东明; K·A·史蒂文斯; I·C·蔡; A·H·斯利姆
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: EP4716709A1; WO2024242932A1

Abstract

The present disclosure relates to catalysts, polyethylene polymers, polymerization processes for preparing such polyethylene polymers, and films prepared therefrom. In some embodiments, the catalyst system comprises a first catalyst compound. The first catalyst compound is represented by formula (I). At least one pair of R ⁴ and R ⁵、R⁵ and R ⁶ or R ⁶ and R ⁷ of formula (I) are linked to form a first substituted or unsubstituted fully saturated ring fused to an indenyl ring, and at least one pair of R ¹¹ and R ¹²、R¹² and R ¹³ or R ¹³ and R ¹⁴ are linked to form a second substituted or unsubstituted fully saturated ring fused to an indenyl ring. The catalyst system further includes a second catalyst represented by formula (III). R ⁷ and R ⁸、R⁸ and R ⁹ of formula (III), Or at least one pair of R ⁹ and R ¹⁰ is linked to form a substituted or unsubstituted fully saturated ring fused to the indenyl ring.

Description

Polyethylene, catalyst for their polymerization and film thereof

Cross Reference to Related Applications

The application claims the benefit of U.S. provisional application 63/503893 entitled "polyethylene, catalyst for their polymerization and films thereof" filed on day 5/23 of 2023, the entire contents of which are incorporated herein by reference.

Technical Field

The present disclosure relates to catalysts, catalyst systems, polyethylene polymers, polymerization processes for preparing such polyethylene polymers, and films prepared therefrom.

Background

Low Density Polyethylene (LDPE) is typically synthesized using a high pressure free radical polymerization process to produce polyethylene compositions with good processability and other desirable properties, mainly due to its broad long chain branched LCB structure. Other desirable properties of LDPE formed at high pressure include high melt strength, high shrinkage, and good optical properties. However, high pressure formed LDPE typically suffers from poor mechanical properties such as low TD tear and dart impact. Furthermore, the high pressure process involves a higher energy consumption than the low pressure process.

Or Linear Low Density Polyethylene (LLDPE) is a substantially linear polymer composed of ethylene monomer units and alpha-olefin comonomer units. Typical comonomer units used are derived from 1-butene, 1-hexene or 1-octene. LLDPE can be distinguished from conventional LDPE in several ways, including its different manufacturing process and different rheological and mechanical properties, such as tear properties, compared to LDPE.

LLDPE formed using metallocene catalysts is referred to as "mLLDPE". Extrusion of mLLDPE requires more motor power and higher extruder pressure to match the extrusion rate of the LDPE. In fact, commercial mLLDPE presents flow challenges in dies and extruders used in cast film lines, resulting in high melt pressures, high motor loads, and suboptimal flow to the edges in the die, which can lead to adjacent resin layer encapsulation. Irrespective of processing and rheology challenges, mLLDPE does exhibit superior physical properties compared to LDPE.

In the past, various levels of LDPE have been blended with mLLDPE to increase melt strength, improve shear sensitivity, such as improving flow in an extruder at commercial shear rates, and reduce the propensity for melt fracture. However, such blends typically have poor mechanical properties compared to neat mLLDPE. Indeed, improving the processability of mLLDPE without sacrificing physical properties is a challenge.

In summary, there remains a need for new polyethylenes with a medium LCB polyethylene composition that have extrusion processability as LDPE while also maintaining good tear properties and dart impact strength to match those of mLLDPE. This new LLDPE will provide the benefits of increased processability as well as increased tear balance, increased TD tear and much better draw down characteristics (drawdown characteristics) making it easier to produce, stronger films without having to resort to many of the complexities and compromises associated with blending mLLDPE and LDPE.

Some references of potential interest in this regard include U.S. Pat. Nos. 6,479,424, 7,601,666, 8,829,115, 9,068,033, 10,633,471, 11,267,917 and 11,352,386;WO2021/257264;WO2022/015094;US2006/0122342;US2021/0332169;US2021/0388191;US2021/0395404;US2022/0185916;US2022/0315680;US2022/0064344;KR10-2022-0009900,KR10-2022-0009782;KR10-2021-0080974;KR10-2021-0038379;KR10-2020-0089599;KR10-2018-0063669;KR10-2007-0098276, and Foster et al Journal of Organometallic Chemistry,571 (1998) 171.

Disclosure of Invention

The present disclosure relates to support-bound activators, supported catalyst systems, and methods of use thereof.

In some embodiments, the catalyst system comprises a first catalyst compound. The first catalyst compound is represented by the following formula (I):

Wherein:

m of formula (I) is a group 4 metal;

Each of R¹、R²、R³、R⁴、R⁵、R⁶、R⁷、R⁸、R⁹、R¹⁰、R¹¹、R¹²、R¹³ and R ¹⁴ of formula (I) 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 ¹ and R ²、R⁴ and R ⁵、R⁵ and R ⁶、R⁶ and R ⁷、R⁹ and R ¹⁰、R¹¹ and R ¹²、R¹² and R ¹³, and R ¹³ and R ¹⁴ are linked to form a substituted or unsubstituted fully saturated ring or a substituted or unsubstituted aromatic ring;

Wherein at least one pair of R ⁴ and R ⁵、R⁵ and R ⁶ or R ⁶ and R ⁷ of formula (I) are linked to form a first substituted or unsubstituted fully saturated ring fused to an indenyl ring and at least one pair of R ¹¹ and R ¹²、R¹² and R ¹³ or R ¹³ and R ¹⁴ are linked to form a second substituted or unsubstituted fully saturated ring fused to an indenyl ring, and

Each X of formula (I) is independently halo (a halide), substituted or unsubstituted hydrocarbyl, hydride, amino (amide), substituted or unsubstituted alkoxy (alkoxide), thio (sulfade), phospho (phospho), or a combination thereof, or two of X are joined together to form a substituted or unsubstituted metallocycle ring (metallocycle ring), or two of X are joined to form a chelating ligand, diene ligand, or alkylidene (alkylidene).

The catalyst system may further include a second catalyst represented by the following formula (III):

Wherein:

M of formula (III) is a group 4 metal;

Each of R ¹、R²、R³、R⁴、R⁵、R⁶、R⁷、R⁸、R⁹ and R ¹⁰ of formula (III) 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, are linked to form a substituted or unsubstituted fully saturated ring or a substituted or unsubstituted aromatic ring, wherein at least one pair of R ⁷ and R ⁸、R⁸ and R ⁹, or R ⁹ and R ¹⁰ are linked to form a substituted or unsubstituted fully saturated ring fused to an indenyl ring;

T of formula (III) 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 comprising a substituted or unsubstituted fully saturated ring or a substituted or unsubstituted aromatic ring, and

Each X of formula (III) is independently halo, substituted or unsubstituted hydrocarbyl, hydrogen, amino, substituted or unsubstituted alkoxy, thio, phosphorus, or a combination thereof, or two of X are joined together to form a substituted or unsubstituted metallocycle ring, or two of X are joined to form a chelating ligand, diene ligand, or alkylidene.

In some embodiments, the polyethylene copolymer comprises ethylene derived units and the remainder is C ₃-C₂₀ comonomer derived units. The polyethylene copolymer has a broad orthogonal composition distribution (a broad orthogonal composition distribution), a density of about 0.914 g/cm ³ to about 0.925 g/cm ³, a melt index of about 0.6 g/10min to about 1.3 g/10min, an olefin comonomer content of about 10% to about 13% by weight, a High Load Melt Index (HLMI) of about 80 g/10min to about 90 g/10min, a Melt Index Ratio (MIR) of about 60 to about 98, and a polydispersity index (PDI, defined as Mw/Mn) of about 8 to about 10.

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 graphic illustration of GPC illustrating a polyethylene copolymer according to various embodiments, including both polymer chain distribution (which may be labeled as dwt d (log M) or equivalently as MWD (IR)) on the y-axis, the y-axis value to reflect molecular weight distribution being a measure of the relative number of polymer molecules of a given molecular weight in a population of polymer molecules analyzed in the polymer composition, and g' vis value (also labeled on the y-axis) as a function of log (molecular weight) (which may be labeled as log M) on the x-axis. It should be noted that the MWD (IR) used in the labeling of fig. 1 is not necessarily identical to the mathematical term MWD (defined as Mw/Mn, also referred to as polydispersity index or PDI, see below), but rather it merely means the distribution (i.e., relative amounts) of polymer chains of different molecular weights, shown in fig. 1 as a function of molecular weight.

FIG. 2 is a graphic illustration of GPC of polyethylene copolymers according to various embodiments, including both molecular weight distribution (labeled MWD (IR) on the left y-axis) and comonomer weight percent (labeled wt% C6 on the right y-axis) as a function of log (molecular weight). The MWD (IR) mark in fig. 2 is used in the same way as in fig. 1.

Definition of the definition

As used herein, "olefin," or "olefinic hydrocarbon," is a linear, branched, or cyclic compound of carbon and hydrogen having at least one double bond. For purposes of this specification and the claims appended hereto, 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 about 35 wt% to about 55 wt%, it is understood that the mer units in the copolymer are derived from ethylene in the polymerization reaction and that the derived units are present at about 35 wt% to about 55 wt% based on the weight of the copolymer.

The terms "polyethylene polymer", "polyethylene copolymer", "polyethylene", "ethylene polymer", "ethylene copolymer" and "ethylene polymer" as used herein refer to a polymer or copolymer comprising at least 50 mole% ethylene units, or at least 70 mole% ethylene units, or at least 80 mole% ethylene units, or at least 90 mole% ethylene units, or at least 95 mole% ethylene units, or 100 mole% 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 differ from each other. "terpolymer" is a polymer having three monomer units that differ from one another. The term "different" as used in reference to monomer units indicates that the monomer units differ from each other in at least one atom or are isomerically different. Accordingly, the definition of copolymer as used herein includes terpolymers and the like. Likewise, the definition of polymer as used herein includes copolymers and the like.

As used herein, ethylene polymers having a density of greater than 0.860 to less than 0.910g/cm ³ may be referred to as ethylene plastomers or plastomers, ethylene polymers having a density of 0.910 to less than 0.925g/cm ³ may be referred to as "linear low density polyethylene" (LLDPE) when substantially linear (with little or no long chain branching), as is the case for ziegler-natta or metallocene-catalyzed PEs, or branched Low Density Polyethylene (LDPE) when significantly branched (with highly long chain branching), as is the case for PE that is free-radically polymerized, 0.925 to 0.940 g/cm ³ may be referred to as "medium density polyethylene" (MDPE), and ethylene polymers having a density of greater than 0.940 g/cm ³ may be referred to as "high density polyethylene" (HDPE). Density is determined according to ASTM D792. Samples were prepared according to ASTM D4703-appendix 1 procedure C and then conditioned according to ASTM D618-procedure a prior to testing.

As used herein and unless otherwise specified, the term "hydrocarbon" refers to a class of compounds containing carbon-bonded hydrogen and encompasses mixtures of (i) saturated hydrocarbon compounds, (ii) unsaturated hydrocarbon compounds, and (iii) 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 means that the composition/film is substantially free of the component, or contains the component in an amount of less than 0.01 wt% based on the weight of the total composition.

The term "polymerization conditions" as used herein refers to conditions that favor the reaction of one or more olefin monomers to produce a polyolefin polymer when contacted 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 the purposes of this disclosure, the new numbering scheme for the groups of the periodic table is used as described in CHEMICAL AND ENGINEERING NEWS,63 (5), pg. 27, (1985).

The abbreviations used herein are Me is methyl, et is ethyl, ph is phenyl, 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, "olefin polymerization catalyst(s)" refers to any catalyst capable of coordination polymerization addition, for example, an organometallic complex or compound in which a continuous monomer is added in a monomer chain at an organometallic active center.

The terms "substituent", "group" and "moiety" are used interchangeably.

The term "α -olefin" refers to an olefin having a terminal carbon-carbon double bond in its structure ((R "R '") -c=ch ₂, where R "and R '" can independently be hydrogen or any hydrocarbyl group, e.g., R "is hydrogen and R '" is alkyl). "Linear alpha-olefins" are alpha-olefins as defined in this paragraph wherein R ' ' is hydrogen and R ' ' ' is hydrogen or linear alkyl.

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

As used herein and unless otherwise specified, the term "Cn" refers to hydrocarbon(s) containing n carbon atom(s) per molecule, where n is a positive integer. The term "hydrocarbon" refers to a class of compounds containing carbon-bonded hydrogen and encompasses (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 that contains carbon atoms in the total number of m to y. Thus, C ₁-C₅₀ alkyl refers to alkyl groups containing carbon atoms in a total number of about 1 to about 50.

Unless otherwise indicated (e.g., definition of "substituted hydrocarbyl", "substituted aromatic", etc.), the term "substituted" refers to at least one hydrogen atom that has been replaced with at least one non-hydrogen group, such as a hydrocarbyl, heteroatom, or heteroatom-containing group, such as a halo (e.g., 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 a hydrocarbyl or halogenated hydrocarbyl (halocarbyl radical), and two or more R may be joined together to form a substituted or unsubstituted fully saturated, partially unsaturated, or aromatic cyclic or polycyclic ring structure), or where at least one heteroatom has been inserted within the hydrocarbyl ring.

The term "substituted hydrocarbyl" refers to a hydrocarbyl wherein at least one hydrogen atom of the hydrocarbyl has been substituted with at least one heteroatom (e.g., halo, such as Br, cl, F, or I) or heteroatom-containing group (e.g., a 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, wherein each R is independently hydrocarbyl or halocarbyl, and two or more R may be joined together to form a substituted or unsubstituted fully saturated, partially unsaturated, or aromatic cyclic or polycyclic ring structure), or wherein at least one heteroatom has been inserted within the hydrocarbyl ring.

The term "substituted aromatic" refers to an aromatic group having 1 or more hydrogen groups 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, may be 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 terms "alkoxy" and "alkoxy" refer to an alkyl or aryl group bonded to an oxygen atom, such as an alkyl ether or aryl ether group attached to an oxygen atom, and may include those wherein the alkyl/aryl group is a C ₁-C₁₀ hydrocarbon group. The alkyl group may be a linear, branched or cyclic alkyl group. 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" refers to 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 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, i-propyl, 2-butyl, sec-pentyl, sec-hexyl, and the like.

The term "aryl" or "aryl group" refers to aromatic rings and substituted variants thereof, such as phenyl, 2-methyl-phenyl, xylyl, 4-bromo-xylyl. Likewise, "heteroaryl" refers to an aryl group in which one ring carbon atom (or two or three ring carbon atoms) has been replaced with a heteroatom, such as N, O or S. The term "aromatic" as used herein also refers to aromatic (pseudoaromatic) heterocycles which are heterocyclic compounds having similar properties and structure (nearly planar) as aromatic heterocyclic ligands, but which do not belong to the heterocyclic substituents defining aromatic groups, and as such, the term aromatic also refers to substituted aromatic compounds.

When isomers of an alkyl, alkenyl, alkoxy, or aryl group specified (e.g., n-butyl, isobutyl, sec-butyl, and tert-butyl) are present, references to alkyl, alkenyl, alkoxy, or aryl groups without specifying the particular isomer (e.g., butyl) explicitly disclose all isomers (e.g., n-butyl, isobutyl, sec-butyl, and tert-butyl).

The term "ring atom" refers to an atom belonging to a cyclic ring structure. According to this definition, benzyl has 6 ring atoms and tetrahydrofuran has 5 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 and 4-N, N-dimethylamino-phenyl is a heteroatom-substituted ring. Other examples of heterocycles may include pyridine, imidazole, and thiazole.

Mn as used herein is the number average molecular weight, mw is the weight average molecular weight, 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 index (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", "procatalyst compound" and "precatalyst complex" are used interchangeably.

A "catalyst system" is a combination of at least one catalyst compound, at least one activator, optionally a coactivator (coactivator), and optionally a support material. When "catalyst system" is used to describe such pairing prior to activation, it refers to the unactivated catalyst complex (procatalyst) together with the activator and, optionally, the co-activator. When it is used to describe such pairing after activation, it refers to activating the complex and activator or other charge balancing moiety. The catalyst compound may be neutral, as in the procatalyst, or a charged species with a counterion, as in the activated catalyst system. For the purposes of this disclosure and the claims thereto, when the catalyst system is described as comprising a neutral stable form of a component, those skilled in the art will understand that the ionic form of the component 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 structural formulae herein are intended to encompass both neutral and ionic forms of the catalyst compounds and activators.

An "anionic ligand" is a negatively charged ligand that contributes one or more electron pairs to a metal ion. A "Lewis base" or "neutral donor ligand" is an electrically neutral 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 may 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 (not scavengers) may also be used in combination with the activators to form active catalysts. 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" refers to a system that does not interrupt or stop operation for an extended period of time. For example, a continuous process for preparing a polymer will be one in which reactants are continuously introduced into one or more reactors and polymer product is continuously withdrawn.

Solution polymerization refers to a polymerization process in which the polymer is dissolved in a liquid phase polymerization medium, such as an inert diluent or monomer(s) or blends thereof. The solution polymerization may be a homogeneous solution polymerization. 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, vol. 29, p.4627.

Bulk polymerization refers to a polymerization process in which the monomer and/or comonomer being polymerized is used as a solvent or diluent with little or no use of an inert solvent as a solvent or diluent. A small portion of the inert solvent/diluent may serve as a support for the catalyst and scavenger. The bulk polymerization system contains less than about 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, but such catalyst compound may comprise and be used as a mixture of isomers, such as stereoisomer (stereoisomer).

Catalyst systems using a single catalyst compound refer to catalyst systems prepared using only a single catalyst compound in the preparation of the catalyst system. Thus, such catalyst systems differ from, for example, "dual" catalyst systems, which are prepared using two catalyst compounds having different structural formulas, e.g., the connection 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 if it differs from another catalyst compound by at least one atom (number, type, or linkage). For example, bis-indenyl zirconium dichloride is different from (indenyl) (2-methylindenyl) zirconium dichloride, which is different from (indenyl) (2-methylindenyl) hafnium dichloride. Unless otherwise indicated, catalyst compounds differing only in that they are stereoisomers of each other are not considered to be different catalyst compounds. For example, rac-dimethylsilylbis (2-methyl-4-phenyl) hafnium and meso-dimethylsilylbis (2-methyl-4-phenyl) hafnium are not considered to be different.

The terms "cocatalyst" and "activator" are used interchangeably herein and are defined as any compound capable of activating any of the above-mentioned catalyst compounds by converting a neutral catalyst compound into a catalytically active catalyst compound cation.

During extrusion, "viscosity" is a measure of the resistance to shear flow. Shearing is a laminar (layer-by-layer) motion of a fluid, such as a stack of cards. As the polymer flows through a straight pipe or channel, the polymer is sheared and the resistance is expressed as viscosity.

"Elongation" or "elongational viscosity (elongational viscosity)" is the resistance to extension. In fiber spinning, film blowing and other processes for stretching melt polymers, the elongational viscosity plays a role. For example, for certain liquids, the tensile resistance may be three times greater than the shear resistance. For some polymer liquids, the elongational viscosity may increase with rate (stretch hardening), although the shear viscosity decreases.

The term "melt index" ("MI") is the number of grams extruded in 10 minutes under standard load (2.16 kg) and is inversely proportional to viscosity. A high MI means low viscosity and a low MI means high viscosity. Furthermore, the polymers may have a shear thinning behaviour, which means that their flow resistance decreases with increasing shear rate. This is due to, for example, molecular alignment in the direction of flow and disentanglement. As provided herein, MI (I ₂) is determined according to ASTM D1238-E (190 ℃ C./2.16 kg), sometimes also referred to as I ₂ or I _2.16.

The term "high load melt index" ("HLMI") is the number of grams extruded in 10 minutes under standard load (21.6 kg) and is inversely proportional to 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 "melt index ratio" ("MIR") provides an indication of the amount of shear thinning behavior of the polymer and is a parameter that can be correlated to the total polymer mixture molecular weight distribution data obtained by using gel permeation chromatography ("GPC") and possibly in combination with another polymer analysis including TREF alone. MIR is the ratio of I ₂₁/I₂ (also known as HLMI/MI).

The term "melt strength" is a measure of the elongational viscosity and represents the maximum tension that can be applied to the melt without breaking. The elongational viscosity is the ability of a polyethylene to resist thinning at high draw rates and high draw ratios. In the melt processing of polyolefins, melt strength is defined by characteristics that can be quantified in process related terms and rheological terms. In extrusion blow molding and melt phase thermoforming, branched polyolefins of suitable molecular weight may support the weight of the fully melted sheet or extruded part prior to the molding stage. This behavior is sometimes referred to as sag resistance (SAG RESISTANCE).

For simplicity, only certain numerical ranges are explicitly disclosed herein. However, a lower limit may be combined with any other upper limit to define a range not explicitly recited, and similarly, a lower limit may be combined with any other lower limit to define a range not explicitly recited, and likewise, an upper limit may be combined with any upper limit to define a range not explicitly recited. In addition, "in a range" or "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 itself may be used as a lower or upper limit in combination with other points or individual values or other lower or upper limits to define a range not explicitly recited.

Detailed Description

Various embodiments, forms 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 use of a header is merely for convenience and does not limit the scope of the disclosure.

The present disclosure relates to catalysts, catalyst systems, polyethylene polymers, polymerization processes for preparing such polyethylene polymers, and films prepared therefrom. The catalyst systems and methods described herein employ a dual catalyst system of a first metallocene catalyst and a second metallocene catalyst for polymerization. The catalyst ratios of the first metallocene catalyst and the second metallocene catalyst can be adjusted to react at low pressure to produce a polyethylene composition having a significant level of long branching and a high level of broad orthogonal comonomer distribution characteristics in a gas phase polymerization process.

In some embodiments, the catalyst ratio of the first metallocene catalyst and the second metallocene catalyst can be adjusted by using a "trim" method.

The polyethylene copolymers of the present disclosure have increased long chain branching (also referred to as "LCB") and increased wide orthogonal comonomer incorporation (BOCD) in the copolymer, as compared to conventional LLDPE, thereby providing reduced neck-in and increased draw stability. The polyethylene copolymers of the present disclosure may exhibit lower zero shear viscosity, resulting in lower motor torque and lower melt pressure and melt temperature during extrusion, providing increased yield of extruded polyethylene copolymer product. Furthermore, because LCBs and BOCD are controlled (adjustable by the ratio of the first metallocene to the second metallocene), the advantageous tear properties and dart properties can also be controlled (adjustable) to 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 and increased BOCD. LCBs may be demonstrated by, for example, lower g' values, high melt index ratios, and/or increased rheology. BOCD can be demonstrated by, for example, high T ₇₅-T₂₅ values, high CBDI, high melt index ratios, and/or increased rheological properties, such as Small Angle Oscillatory Shear (SAOS) experiments.

Furthermore, it has been found that the polyethylene copolymers of the present disclosure can provide excellent tear properties and dart impact strength, overcoming the key weakness of LDPE. For example, due to improved flow behavior, the polyethylene copolymers of the present disclosure may provide films formed with reduced motor load and melt pressure (which increases throughput) compared to conventional LLDPE. For example, a reduction in melt pressure and a reduction in melt temperature may be provided during film manufacture. The films of the present disclosure may be particularly useful as shrink wrap films (improved by the presence of LCB and BOCD in the polyethylene copolymers of the present disclosure).

Indeed, the dual catalysts and methods of the present disclosure can provide gas phase polymerization to provide LCB polyethylene products with excellent extrusion processability as well as good tear properties and dart impact strength. Furthermore, the tear balance of the polyethylene copolymers described herein may have high TD tear, which is desirable in many end use applications. Another advantage includes improved draw down characteristics, which provide for easier production of thin films.

Further, the dual catalysts and methods of the present disclosure can provide trim (e.g., in-line trim) of the first catalyst that facilitates LCB onto a supported catalyst that provides BOCD to control (adjust) the melt index ratio of the polyethylene copolymer formed in the reactor. Catalysts used for polishing may provide different molecular weight capabilities than, for example, on-line supported catalysts. The different molecular weight capabilities of the catalyst provide a bimodal composition distribution of the polyethylene copolymer formed in the reactor.

In at least one embodiment, the properties and performance of the polyethylene can be improved by (1) changing the reactor conditions such as reactor temperature, reactor pressure, hydrogen concentration, comonomer concentration, etc., and (2) selecting and feeding a dual catalyst system having a first catalyst and a second catalyst, with or without trimming the first catalyst, the second catalyst, or the third catalyst.

For at least one embodiment of the catalyst system, the first catalyst is a high molecular weight component and the second catalyst is a low molecular weight component. In other words, the first catalyst may provide predominantly the high molecular weight portion of the polyethylene polymer and the second catalyst may provide predominantly the low molecular weight portion of the polyethylene polymer.

In at least one embodiment, the amount of the first or second catalyst (or catalyst trim ratio) fed, the amount of the third catalyst fed, and/or reactor conditions (e.g., pressure, temperature, and hydrogen concentration) can be varied to give a range of MI and MIR while maintaining polyethylene density. Embodiments of the methods described herein can advantageously provide a wide range of MI with the same catalyst system, e.g., the same dual catalyst system. For the catalyst system fed to the polymerization reactor, the polymers MI, MIR, and density can be controlled by varying the reactor conditions, including, for example, the reactor mixture of additional catalyst added, the operating temperature, the operating pressure, the hydrogen concentration, and the comonomer concentration in the reaction mixture.

By preparing the polymer product in one reactor rather than multiple reactors, it may be economically advantageous to use multiple procatalysts co-supported on a single support (e.g., methylaluminoxane (MAO)) mixed with the activator. In addition, the use of a single support also facilitates uniform mixing of the formed polymers while improving the process relative to preparing the mixture by post-reactor blending of polymers of different Mw and density in a single reactor independent of multiple catalysts. The catalysts may be co-supported in a single operation or may be used in a finishing operation wherein one or more additional catalysts are added to the supported catalyst.

Evidence of comonomer incorporation into the polymer is indicated by the density of the polyethylene copolymer, with lower densities indicating higher incorporation rates. The difference in density of the Low Molecular Weight (LMW) component and the High Molecular Weight (HMW) component will preferably be greater than about 0.02, or greater than about 0.04, where the HMW component has a lower density than the LMW component. Satisfactory control of the MWD results in adjustment of these factors, which can be adjusted by adjusting the relative amounts of the two metallocene catalysts used in the polymerizations of the present disclosure. In addition, the catalyst addition amount can be controlled using feedback of the obtained polymer property data.

In addition, various polymers having different MWD and LCBD can be prepared from a limited number of catalysts. In at least one embodiment, the hybrid catalyst system provides a blend of beneficial properties to the polymer due to the tailored combination of MWD, polymer branching, and BOCD. The ability to control MWD and polymer branching may be important in determining the processability and strength of the resulting polymer.

Other embodiments provide a process for producing polyethylene comprising polymerizing ethylene in a reactor in the presence of a catalyst system to form polyethylene, wherein the catalyst system comprises a first catalyst and a second catalyst, and adjusting reactor pressure, reactor temperature, reactor hydrogen concentration, and/or the amount of trim catalyst (e.g., first catalyst, second catalyst, or third catalyst) fed to the reactor to obtain a narrower range of MIR of the polyethylene while maintaining, for example, BOCD, LCB, and MI of the polyethylene. At least one embodiment provides a system and method for producing polyethylene comprising polymerizing ethylene in a reactor in the presence of a catalyst system to form polyethylene, wherein the catalyst system comprises a first catalyst and a second catalyst, and adjusting reactor conditions and the amount of trim catalyst (e.g., first catalyst, second catalyst, or third catalyst) fed to the reactor to adjust MI, BOCD, LCB and MIR of the polymer product.

Polymerization process

The polymerization process may comprise a gas phase polymerization, in particular a fluidized bed gas phase polymerization. Generally, in a gas fluidized bed process for preparing polymers, a gaseous stream comprising 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 converts to a gas during polymerization, such as isopentane, isohexane, or isobutane. The gaseous stream is withdrawn from the fluidised bed and recycled back to the reactor. Simultaneously, 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; all of which are incorporated herein by reference). The gas phase polymerization may be carried out in any suitable reactor system, for example a stirred or paddle type reactor system. 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 for a discussion of suitable gas phase fluidized bed polymerization systems, 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 can condense during polymerization to remove the heat of reaction. In some embodiments, the non-reactive alkane is selected from C ₁-C₆ alkanes, such as one or more of propane, butane, isobutane, pentane, isopentane, hexane, and 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 can be from 100psig (680 kPag) to 500psig (3448 kPag), such as from 200psig (1379 kPag) to 400psig (2759 kPag), such as from 250psig (1724 kPag) to 350psig (2414 kPag). In some embodiments, the reactor is operated at a temperature of 60 ℃ to 110 ℃, such as 60 ℃ to 100 ℃, such as 70 ℃ to 90 ℃, such as 80 ℃ to 92 ℃, such as 82 ℃. The ratio of hydrogen to ethylene may be from 8 to 30ppm/mol%, for example from 8 to 15ppm/mol%, for example from 9 to 11ppm/mol%.

The mole% of ethylene (based on total monomer) may be 25 to 90 mole%, such as 50 to 90 mole%, or 60.0 to 75.0 mole%, and the ethylene partial pressure (in the reactor) may be 75psia (517 kPa) to 300 psia (2069 kPa), or 100 to 275 psia (689 to 1894 kPa), or 150 to 265 psia (1034 to 1826 kPa), or 180 to 200 psia. The ethylene concentration in the reactor may also be in the range of 35-95 mole%, for example in the range of a lower limit of 35, 40, 45, 50 or 55 mole% to an upper limit of 70, 75, 80, 85, 90 or 95 mole%, and further wherein the ethylene mole% is measured based on the total moles of gas in the reactor, including (if present) ethylene and/or comonomer gases and one or more of inert gases such as nitrogen, isopentane or other ICA(s), etc.), as in the case of vol-ppm hydrogen, this measurement may be made in the recycle gas outlet for convenience rather than in the reactor itself. The comonomer concentration may be from 0.2 to 2 mole%, for example from a lower limit of 0.2, 0.3, 0.4 or 0.5 mole% to an upper limit of 0.65, 0.70, 0.75, 0.80, 0.85, 0.90, 0.95, 1.0, 1.5 or 2 mole%.

Polymerization using finishing

The polymerization process of the present disclosure may be performed using a "finishing" process. According to such methods, the first catalyst-containing mixture (which may be referred to as a catalyst component slurry) comprises a support material, at least one activator, and at least one catalyst compound (optionally also including a second, third, or more catalyst compounds) suspended in a suitable carrier liquid. Preferably, the catalyst component slurry comprises at least a first and a second catalyst compound.

A second catalyst-containing mixture (which may be referred to as a catalyst component solution) containing one or more catalyst compounds (e.g., a first catalyst compound and/or a second, third, fourth, etc. catalyst compound) that are the same as the catalyst compound(s) found on the supported catalyst of the slurry may be added (i.e., "trimmed") to the slurry to achieve on-line and on-line adjustment of the proportions of catalyst components in the catalyst system delivered to the polymerization reactor. Adjusting the catalyst component proportions enables one or more properties of the polymer being formed in the reactor to be adjusted, as described herein. Such "finishing" processes are very economical because they do not require stopping the polymerization to adjust polymer properties in the event that the catalyst system does not behave in the desired manner, or in the event of a desired grade change as part of the polymer production campaign.

The first catalyst and the second catalyst are described below, which together make a particularly useful dual catalyst system. Thus, these catalysts can be used in the finishing process just described. For example, the catalyst component slurry may comprise the first catalyst described below and/or the second catalyst described below (preferably both), a support, and at least one activator in a diluent. Thus, the first and/or second catalyst is preferably provided in activated form on a support in the diluent. The catalyst component solution may comprise either or both of the following first and second catalysts (preferably, the second catalyst or one of the first catalysts) suspended in a diluent (which may be the same as or different from the diluent of the slurry). Optionally, the activator may be contained in a solution. The finishing process will include introducing the catalyst component solution in-line into the catalyst component slurry to form a modified catalyst slurry comprising the catalyst system (supported, activated first and second catalysts in the desired proportions) for delivery to the polymerization reactor.

Thus, it is contemplated that for a different catalyst 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 the second catalyst added as trim to achieve the final desired ratio of the first and second catalysts. Or the slurry may include only the first catalyst or only the second catalyst and the solution may contain only the other catalyst.

In still other embodiments, either of the first catalyst and the second catalyst described below may be combined (in a finishing process or otherwise) with different catalysts in different dual catalyst systems. For example, the first catalyst described below may be combined with additional metallocene catalysts, rather than (or in addition to) the second catalyst described below, as well as with the second catalyst described below. Examples of such additional metallocene catalysts include, for example, those described in U.S. Pat. No. 5,278,272, U.S. Pat. No. 5,763,543, U.S. Pat. No. 6,255,426, and U.S. Pat. No. 7,951,873, each of which is incorporated herein by reference. For example, the catalyst may be a silica supported metallocene catalyst prepared from a composition comprising a metallocene catalyst compound and a methylaluminoxane cocatalyst. In some embodiments, the metallocene catalyst compound is rac-meso-bis (1-ethylindenyl) ₂ zirconium, dimethylsilylbis (tetrahydroindenyl) zirconium metallocene, dimethylsilylbis (tetrahydroindenyl) zirconium dimethyl, dimethylsilylbis (n-propylcyclopentadienyl) ₂ hafnium or a combination thereof.

As noted, 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 trim catalyst solution. Toluene is one example of a diluent, but other suitable diluents may include, but are not limited to, ethylbenzene, xylenes, pentanes, hexanes, heptanes, octanes, other hydrocarbons (particularly aliphatic hydrocarbons), or any combination thereof.

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

The diluent may further include a wax, which may provide an increased viscosity to the slurry (e.g., mineral oil slurry). The wax is food grade petrolatum (petrolatum) also known as petrolatum (petrolatum). The wax may be paraffin wax. Paraffin waxes include SONO JELL ^® paraffin waxes available from Sonneborn, LLC, such as SONO JELL ^® and SONO JELL ^® 9. In at least one embodiment, the slurry has 5 wt% or more wax, 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. For example, the mineral oil slurry may have about 70 wt% mineral oil, about 10 wt% wax, and about 20 wt% supported catalyst(s) (e.g., supported dual catalyst). The increased viscosity provided by the wax in the slurry (e.g., mineral oil slurry) provides reduced deposition of the supported catalyst(s) in the trim vessel (TRIM VESSEL) or catalyst tank (for introducing the supported catalyst into the pipeline). In addition, the use of mineral oil slurries with increased viscosity does not inhibit the dressing efficiency (TRIM EFFICIENCY). 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 ℃), for example 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 slurry and/or modified catalyst slurry may be further conveyed with a carrier fluid, which may advantageously comprise a fluid that is otherwise used in the polymerization. For example, in gas phase polymerization, molecular nitrogen, induced condensing agent (ICA (s)) and/or recycle gas may be used to carry the catalyst slurry and/or modified catalyst slurry (recycle gas typically includes one or more of nitrogen, ICA (s)) and gaseous monomer/comonomer. ICA may be or include, but is not limited to, one or more alkanes. Illustrative alkanes may be or include, but are not limited to, propane, n-butane, isobutane, n-pentane, isopentane, neopentane, n-hexane, isohexane, n-heptane, n-octane, or any mixture thereof. Further details on inducing condensing agents can be found in U.S. Pat. Nos. 5,352,749, 5,405,922, 5,436,304 and 7,122,607, and International patent application publication No. WO 2005/113615 (A2).

In some embodiments, the catalyst is not limited to slurry and/or trim configurations, as the mixed catalyst system may be prepared on a support and dried. The dried catalyst system may then be fed to the reactor via a dry feed system.

In a gas phase polyethylene production process, 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, affects or drives the static charge (negative, positive, or to zero) 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 being prepared and the single site catalyst compound being used.

Control agents such as aluminum stearate may be used. The static control agent used may be selected based on 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.

First catalyst

The first catalyst may be unsupported or supported on a support material.

In some embodiments, the first catalyst is an unbridged metallocene catalyst represented by the following formula (I):

Wherein M is a group 4 metal ;R¹、R²、R³、R⁴、R⁵、R⁶、R⁷、R⁸、R⁹、R¹⁰、R¹¹、R¹²、R¹³ and R ¹⁴ are each independently hydrogen, substituted or unsubstituted hydrocarbyl, A substituted or unsubstituted heteroatom or a substituted or unsubstituted heteroatom-containing group, or one or more pairs of R ¹ and R ²、R⁴ and R ⁵、R⁵ and R ⁶、R⁶ and R ⁷、R⁹ and R ¹⁰、R¹¹ and R ¹²、R¹² and R ¹³ and R ¹³ and R ¹⁴ are linked to form a substituted or unsubstituted fully saturated ring, Or a substituted or unsubstituted aromatic ring, wherein at least one pair of R ⁴ and R ⁵、R⁵ and R ⁶ or R ⁶ and R ⁷ is linked to form a first substituted or unsubstituted fully saturated ring fused to an indenyl ring, and at least one pair of R ¹¹ and R ¹²、R¹² and R ¹³ or R ¹³ and R ¹⁴ is linked to form a second substituted or unsubstituted fully saturated ring fused to an indenyl ring, wherein if R ¹² and R ¹³ are linked to form a substituted or unsubstituted fully saturated ring, R ⁹ is not a substituted or unsubstituted hydrocarbyl group, wherein if R ⁵ and R ⁶ are linked to form a substituted or unsubstituted fully saturated ring, R ² is not a substituted or unsubstituted hydrocarbyl group, and each X is independently a halo group, a substituted or unsubstituted hydrocarbyl, a hydrogen group, an amino group, a substituted or unsubstituted alkoxy group, a thio group, a phosphorus group, or combinations thereof, or two of X are joined together to form a substituted or unsubstituted metallocycle ring, or two of X are joined to form a chelating ligand, a diene ligand, or an alkylidene group.

In some embodiments, each of R ⁴、R⁵、R⁶、R⁷、R¹¹、R¹²、R¹³ and R ¹⁴ of formula (I) is independently hydrogen or C ₁-C₁₀ alkyl (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, or decyl), wherein at least one pair of (1) R ⁴ and R ⁵、(2)R⁵ and R ⁶ or (3) R ⁶ and R ⁷ are linked to form a first substituted or unsubstituted fully saturated ring fused to an indenyl ring shown in formula (I), and at least one pair of (1) R ¹¹ and R ¹²、(2)R¹² and R ¹³ or (3) R ¹³ and R ¹⁴ are linked to form a second substituted or unsubstituted fully saturated ring fused to an indenyl ring shown in formula (I).

In some embodiments, at least one pair of (1) R ⁴ and R ⁵,(2)R⁵ and R ⁶ or (3) R ⁶ and R ⁷ is linked to form a first substituted or unsubstituted fully saturated ring fused to an indenyl ring shown in formula (I). In some embodiments, R ⁴ and R ⁵ are linked 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 condensed with the indenyl ring shown in the formula (I). In some embodiments, R ⁵ and R ⁶ are linked 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 condensed with the indenyl ring shown in the formula (I). In some embodiments, R ⁶ and R ⁷ are linked 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 condensed with the indenyl ring shown in the formula (I).

In some embodiments, at least one pair of (1) R ¹¹ and R ¹²、(2)R¹² and R ¹³ or (3) R ¹³ and R ¹⁴ is linked to form a first substituted or unsubstituted fully saturated ring fused to an indenyl ring shown in formula (I). In some embodiments, R ¹¹ and R ¹² are linked 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 condensed with the indenyl ring shown in the formula (I). In some embodiments, R ¹² and R ¹³ are linked 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 condensed with the indenyl ring shown in the formula (I). In some embodiments, R ¹³ and R ¹⁴ are linked 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 condensed with the indenyl ring shown in the formula (I).

In some embodiments, each of R ¹、R²、R³、R⁸、R⁹ and R ¹⁰ of formula (I) is hydrogen or C ₁-C₁₀ alkyl (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, or decyl). In some embodiments, each of R ¹、R²、R³、R⁸、R⁹ and R ¹⁰ is independently hydrogen, methyl, ethyl, or propyl. in some embodiments, each of R ¹、R²、R³、R⁸、R⁹ and R ¹⁰ is hydrogen. In some embodiments, each of R ¹、R²、R³、R⁸、R⁹ and R ¹⁰ is methyl. In some embodiments, at least one of R ³ and R ¹⁰ is C ₁-C₁₀ alkyl. In some embodiments, each of R ³ and R ¹⁰ is independently C ₁-C₁₀ alkyl. In some embodiments, each of R ³ and R ¹⁰ is independently C ₁-C₁₀ alkyl (e.g., methyl), and R¹、R²、R⁴、R⁵、R⁶、R⁷、R⁸、R⁹、R¹¹、R¹²、R¹³ and R ¹⁴ are hydrogen.

In some embodiments, one or more of R¹、R²、R³、R⁴、R⁵、R⁶、R⁷、R⁸、R⁹、R¹⁰、R¹¹、R¹²、R¹³ and R ¹⁴ of formula (I) are independently hydrogen, hydrocarbyl, silylhydrocarbyl (silylcarbyl), alkoxy, halo, or siloxy (siloxyl).

In some embodiments of formula (I), M is a group 4 metal, such as titanium (Ti), zirconium (Zr), or hafnium (Hf), such as 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, chlorine, fluorine, bromine, iodine, triflate (trifluoromethanesulfonate), dimethylamino (dimethylamido), diethylamino (diethylamido), dipropylamino (dipropylamido), and diisopropylamino (diisopropylamido).

In some embodiments of formula (I), (1) M is Zr or Hf, (2) X is chloro, (3) R ¹、R²、R³、R⁴、R⁵、R⁶ and R ⁷ are independently hydrogen or substituted or unsubstituted C ₁-C₁₀ alkyl, (4) R ⁸、R⁹、R¹⁰、R¹¹、R¹²、R¹³ and R ¹⁴ are independently hydrogen or substituted or unsubstituted C ₁-C₁₀ alkyl, (5) at least one of R ³ and R ¹⁰ is C ₁-C₁₀ alkyl, (6) at least one pair of R ⁴ and R ⁵、R⁵ and R ⁶ or R ⁶ and R ⁷ are linked to form a substituted fully saturated ring fused to an indenyl ring of formula (I), and (7) R ¹¹ and R ¹²、R¹² and R ¹³ or R ¹³ and R ¹⁴ are linked to form a substituted fully saturated ring fused to an indenyl ring of formula (I).

The first catalyst may be, for example, an unbridged metallocene catalyst represented by formula (II):

Wherein:

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

R¹、R²、R³、R⁴、R⁷、R⁸、R⁹、R¹⁰、R¹¹、R¹⁴、R¹⁵、R^15'、R¹⁶、R^16'、R¹⁷、R^17'、R¹⁸、R^18'、R¹⁹、R^19'、R²⁰、R^20'、R²¹、R^21'、R²² And each of R ^22' is independently hydrogen, substituted or unsubstituted hydrocarbyl, substituted or unsubstituted heteroatom, or substituted or unsubstituted heteroatom-containing group, and

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

In some embodiments, each of R⁴、R⁷、R¹¹、R¹⁴、R¹⁵、R^15'、R¹⁶、R^16'、R¹⁷、R^17'、R¹⁸、R^18'、R¹⁹、R^19'、R²⁰、R^20'、R²¹、R^21'、R²² and R ^22' of formula (II) is independently hydrogen or C ₁-C₁₀ alkyl (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, or decyl). In some embodiments, each of R ¹⁵、R^15'、R¹⁸、R^18'、R¹⁹、R^19'、R²² and R ^22' is independently hydrogen, methyl, ethyl, or propyl. In some embodiments, each of R ¹⁵、R^15'、R¹⁸、R^18'、R¹⁹、R^19'、R²² and R ^22' is hydrogen. In some embodiments, each of R ¹⁵、R^15'、R¹⁸、R^18'、R¹⁹、R^19'、R²² and R ^22' is C ₁-C₁₀ alkyl (e.g., methyl). In some embodiments each of ,R⁴、R⁷、R¹¹、R¹⁴、R¹⁶、R^16'、R¹⁷、R^17'、R²⁰、R^20'、R²¹ and R ^21' is hydrogen.

In some embodiments, each of R ¹、R²、R³、R⁸、R⁹ and R ¹⁰ of formula (II) is hydrogen or C ₁-C₁₀ alkyl (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, or decyl). In some embodiments, each of R ¹、R²、R³、R⁸、R⁹ and R ¹⁰ is independently hydrogen, methyl, ethyl, or propyl. in some embodiments, each of R ¹、R²、R³、R⁸、R⁹ and R ¹⁰ is hydrogen. In some embodiments, each of R ¹、R²、R³、R⁸、R⁹ and R ¹⁰ is methyl. In some embodiments, at least one of R ³ and R ¹⁰ is C ₁-C₁₀ alkyl. In some embodiments, each of R ³ and R ¹⁰ is independently C ₁-C₁₀ alkyl. In some embodiments, R ³ and R ¹⁰ are C ₁-C₁₀ alkyl (e.g., methyl), and R ¹、R²、R⁸ and R ⁹ are hydrogen.

In some embodiments of formula (II), M is a group 4 metal, such as titanium (Ti), zirconium (Zr), or hafnium (Hf), such as 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 (II), (1) M is Zr or Hf, (2) X is chloro ,(3)R¹、R²、R³、R⁴、R⁷、R¹⁵、R^15'、R¹⁶、R^16'、R¹⁷、R^17'、R¹⁸ and R ^18' are independently hydrogen or substituted or unsubstituted C ₁-C₁₀ alkyl ,(4)R⁸、R⁹、R¹⁰、R¹¹、R¹⁴、R¹⁹、R^19'、R²⁰、R^20'、R²¹、R^21'、R²² and R ^22' are independently hydrogen or substituted or unsubstituted C ₁-C₁₀ alkyl, and (5) at least one of R ³ and R ¹⁰ is C ₁-C₁₀ alkyl.

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

Second catalyst

The second catalyst of the present disclosure includes a second catalyst, which may be unsupported or supported on a support along with the first catalyst to form a dual catalyst system. The second catalyst may be unsupported or supported and the dual catalyst system may be isolated. Or the second catalyst may be provided as a "trim" catalyst to the supported first catalyst, for example, on-line 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 a bridged metallocene catalyst represented by the following formula (III):

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 (preferably one pair of R ⁷ and R ⁸、R⁸ and R ⁹ and R ⁹ and R ¹⁰) are linked to form a substituted or unsubstituted fully saturated ring or a substituted or unsubstituted aromatic ring fused to an indenyl ring shown in formula (III);

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

In some embodiments, each of R ⁷、R⁸、R⁹ and R ¹⁰ of formula (III) is independently hydrogen or C ₁-C₁₀ alkyl (e.g., 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, are linked to form a substituted or unsubstituted fully saturated ring fused to an indenyl ring shown in formula (III). The substituted or unsubstituted ring may be, for example, a C ₅、C₆ or C ₇ ring fused with an indenyl ring shown in formula (III).

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

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, 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 (III) are independently hydrogen, hydrocarbyl, silylhydrocarbyl, 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, 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, each X is chloro.

In some embodiments of formula (III), (1) M is Zr or Hf, (2) X is chloro, (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 linked to form a substituted or unsubstituted fully saturated ring fused to an indenyl ring shown in formula (III), and (6) R ¹、R²、R³ and R ⁴ are independently methyl, ethyl or propyl.

In some embodiments of formula (III), the second catalyst is:。

Or the second catalyst may be an analog of the catalyst just shown, wherein ZrCl ₂ is replaced with ZrMe ₂ (i.e., the catalyst may be a zirconium dimethyloxide analog of the catalyst just shown). Additionally or alternatively, the second catalyst of the various embodiments may be according to the catalyst formula just shown, except that any one or more of the methyl side chains on the cyclopentadienyl moiety are replaced by a C ₂-C₁₀ alkyl group (preferably ethyl or propyl).

In still other embodiments, the above description of the second catalyst of formula (III) may be as just described, except that in these embodiments at least one pair of R ⁷ and R ⁸、R⁸ and R ⁹ or R ⁹ and R ¹⁰ are linked to form a substituted or unsubstituted aromatic ring fused to the indenyl ring of formula (III), instead of at least one pair of R ⁷ and R ⁸、R⁸ and R ⁹ or R ⁹ and R ¹⁰ being linked to form a substituted or unsubstituted fully saturated ring fused to the indenyl ring shown in formula (III). Thus, specific examples of catalysts according to such embodiments include:

Or any one or more of the methyl side groups on the cyclopentadienyl moiety in the catalyst formula just shown may alternatively be a C ₂-C₁₀ alkyl group (preferably ethyl or propyl).

Activating agent

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

The catalyst systems described herein may include the catalyst compound(s) 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 in the literature, including combining them with a support such as silica. The catalyst system may also be added to or result from solution polymerization 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 above-described catalyst compounds 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 may include aluminoxane compounds, modified aluminoxane compounds, and ionizing anion precursor compounds that abstract reactive, sigma-bonded metal ligands, thereby cationizing the metal compounds and providing charge-balancing non-coordinating or weakly coordinating anions, such as non-coordinating anions.

In some embodiments, the catalyst system comprises an activator and a catalyst compound of formula (I), formula (II), and/or formula (III).

Aluminoxane activator

Aluminoxane activators are useful as activators 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, for example when the abstractable ligand is an alkyl, halogen, alkoxy or amino (amide). Mixtures of different aluminoxanes and modified aluminoxanes can also be used. Optically transparent methylaluminoxane may be suitably used. The cloudy or gel aluminoxane can be filtered to prepare a clear solution or the clear aluminoxane can be decanted from the cloudy solution. Useful aluminoxanes are Modified Methylaluminoxane (MMAO) co-catalyst type 3A (commercially available from Akzo Chemicals, inc. Under the trade name modified methylaluminoxane type 3A, covered by U.S. Pat. No. 5,041,584, incorporated herein by reference). Another useful aluminoxane is solid polymethylaluminoxane, as described in US 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, an activator amount of up to 5,000-fold molar excess of Al/M relative to the catalyst compound (per metal catalytic site) may be used. The minimum activator to catalyst compound ratio may be 1:1 molar ratio. Alternative ranges may include about 1:1 to about 500:1, or about 1:1 to about 200:1, or about 1:1 to about 100:1, or about 1:1 to about 50:1.

In an alternative embodiment, little or no aluminoxane is used in the polymerization process described herein. For example, the aluminoxane can be present in a zero mole percent, alternatively, the aluminoxane can be present in a mole ratio of aluminum to catalyst compound transition metal 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) refers to an anion that is not or only weakly coordinated to the cation, and thus remains 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 is decomposed. In addition, the anion does not transfer an anionic substituent or fragment to the cation, allowing it to form a neutral transition metal compound and a neutral by-product from the anion. Non-coordinating anions that can be used in accordance with the present disclosure are anions that are compatible in the sense that they stabilize the transition metal cation at +1 in the sense that their ionic charge is balanced, yet remain sufficiently labile to allow for displacement during polymerization. Suitable ionizing activators may include NCA, such as compatible NCA. It is within the scope of this disclosure to use ionizing activators (neutral or ionic). 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 a description of some suitable activators and activator combinations, as well as the relative amounts of activators and catalyst compounds, and optional chain transfer agents used in combination with these catalyst compounds, see U.S. 8,658,556 and U.S. 6,211,105, which are incorporated herein by reference, and U.S. patent publication No. 2021/0179650, particularly paragraphs [0084] to [0135] of WIPO patent publication No. WO2021/257264, which descriptions are incorporated herein by reference (including the various descriptions incorporated herein by reference, e.g., pages WO2004/026921, 72, paragraphs [00119] to 81, and WO2004/046214, 72, paragraphs [00177] to 74, paragraphs [ 00178).

Further, the catalyst system of the present disclosure may comprise a metal hydrocarbenyl chain transfer agent represented by the following formula:

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 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 an inorganic oxide. 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 used 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 supports may include magnesia, titania, zirconia, montmorillonite, phyllosilicate, zeolite, talc, clay. Furthermore, 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 700m ²/g, a pore volume of about 0.1cm ³/g to about 4.0cm ³/g, and an average particle size of about 5 μm to about 500 μm. The support material may have a surface area of about 50m ²/g to about 500m ²/g, a pore volume of about 0.5cm ³/g to about 3.5cm ³/g, and an average particle size of about 10 μm to about 200 μm. For example, the support material may have a surface area of about 100m ²/g to about 400m ²/g, a pore volume of about 0.8cm ³/g to about 3cm ³/g, and an average particle size of about 5 μm to about 100 μm. The average pore size of the support materials useful in the present disclosure may be from about 10 a to about 1000 a, such as from about 50 a to about 500 a, 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 = 300 m ²/gm; pore volume 1.65 cm ³/gm). For example, a suitable silica may be one sold under the trade name Davison ^TM 952 or Davison ^TM 955 by Davison Chemical Division of w.r. Grace and Company. In other embodiments DAVISON ^TM 948 is used. Or the silica may be, for example, ES-70 ^TM silica (PQ Corporation, malvern, pennsylvania) that has been calcined (e.g., calcined at 875 ℃).

The support material should be dry, i.e. free or substantially free of adsorbed water. Drying of the support material may be carried out by heating or calcining at a temperature of from about 100 ℃ to about 1000 ℃, for example 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 ℃, for example about 600 ℃, and maintained for a period of time 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 make 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.

The support material having reactive surface groups (e.g., hydroxyl groups) is slurried in a non-polar diluent and the resulting slurry is contacted with a solution of the catalyst compound and the activator. In at least one embodiment, the slurry of support material is first contacted with the activator for a period of time ranging from about 0.5 h to about 24 h, 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 isolated 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 ranging from about 0.5 h to about 24 h, 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 catalyst(s), activator(s) and support is heated to about 0 ℃ to about 70 ℃, e.g., about 23 ℃ to about 60 ℃, e.g., at room temperature. The contact time may be from about 0.5 hours to about 24 hours, such as from about 2 hours to about 16 hours, or from about 4 hours to about 8 hours.

Suitable non-polar diluents are materials in which all of the reactants (e.g., activators and catalyst compounds) used herein are at least partially soluble and are liquid or gaseous at the reaction temperature. The nonpolar diluent may be an alkane such as isopentane, hexane, n-heptane, octane, nonane, and decane, but various 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, broad Orthogonal Composition Distribution (BOCD), and bimodal composition distribution. The combination of long chain branching and BOCD may be particularly advantageous for achieving a strong balance of excellent mechanical properties and excellent workability. Thus, the polyethylene copolymer and films thereof can be formed by commercially desirable polymerization and extrusion of the polyethylene copolymer.

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

A density in the range of about 0.910 to about 0.925g/cm ³, such as from a lower limit of any of 0.910, 0.912, 0.914, 0.915, 0.916, 0.917, 0.918, 0.919, or 0.92g/cm ³ to an upper limit of any of 0.925, 0.924, 0.923, 0.922, 0.921, 0.920, or 0.919g/cm ³, such as about 0.915g/cm ³ to about 0.920g/cm ³, or about 0.918g/cm ³ to about 0.922g/cm ³, with the proviso that the upper limit is greater than the lower limit, such as about 0.916 to about 0.921g/cm ³, such as about 0.918 to about 0.92g/cm ³.

Melt index (MI, also referred to as I ₂ or I _2.16, considering the 2.16kg load used in the test) is about 0.1 or greater g/10min (ASTM D1238,190 ℃,2.16 kg), e.g., from a lower limit of 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 1.5g/10 min to an upper limit 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, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3, 4, or 5g/10min, wherein ranges from any lower limit to any upper limit (provided that the upper limit is greater than the lower limit) are contemplated herein, such as from about 0.1 to about 1.2g/10min, such as from about 0.3 to about 1.1g/10min, such as from about 0.7 to about 1.1, 1.2, or 1.3g/10min, and the like.

In addition, 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 contain 3 to 12 carbon atoms, or 4 to 10 carbon atoms, or 4 to 8 carbon atoms. The olefin comonomer may be selected from 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 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 be in the range of about 0.1, 5, 5.5, 6, 6.5, 7, 7.5, 8 or 8.5 weight percent lower limit to about 20, 15, 13, 12.5, 12, 11.5, 11, 10.5, 10, 9.5 or 9 weight percent upper limit based on the total weight of monomers in the polyethylene copolymer. The balance of polyethylene comonomer is made up of units derived from ethylene (e.g., from a lower limit of about 80, 85, 88, 90, 91, 92, 92.5, 93, 93.5, or 94 wt% to an upper limit of about 90, 91, 92, 92.5, 93, 93.5, 94, 94.5, 95, 95.5, 96, 97, 99, or 99.9 wt%). Ranges from any of the foregoing lower limits to any of the foregoing upper limits are contemplated herein (e.g., from about 85 to about 93 weight percent, such as from about 87 to about 90 weight percent, of ethylene-derived units and the balance olefin comonomer-derived content).

Molecular weight Properties

The polyethylene copolymer may also have a molecular weight distribution (MWD, defined in the context of polymer properties as Mw/Mn, sometimes also referred to as polydispersity index (PDI)) of about 5 to about 15. The MWD or PDI may also be within a range from a lower limit of about 5, 5.1, 5.2, 5.3, 5.4, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, or 9 to an upper limit of about 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, 10, 10.5, 11, 12, 13, 14, or 15, where any of the foregoing lower limits to any of the foregoing upper limits are contemplated, provided that the upper limit of the range is greater than the lower limit (e.g., within a range of 7 to 15, such as 8 to 12 or 7 to 10, etc.).

The weight average molecular weight (Mw) of the polyethylene copolymer of various embodiments may be in the range of about 70,000 to about 200,000g/mol, such as about 75,000, about 80,000, or about 90,000 to about 125,000, 130,000, 135,000, 140,000, 145,000, or 150,000g/mol, such as about 90,000 to about 130,000g/mol, such as about 120,000 to about 130,000g/mol, with ranges from any of the foregoing lower limits to any of the foregoing upper limits being contemplated.

The number average molecular weight (Mn) of the polyethylene copolymers of various embodiments may range from about 10,000 to about 40,000g/mol, such as from about 10,000 to about 15,000g/mol, 20,000g/mol, 25,000g/mol, or about 30,000g/mol, such as from about 12,000 to about 15,000g/mol, with ranges from any of the foregoing lower limits to any of the foregoing upper limits being contemplated.

The polyethylene copolymer of various embodiments may have a Z average molecular weight (Mz) in the range of about 300,000 to about 1,200,000g/mol, such as in the range of any of about 300,000, 400,000, 500,000, 600,000, or 650,000 to about 750,000, 800,000, 850,000, 900,000, 950,000, 1,000,000, 1,100,000, or 1,200,000g/mol, where any of the foregoing lower limits to any of the foregoing upper limits (e.g., in the range of about 650,000 to about 750,000g/mol, or about 400,000 to about 800,000g/mol, or about 500,000 to about 1,000,000g/mol, etc.) are also contemplated herein.

The distribution and the components (movement) of the molecular weights (Mw, mn, mw/Mn, etc.) and of the branching index (g' vis) are determined by using high temperature gel permeation chromatography (Polymer Char GPC-IR) equipped with an infrared detector IR5 based on a multichannel band pass filter, an 18-angle WYATT DAWN Heleos light scattering detector and a 4-capillary viscometer with a Wheatstone bridge configuration. Three AGILENT PLGEL, 10 μm hybrid-B LS columns were used to provide polymer separation. Aldrich reagent grade 1,2, 4-Trichlorobenzene (TCB) containing 300 ppm antioxidant Butylated Hydroxytoluene (BHT) was used as mobile phase. The TCB mixture was filtered through a 0.1 μm 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 injection volume was 200 μl. An oven maintained at 145 ℃ was charged with the entire system including the transfer line, column, and viscometer detector. The polymer sample was weighed and sealed in a standard vial to which 80 μl of flow marker (heptane) was added. After loading the vial into the autosampler, the polymer was automatically dissolved in the instrument with 8mL of added TCB solvent. The polymer was dissolved with continuous vibration at 160 ℃ for about 2 hours. The concentration (c) of each point in the chromatogram is calculated from the IR5 broadband signal intensity (I) minus the baseline using the equation c=βi, where β is the mass constant. Mass recovery was calculated from the ratio of the integrated area of concentration chromatography to the elution volume and injection mass was equal to the predicted concentration times the injection loop volume. Conventional molecular weights (IR MW) were determined by combining a universal calibration relationship with column calibration with a series of 700 to 10 million g/mol monodisperse Polystyrene (PS) standard samples. MW at each elution volume was calculated by the following equation:

Wherein the variables with the subscript "PS" represent polystyrene, and those without the subscript are test samples. In this method, α _PS =0.67 and K _PS = 0.000175, while α and K are for ethylene-hexene copolymers, as calculated by the empirical formula (Sun, t. Et al Macromolecules 2001,34,6812), where α=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 standard samples, the nominal values of which are predetermined by NMR or FTIR. Here, the concentration is expressed in g/cm ³, the molecular weight is expressed in g/mol, and the intrinsic viscosity (and thus K in the Mark-Houwink equation) is expressed in dL/g. Unless otherwise indicated herein, any molecular weight value should be assumed to be determined using IR.

Light Scattering MW for any molecular weight value indicated as determined by LS, the LS molecular weight (M) at each point in the chromatogram is determined by analyzing the LS output using a 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 linear 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 Aldade constant and (dn/dc) is the refractive index increment of the system. TCB has a refractive index n=1.500 at 145 ℃ and λ=665 nm. For the purposes of this disclosure and the appended claims, (dn/dc) of ethylene-hexene copolymer= 0.1048.

Viscosity average molecular weight (M _V) 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 and the other sensor between the sides of the bridge measures the pressure difference. The specific viscosity η _s of the solutions flowing through the viscometer is calculated from their outputs. The intrinsic viscosity [ eta ] at each point in the chromatogram is calculated by the equation [ eta ] = eta _s/c, where c is the concentration and is determined by the IR5 broadband channel output. The viscosity MW at each point was calculated asWherein α _ps is 0.67 and Kps is 0.000175. The average intrinsic viscosity [ eta ] _{Average of} of the sample was calculated by the following formula:

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

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

According to this principle, the [ eta _Polymer ] value in the above simplified relationship can be regarded as the weight average intrinsic viscosity [ eta ] _{Average of} of the sample, which is calculated by the following formula (where [ eta ] _avg represents [ eta ] _{Average of}):

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

The branching index g ' vis may be equivalently referred to as g ' _{vis Average of} to reflect that it is the average of g ' measured at each of a plurality of discrete concentration slices. For example, referring to fig. 1, g 'of various polyethylene copolymers plotted as a function of log m (log of molecular weight) can be seen, which means that the g' value can be calculated for a population of polymer chains of a given molecular weight in the polyethylene copolymer composition. The above calculation provides g '_{vis Average of} as a weighted average of these multiple g' values, and when comparing such values between two different copolymer compositions, g '_{vis Average of} can be regarded as a good relative indicator of the presence of long chain branching, where a lower g' _{vis Average of} indicates a 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 in the high molecular weight chains or materials of the polyolefin polymer or composition. For example, the distribution of short chain branches can be measured using Temperature Rising Elution Fractionation (TREF) along with a Light Scattering (LS) detector to determine the weight average molecular weight of molecules eluting from the TREF column at a given temperature. The combination of TREF and LS (TREF-LS) yields information about the breadth of the composition distribution and whether the comonomer content increases, decreases or is uniform along 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 very low composition distribution breadth index (CBDI) value, where the polyethylene copolymer may have a CBDI ranging from a lower limit of any of about 5%, 10%, 15%, 20%, 22%, 23%, 24%, 25%, or 26% to an upper limit of any of about 30%, 31%, 32%, 33%, 34%, 35%, 40%, 45%, or 50%, where any of the foregoing lower limits to any of the foregoing upper limits (e.g., about 5% to about 35%, such as about 20% to about 30%) are contemplated herein.

CDBI is defined as the weight percent of copolymer molecules having a comonomer content within +/-50% of the median mole% value of the comonomer, as described in FIG. 17 incorporated herein on pages 18-19 of WO 1993/003093. This means that for copolymers having a median comonomer mole% value (Cmed) of 8 mole% comonomer on the polymer chain, CDBI is the weight% of copolymer chains having a comonomer mole% between (0.5 x Cmed) and (1.5 x Cmed). In this example, the CDBI is the weight% of copolymer chains having a comonomer mole% between (0.5 x 8) and (1.5 x 8) or a comonomer content between 4 mole% and 12 mole%. WO 1993/003093 also describes a method for determining the weight fraction vs. composition curve (i.e. composition profile) of a polymer using chromatography and C13NMR and determining therefrom the median comonomer composition Cmed, see fig. 16 and 17 of this publication. The CDBI of a copolymer is readily determined using techniques for isolating individual fractions of a copolymer sample. One such technique is to use Temperature Rising Elution Fractionation (TREF) to generate a solubility profile as described in WO 1993003093 (which in this respect is also referred 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 a TREF technique (as described, for example, in the publications just cited). This solubility profile is a graph of the weight fraction of dissolved copolymer as a function of temperature. Such a curve can be converted into a weight fraction versus composition distribution curve. To simplify the dependence of the composition on the elution temperature, weight fractions of less than 15,000 can be omitted. These low weight fractions generally represent a trivial portion of the ethylene-based polymers disclosed herein.

Alternatively or additionally, the composition profile 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 vs. elution temperature) as described in US 2019/019413 (especially in the first paragraph thereof, the description of which is incorporated herein by reference). The narrow composition distribution is reflected in the smaller differences in the T ₇₅-T₂₅ values, while the broad distribution is reflected in the larger differences in the T ₇₅-T₂₅ values, which means that the crystallinity differences between the fractions of the polymer composition are larger. It should also be noted that in case there is a difference between the actual TREF procedure vs. as described in US 2019/019413, 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. (note that the solubility profile of the co-TREF program generated curve-CDBI and the eluted molecular weight vs. elution temperature of T ₇₅-T₂₅, which may have appropriate differences in their generation and analysis of CDBI and T ₇₅-T₂₅.) finally, the generated TREF curve (eluted polymer molecular weight vs. elution temperature) measured in conjunction with 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. Only the solvent response can be produced by running the same method as for the polymer sample, typically prior to the method, but without adding any polymer to the sample vial, using the same solvent reservoir as the polymer sample, and without replenishing fresh solvent, and within a reasonable close time of running the polymer sample.

The temperature axis of the tref curve can be shifted appropriately to correct for delays in the IR signal caused by 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 into the column where the sample was loaded for TREF analysis, then using isothermal methods to direct the hot solution to the detector at a constant flow rate of 1ml/min, and then measuring the time that the HDPE probe peak appears in the IR signal after injection. Thus, the delay volume (ml) is equivalent to the time (min).

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 the polyethylene copolymers of the invention, the broad distribution is reflected in a greater difference in T ₇₅-T₂₅ values of greater than 25 ℃, such as in the range of a lower limit of any of 25, 26, 27, 28, 29, 30, 31, 32, or 33 ℃ to an upper limit of any of 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, or 50 ℃, with ranges from any of the foregoing lower limits to any of the foregoing upper limits (e.g., 25 ℃ to 50 ℃, such as 25 ℃ to 40 ℃ or 30 ℃ to 38 ℃) being contemplated.

Additional polyethylene copolymer rheology

In addition to the Melt Index (MI) values previously mentioned, the polyethylene copolymer may have a High Load Melt Index (HLMI) ranging from a lower limit of about 20, 40, 60, 65, 70, 75, 80, or 85g/10 min to an upper limit of about 120, 110, 100, 95, 90, 85, or 80g/10 min (identifying the 21.6kg load used in the test, also referred to as I ₂₁ or I _21.6), any of which lower limit is contemplated herein to any of the upper limits previously described (e.g., about 60 to about 100g/10min, such as about 80 to about 90g/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 inversely proportional to 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 lower limit of any of 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 71, 72, 73, 74, or 75 to an upper limit of any of 80, 85, 90, 95, 96, 97, 98, 99, 100, 105, 110, 120, 130, 140, or 150, and any of the foregoing lower limits to any of the foregoing upper limits (e.g., 60 or 70 to 105, or 90 to 97 or 70 to 80, etc.) contemplated herein.

As noted, the polyethylene copolymers of the various embodiments may also exhibit medium long chain branching, less than existing LDPE (produced in free radical polymerization with large changes in polymer branching direction and little control over polymer branching direction), but greater than typical metallocene LLDPE. Such moderate amounts of LCB may be demonstrated via, for example, high MIR (as described above) and/or specific rheological properties (e.g., ratios of η _0.01/η₁₀₀, ratios of complex viscosities recorded at shear rates or frequencies of 0.01 and 100 rad/s, respectively) as shown by data obtained by SAOS experiments.

For example, the polyethylene copolymer may have a higher shear thinning index (STI 0.1/100). STI0.1/100 data measures the ratio of complex viscosities at 0.1 and 100 rad/s. The polyethylene copolymer of various embodiments may have STI0.1/100 data greater than 5, such as greater than 6 or even higher. For example, STI0.1/100 may range from a lower limit of any of about 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55 to an upper limit of any of about 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, or 10, with ranges from any of the foregoing lower limits to any of the foregoing upper limits (e.g., about 10 to about 50, such as about 20 to about 40, such as about 25 to about 35) also contemplated.

Further, the LCB or branching index (referred to herein as g '_vis or may also be referred to as g' _{vis Average of}) may be less than 1, for example in the range from a lower limit of any of about 0.67, 0.68, 0.69, 0.70, or 0.71 to an upper limit of any of about 0.73, 0.74, 0.75, 0.76, 0.77, 0.78, 0.79, 0.80, 0.83, 0.85, 0.87, or 0.9, with ranges from any of the foregoing lower limits to any of the foregoing upper limits (e.g., 0.71 to 0.73 or 0.65 to 0.75) being contemplated.

Additionally or alternatively, the polyethylene copolymer may have a G'/g″ at 0.1s ^-1 value (which is a ratio of shear storage modulus (Pa) to shear loss modulus (Pa) at 0.1s ^-1) in the range of from a lower limit of any of 0.5, 0.75, 1.0, 1.25, or 1.5 to an upper limit of any of 2.0, 2.5, 3.0, 3.5, 4.0, or 4.5, or about 0.5 or greater, or about 1.0 or greater, or about 1.25 or greater.

Rheological data, such as "complex shear viscosity (η)", reported in pascal seconds, can be measured at 0.01rad/sec and 100 rad/sec. Complex shear viscosity and other rheological measurements can be obtained from Small Angle Oscillatory Shear (SAOS) experiments.

For example, complex shear viscosity can be measured in dynamic mode under nitrogen atmosphere using a parallel plate (diameter=25 mm) with a rotational rheometer such as Advanced Rheometrics Expansion System (ARES-G2 type) or Discovery Hybrid Rheometer (DHR-3 type). The rheometer can be thermally stable at 190 ℃ for at least 20 minutes prior to inserting the compression molded sample onto the parallel plates. To determine the viscoelastic behaviour of a sample, a frequency sweep in the range of 0.01 to 628rad/s can be performed at a temperature of 190 ℃ under a constant strain that does not affect the measured viscoelastic properties. The scanning frequencies are equally spaced on a logarithmic scale such that 5 frequencies are detected per decade. Depending on molecular weight and temperature, a strain of 3% can be used and the linearity of the response verified. A nitrogen stream was circulated through the oven to minimize chain extension or crosslinking during the experiment. The samples can be compression molded at 190 ℃ without stabilizers. Sinusoidal shear strain may be applied. If the strain amplitude is small enough, the material exhibits linear behavior. As will be appreciated by those skilled in the art, the resulting steady state stress will also oscillate in a sinusoidal manner at the same frequency, but will shift the phase angle δ with respect to the strain wave. The stress leads the strain delta. For a purely elastic material, δ=0 ^o (stress is in phase with strain), and for a purely viscous material, δ=90 ^o (stress leads strain 90 ^o, although stress is in phase with strain rate). For viscoelastic materials, 0< delta <90. The complex viscosity, loss modulus (G "), and storage modulus (G') as a function of frequency were provided by a small amplitude oscillatory shear test. Dynamic viscosity is also known as complex viscosity or dynamic shear viscosity. The phase angle or loss angle δ is the arctangent of the ratio of G "(shear loss modulus) to G' (shear storage modulus). The Shear Thinning Slope (STS) may be measured using a plot of the logarithm of the dynamic viscosity (dynamic viscosity) (base 10) versus the logarithm of the frequency (base 10). The slope is the difference between the log (dynamic viscosity) at a frequency of 100s ^-1 and the log (dynamic viscosity) at a frequency of 0.01s ^-1 divided by 4. The complex shear viscosity (η) versus frequency (ω) curve may be fitted using a Carreau-Yasuda model:

。

Five parameters in this model are η ₀, zero shear viscosity, λ, relaxation time, n, power law index, η infinity, infinite rate viscosity, and a, transition index. When the dynamic viscosity is independent of frequency, the zero shear viscosity is a value at a plateau in the newtonian region of the flow curve at low frequencies. The relaxation time corresponds to the inverse of the frequency at which the shear-thinning begins. The power law index describes the degree of shear thinning because the magnitude of the slope of the flow curve at high frequencies is close to n-1 on a log (η) -log (ω) plot. For newtonian fluids, n=1 and the dynamic complex viscosity is independent of frequency.

In addition to dynamic and complex viscosities (each in pascal seconds), various other parameters were collected at each frequency sweep in the SAOS experiment, including storage modulus (Pa), loss modulus (Pa), complex modulus (Pa), tan (δ), and phase angle. Plotting phase angle versus complex shear modulus from rheological experiments produces Van Gurp Palmen plots that can be used to extract some information about molecular characteristics, e.g., linear vs. long chain branching chains, long chain branching types, polydispersity (Dealy,M.J.,Larson,R.G.,"Structure and Rheology of Melted Polymers",Carl Hanser Verlag,Munich 182-183(2006))., van Gurp Palmen plots have also been suggested to be useful in revealing the presence of long chain branching in polyethylene. See Trinkle,S.、Walter,P.、Friedrich,C."Van Gurp-Palmen Plot II-Classification of long chain branched polymers by their topology", in 41 Rheol Acta 103-113 (2002).

"Shear thinning index" (which is reported as the number of units free) is characterized by a decrease in complex viscosity with increasing shear rate. In this context, shear thinning can be determined as the ratio of complex viscosity at a frequency of 0.01 rad/s to complex viscosity at a frequency of 100 rad/s.

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-adhesion 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 0.1 ppm to 5.0 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, particularly blown films, may be free or substantially free of polymeric processing aids, particularly polymeric processing aids comprising fluorine, where "substantially free" means free of any intentionally added component, but allowing up to 100ppm of such component(s) as impurities).

Article of manufacture

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

Furthermore, it has been found that the polyethylene copolymers of the present disclosure can provide excellent tear properties and dart impact strength, overcoming the key weakness of LDPE. Additionally, due to the improved flow behavior, the polyethylene copolymers of the present disclosure may provide films formed with reduced motor load and melt pressure (which increases throughput) as compared to conventional LLDPE. For example, a reduction in melt pressure and a reduction in melt temperature may be provided during film manufacture. The films of the present disclosure may be particularly useful as shrink wrap films (improved by the presence of LCB and BOCD in the polyethylene copolymers of the present disclosure).

The polyethylene copolymers of the present disclosure (or blends thereof) may be used in forming operations such 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, useful as shrink films, cling films, stretch films, sealing films, oriented films, snack packaging, heavy duty bags, grocery bags, baked and frozen food packaging, pharmaceutical packaging, industrial liners, membranes, and the like in food-contact and non-food contact applications. For example, the polyethylene copolymers of the present disclosure provide improved shrink wrapping capability due to the broad orthogonal composition distribution and long chain branching properties. Fibers include melt spinning, solution spinning, and melt blown fiber operations for use in the manufacture of filters, diaper fabrics, medical garments, geotextiles, and the like, in woven or nonwoven form. Extruded articles include medical tubing, wire and cable coatings, tubing, geomembranes, and pond liners. Molded articles include single and multi-story buildings in the form of bottles, grooves, 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 tube film method, followed by orientation in a uniaxial direction or in two mutually perpendicular directions in the plane of the film. One or more of the film layers may be oriented in the transverse and/or longitudinal directions to the same or different extents. This orientation may be performed before or after the assembly of the various layers. 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 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, mechanical stretch wrap, shrink films, shrink wrap films, greenhouse films, laminates, and laminated films. Exemplary films may be prepared by any conventional method known to those skilled in the art, such as by techniques for preparing blown, extruded, and/or cast stretched and/or shrink films, including shrink-on-shrink applications.

In at least one embodiment, the multilayer film (or films) may be formed by a suitable method. The total thickness of the multilayer film may vary based on the desired application. Total film thicknesses of 5-100 μm, e.g. 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 depending on the desired end use properties, the polymer(s) used, the equipment throughput, and other factors. The materials forming each layer may be coextruded through a coextrusion feed block and die assembly to produce a film having two or more layers adhered together but differing in composition. Coextrusion may be suitable for simultaneous use in 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) at 23 ℃ according to ASTM D882-18 of about 25,000psi to about 40,000psi, e.g., about 27,000psi to about 40,000psi, e.g., about 28,000psi to about 38,000psi, e.g., about 28,000psi to about 30,000 psi.

Films of the present disclosure may have an Elmendorf Tear (Elmendorf Tear) value according to ASTM D-1922. In at least one embodiment, the film has an elmendorf tear (MD) of at least 30g/mil, such as at least 50g/mil to about 200g/mil, such as about 100g/mil to about 180g/mil, such as about 160g/mil to about 180 g/mil. In at least another embodiment, the film has an elmendorf Tear (TD) of at least 300g/mil, such as from about 400g/mil to about 600g/mil, such as from about 410g/mil to about 460g/mil, such as from about 440g/mil to about 470 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 100g/mil, such as at least about 120g/mil, such as at least about 130 g/mil. For example, the dart impact may be about 100g/mil to about 200g/mil, such as about 120g/mil to about 170g/mil, such as about 130g/mil to about 160g/mil.

Shrinkage (reported as a percentage) of the film can be measured by cutting a round specimen from the film using a 100 mm die. They can be marked in the respective directions of the samples, 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 dimensional expansion after heating when compared to its pre-heated 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 60% to about 70%. The films of the present disclosure may have a shrinkage (cross direction) of from about 0% to about 6%, such as from about 0.5% to about 5%, such as from about 2% to about 5%.

In certain embodiments, the film may have a break puncture energy (also referred to as puncture break energy) of at least about 5in-lbs/mil, such as at least about 10in-lbs/mil, such as at least about 15in-lbs/mil, such as in the range of about 10, 11, 12, or 13 to about 20 or 25in-lbs/mil, according to the modified BSI CEN 14477.

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 clarity (defined as regularly transmitted light that deflects less than 0.1 from the axis of incident light passing through the film sample body) of about 80% or greater, about 85% or greater, or about 90% or greater as determined by ASTM D1746.

In at least one embodiment, the films of the present disclosure have a gloss (MD) as determined by ASTM D-2457 of about 10GU or about 15GU or greater, for example in the range of 10, 15, 16, 17, 18 or 19GU to about 25, 26, 27, 28, 29, 30, 35 or 40GU, wherein a light source is illuminated onto the film surface at an angle of 45 ° 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 industrial and retail bundling 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.7,235,607, incorporated herein by reference.

Industrial shrink films can 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 supermarket goods. Such films are typically formed in a single bubble blow extrusion process to a thickness of about 35 μm to 80 μm.

The film may be used in "shrink-on-shrink" applications. As used herein, "shrink-on-shrink" refers to a process of applying an outer shrink wrap layer around one or more articles that have been shrink wrapped individually (herein, the wrapped "inner layer"). In these methods, it may be desirable for the film used to wrap 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, the desired level of shrinkage in the outer layer may be achieved while preventing the inner layer from melting, further shrinking, or otherwise not distorting 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 at high heat setting, indicating that they may be particularly suitable for use as inner layers in various shrink-on-shrink applications.

Experiment

Relaxation time and Crohn equation (Cross Equation) constants relaxation time τ and/or Crohn equation values (particularly viscosity, time and power law constants) can help indicate polydispersity/MWD and/or the presence of long chain branching in the polymer composition (or the behavior of the polymer composition to mimic the manner of long chain branched polymer), in addition to SAOS and other parameters described elsewhere herein. The relaxation time τ may be determined by the kronet equation used to model the viscosity data collected over the frequency range. Viscosity data collected over a range of frequencies can be fitted using the general form of the kronese equation (J.M Dealy and K.F Wissbrun,Melt Rheology and Its Role in Plastics Processing Theory and Applications;Van Nostrand Reinhold： new york, page 162 (1990):

Where η is the dynamic viscosity, η ₀ is the finite zero shear viscosity, η _∞ is the infinite shear viscosity, τ is the relaxation time at a given input shear frequency γ, and n is the power law index, which can describe the degree of shear thinning. For newtonian fluids, n=l and the dynamic complex viscosity is independent of frequency. For the polymers of interest herein, n < l, such that enhanced shear-thinning behavior is represented by a decrease in n ((1-n) increase). The term η _∞ is 0 from the curve fit, as a result of which the expression reduces to three parameters:

This expression gives the relaxation time when tested at constant strain and constant temperature. As noted, the relaxation time τ in the Cross Model can be correlated to the polydispersity and/or long chain branching in the polymer. For increased branching levels (and/or polymer compositions that mimic increased branching levels), it is expected that τ will be higher compared to a linear polymer of the same molecular weight. The three Crossparameters (Cross parameter) viscosity (. Eta. ₀), time (. Tau.) and power law (n) constants can also be labeled as Crossequation constants A1, A2 and A3, respectively.

General considerations and reagents:

Unless otherwise indicated, all operations were performed under an inert atmosphere using glove box technology. Before use, diethyl ether, pentane, hexane, 1,2 dimethoxyethane, and dichloromethane (SIGMA ALDRICH) were degassed and dried over 3 a molecular sieve overnight. N-butyllithium, methyl iodide in hexane was purchased from SIGMA ALDRICH and used as received. ZrCl ₄ was purchased from STREM CHEMICALS and used as received. Methylaluminoxane was purchased from Grace and used as received.

Catalyst 1 and catalyst 2a were synthesized as described below for producing a dual metallocene catalyst system for polymerization according to various embodiments described herein. Catalyst 1 was also used as the sole catalyst compound in the comparative example, as shown in tables 1B and 2B. Catalyst 2B was also obtained and used as a single catalyst for the comparative examples shown in tables 1B and 2B.

And (3) synthesis:

Synthesis of catalyst 1:

Synthesis of (5, 8-tetramethyl-6, 7-dihydro-3H-cyclopenta [ b ] naphthalene (cyclopenta [ b ] naphthalen) -3-yl) lithium

To a vigorously stirred white suspension of 5, 8-tetramethyl-6, 7-dihydro-1H-cyclopenta [ b ] naphthalene (20.18 g,89.2mmol,1.00 eq.) in diethyl ether (250 mL) at-35℃was added n-butyllithium in hexane (36 mL,90.0mmol,1.01 eq.) to give a cold, cloudy, pale yellow mixture. After stirring for 20 minutes, the reaction turned cloudy bright yellow. The reaction was stirred overnight and then evaporated under vacuum leaving a dirty white solid. The solid was washed with pentane (100 mL) and the solid was filtered to give a bright white solid. The yield was 18.8 g (91%) as a bright white powder. ¹H NMR(THF-D₈ ) 7.46 (S, 2H), 6.50 (t, 1H), 5.81 (dt, 1H), 1.72 (S, 4H), 1.34 (S, 12H).

Synthesis of 3,5, 8-pentamethyl-6, 7-dihydro-3H-cyclopenta [ b ] naphthalene:

To a colorless solution of methyl iodide (7.47 g,52.6mmol,2.0 eq.) in diethyl ether (200 ml) was added (5, 8-tetramethyl-6, 7-dihydro-3H-cyclopenta [ b ] naphthalen-3-yl) lithium (6.12 g,26.3mmol,1.0 eq.) at-35℃to give a cloudy white mixture. The reaction mixture was stirred at room temperature overnight. 1, 2-Dimethoxyethane (6 g) was added to the clear yellow reaction mixture, resulting in the formation of a white precipitate. The solvent was removed in vacuo leaving a white solid. The product was extracted with pentane (100 mL) and filtered to give an amber solution and a white precipitate. The amber solution was dried under vacuum to give a yellow viscous oil. Yield was 18.8 g (91%) as bright white powder .¹H NMR(C₆D₆)7.34(dt,2H),6.71(dt,1H),6.23(dt,1H),3.29,(m,1H),1.65(S,4H),1.30,(dt of dt,12H),1.15(dt,3H).

Synthesis of (3, 5, 8-pentamethyl-6, 7-dihydro-1H-cyclopenta [ b ] naphthalen-1-yl) lithium:

To a vigorously stirred white suspension of 3,5, 8-pentamethyl-6, 7-dihydro-3H-cyclopenta [ b ] naphthalene (6.48 g,27.0mmol,1.00 eq.) in diethyl ether (250 mL) at-35℃was added n-butyllithium in hexane (10.9 mL,27.2mmol,1.01 eq.) to give a cool, cloudy, pale yellow mixture. After stirring for 20 minutes, the reaction turned cloudy bright yellow. The reaction was stirred overnight and then evaporated under vacuum leaving a dirty white solid. The solid was washed with pentane (100 mL) and the solid was filtered to give a bright white solid. Yield 6.30g (95%) of a bright white powder .¹H NMR(THF-D₈)7.28(dt,2H),6.30(dt,1H),5.61(dt,1H),2.43(S,3H),1.72(S,4H),1.35(dt,12H).

Synthesis of bis (3, 5, 8-pentamethyl-6, 7-dihydro-1H-cyclopenta [ b ] naphthalen-1-yl) zirconium dichloride:

To a vigorously stirred white suspension of zirconium tetrachloride (2.98 g,12.8mmol,1.00 eq.) in diethyl ether (200 mL) was added (3, 5, 8-pentamethyl-6, 7-dihydro-1H-cyclopenta [ b ] naphthalen-1-yl) lithium (6.30 g,25.6mmol,2.00 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 overnight and then evaporated under vacuum leaving a bright yellow solid. The solid was extracted with dichloromethane (100 mL) and the extract was filtered to give a bright yellow solid. The solid was washed with cold pentane (50 mL) and dried under vacuum. Yield was 16.01 g (97%) of bright yellow powder .¹HNMR(CD2Cl2)7.57(S,1H),7.50(D,2H),7.42(s,1H),6.15(dt,1H),5.89(dt,1H),5.71(dt,1H),5.50(dt,1H),2.42(s,3H),2.34(s,3H),1.43(m,8H),1.36(m,24H).

Synthesis of catalyst 2 a:

synthesis of (1, 5,6, 7-tetrahydro-s-indacen) -1-yl) lithium:

To a vigorously stirred white suspension of 1,2,3, 5-tetrahydro-s-indacene (9.70 g,62.1mmol,1.00 eq.) in diethyl ether (250 mL) at-35 ℃ was added n-butyllithium in hexane (36 ml,90.0mmol,1.01 eq.) to give a pink precipitate. The reaction was stirred overnight and then evaporated under vacuum leaving a pink solid. The solid was washed with pentane (100 mL) and the solid was filtered to give a bright white solid. The yield was 8.85 g (88%) of a pink powder. ¹H NMR(THF-D₈ ) 7.15 (s, 2H), 6.42 (t, 1H), 5.81 (dt, 1H), 2.83 (m, 4H), 1.95 (m, 2H).

Synthesis of dimethyl (2, 3,4, 5-tetramethylcyclopent-2, 4-dien-1-yl) silyl triflate:

To a pale amber solution of Me4CpSiMe Cl (30.0 g,140mmol,1.0 eq.) in 100mL toluene was added AgOTf (38.00 g,148mmol,1.06 eq.) in portions. The reaction mixture became cloudy white and warmed upon addition of AgOTf. The reaction mixture quickly became a gray-pink precipitate and was stirred at room temperature for 4 hours. The solvent was removed in vacuo leaving a dark grey mixture. The product was extracted with pentane (100 ml) and the yellow solution was filtered to give a brown solid. Pentane was removed from the yellow solution leaving a pale yellow solid in a yield of 8.85g (88%). ¹H NMR(C₆D₆ ) 1.72 (s, 6H), 1.60 (s, 6H), 0.43 (s, 6H).

Synthesis of dimethyl (1, 5,6, 7-tetrahydro-s-indacen-1-yl) (2, 3,4, 5-tetramethylcyclopent-2, 4-dien-1-yl) silane:

To an amber-yellow solution of (2, 3,4, 5-tetramethylcyclopent-2, 4-dien-1-yl) silyl triflate (5.00 g,15.2mmol,1.0 eq.) in diethyl ether (50 ml) was added (1, 5,6, 7-tetrahydrochysene-1-yl) lithium (2.65 g,16.2mmol,1.07 eq.) at-35 ℃ to give a cloudy yellow-orange mixture. The reaction mixture was stirred at room temperature overnight. The solvent was removed in vacuo leaving a pink-orange solid. The product was extracted with pentane (100 ml) and the amber solution was filtered. Pentane was then removed under vacuum. The yield is 5.04 g(99%).¹HNMR(C₆D₆)7.51(S,1H),7.34(S,1H),6.90(t,1H),6.489(t,1H),3.64(s,1H),2.86(m,5H),1.95(m,8H),1.92(s,6H),0.09(s,3H),0.03(s,3H).

Synthesis of lithium dimethyl (1, 5,6, 7-tetrahydro-s-indacen-1-yl) (2, 3,4, 5-tetramethylcyclopent-2, 4-dien-1-yl) silyl):

To an orange solution of dimethyl (1, 5,6, 7-tetrahydrosymmetrical indacen-1-yl) (2, 3,4, 5-tetramethylcyclopent-2, 4-dien-1-yl) silane (5.0 g,14.9mmol,1.0 eq.) in diethyl ether (50 ml) was added n-butyllithium (11.3 ml,31.0mmol,2.07 eq.) at-35 ℃ to give an amber solution. The reaction mixture was stirred at room temperature overnight. The solvent was removed in vacuo and the product was washed with pentane (100 ml) and filtered to give a pale yellow solid 5.86g(93%).¹HNMR(THFD₈)7.46(s,1H),7.16(s,1H),6.65(dt,1H),5.91(dt,1H),2.81(m,5H),2.10(s,6H),1.95(m,3H),1.92(s,6H),0.59(s,6H).

Synthesis of zirconium dichloride (1, 5,6, 7-tetrahydro-s-indacen-1-yl) (2, 3,4, 5-tetramethylcyclopentadienyl) silyl) (catalyst 2 a):

To a vigorously stirred white suspension of zirconium tetrachloride (3.17 g,8.31mmol,1.00 eq.) in diethyl ether (200 mL) was added (1, 5,6, 7-tetrahydro-s-indacen-1-yl) (2, 3,4, 5-tetramethylcyclopent-2, 4-dien-1-yl) silyl) lithium (3.50 g,8.32mmol,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 overnight and then evaporated under vacuum leaving a bright yellow solid. The solid was extracted with dichloromethane (100 mL) and the extract was filtered to give a bright yellow solid. The solid was washed with cold pentane (50 mL) and dried under vacuum. Yield was 3.68 g (90%) bright yellow powder .¹HNMR(CD2Cl2)7.57(S,1H),7.3(S,1H),7.0(s,1H),5.87(s,1H),3.0-2.8(m,5H),2.65(m,3H),1.9(d,12H),1.1(s,3H),0.9(s,3H).

Load procedure:

MAO (42.5 g, 30 wt% in toluene) was added to Celestir along with 200 ml toluene. The solution was allowed to stir for two minutes. Catalyst 1 (949 mg) was dissolved in 50 ml toluene and added slowly drop wise to the MAO solution. The reaction mixture was stirred at room temperature for one hour. ES70 875 silica (35.2 g) was then added to the above mixture and stirred for an additional 1 hour. The solid support was filtered and washed with 200 ml pentane. The supported catalyst was then dried under vacuum for 8 hours, yielding a dried support. The supported catalyst was slurried with 10% SonoJell wax.

Co-load procedure for zirconium dichloride (3, 5, 8-pentamethyl-6, 7-dihydro-1H-cyclopenta [ b ] naphthalen-1-yl) (catalyst 1) and zirconium dichloride dimethyl (1, 5,6, 7-tetrahydro-s-indacen-1-yl) (2, 3,4, 5-tetramethylcyclopentadienyl) silyl) (catalyst 2 a):

MAO (42.5 g, 30 wt% in toluene) was added to Celestir along with 200 ml toluene. The solution was allowed to stir for two minutes. The catalysts (catalyst 1 (492 mg) and catalyst 2 (569 mg)) were dissolved in 50 ml toluene and added slowly drop-wise to the MAO solution. The reaction mixture was stirred at room temperature for one hour. ES70 875 silica (35.2 g) was then added to the above mixture and stirred for an additional 1 hour. The solid support was filtered and washed with 200 ml pentane. The supported catalyst was then dried under vacuum for 8 hours, yielding a dried support.

Catalyst 2b tetramethylcyclopentadienyl dimethylsilyl (3-benzo [ e ] indenyl) ] zirconium dichloride

Catalyst 2B was synthesized in a similar manner to the synthesis of catalyst 2a, obtaining the following resulting compounds for use as shown in tables 1B and 2B below:

Polymerization:

PE resins (examples 1 and 2, and comparative examples 1-4) were produced in a 6' diameter small gas phase fluidized bed reactor in continuous operation. Tables 1A and 1B list the catalysts or catalyst systems used and the polymerization conditions used in examples 1-2 and comparative examples 1-4.

TABLE 1A

TABLE 1B

PE resin in pellet form from a gas phase reactor was dry blended in a tumbler mixer with 500ppm Irganox ^TM -1076, 1,000ppm Irgafos ^TM and 600ppm Dynamar ^TM FX5920A, then compounded on a laboratory scale twin screw extruder (Leistritz 27 or Leistritz 18) under typical PE compounding conditions. The QC properties and compositional characteristics of the resulting stabilized PE pellets were characterized. Tables 2A and 2B list the results of characterization of the products of examples 1-2 and comparative examples 1-5. Comparative example 5 was obtained as LD103.09 (high pressure radical LDPE available from ExxonMobil).

TABLE 2A

TABLE 2B

The density test follows ASTM D1505, column density. Samples were molded under ASTM D4703-10a, procedure C, and then conditioned under ASTM D618-08 (23 ^o.+ -. 2 ℃ and 50.+ -. 10% relative humidity) for 40 hours prior to testing.

Melt Index (MI) and high load melt index (HLMI or FI) were in accordance with ASTM D-1238 at 190℃at 2.16kg and 21.6kg, respectively.

Rheological characterization a small amplitude oscillatory shear test on a RAS-G2 instrument was used, with a strain of 4% to 6% at 190℃in the frequency range of 0.01rad/s to 626 rad/s. The resulting data were fitted by the Krauss equation to obtain viscosity, time and power law constants A1, A2 and A3. G'/G "at 0.1s ^-1 is the ratio of storage modulus to loss modulus at 0.1s ^-1 frequency. The shear thinning index STI0.1/100 is the ratio of complex viscosity at 0.1s ^-1 to complex viscosity at 100s ^-1.

All comparative examples and PE samples of the present invention were made into nominal 1 mil and/or 2 mil films on a LITTLE GIANT blown film line from Cyber PLASTIC MACHINERY. It has a2 "universal screw with an L/D ratio of 30. There are a total of nine heating zones, four on the extruder, two on the die, and one each for the screen changer, adapter and block zone before the die. Typical temperatures (^o F) are set as follows for barrel 1, barrel 2, barrel 3, barrel 4, screen changer, adapter, block zone, die zone 1, die zone 2, 300, 350, 355, 340, 350, 355, 360, 370, and 370, respectively.

TABLE 3A film manufacturing conditions and performance Properties for examples 1-2

TABLE 3 conditions and performance Properties for film manufacture of comparative examples 1-5

FIG. 1 is a graphic showing GPC of polyethylene copolymers according to various embodiments, including both polymer chain distribution and g' vis values as a function of log (molecular weight).

Fig. 2 is a diagram showing GPC of a polyethylene copolymer according to various embodiments, including both molecular weight distribution and comonomer weight percent as a function of log (molecular weight). In general, the process, catalyst and film of the present invention provide polyethylene compositions formed in a low pressure process to produce LCB polyethylene compositions having LDPE-like extrusion processability but also good tear properties and dart impact strength to match those of mLLDPE. This new LLDPE achieves increased processability, has an increased tear balance, increased TD tear and much better drawdown characteristics, making it easier to produce thin film thickness.

Unless otherwise specified, the phrase "consisting essentially of" does not exclude the presence of other steps, elements or materials (whether or not specifically mentioned in the specification), provided that such steps, elements or materials do not affect the basic and novel characteristics of the present disclosure, and furthermore, they do not exclude impurities and variations commonly associated with the elements and materials used.

For simplicity, only certain numerical ranges are explicitly disclosed herein. However, a lower limit may be combined with any other upper limit to define a range not explicitly recited, and similarly, a lower limit may be combined with any other lower limit to define a range not explicitly recited, and likewise, an upper limit may be combined with any upper limit to define a range not explicitly recited. In addition, each point or individual value between two points is included within the scope even if not explicitly recited. Thus, each point or individual value itself may be used as a lower or upper limit in combination with other points or individual values or other lower or upper limits to define a range not explicitly recited.

All documents described herein, including any priority documents and/or test procedures, are incorporated by reference to the extent such documents are not inconsistent with this disclosure. It will be apparent from the foregoing summary and specific embodiments that, while forms of the disclosure have been illustrated and described, various modifications can be made without departing from the spirit and scope of the disclosure. Accordingly, this disclosure is not intended to be so limited. Likewise, the term "comprising" is considered synonymous with the term "including". Likewise, whenever a composition, element, or group of elements is in front of the transitional term "comprising," it is understood that the transitional term "consisting essentially of," consisting of, "or" being the same composition or group of elements in front of the recited composition, element, or elements is also contemplated, and vice versa.

While the present disclosure has been described in terms of a number of embodiments and examples, those skilled in the art, upon reading 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 catalyst system comprising:

a first catalyst compound, wherein the first catalyst compound is represented by the following formula (I):

Wherein:

m of formula (I) is a group 4 metal;

Each X of formula (I) is independently halo, substituted or unsubstituted hydrocarbyl, hydrogen, amino, substituted or unsubstituted alkoxy, thio, phosphorus, or a combination thereof, or two of X are joined together to form a substituted or unsubstituted metallocycle ring, or two of X are joined to form a chelating ligand, diene ligand, or alkylidene, and

A second catalyst represented by formula (III):

Wherein:

M of formula (III) is a group 4 metal;

2. The catalyst system of claim 1, wherein the first catalyst compound of formula (I) is represented by formula (II):

Wherein:

M is a group 4 metal;

3. The catalyst system of claim 2, wherein formula (II) is further characterized by one of the following (i), (II) or (iii):

(i) Each X of formula (II) is halo, each of R ³、R¹⁰、R¹⁵、R^15'、R¹⁸、R^18'、R¹⁹、R^19'、R²² and R ^22' of formula (II) is independently C ₁-C₁₀ alkyl, and each of R¹、R²、R⁴、R⁷、R⁸、R⁹、R¹¹、R¹⁴、R¹⁶、R^16'、R¹⁷、R^17'、R²⁰、R^20'、R²¹ and R ^21' of formula (II) is hydrogen;

(ii) Each X of formula (II) is independently C ₁-C₄ alkyl or halo, each of R ¹⁵、R^15'、R¹⁸、R^18'、R¹⁹、R^19'、R²² and R ^22' of formula (II) is independently C ₁-C₁₀ alkyl, and each of R¹、R²、R³、R⁴、R⁷、R⁸、R⁹、R¹⁰、R¹¹、R¹⁴、R¹⁶、R^16'、R¹⁷、R^17'、R²⁰、R^20'、R²¹ and R ^21' of formula (II) is hydrogen, or

(Iii) Each X of formula (II) is independently C ₁-C₄ alkyl, one of R ¹、R² and R ³ of formula (II) is C ₁-C₁₀ alkyl and the remainder of R ¹、R² and R ³ are each hydrogen, one of R ⁸、R⁹ and R ¹⁰ of formula (II) is C ₁-C₁₀ alkyl and the remainder of R ⁸、R⁹ and R ¹⁰ are each hydrogen, each of R ¹⁵、R^15'、R¹⁸、R^18'、R¹⁹、R^19'、R²² and R ^22' of formula (II) is independently C ₁-C₁₀ alkyl, and each of R⁴、R⁷、R¹¹、R¹⁴、R¹⁶、R^16'、R¹⁷、R^17'、R²⁰、R^20'、R²¹ and R ^21' of formula (II) is hydrogen.

4. The catalyst system of claim 2 or claim 3, wherein each of R ¹⁵、R^15'、R¹⁸、R^18'、R¹⁹、R^19'、R²² and R ^22' in formula (II) is methyl.

5. The catalyst system of claim 2 or any of claims 3-4, wherein the first catalyst compound is represented by one of the following structures (II-a), (II-b), or (II-c):

。

6. The catalyst system of any of the preceding claims, wherein the second catalyst compound is represented by any of the following structures (III-a) or (III-b):

。

7. The catalyst system of claim 5 or 6, further comprising a support material and, optionally, an activator.

8. A method of making a polyethylene composition comprising:

Introducing ethylene and a C ₃-C₄₀ alpha-olefin into a reactor under first polymerization conditions together with the catalyst system of any one of claims 1-7 and forming a polyethylene copolymer.

9. The process of claim 8, wherein the polymerization conditions comprise a reactor pressure of 250 to 350 psig and a reactor temperature of 60 ℃ to 110 ℃.

10. The method of claim 8 or claim 9, wherein the polyethylene copolymer has a broad orthogonal composition distribution, and additionally has one or more of the following properties:

(a) A density of about 0.914 g/cm ³ to about 0.925 g/cm ³;

(b) A melt index of about 0.5 g/10min to about 1.5 g/min (190 ℃,2.16 kg);

(c) A High Load Melt Index (HLMI) of about 80 g/10min to about 90 g/10min (190 ℃,21.6 kg);

(d) A melt index ratio (MIR, HLMI/MI ratio) of about 60 to about 98;

(e) A Molecular Weight Distribution (MWD) of about 8 to about 10.

11. The method of claim 10, wherein the polyethylene copolymer has all of properties (a) - (e).

12. The method of claim 10 or claim 11, wherein the broad orthogonal composition distribution of the polyethylene copolymer is characterized by the polyethylene copolymer having a Composition Distribution Breadth Index (CDBI) of about 5% to about 40% and/or a T ₇₅-T₂₅ value of about 30 to about 40.

13. The method of any one of claims 10-12, wherein the polyethylene copolymer further has a g' vis _{Average of} value of about 0.7 to about 0.8.

14. The method of any of claims 10-13, wherein the polyethylene copolymer has an olefin comonomer derived content of from about 10 weight percent to about 13 weight percent, based on the total mass of the olefin comonomer derived content and the ethylene derived content.

15. The method of any of claims 10-14, wherein the polyethylene copolymer has a melt index of about 0.8 g/10min to about 1.1 g/10 min.

16. A polyethylene copolymer comprising:

Ethylene derived units, and

The remainder being C ₃-C₂₀ comonomer-derived units;

the polyethylene copolymer has:

A broad orthogonal composition distribution,

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

A melt index of about 0.6 g/10min to about 1.3 g/10min,

An olefin comonomer content of about 10 to about 13 weight percent,

A High Load Melt Index (HLMI) of about 80 g/10min to about 90 g/10min,

A Melt Index Ratio (MIR) of about 60 to about 98, and

A Molecular Weight Distribution (MWD) of about 8 to about 10.

17. The polyethylene copolymer of claim 15, wherein the polyethylene copolymer has a melt index of from about 0.8 g/10min to about 1.1 g/10 min.

18. The polyethylene copolymer of claim 28 or 29, wherein the polyethylene copolymer has a g' vis _{Average of} value of from about 0.7 to about 0.8.

19. A film comprising the polyethylene copolymer of any one of claims 16-18, wherein the film has:

An elmendorf tear value (MD) of from about 150 g/mil to about 180 g/mil, and

Dart impact of about 140 g/mil to about 160 g/mil.