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WO2019108327A1 - Films comprenant une composition de polyéthylène - Google Patents

Films comprenant une composition de polyéthylène Download PDF

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Publication number
WO2019108327A1
WO2019108327A1 PCT/US2018/057638 US2018057638W WO2019108327A1 WO 2019108327 A1 WO2019108327 A1 WO 2019108327A1 US 2018057638 W US2018057638 W US 2018057638W WO 2019108327 A1 WO2019108327 A1 WO 2019108327A1
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Prior art keywords
film
psi
mil
polymer
polyethylene composition
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Inventor
Dongming Li
David M. Fiscus
Matthew W. Holtcamp
Kevin A. STEVENS
Laughlin G. Mccullough
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ExxonMobil Chemical Patents Inc
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ExxonMobil Chemical Patents Inc
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/08—Copolymers of ethene

Definitions

  • the present disclosure provides films comprising a polyethylene (PE) composition and processes for forming films.
  • PE polyethylene
  • Olefin polymerization catalysts are of great use in industry to produce polyolefin polymers. Hence, there is interest in finding new catalyst systems to use in polymerization processes that increase the commercial usefulness of the catalyst systems and allow the production of polyolefin polymers having improved properties or a new combination of properties.
  • the composition distribution of an ethylene alpha-olefin copolymer refers to the distribution of comonomer (short chain branches) among the molecules that comprise the polyethylene polymer.
  • BCD Broad Composition Distribution
  • NCD Narrow Composition Distribution
  • composition distribution influences the properties of copolymers, for example, extractables content, environmental stress crack resistance, heat sealing, dart drop impact resistance, and tear resistance or strength.
  • the composition distribution of a polyolefin may be measured by, for example, Temperature Rising Elution Fractionation (TREF) or Crystallization Analysis Fractionation (CRYSTAF). See, for example, U.S. Patent No. 8,378,043, Col. 3 and Col. 4.
  • Ethylene alpha-olefin copolymers may be produced in a low pressure reactor, utilizing, for example, solution, slurry, and/or gas phase polymerization processes. Polymerization takes place in the presence of activated catalyst systems such as those employing a Ziegler-Natta catalyst, a chromium based catalyst, a vanadium catalyst, a metallocene catalyst, a mixed catalyst (i.e., two or more different catalysts co-supported on the same carrier such as a bimodal catalyst), other advanced catalysts, or combinations thereof.
  • activated catalyst systems such as those employing a Ziegler-Natta catalyst, a chromium based catalyst, a vanadium catalyst, a metallocene catalyst, a mixed catalyst (i.e., two or more different catalysts co-supported on the same carrier such as a bimodal catalyst), other advanced catalysts, or combinations thereof.
  • these catalysts when used in a catalyst system all produce a variety of polymer chains in a polyolefin polymer composition that vary in molecular weight and comonomer incorporation. In some cases, this variation becomes a“signature” to the catalyst itself.
  • a polyolefin's composition distribution is largely dictated by the type of catalyst used.
  • Broad Composition Distribution or BCD refers to polymers in which the length of the molecules would be substantially the same but the amount of the comonomer would vary along the length, for example, for an ethylene-hexene copolymer, hexene distribution varies from low to high while the molecular weight is roughly the same or the Polydispersity Index (PDI) is narrow.
  • BCD Broad Composition Distribution
  • PDI Polydispersity Index
  • metallocene catalysts can produce a polyolefin polymer composition with an NCD.
  • a metallocene catalyst is generally a metal complex of a transitional metal, such as a Group 4 metal, and one or more cyclopentadienyl (Cp) ligands or rings.
  • Cp cyclopentadienyl
  • NCD generally refers to the comonomer being evenly distributed or not vary much along the polymer chain. An illustration is provided below.
  • BOCD refers to incorporating the comonomer predominantly in the high molecular weight chains.
  • the distribution of the short chain branches can be measured, for example, using Temperature Raising Elution Fractionation (TREF) in connection with a Light Scattering (LS) detector to determine the weight average molecular weight of the molecules eluted from the TREF column at a given temperature.
  • the combination of TREF and LS yields information about the breadth of the composition distribution and whether the comonomer content increases, decreases, or is uniform across the chains of different molecular weights.
  • BOCD structure means a structure in which the content of the comonomer such as alpha olefins is mainly high at a high molecular weight main chain, that is, a novel structure in which the content of a short chain branching (SCB) is increased as moving toward the high molecular weight.
  • SCB short chain branching
  • The‘593 Patent also teaches a BOCD Index.
  • the BOCD Index may be defined by the following equation:
  • the“Content of SCB at the high molecular weight side” means the content of the SCB (the number of branches/lOOO carbon atoms) included in a polymer chain having a molecular weight of Mw of the polyolefin or more and 1.3 c Mw or less
  • the“Content of SCB at the low molecular weight side” means the content of the SCB (the number of branches/l 000 carbon atoms) included in a polymer chain having a molecular weight of 0.7 c Mw of the polyolefin or more and less than Mw.
  • the BOCD Index defined by the equation above may be in the range of 1 to 5, such as 2 to 4, such as 2 to 3.5. See, also, Figure 1 and Figure 2 of the‘593 Patent (characterizing BOCD polymer structures using GPC-FTIR data).
  • BOCD behavior in a polymer composition has been associated with a good balance of mechanical and optical properties and has been an important goal in the development of new polymer products.
  • MDPE Medium Density polyethylene
  • medium density polyethylene is polyethylene having a density of from 0.910 g/cm 3 to 0.935 g/cm 3 .
  • a change in polymer stiffness will not affect processability, and vice versa.
  • stiffness and processability are inversely related with toughness. Thus, to improve stiffness and toughness while maintaining good processability remains a challenge.
  • a film includes a polyethylene having at least 50 wt% ethylene derived units and from 0 to 50 wt% of C3-C40 olefin comonomer content based upon the total weight of the polyethylene composition.
  • the polyethylene composition has a melt temperature of from 250°C to 600°C.
  • the film has an average of the MD and TD 1% secant moduli of 30,000 psi or greater, and a Dart Drop Impact of from 100 g/mil to 500 g/mil.
  • the present disclosure provides for a process to make a film.
  • FIG. 1 is a graph illustrating a temperature rising elution fractionation curve of a mixed catalyst system under polymerization conditions, according to one embodiment.
  • FIG. 2 is a graph illustrating a temperature rising elution fractionation curve of a mixed catalyst system under polymerization conditions, according to one embodiment.
  • FIG. 3A is a graph illustrating melt index ratio and C6/C2 flow ratio versus time (hours), according to one embodiment.
  • FIG. 3B is a graph illustrating C6/C2 flow ratio and density versus time (hours), according to one embodiment.
  • FIG. 4 is a gel permeation chromatography spectrum of an ethylene hexene copolymer formed by a catalyst system under polymerization conditions, according to one embodiment.
  • FIG. 5 is a gel permeation chromatography spectrum of an ethylene hexene copolymer formed by a catalyst system under polymerization conditions, according to one embodiment.
  • the present disclosure provides films comprising polyethylene (PE) composition(s).
  • PE polyethylene
  • the present disclosure provides films comprising polyethylene composition(s) that can exhibit, for example, BOCD behavior to produce the films or other useful articles with a good balance of one or more of high stiffness, toughness, and processability.
  • Films of the present disclosure can have a combination of good Dart (e.g., 320 g/mil (Dart method A)) and high stiffness (e.g. 70,000 psi avg.).
  • Films of the present disclosure can be obtained from polyethylene compositions having a medium density.
  • Polyethylene compositions can be formed by catalyst systems and processes of the present disclosure to provide ethylene polymers having medium density with comonomer content.
  • a combination of high density material and high comonomer content can provide a stiffer and tougher polymer.
  • Catalyst systems and processes of the present disclosure can provide ethylene polymers having the unique properties of high stiffness, high toughness and processability.
  • Catalyst systems used to form polyethylene (PE) compositions can include an unbridged Group 4 indenyl metallocene catalyst and a 2,6-bis(imino)pyridyl iron complex.
  • Polyethylene compositions can be obtained from the catalyst systems and can have a melt index ratio (MIR or 121/12) of from about 20 to about 110 with the MIR being tunable based on the amount of hexene in a gas phase reactor.
  • MIR melt index ratio
  • MIR is High Load Melt Index (HLMI) divided by Melt Index (MI) as determined by ASTM D1238.
  • MI Melt index
  • MI Melt index
  • E Melt index
  • I21 High load melt index
  • the present disclosure is directed to films comprising polyolefins prepared in gas phase, slurry phase, or solution polymerizations and utilizing catalyst systems of the present disclosure.
  • a film has a polyethylene composition, comprising: at least 50 wt% ethylene derived units and from 0 to 50 wt% of C3-C40 olefin comonomer content based upon the total weight of the polyethylene composition, the polyethylene composition having a melt temperature of from 250°F to 600°F (l2l°C to 3l5°C), and the film having an average of the MD and TD 1% secant moduli of 30,000 psi or greater, and a Dart Drop Impact of from 100 g/mil to 500 g/mil.
  • the polyethylene composition of the film can have one or more of: (i) from 6 wt% to 10 wt% of comonomer content, such as a comonomer content of 7 wt% or greater based upon the total weight of the polyethylene composition, (ii) the C3-C40 olefin comonomer is hexene, (iii) an MIR of 90 or greater or an MIR of 50 or less, (iv) a g’vis of 0.97 or greater or a g’vis of 0.9 or less, (v) an Mw/Mn value of from 8 to 11, (vi) a combination of internal and terminal unsaturation of 0.9 or greater unsaturations per 1,000 carbon atoms and a ratio of terminal unsaturation to internal unsaturation of from 5: 1 to 20: 1, (vii) a density of from 0.92 g/cm 3 to 0.94 g/cm 3 , an RCI,m of from 60 to 500, a CDR-2
  • the film can have one or more of: (i) an average of the MD and TD 1% secant moduli of from 60,000 psi to 90,000 psi, such as from 68,000 psi to 77,000 psi, (ii) a Dart Drop Impact of from 100 g/mil to 400 g/mil, such as 300 g/mil to 400 g/mil, alternatively from 175 g/mil to 225 g/mil, (iii) a Tensile Strength in the machine direction of from 3,000 psi to 12,000 psi, such as from 7,500 psi to 8,500 psi, (iv) a Tensile Strength in the transverse direction of from 3,000 psi to 12,000 psi, such as from 4,500 psi to 7,500 psi, (v) a Tensile Strength at Yield in the machine direction of from 1,000 psi to 4,000 psi, such as from
  • the present disclosure further provides for processes of forming films, comprising: extruding the polyethylene composition through a die at a die pressure of 3,000 psi or lower; and obtaining the film.
  • the die pressure can be 1,700 psi or lower.
  • the present disclosure further provides for films comprising ethylene polymer compositions, the ethylene polymer compositions formed by a process comprising: i) contacting in a single reaction zone, in the gas phase or slurry phase, ethylene and C3 to C20 comonomer with a catalyst system comprising a support, an activator, and the catalyst system described above, and obtaining an ethylene polymer having: a) a melt index of 0.2 to 10 g/lO min, such as 1.5 g/lO min or greater, a density of 0.92 g/cm 3 or greater, a melt index ratio of 90 or greater, and a comonomer content (hexene) of 7 wt% or greater; or b) a melt index of 0.2 to 10 g/lO min, such as 1.5 g/lO min or less, a density of 0.92 g/cm 3 or greater, a melt index ratio of 50 or less, and a comonomer content (hexene) of
  • the numbering scheme for the Periodic Table Groups is according to the new notation of the IUPAC Periodic Table of Elements.
  • a“catalyst system” is a combination of at least two catalyst compounds, an optional activator, and an optional support material.
  • the catalyst systems may further comprise one or more additional catalyst compounds.
  • the terms “mixed catalyst system”,“dual catalyst system”,“mixed catalyst”, and“supported catalyst system” may be used interchangeably herein with“catalyst system.”
  • catalyst systems are described as comprising neutral stable forms of the components, it is well understood by one of ordinary skill in the art, that the ionic form of the component is the form that reacts with the monomers to produce polymers.
  • the term“metallocene compound” includes compounds having two or three Cp ligands (cyclopentadienyl and ligands isolobal to cyclopentadienyl, such as indenyl or hydrogenated indenyl) bound to at least one Zr or Hf metal atom, and one or more leaving group(s) bound to the at least one metal atom.
  • substituted means that a hydrogen group has been replaced with a hydrocarbyl group, a heteroatom, or a heteroatom containing group.
  • methyl cyclopentadiene (Cp) is a Cp group substituted with a methyl group.
  • alkoxides include those where the alkyl group is a Ci to C10 hydrocarbyl.
  • the alkyl group may be straight chain, branched, or cyclic.
  • the alkyl group may be saturated or unsaturated.
  • the alkyl group may comprise at least one aromatic group.
  • the term“complex” is used to describe molecules in which an ancillary ligand is coordinated to a central transition metal atom.
  • the ligand is bulky and stably bonded to the transition metal so as to maintain its influence during use of the catalyst, such as polymerization.
  • the ligand may be coordinated to the transition metal by covalent bond and/or electron donation coordination or intermediate bonds.
  • the transition metal complexes are generally subjected to activation to perform their polymerization function using an activator which is believed to create a cation as a result of the removal of an anionic group, often referred to as a leaving group, from the transition metal.
  • “Complex,” as used herein, is also often referred to as“catalyst precursor,”“pre-catalyst,”“catalyst,”“catalyst compound,”“metal compound,”“metal catalyst compound”,“transition metal compound,” or“transition metal complex.” These words are used interchangeably. “Activator” and“cocatalyst” are also used interchangeably.
  • hydrocarbyl radical is defined to be Ci-Cioo radicals, that may be linear, branched, or cyclic, and when cyclic, aromatic or non-aromatic.
  • substituted hydrocarbyl radicals are radicals in which at least one hydrogen atom of the hydrocarbyl radical has been substituted with at least one functional group such as Cl, Br, F, I, NR*2, OR*, SeR*, TeR*, PR*2, AsR*2, SbR*2, SR*, BR*2, SiR*3, GeR*3, SnR*3, PbR*3 and the like (where R* is H or a Ci to C20 hydrocarbyl group), or where at least one heteroatom has been inserted within a hydrocarbyl ring.
  • functional group such as Cl, Br, F, I, NR*2, OR*, SeR*, TeR*, PR*2, AsR*2, SbR*2, SR*, BR*2, SiR*3, GeR*3, SnR*3, PbR*3 and the like (where R* is H or a Ci to C20 hydrocarbyl group), or where at least one heteroatom has been inserted within a hydrocarbyl ring.
  • ring atom means an atom that is part of a cyclic ring structure.
  • a benzyl group has six ring atoms and tetrahydrofuran has 5 ring atoms.
  • A“ring carbon atom” is a carbon atom that is part of a cyclic ring structure.
  • a benzyl group has six ring carbon atoms and para-methylstyrene also has six ring carbon atoms.
  • references to an alkyl, alkenyl, alkoxide, or aryl group without specifying a particular isomer expressly discloses all isomers (e.g., n-butyl, iso-butyl, sec-butyl, and tert-butyl), unless otherwise indicated.
  • aryl or“aryl group” means a six carbon aromatic ring and the substituted variants thereof, including but not limited to, phenyl, 2-methyl-phenyl, xylyl, 4-bromo-xylyl.
  • heteroaryl means an aryl group where a ring carbon atom (or two or three ring carbon atoms) has been replaced with a heteroatom, such as, N, O, or S.
  • arylalkyl is an aryl-substituted alkyl radical and may be used interchangeably with the term“aralkyl”. Examples of aralkyl include benzyl, diphenylmethyl, triphenylmethyl, phenylethyl and diphenylethyl.
  • Cn hydrocarbon(s) having n carbon atom(s) per molecule, wherein n is a positive integer.
  • hydrocarbon means a class of compounds containing hydrogen bound to carbon, 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 values of n.
  • alkenyl means a straight-chain, branched-chain, or cyclic hydrocarbon radical having one or more carbon-carbon double bonds. These alkenyl radicals may be substituted. Examples of suitable alkenyl radicals can include ethenyl, propenyl, allyl, 1,4- butadienyl cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloctenyl and the like including their substituted analogues.
  • A“heterocyclic ring” is a ring having a heteroatom in the ring structure as opposed to a heteroatom substituted ring where a hydrogen on a ring atom is replaced with a heteroatom.
  • tetrahydrofuran is a heterocyclic ring and 4-N,N-dimethylamino-phenyl is a heteroatom substituted ring.
  • aromatic also refers to pseudo aromatic heterocycles which are heterocyclic substituents that have similar properties and structures (nearly planar) to aromatic heterocyclic ligands, but are not by definition aromatic; likewise, the term aromatic also refers to substituted aromatics.
  • the term“contact product” or“the product of the combination of’ is used herein to describe compositions wherein the components are contacted together in any order, in any manner, and for any length of time.
  • the components can be contacted by blending or mixing.
  • contacting of any component can occur in the presence or absence of any other component of the compositions described herein.
  • Combining additional materials or components can be done by any suitable method.
  • the term“contact product” includes mixtures, blends, solutions, slurries, reaction products, and the like, or combinations thereof.
  • “contact product” can include reaction products, it is not required for the respective components to react with one another or react in the manner as theorized.
  • the term “contacting” is used herein to refer to materials which may be blended, mixed, slurried, dissolved, reacted, treated, or otherwise contacted in some other manner.
  • alkyl refers to a saturated hydrocarbon radical having from 1 to 12 carbon atoms (i.e.. C1-C12 alkyl), particularly from 1 to 8 carbon atoms (i.e.. Ci-Ce alkyl), particularly from 1 to 6 carbon atoms (i.e.. Ci-Ce alkyl), and particularly from 1 to 4 carbon atoms (i.e.. C1-C4 alkyl).
  • alkyl groups include, but are not limited to, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl, and so forth.
  • alkyl group may be linear, branched or cyclic. “Alkyl” is intended to embrace all structural isomeric forms of an alkyl group. For example, as used herein, propyl encompasses both n-propyl and isopropyl; butyl encompasses n-butyl, sec-butyl, isobutyl and tert-butyl and so forth.
  • “Ci alkyl” refers to methyl (-CEE)
  • “C2 alkyl” refers to ethyl (- CH2CH3)
  • “C3 alkyl” refers to propyl (-CH2CH2CH3)
  • “C4 alkyl” refers to butyl (e.g., - CH 2 CH2CH2CH3,-(CH3)CHCH 2 CH3, -CH 2 CH(CH 3 )2, etc ).
  • “Me” refers to methyl
  • “Et” refers to ethyl
  • “i-Pr” refers to isopropyl
  • “t-Bu” refers to tert-butyl
  • “Np” refers to neopentyl.
  • alkylene refers to a divalent alkyl moiety containing 1 to 12 carbon atoms (i.e.. C1-C12 alkylene) in length and meaning the alkylene moiety is attached to the rest of the molecule at both ends of the alkyl unit.
  • alkylenes include, but are not limited to, -CEE-, -CH2CH2-, - CH(CH3)CH2-, -CH2CH2CH2-, etc.
  • the alkylene group may be linear or branched.
  • alkenyl refers to an unsaturated hydrocarbon radical having from 2 to 12 carbon atoms (i.e., C2-C12 alkenyl), particularly from 2 to 8 carbon atoms (i.e.. C2-C8 alkenyl), particularly from 2 to 6 carbon atoms (i.e., C2-C6 alkenyl), and having one or more (e.g., 2, 3, etc.,) carbon-carbon double bonds.
  • the alkenyl group may be linear, branched or cyclic.
  • alkenyls include, but are not limited to ethenyl (vinyl), 2-propenyl, 3-propenyl, 1 ,4-pentadienyl, l,4-butadienyl, l-butenyl, 2-butenyl and 3-butenyl.
  • Alkenyl is intended to embrace all structural isomeric forms of an alkenyl. For example, butenyl encompasses l,4-butadienyl, l-butenyl, 2-butenyl and 3-butenyl, etc.
  • alkenylene refers to a divalent alkenyl moiety containing 2 to about 12 carbon atoms (i.e.. C2-C12 alkenylene) in length and meaning that the alkylene moiety is attached to the rest of the molecule at both ends of the alkyl unit.
  • the alkenylene group may be linear or branched.
  • alkynyl refers to an unsaturated hydrocarbon radical having from 2 to 12 carbon atoms (i.e., C2-C12 alkynyl), particularly from 2 to 8 carbon atoms (i.e.. C2-C8 alkynyl), particularly from 2 to 6 carbon atoms (/. e. , C2-C6 alkynyl), and having one or more (e.g. , 2, 3, etc.) carbon-carbon triple bonds.
  • the alkynyl group may be linear, branched or cyclic.
  • alkynyls include, but are not limited to ethynyl, l-propynyl, 2-butynyl, and l,3-butadiynyl.
  • Alkynyl is intended to embrace all structural isomeric forms of an alkynyl. For example, butynyl encompasses 2- butynyl, and l,3-butadiynyl and propynyl encompasses l-propynyl and 2-propynyl (propargyl).
  • alkynylene refers to a divalent alkynyl moiety containing 2 to about 12 carbon atoms (i.e.. C2-C12 alkenylene) in length and meaning that the alkylene moiety is atached to the rest of the molecule at both ends of the alkyl unit.
  • alkenylenes include, but are not limited to, -CoC-, CoCCH2-, -CoCCH2CoC-, -CH2CH2CoCCH2-.
  • the alkynylene group may be linear or branched.
  • alkoxy refers to— O— alkyl containing from 1 to about 10 carbon atoms.
  • the alkoxy may be straight-chain or branched-chain.
  • Non-limiting examples include methoxy, ethoxy, propoxy, butoxy, isobutoxy, tert-butoxy, pentoxy, and hexoxy.
  • “Ci alkoxy” refers to methoxy
  • “C2 alkoxy” refers to ethoxy
  • C3 alkoxy refers to propoxy
  • C4 alkoxy refers to butoxy.
  • OMe refers to methoxy and“OEt” refers to ethoxy.
  • aromatic refers to unsaturated cyclic hydrocarbons having a delocalized conjugated p system and having from 5 to 20 carbon atoms (aromatic C5-C20 hydrocarbon), particularly from 5 to 12 carbon atoms (aromatic C5-C 12 hydrocarbon), and particularly from 5 to 10 carbon atoms (aromatic C5-C12 hydrocarbon).
  • Exemplary aromatics include, but are not limited to benzene, toluene, xylenes, mesitylene, ethylbenzenes, cumene, naphthalene, methylnaphthalene, dimethylnaphthalenes, ethylnaphthalenes, acenaphthalene, anthracene, phenanthrene, tetraphene, naphthacene, benzanthracenes, fluoranthrene, pyrene, chrysene, triphenylene, and the like, and combinations thereof.
  • isomers of a named alkyl, alkenyl, alkoxy, or aryl group exist (e.g., n-butyl, iso-butyl, sec-butyl, and tert-butyl) reference to one member of the group (e.g., n-butyl) shall expressly disclose the remaining isomers (e.g., iso-butyl, sec- butyl, and tert-butyl) in the family.
  • alkyl, alkenyl, alkoxide, or aryl group without specifying a particular isomer (e.g., butyl) expressly discloses all isomers (e.g., n-butyl, iso-butyl, sec-butyl, and tert-butyl).
  • hydroxyl refers to an -OH group.
  • oxygenate refers to a saturated, unsaturated, or polycyclic cycbzed hydrocarbon radical containing from 1 to 40 carbon atoms and further containing one or more oxygen heteroatoms.
  • aluminum alkyl adducts refers to the reaction product of aluminum alkyls and/or alumoxanes with quenching agents, such as water and/or methanol.
  • An“olefin,” alternatively referred to as“alkene,” is a linear, branched, or cyclic compound of carbon and hydrogen having at least one double bond.
  • the olefin present in such polymer or copolymer is the polymerized form of the olefin.
  • ethylene content of 35 wt% to 55 wt%
  • the mer unit in the copolymer is derived from ethylene in the polymerization reaction and said derived units are present at 35 wt% to 55 wt% based upon the weight of the copolymer.
  • A“polymer” has two or more of the same or different mer units.
  • A“homopolymer” is a polymer having mer units that are the same.
  • A“copolymer” is a polymer having two or more mer units that are distinct or different from each other.
  • A“terpolymer” is a polymer having three mer units that are distinct or different from each other. “Distinct” or“different” as used to refer to mer units indicates that the mer units differ from each other by at least one atom or are different isomerically. Accordingly, the definition of copolymer, as used herein, includes terpolymers and the like.
  • ethylene polymer or "ethylene copolymer” is a polymer or copolymer comprising at least 50 mol% ethylene derived units
  • a "propylene polymer” or “propylene copolymer” is a polymer or copolymer comprising at least 50 mol% propylene derived units, and so on.
  • Polymerizable conditions refer those conditions including a skilled artisan’s selection of temperature, pressure, reactant concentrations, optional solvent/diluents, reactant mixing/addition parameters, and other conditions within at least one polymerization reactor that are conducive to the reaction of one or more olefin monomers when contacted with an activated olefin polymerization catalyst to produce the desired polyolefin polymer through suitable coordination polymerization.
  • BOCD refers to a Broad Orthogonal Composition Distribution in which the comonomer of a copolymer is incorporated predominantly in the high molecular weight chains or species of a polyolefin polymer or composition.
  • the distribution of the short chain branches can be measured, for example, using Temperature Raising Elution Fractionation (TREF) in connection with a Light Scattering (LS) detector to determine the weight average molecular weight of the molecules eluted 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 across the chains of different molecular weights of polymer chains.
  • BOCD has been described, for example, in U.S. Patent Nos. 8,378,043, Col. 3, line 34, bridging Col. 4, line 19, and 8,476,392, line 43, bridging Col. 16, line 54.
  • the breadth of the composition distribution is characterized by the T75- T25 value, wherein T25 is the temperature at which 25% of the eluted polymer is obtained and T75 is the temperature at which 75% of the eluted polymer is obtained in a TREF experiment as described herein.
  • the composition distribution is further characterized by the Fxo value, which is the fraction of polymer that elutes below 80°C in a TREF-LS experiment as described herein. A higher Fxo value indicates a higher fraction of comonomer in the polymer molecule.
  • An orthogonal composition distribution is defined by a M60/M90 value that is greater than 1, wherein Mbo is the molecular weight of the polymer fraction that elutes at 60°C in a TREF-LS experiment and M90 is the molecular weight of the polymer fraction that elutes at 90°C in a TREF-LS experiment as described herein.
  • the polymers as described herein may have a BOCD characterized in that the T75-T25 value is 1 or greater, 2.0 or greater, 2.5 or greater, 4.0 or greater, 5.0 or greater, 7.0 or greater, 10.0 or greater, 11.5 or greater, 15.0 or greater, 17.5 or greater, 20.0 or greater, 25.0 or greater, 30.0 or greater, 35.0 or greater, 40.0 or greater, or 45.0 or greater, wherein T25 is the temperature at which 25% of the eluted polymer is obtained and T75 is the temperature at which 75% of the eluted polymer is obtained in a TREF experiment as described herein.
  • the polymers as described herein may further have a BOCD characterized in that M60/M90 value is 1.5 or greater, 2.0 or greater, 2.25 or greater, 2.50 or greater, 3.0 or greater, 3.5 or greater, 4.0 or greater, 4.5 or greater, or 5.0 or greater, wherein Mbo is the molecular weight of the polymer fraction that elutes at 60°C in a TREF-LS experiment and M90 is the molecular weight of the polymer fraction that elutes at 90°C in a TREF-LS experiment as described herein.
  • Mbo is the molecular weight of the polymer fraction that elutes at 60°C in a TREF-LS experiment
  • M90 is the molecular weight of the polymer fraction that elutes at 90°C in a TREF-LS experiment as described herein.
  • a catalyst may be described as a catalyst precursor, a pre catalyst compound, metallocene catalyst compound or a transition metal compound, and these terms are used interchangeably.
  • a polymerization catalyst system is a catalyst system that can polymerize monomers into polymer.
  • An“anionic ligand” is a negatively charged ligand which donates one or more pairs of electrons to a metal ion.
  • A“neutral donor ligand” is a neutrally charged ligand which donates one or more pairs of electrons to a metal ion.
  • continuous means a system that operates without interruption or cessation for a period of time, such as where reactants are continually fed into a reaction zone and products are continually or regularly withdrawn without stopping the reaction in the reaction zone.
  • a continuous process to produce a polymer would be one where the reactants are continually introduced into one or more reactors and polymer product is continually withdrawn.
  • a “solution polymerization” means a polymerization process in which the polymerization is conducted in a liquid polymerization medium, such as an inert solvent or monomer(s) or their blends.
  • a suitable solution polymerization can be homogeneous.
  • a homogeneous polymerization is one where the polymer product is dissolved in the polymerization medium.
  • Such systems are preferably not turbid as described in J. Vladimir Oliveira, C. Dariva and J. C. Pinto, Ind. Eng. Chem. Res., 2000, 29, 4627.
  • a bulk polymerization means a polymerization process in which the monomers and/or comonomers being polymerized are used as a solvent or diluent using little or no inert solvent or diluent.
  • a small fraction of inert solvent might be used as a carrier for catalyst and scavenger.
  • a bulk polymerization system contains less than about 25 wt% of inert solvent or diluent, such as less than about 10 wt%, such as less than about 1 wt%, such as 0 wt%.
  • Catalyst productivity is a measure of how many grams of polymer (P) are produced using a polymerization catalyst comprising W g of catalyst (cat), over a period of time of T hours; and may be expressed by the following formula: P/(T x W) and expressed in units of gPgcar'hr 1 .
  • Conversion is the amount of monomer that is converted to polymer product, and is reported as mol% and is calculated based on the polymer yield and the amount of monomer fed into the reactor.
  • Catalyst activity is a measure of the level of activity of the catalyst and is reported as the mass of product polymer (P) produced per mole (or mmol) of catalyst (cat) used (kgP/molcat or gP/mmolCat), and catalyst activity can also be expressed per unit of time, for example, per hour (hr).
  • An“olefin,” is a linear, branched, or cyclic compound of carbon and hydrogen having at least one double bond.
  • the olefin present in such polymer or copolymer is the polymerized form of the olefin.
  • a copolymer is said to have an“ethylene” content of 35 wt% to 55 wt%, it is understood that the mer unit in the copolymer is derived from ethylene in the polymerization reaction and said derived units are present at 35 wt% to 55 wt% based upon the weight of the copolymer.
  • a “polymer” has two or more of the same or different mer units.
  • A“homopolymer” is a polymer having mer units that are the same.
  • A“copolymer” is a polymer having two or more mer units that are different from each other. “Different” as used to refer to mer units indicates that the mer units differ from each other by at least one atom or are different isomerically . Accordingly, the definition of copolymer, as used herein, includes terpolymers and the like.
  • An“ethylene polymer” or“ethylene copolymer” is a polymer or copolymer comprising at least 50 mol% ethylene derived units
  • a“propylene polymer” or“propylene copolymer” is a polymer or copolymer comprising at least 50 mol% propylene derived units, and so on.
  • an ethylene polymer having a density of 0.86 g/cm 3 or less is referred to as an ethylene elastomer or elastomer; an ethylene polymer having a density of more than 0.86 to less than 0.910 g/cm 3 is referred to as an ethylene plastomer or plastomer; an ethylene polymer having a density of 0.910 to 0.940 g/cm 3 is referred to as a low density polyethylene; and an ethylene polymer having a density of more than 0.940 g/cm 3 is referred to as a high density polyethylene (HDPE).
  • HDPE high density polyethylene
  • Density is determined according to ASTM D 1505 using a density -gradient column on a compression-molded specimen that has been slowly cooled to room temperature (i.e., over a period of 10 minutes or more) and allowed to age for a sufficient time that the density is constant within +/- 0.001 g/cm 3 ).
  • Linear polyethylene means that the polyethylene has no long chain branches and is referred to as a branching index (g' vis ) °f 0.97 or above, such as 0.98 or above. Branching index, gVis, is measured by GPC-4D as described below. [0079] For purposes of the present disclosure, ethylene shall be considered an alpha-olefin (a-olefm).
  • M n is number average molecular weight
  • M w is weight average molecular weight
  • M z is z average molecular weight
  • wt% is weight percent
  • mol% is mole percent.
  • Mw, Mn, Mz all average molecular weights (e.g., Mw, Mn, Mz) are reported in units of g/mol.
  • Molecular weight distribution (MWD) also referred to as polydispersity index (PDI) is defined to be Mw divided by Mn.
  • Me is methyl
  • Et is ethyl
  • t-Bu and l Bu are tertiary butyl
  • iPr and ' Pr are isopropyl
  • Cy is cyclohexyl
  • THF also referred to as thf
  • Bn is benzyl
  • Ph is phenyl
  • Cp is cyclopentadienyl
  • Cp* is pentamethyl cyclopentadienyl
  • Ind is indenyl
  • Flu is fluorenyl
  • MAO is methylalumoxane.
  • one catalyst compound is considered different from another if they differ by at least one atom.
  • “bisindenyl zirconium dichloride” is different from“(indenyl)(2-methylindenyl) zirconium dichloride” which is different from“(indenyl)(2-methylindenyl) hafnium di chloride.”
  • Catalyst compounds that differ only by isomer are considered the same for purposes of the present disclosure, e.g., rac- bis(l-methylindenyl)hafnium dimethyl is considered to be the same as /we.v -bis( 1 -methyl- indenyl)hafnium dimethyl.
  • a single catalyst component having a racemic and/or meso isomer does not, itself, constitute two different catalyst components.
  • the catalyst systems comprise a Group 4 metallocene catalyst represented by formula (I):
  • M is a group 4 metal such as hafnium (Hf) or zirconium (Zr) in at least one embodiment, M is hafnium.
  • X 1 and X 2 are independently a univalent anionic ligand, a diene ligand, an alk lidene ligand, or X 1 and X 2 are joined to form a metallocyclic ring.
  • X 1 and X 2 can be independently a halide, a hydride, an alkyl group, an alkenyl group or an arylalkyl group.
  • X 1 and X 2 are independently selected from hydrocarbyl radicals having from 1 to 20 carbon atoms, aryls, hydrides, amides, alkoxides, sulfides, phosphides, halides, dienes, amines, phosphines, ethers, and a combination thereof, (X 1 and X 2 may form a part of a fused ring or a ring system), such as X 1 and X 2 are independently selected from halides, aryls and Ci to Cs alkyl groups, such as X 1 and X 2 is independently a phenyl, methyl, ethyl, propyl, butyl, pentyl, or chloride group. In at least one embodiment, X 1 and X 2 are chloride.
  • Each of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 13 , R 14 , R 15 , and R 16 is independently selected from hydrogen, halogen, C1-C40 hydrocarbyl, substituted C1-C40 hydrocarbyl, -NR'2, -SR', -OR’, - OSiR'3, or -PR'2, wherein each R' is independently hydrogen, halogen, C1-C10 alkyl, or C6-C10 aryl, or one or more of R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 4 and R 5 , R 1 and R 5 , R 14 and R 15 , and R 15 and R 16 are joined to form a saturated ring, unsaturated ring, substituted saturated ring, or substituted unsaturated ring.
  • each of R 6 and R 13 is hydrogen. In at least one embodiment, one or more of R 1 , R 2 , R 3 , R 4 , and R 5 is -CH2-Si-(CH3)3. In at least one embodiment, R 1 , R 2 , R 3 , and R 4 are each hydrogen and R 5 is -CH2-Si-(CH3)3. In at least one embodiment, each of R 14 , R 15 , and R 16 is hydrogen.
  • Each of R 7 , R 8 , R 9 , R 10 , R 11 , and R 12 is independently selected from hydrogen, halogen, C1-C40 hydrocarbyl, substituted C1-C40 hydrocarbyl, aryl, substituted aryl, -NR'2, -SR', -OR’, -OSiR'3, or -PR'2, wherein each R' is independently hydrogen, halogen, C1-C10 alkyl, or C6-C10 aryl, or one or more of R 7 and R 8 , R 8 and R 10 , and R 10 and R 12 are joined to form a saturated ring, unsaturated ring, substituted saturated ring, or substituted unsaturated ring.
  • each of R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , and R 13 is hydrogen.
  • each of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , and R 16 is independently is independently hydrogen, halide, alkoxide or Ci to C40 substituted or unsubstituted hydrocarbyl (such as Ci to C12 substituted or unsubstituted hydrocarbyl), or -R -SiR'3 or -R -CR'3 where R is Ci to C4 hydrocarbyl (such as -CH2-; - CH2CH2-; -(Me)CHCH2-; or -(Me)CH-), and each R' is independently Ci to C20 substituted or unsubstituted hydrocarbyl and at least one R' is Ci to C20 substituted or unsubstituted hydrocarbyl.
  • each R’ is independently selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, phenyl, biphenyl, or an isomer thereof
  • R' is a Ci to C20 alkyl or aryl, such as methyl, methyl phenyl, phenyl, biphenyl, pentamethylphenyl, tetramethylphenyl, or di-t-butylphenyl, provided that at least one R' is not H, alternatively 2 R' are not H, alternatively 3 R' are not H.
  • C 1-C40 hydrocarbyl, C1-20 hydrocarbyl, or C1-C12 hydrocarbyl is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, n- pentyl, isopentyl, sec-pentyl, n-hexyl, isohexyl, sec-hexyl, n-heptyl, isoheptyl, sec-heptyl, n- octyl, isooctyl, sec-octyl, n-nonyl, isononyl, sec-nonyl, n-decyl, isodecyl, or sec-decyl.
  • each of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , and R 16 is independently hydrogen, -CH2-SiMe3, -CH2-SiEt3, -CEh-SiPn, - CH2-S1BU3, -CH 2 -SiCy 3 , -CH 2 -C(CH 3 )3, -CH 2 -CH(CH3) 2 , -CH 2 CPh 3 , -CltyCeMes), -CH 2 - C(CH 3 ) 2 Ph, -CH 2 -C(Cy)Ph 2 , -CH 2 SiPh 3 , -CH 2 -Si(CH3) 2 Ph, -CH 2 -Si(CH3) 2 Ph, -CH 2 - Si(CH 3 , -CH 2 -S
  • each of R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , and R 13 is hydrogen and each of R 1 , R 2 , R 3 , R 4 , R 5 , R 14 , R 15 , and R 16 is independently hydrogen, -CEh-SilVte, - CH 2 -SiEt 3 , -CH 2 -SiPr 3 , -CH2-S1BU3, -CH 2 -SiCy 3 , -CH 2 -C(CH 3 )3, -CH 2 -CH(CH3) 2 , - CH 2 CPh 3 , -CH 2 (C6Me 5 ), -CH 2 -C(CH3) 2 Ph, -CH 2 -C(Cy)Ph 2 , -CH 2 SiPh 3 , -CH 2 -Si(CH3) 2 Ph, - CH 2 -Si(CH 3 )
  • each of R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , and R 16 is hydrogen and each of R 1 , R 2 , R 3 , R 4 , and R 5 is independently hydrogen, -CH2-SiMe3, - CH 2 -SiEt3, -CEh-SiPn, -CH2-S1BU3, -CTB-SiCys, -CH2-C(CH 3 )3, -CH 2 -CH(CH3) 2 , - CH 2 CPh 3 , -CH 2 (C6Me 5 ), -CH 2 -C(CH3) 2 Ph, -CH 2 -C(Cy)Ph 2 , -CH 2 SiPh 3 , -CH 2 -Si(CH3) 2 Ph, - CH 2 -Si(CH 3 )2Ph, -CH 2 -S
  • a catalyst represented by formula (I) can be an asymmetric catalyst.
  • Useful asymmetric catalysts can be such that a mirror plane cannot be drawn through the metal center and the cyclopentadienyl moieties bridged to the metal center are structurally different.
  • the Group 4 metallocene catalyst represented by formula (I) is one or more of:
  • the Group 4 metallocene catalyst represented by formula (I) is one or more of:
  • the second catalyst may be an iron complex represented by formula (II):
  • R 6a and R 15a are independently halogen, -CF3, hydrogen, or Ci-C22-alkyl, or -OR’. In at least one embodiment, R 6a and R 15a are independently fluorine, chlorine, bromine, or iodine. In at least one embodiment, R 6a and R 15a are chlorine.
  • R la and R 2a is independently hydrogen, Ci-C22-alkyl, C2-C22-alkenyl, Ce-
  • R la and R 2a are independently Ci-C22-alkyl, substituted Ci-C22-alkyl, unsubstituted phenyl, or substituted phenyl.
  • each of R la and R 2a is independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, tert-pentyl, n-hexyl, isohexyl, sec-hexyl, tert-hexyl, n-heptyl, isoheptyl, sec-heptyl, tert-heptyl, n-octyl, isooctyl, sec-octyl, tert-octyl, n-nonyl,
  • Each of R 3a , R 4a , R 5a , R 7a , R 8a , R 9a , R 10a , R l la , R 12a , R 13a , and R 14a is independently hydrogen, Ci-C22-alkyl, C2-C22-alkenyl, C6-C22-aryl, arylalkyl wherein alkyl has from 1 to 10 carbon atoms and aryl has from 6 to 20 carbon atoms, -NR 2, -OR , halogen, -SiR 3 or five-, six- or seven-membered heterocyclyl comprising at least one atom selected from N, P, O and S.
  • each of R 3a , R 4a , R 5a , R 7a , R 8a , R 9a , R 10a , R l la , R 12a , R 13a , and R 14a is independently optionally substituted by halogen, -NR 2, -OR or -SiR 3.
  • each of R 8a , R 10a , R l la , and R 13a is independently selected from Ci-C22-alkyl, wherein each of R 8a , R 10a , R l la , and R 13a is independently optionally substituted by halogen, -NR 2, -OR or -SiR 3.
  • R 7a , R 9a , R 12a , and R 14a is hydrogen.
  • each of R 3a , R 4a , and R 5a is hydrogen.
  • X la and X 2a are independently halogen, hydrogen, Ci-C2o-alkyl, C2-C 10-alkenyl, CV C2o-aryl, arylalkyl wherein alkyl has from 1 to 10 carbon atoms and aryl has from 6 to 20 carbon atoms, -NR 2, -OR , -SR , -SO3R , -OC(0)R , -CN, -SCN, b-diketonate, -CO, -BFG, - PFe or bulky non-coordinating anion, or X la and X 2a optionally bond to form a five- or six- membered ring.
  • Each R is independently hydrogen, Ci-C22-alkyl, C2-C22-alkenyl, C6-C22-aryl, arylalkyl wherein alkyl has from 1 to 10 carbon atoms and aryl has from 6 to 20 carbon atoms, or -SiR 3, wherein R is optionally substituted by halogen or nitrogen- or oxygen-containing groups, or two R radicals optionally bond to form a five- or six-membered ring.
  • Each R is independently hydrogen, Ci-C22-alkyl, C2-C22-alkenyl, C6-C22-aryl, arylalkyl wherein alkyl has from 1 to 10 carbon atoms and aryl has from 6 to 20 carbon atoms, wherein each R is optionally substituted by halogen or nitrogen- or oxygen-containing groups, or two R radicals optionally bond to form a five- or six-membered ring.
  • X la and X 2a are chlorine.
  • each of R 6a and R 15a is chlorine; each of R la and R 2a is C1-C20 hydrocarbyl; each of R 3a , R 4a , and R 5a is hydrogen; each of R 8a , R 10a , R l la and R 13a is C1-C20 hydrocarbyl; each of R 7a , R 9a , R 12a and R 14a is independently hydrogen, Ci-C22-alkyl, C2-C22-alkenyl, C6-C22-aryl, arylalkyl where alkyl has from 1 to 10 carbon atoms and aryl has from 6 to 20 carbon atoms, -NR 2, -OR , halogen, -SiR 3 or five-, six- or seven-membered heterocyclyl comprising at least one atom selected from the group consisting of N, P, O and S; R i a, p i a RY R 4a .
  • R 1 l a . R l 2a . and R 13a are optionally substituted by halogen, -NR 2, -OR or -SiR 3;
  • each R is independently hydrogen, Ci-C22-alkyl, C2-C22- alkenyl, C6-C22-aryl, arylalkyl where alkyl has from 1 to 10 carbon atoms and aryl has from 6 to 20 carbon atoms, or -SiR 3, wherein R is optionally substituted by halogen, or two R radicals optionally bond to form a five- or six-membered ring;
  • each R is independently hydrogen, Ci-C22-alkyl, C2-C22-alkenyl, C6-C22-aryl or arylalkyl where alkyl has from 1 to 10 carbon atoms and aryl has from 6 to 20 carbon atoms,
  • an iron catalyst represented by formula (II) is one or more of:
  • an iron catalyst represented by formula (II) is one or more of:
  • the catalyst systems comprise the product of the combination of one or more support materials.
  • a support material is a porous support material, for example, talc, and inorganic oxides.
  • Other support materials include zeolites, clays, organoclays, or any other organic or inorganic support material, or mixtures thereof.
  • “support” and“support material” are used interchangeably.
  • a support material is an inorganic oxide in a finely divided form.
  • Suitable inorganic oxide materials for use in the supported catalyst systems herein include Groups 2, 4, 13, and 14 metal oxides such as silica, alumina, and mixtures thereof.
  • Other inorganic oxides that may be employed, either alone or in combination, with the silica or alumina are magnesia, titania, zirconia, and the like.
  • Other suitable support materials can be employed, for example, finely divided functionalized polyolefins such as finely divided polyethylene.
  • Particularly useful supports include magnesia, titania, zirconia, montmorillonite, phyllosilicate, zeolites, talc, clays, and the like. Also, combinations of these support materials may be used, for example, silica-chromium, silica-alumina, silica- titania, and the like. Exemplary support materials include AI2O3, ZrOi. S1O2, and combinations thereof, such as, S1O2, AI2O3, or S1O2/AI2O3.
  • a support material such as an inorganic oxide, can have a surface area in the range of from about 10 m 2 /g to about 700 m 2 /g, pore volume in the range of from about 0.1 cc/g to about 4.0 cc/g, and average particle size in the range of from about 5 pm to about 500 pm.
  • the surface area of a support material is in the range of from about 50 m 2 /g to about 500 m 2 /g, pore volume of from about 0.5 cc/g to about 3.5 cc/g, and average particle size of from about 10 pm to about 200 pm.
  • the surface area of a support material is in the range of from about 100 m 2 /g to about 400 m 2 /g, pore volume from about 0.8 cc/g to about 3.0 cc/g, and average particle size is from about 5 pm to about 100 pm.
  • the average pore size of a support material useful in at least one embodiment of the present disclosure is in the range of from 10 to 1,000 A, such as 50 to about 500 A, such as 75 to about 350 A.
  • a support material is a high surface area, amorphous silica (surface area > 300 m 2 /gm, pore volume > 1.65 cm 3 /gm), and is marketed under the trade names of DAVISON 952 or DAVISON 955 by the Davison Chemical Division of W. R. Grace and Company, are particularly useful. In other embodiments, DAVIDSON 948 is used.
  • a support material may be dry, that is, free of absorbed water. Drying of the support material can be achieved by heating or calcining at about l00°C to about l000°C, such as at least about 600°C.
  • a support material is silica
  • it is heated to at least 200°C, such as about 200°C to about 850°C, such as at about 600°C; and for a time of 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 can have at least some reactive hydroxyl (OH) groups.
  • the above two catalysts (represented by I and II) described herein are generally deposited on a support material at a loading level of 10-100 micromoles of metal per gram of solid support; alternatively 20-80 micromoles of metal per gram of solid support; or 40-60 micromoles of metal per gram of support. But greater or lesser values may be used provided that the total amount of solid complex does not exceed the support's pore volume.
  • the catalyst systems (which can be supported on one or more support materials) can include activators and be combined in any suitable manner.
  • Activators are defined to be any compound which can activate any one of the catalyst compounds described above by converting the neutral metal catalyst compound to a catalytically active metal catalyst compound cation.
  • Non-limiting activators include alumoxanes, aluminum alkyls, ionizing activators, which may be neutral or ionic, and conventional-type cocatalysts.
  • Exemplary activators can include alumoxane compounds, modified alumoxane compounds, and ionizing anion precursor compounds that abstract a reactive, s-bound, metal ligand making the metal catalyst compound cationic and providing a charge-balancing non-coordinating or weakly coordinating anion.
  • Alumoxane activators can be utilized as activators in the catalyst systems described herein.
  • Alumoxanes are generally oligomeric compounds containing -A ⁇ R ⁇ -O- sub-units, where R 1 is an alkyl group.
  • Examples of alumoxanes include methylalumoxane (MAO), modified methylalumoxane (MMAO), ethylalumoxane and isobutylalumoxane.
  • Alkylalumoxanes and modified alkylalumoxanes are suitable as catalyst activators, particularly when the abstractable ligand is an alkyl, halide, alkoxide or amide.
  • alumoxanes and modified alumoxanes may also be used. It may be more suitable to use a visually clear methylalumoxane.
  • a cloudy or gelled alumoxane can be filtered to produce a clear solution or clear alumoxane can be decanted from the cloudy solution.
  • a useful alumoxane is a modified methyl alumoxane (MMAO) cocatalyst type 3A (commercially available from Akzo Chemicals, Inc. under the trade name Modified Methylalumoxane type 3 A, covered under U.S. Patent No. 5,041,584).
  • MMAO modified methyl alumoxane
  • alumoxane is solid polymethylaluminoxane as described in US Patent Nos. 9,340,630; 8,404,880; and 8,975,209.
  • Aluminum alkyls are available as hydrocarbon solutions from commercial sources.
  • Methylalumoxane (“MAO") is available from Albemarle as a 30 wt% solution in toluene.
  • the activator is an alumoxane (modified or unmodified)
  • at least one embodiment select the maximum amount of activator such as at up to a 5000-fold molar excess Al/M over one of the catalyst compounds (per metal catalytic site).
  • the minimum activator-to-catalyst-compound is a 1 : 1 molar ratio. Alternate ranges include from 1 : 1 to 500: 1, alternatively from 1 : 1 to 200:1, alternatively from 1: 1 to 100: 1, or alternatively from 1: 1 to 50: 1.
  • alumoxane is present at zero mol%, alternatively the alumoxane is present at a molar ratio of aluminum to catalyst compound transition metal less than 500: 1, such as less than 300: 1, such as less than 100: 1, such as less than 1 : 1.
  • a non-coordinating anion is an anion either that does not coordinate to the catalyst metal cation or that does coordinate to the metal cation, but only weakly.
  • NCA is also defined to include multicomponent NCA-containing activators, such as N,N- dimethylanilinium tetrakis(pentafluorophenyl)borate, that contain an acidic cationic group and the non-coordinating anion.
  • NCA is also defined to include neutral Lewis acids, such as tris(pentafluorophenyl)boron, that can react with a catalyst to form an activated species by abstraction of an anionic group.
  • NCA coordinates weakly enough that a neutral Lewis base, such as an olefmically or acetylenically unsaturated monomer can displace it from the catalyst center.
  • a neutral Lewis base such as an olefmically or acetylenically unsaturated monomer can displace it from the catalyst center.
  • Any metal or metalloid that can form a compatible, weakly coordinating complex may be used or contained in the non-coordinating anion.
  • Suitable metals can include aluminum, gold, and platinum.
  • Suitable metalloids can include boron, aluminum, phosphorus, and silicon.
  • Non-coordinating anions are those which are not degraded to neutrality when the initially formed complex decomposes. Further, the anion will not transfer an anionic substituent or fragment to the cation so as to cause it to form a neutral transition metal compound and a neutral by-product from the anion.
  • Non-coordinating anions useful in accordance with the present disclosure are those that are compatible, stabilize the transition metal cation in the sense of balancing its ionic charge at +1, and yet retain sufficient lability to permit displacement during polymerization.
  • Activation may be performed using non-coordinating anions (NCAs) of the type, for example, described in EP 277 003 Al and EP 277 004 Al.
  • NCA may be added in the form of an ion pair using, for example, [DMAH]+ [NCA]- in which the N,N-dimethylanilinium (DMAH) cation reacts with a basic leaving group on the transition metal complex to form a transition metal complex cation and [NCA]-.
  • the cation in the precursor may, alternatively, be trityl ((Ph)3C + ).
  • the transition metal complex may be reacted with a neutral NCA precursor, such as B(C6F5)3, which abstracts an anionic group from the complex to form an activated species.
  • a neutral NCA precursor such as B(C6F5)3 abstracts an anionic group from the complex to form an activated species.
  • Useful activators include N,N-dimethylanilinium tetrakis (pentafluorophenyl)borate (i.e., [PhNMe2H]B(C6F5)4) and N,N-dimethylanilinium tetrakis (heptafluoronaphthyl)borate, where Ph is phenyl, and Me is methyl.
  • Aluminum alkyl or organoaluminum compounds which may be utilized as co activators include, for example, trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, diethyl zinc, tri-n-butylaluminum, diisobutylaluminum hydride, or combinations thereof.
  • the catalyst systems will additionally comprise one or more scavenging compounds.
  • the term“scavenger” means a compound that removes polar impurities from the reaction environment. These impurities adversely affect catalyst activity and stability.
  • the scavenging compound will be an organometallic compound such as the Group-l3 organometallic compounds of U.S. Patent Nos. 5,153,157; 5,241,025; and WO 91/09882; WO 94/03506; WO 93/14132; and that of WO 95/07941.
  • Exemplary compounds include triethyl aluminum, triethyl borane, tri-Ao-butyl aluminum, methyl alumoxane, Ao-butyl alumoxane, and tri-n-octyl aluminum.
  • Those scavenging compounds having bulky or C6-C20 linear hydrocarbyl substituents connected to the metal or metalloid center usually minimize adverse interaction with the active catalyst.
  • Examples include triethyl aluminum, and bulky compounds such as tri-Ao-butyl aluminum, tri-Ao-prenyl aluminum, and long-chain linear alkyl-substituted aluminum compounds, such as tri-n-hexyl aluminum, tri-n-octyl aluminum, or tri-n-dodecyl aluminum.
  • triethyl aluminum and bulky compounds such as tri-Ao-butyl aluminum, tri-Ao-prenyl aluminum, and long-chain linear alkyl-substituted aluminum compounds, such as tri-n-hexyl aluminum, tri-n-octyl aluminum, or tri-n-dodecyl aluminum.
  • Exemplary aluminum scavengers include those where there is oxygen present. That is, the material per se or the aluminum mixture used as a scavenger, includes an aluminum/oxygen species, such as an alumoxane or alkylaluminum oxides, e.g., dialkyaluminum oxides, such as bis(diisobutylaluminum) oxide.
  • aluminum containing scavengers can be represented by the formula ((Rz-Al-) y O-) x , wherein z is 1-2, y is 1-2, x is 1-100, and R is a C1-C12 hydrocarbyl group.
  • the scavenger has an oxygen to aluminum (O/AI) molar ratio of from about 0.25 to about 1.5, more particularly from about 0.5 to about 1.
  • the above two catalyst types can be combined to form a mixed catalyst system.
  • the two or more metal catalysts can be added together in a desired ratio when combined, contacted with an activator, or contacted with a support material or a supported activator.
  • the metal catalyst compounds may be added to the mixture sequentially or simultaneously.
  • the molar ratio of a catalyst represented by formula (I) to a catalyst represented by formula (II) can vary depending on the balance of processability versus physical characteristics of the desired polymer.
  • the molar ratio (I) : (II) can range from 20: 1 to 1 : 1, such as from 1: 1 to 20: 1, such as from 1 : 1 to 3: 1, such as from 0.6:0.4 to 0.8:0.2, for example 0.7:0.3.
  • the first metal catalyst compound may be supported via contact with a support material for a reaction time.
  • the resulting supported catalyst composition may then be mixed with mineral oil to form a slurry, which may or may not include an activator.
  • the slurry may then be admixed with a second metal catalyst compound prior to introduction of the resulting mixed catalyst system to a polymerization reactor.
  • the second metal catalyst compounds may be admixed at any point prior to introduction to the reactor, such as in a polymerization feed vessel or in-line in a catalyst delivery system.
  • the mixed catalyst system may be formed by combining a first metal catalyst compound (for example a metal catalyst compound useful for producing a first polymer attribute, such as a high molecular weight polymer fraction) with a support and activator, desirably in a first diluent such as an alkane or toluene, to produce a supported, activated catalyst compound.
  • a first metal catalyst compound for example a metal catalyst compound useful for producing a first polymer attribute, such as a high molecular weight polymer fraction
  • a support and activator desirably in a first diluent such as an alkane or toluene
  • the supported activated catalyst compound is then combined in one embodiment with a high viscosity diluent such as mineral or silicon oil, or an alkane diluent comprising from 5 to 99 wt% mineral or silicon oil to form a slurry of the supported metal catalyst compound, followed by, or simultaneous to combining with a second metal catalyst compound (for example, a metal catalyst compound useful for producing a second polymer attribute, such as a low molecular weight polymer fraction or low comonomer content), either in a diluent or as the dry solid compound, to form a supported activated mixed catalyst system (“mixed catalyst system”).
  • a high viscosity diluent such as mineral or silicon oil, or an alkane diluent comprising from 5 to 99 wt% mineral or silicon oil
  • a second metal catalyst compound for example, a metal catalyst compound useful for producing a second polymer attribute, such as a low molecular weight polymer fraction or low comonomer content
  • the mixed catalyst system thus produced may be a supported and activated first metal catalyst compound in a slurry, the slurry comprising mineral or silicon oil, with a second metal catalyst compound that is not supported and not combined with additional activator, where the second metal catalyst compound may or may not be partially or completely soluble in the slurry.
  • the diluent consists of mineral oil.
  • Mineral oil or“high viscosity diluents,” as used herein refers to petroleum hydrocarbons and mixtures of hydrocarbons that may include aliphatic, aromatic, and/or paraffinic components that are liquids at 23°C and above, and can have a molecular weight of at least 300 amu to 500 amu or more, and a viscosity at 40°C of from 40 cSt to 300 cSt or greater, or from 50 cSt to 200 cSt in a particular embodiment.
  • mineral oil includes synthetic oils or liquid polymers, polybutenes, refined naphthenic hydrocarbons, and refined paraffins, such as disclosed in BLUE BOOK 2001, MATERIALS, COMPOUNDING INGREDIENTS, MACHINERY AND SERVICES FOR RUBBER 189 247 (J. H. Lippincott, D. R. Smith, K. Kish & B. Gordon eds. Lippincott & Peto Inc. 2001).
  • Exemplary mineral and silicon oils are those that exclude moieties that are reactive with metallocene catalysts, examples of which include hydroxyl and carboxyl groups.
  • the diluent may comprise a blend of a mineral, silicon oil, and/or a hydrocarbon selected from the group consisting of Ci to Cio alkanes, Ce to C20 aromatic hydrocarbons, C7 to C21 alkyl-substituted hydrocarbons, and mixtures thereof.
  • the diluent may comprise from 5 to 99 wt% mineral oil.
  • the diluent may consist essentially of mineral oil.
  • the first metal catalyst compound is combined with an activator and a first diluent to form a catalyst slurry that is then combined with a support material. Until such contact is made, the support particles might not be previously activated.
  • the first metal catalyst compound can be in any desirable form such as a dry powder, suspension in a diluent, solution in a diluent, liquid, etc.
  • the catalyst slurry and support particles are then mixed thoroughly, in one embodiment at an elevated temperature, so that both the first metal catalyst compound and the activator are deposited on the support particles to form a support slurry.
  • a second metal catalyst compound may then be combined with the supported first metal catalyst compound, wherein the second is combined with a diluent comprising mineral or silicon oil by any suitable means either before, simultaneous to, or after contacting the second metal catalyst compound with the supported first metal catalyst compound.
  • the first metal catalyst compound is isolated from the first diluent to a dry state before combining with the second metal catalyst compound.
  • the second metal catalyst compound is not activated, that is, not combined with any activator, before being combined with the supported first metal catalyst compound.
  • the resulting solids slurry (including both the supported first and second metal catalyst compounds) is then mixed thoroughly at an elevated temperature.
  • a wide range of mixing temperatures may be used at various stages of making the mixed catalyst system.
  • the first metal catalyst compound and at least one activator, such as methylalumoxane are combined with a first diluent to form a mixture
  • the mixture is heated to a first temperature of from 25°C to l50°C, such as from 50°C to l25°C, such as from 75°C to l00°C, such as from 80°C to l00°C and stirred for a period of time from 30 seconds to 12 hours, such as from 1 minute to 6 hours, such as from 10 minutes to 4 hours, such as from 30 minutes to 3 hours.
  • the first support slurry is mixed at a temperature greater than 50°C, such as greater than 70°C, such as greater than 80°C such as greater than 85°C, for a period of time from 30 seconds to 12 hours, such as from 1 minute to 6 hours, such as from 10 minutes to 4 hours, such as from 30 minutes to 3 hours.
  • the support slurry is mixed for a time sufficient to provide a collection of activated support particles that have the first metal catalyst compound deposited thereto.
  • the first diluent can then be removed from the first support slurry to provide a dried supported first catalyst compound.
  • the first diluent can be removed under vacuum or by nitrogen purge.
  • the second metal catalyst compound is combined with the activated first metal catalyst compound in the presence of a diluent comprising mineral or silicon oil in one embodiment.
  • the second metal catalyst compound can be added in a molar ratio to the first metal catalyst compound in the range from 20: 1 to 1: 1, such as from 1: 1 to 20: 1, such as from 1 :1 to 3: 1, such as from 0.6:0.4 to 0.8:0.2, for example 0.7:0.3.
  • the molar ratio is approximately 1: 1.
  • the resultant slurry (or first support slurry) can be heated to a first temperature from 25°C to l50°C, such as from 50°C to l25°C, such as from 75°C to l00°C, such as from 80°C to l00°C and stirred for a period of time from 30 seconds to 12 hours, such as from 1 minute to 6 hours, such as from 10 minutes to 4 hours, such as from 30 minutes to 3 hours.
  • the first diluent is an aromatic or alkane, such as hydrocarbon diluent having a boiling point of less than 200°C such as toluene, xylene, hexane, etc., may be removed from the supported first metal catalyst compound under vacuum or by nitrogen purge to provide a supported mixed catalyst system. Even after addition of the oil and/or the second (or other) catalyst compound, it may be desirable to treat the slurry to further remove any remaining solvents such as toluene. This can be accomplished by an N 2 purge or vacuum, for example. Depending upon the level of mineral oil added, the resultant mixed catalyst system may still be a slurry or may be a free flowing powder that comprises an amount of mineral oil.
  • the mixed catalyst system while a slurry of solids in mineral oil in one embodiment, may take any physical form such as a free flowing solid.
  • the mixed catalyst system may range from 1 to 99 wt% solids content by weight of the mixed catalyst system (mineral oil, support, all catalyst compounds and activator(s)) in one embodiment.
  • the catalyst compound may be the first or second compound, such as the second compound.
  • the present disclosure provides polymerization processes where monomer (such as ethylene), and, optionally, comonomer (such as hexene), are contacted with a catalyst system comprising a catalyst compound represented by formula (I), a catalyst compound represented by formula (II), an activator, and an optional support material as described above.
  • a catalyst system comprising a catalyst compound represented by formula (I), a catalyst compound represented by formula (II), an activator, and an optional support material as described above.
  • MIR melt index ratio
  • MIR can be increased by increasing the mol% of a comonomer, such as hexene, as compared to a polymerization process using less comonomer.
  • a polymer formed by a polymerization process of the present disclosure has a melt index ratio of from 20 to 140, such as from 25 to 125, such as from 25 to 50, such as from 80 to 110.
  • MIR can be controlled while increasing the activity of the hydroindenyl metallocene represented by formula (I) without substantially changing the comonomer content of the polymer formed under the polymerization conditions.
  • This advantage provides polyolefins having a density of, for example, 0.92 to 0.94 g/cm 3 and a high comonomer content, such as from 6 wt% to 10 wt%. This density range provides stiffness to the polymer while maintaining the advantageous comonomer content which adds toughness.
  • Monomers can include substituted or unsubstituted C2 to C40 alpha olefins, such as C2 to C20 alpha olefins, such as C2 to C12 alpha olefins, such as ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene and isomers thereof.
  • the monomers comprise ethylene and, optional, comonomers comprising one or more C 3 to C 40 olefins, such as C 4 to C 20 olefins, such as C 6 to C 12 olefins.
  • the C 3 to C 40 olefin monomers may be linear, branched, or cyclic.
  • the C 3 to C 40 cyclic olefins may be strained or unstrained, monocyclic or polycyclic, and may, optionally, include heteroatoms and/or one or more functional groups.
  • Exemplary C 3 to C 40 comonomers include propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, norbomene, norbomadiene, dicyclopentadiene, cyclopentene, cycloheptene, cyclooctene, cyclooctadiene, cyclododecene, 7-oxanorbomene, 7-oxanorbomadiene, substituted derivatives thereof, and isomers thereof, such as hexene, heptene, octene, nonene, decene, dodecene, cyclooctene, l,5-cyclooctadiene, l-hydroxy-4-cyclooctene, l-acetoxy-4-cyclooctene, 5-methylcyclopentene,
  • one or more dienes are present in the polymer produced herein at up to 10 wt%, such as at 0.00001 to 1.0 wt%, such as 0.002 to 0.5 wt%, such as 0.003 to 0.2 wt% based upon the total weight of the composition.
  • 500 ppm or less of diene is added to the polymerization, such as 400 ppm or less, such as or 300 ppm or less.
  • at least 50 ppm of diene is added to the polymerization, or 100 ppm or more, or 150 ppm or more.
  • a diolefm monomer includes any hydrocarbon structure, such as C4 to C30, having at least two unsaturated bonds, wherein at least two of the unsaturated bonds are readily incorporated into a polymer by either a stereospecific or a non-stereospecific catalyst(s). It is further exemplary that the diolefm monomers be selected from alpha, omega- diene monomers (i.e., di -vinyl monomers). In one embodiment, the diolefm monomers are linear di-vinyl monomers, such as those containing from 4 to 30 carbon atoms.
  • dienes examples include butadiene, pentadiene, hexadiene, heptadiene, octadiene, nonadiene, decadiene, undecadiene, dodecadiene, tridecadiene, tetradecadiene, pentadecadiene, hexadecadiene, heptadecadiene, octadecadiene, nonadecadiene, icosadiene, heneicosadiene, docosadiene, tricosadiene, tetracosadiene, pentacosadiene, hexacosadiene, heptacosadiene, octacosadiene, nonacosadiene, triacontadiene, particularly exemplary dienes include l,6-heptadiene, 1,7- octadiene, l,8-nonadiene, l,
  • Exemplary cyclic dienes include cyclopentadiene, vinylnorbomene, norbomadiene, ethylidene norbomene, divinylbenzene, dicyclopentadiene or higher ring containing diolefms with or without substituents at various ring positions.
  • a process provides polymerization of ethylene and at least one comonomer having from 3 to 8 carbon atoms, such as 4 to 8 carbon atoms.
  • the comonomers are propylene, l-butene, 4-methyl- l-pentene, 3-methyl-l- pentene, 1 -hexene and l-octene, for example 1 -hexene, l-butene and l-octene.
  • a process provides polymerization of one or more monomers selected from the group consisting of propylene, l-butene, l-pentene, 3 -methyl- 1- pentene, 4-methyl- l-pentene, 1 -hexene, l-octene, l-decene, and combinations thereof.
  • Polymerization processes of the present disclosure can be carried out in any suitable manner. Any suitable suspension, homogeneous, bulk, solution, slurry, and/or gas phase polymerization process can be used. Such processes can be run in a batch, semi-batch, or continuous mode. Gas phase polymerization processes and slurry processes can be used. (A homogeneous polymerization process can be a process where at least 90 wt% of the product is soluble in the reaction media.) A bulk homogeneous process can be used.
  • a bulk process can be a process where monomer concentration in all feeds to the reactor is 70 vol% or more.
  • no solvent or diluent is present or added in the reaction medium (except for the small amounts used as the carrier for the catalyst system or other additives, or amounts found with the monomer; e.g., propane in propylene).
  • the process is a slurry process.
  • slurry polymerization process includes a polymerization process where a supported catalyst is utilized and monomers are polymerized on the supported catalyst particles. At least 95 wt% of polymer products derived from the supported catalyst are in granular form as solid particles (not dissolved in the diluent).
  • Suitable diluents/solvents for polymerization include non-coordinating, inert liquids.
  • examples include straight and branched-chain hydrocarbons, such as isobutane, butane, pentane, isopentane, hexanes, isohexane, heptane, octane, dodecane, and mixtures thereof; cyclic and alicyclic hydrocarbons, such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof, such as can be found commercially (IsoparTM); perhalogenated hydrocarbons, such as perfluorided C4-10 alkanes, chlorobenzene, and aromatic and alkyl substituted aromatic compounds, such as benzene, toluene, mesitylene, and xylene.
  • straight and branched-chain hydrocarbons such as isobutane, butan
  • Suitable solvents also include liquid olefins, which may act as monomers or comonomers, including ethylene, propylene, 1 -butene, 1 -hexene, l-pentene, 3 -methyl- l-pentene, 4-methyl- l-pentene, l-octene, l-decene, and mixtures thereof.
  • liquid olefins which may act as monomers or comonomers, including ethylene, propylene, 1 -butene, 1 -hexene, l-pentene, 3 -methyl- l-pentene, 4-methyl- l-pentene, l-octene, l-decene, and mixtures thereof.
  • aliphatic hydrocarbon solvents are used as the solvent, such as isobutane, butane, pentane, isopentane, hexanes, isohexane, heptane, octane, dodecane, and mixtures thereof; cyclic and alicyclic hydrocarbons, such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof.
  • the solvent is not aromatic, such as aromatics are present in the solvent at less than 1 wt%, such as less than 0.5 wt%, such as less than 0 wt% based upon the weight of the solvents.
  • a gaseous stream containing one or more monomers is continuously cycled through a fluidized bed in the presence of a catalyst under reactive conditions.
  • the gaseous stream is withdrawn from the fluidized bed and recycled back into the reactor.
  • polymer product is withdrawn from the reactor and fresh monomer is added to replace the polymerized monomer.
  • a slurry polymerization process generally operates between 1 to about 50 atmosphere pressure range (15 psi to 735 psi, 103 kPa to 5068 kPa) or even greater and temperatures in the range of 0°C to about l20°C.
  • a suspension of solid, particulate polymer is formed in a liquid polymerization diluent medium to which monomer and comonomers, along with catalysts, are added.
  • the suspension including diluent is intermittently or continuously removed from the reactor where the volatile components are separated from the polymer and recycled, optionally after a distillation, to the reactor.
  • Suitable liquid diluent employed in the polymerization medium can be an alkane having from 3 to 7 carbon atoms, such as a branched alkane.
  • the medium employed should be liquid under the conditions of polymerization and relatively inert. When a propane medium is used, the process must be operated above the reaction diluent critical temperature and pressure. In at least one embodiment, a hexane or an isobutane medium is employed.
  • a polymerization process is referred to as a particle form polymerization, or a slurry process, where the temperature is kept below the temperature at which the polymer goes into solution.
  • a particle form polymerization or a slurry process
  • the temperature in the particle form process can be within the range of about 85°C to about H0°C.
  • Two polymerization methods for the slurry process include those using a loop reactor and those utilizing a plurality of stirred reactors in series, parallel, or combinations thereof.
  • Non-limiting examples of slurry processes include continuous loop or stirred tank processes.
  • other examples of slurry processes are described in U.S. Patent No. 4,613,484, which is herein fully incorporated by reference.
  • the slurry process is carried out continuously in a loop reactor.
  • the catalyst as a slurry in isohexane or as a dry free flowing powder, is injected regularly to the reactor loop, which is itself filled with circulating slurry of growing polymer particles in a diluent of isohexane containing monomer and comonomer.
  • Hydrogen optionally, may be added as a molecular weight control. (In one embodiment hydrogen is added from 50 ppm to 500 ppm, such as from 100 ppm to 400 ppm, such as 150 ppm to 300 ppm.)
  • the reactor may be maintained at a pressure of 2,000 kPa to 5,000 kPa, such as from 3620 kPa to 4309 kPa, and at a temperature in the range of about 60°C to about l20°C depending on the desired polymer melting characteristics.
  • Reaction heat is removed through the loop wall since much of the reactor is in the form of a double-jacketed pipe.
  • the slurry is allowed to exit the reactor at regular intervals or continuously to a heated low pressure flash vessel, rotary dryer and a nitrogen purge column in sequence for removal of the isohexane diluent and all unreacted monomer and comonomers.
  • the resulting hydrocarbon free powder is then compounded for use in various applications.
  • solution polymerization involves polymerization in a continuous reactor in which the polymer formed and the starting monomer and catalyst materials supplied, are agitated to reduce or avoid concentration gradients and in which the monomer acts as a diluent or solvent or in which a hydrocarbon is used as a diluent or solvent.
  • Suitable processes can operate at temperatures from about 0°C to about 250°C, such as from about l0°C to about l50°C, such as from about 40°C to about l40°C, such as from about 50°C to about l20°C and at pressures of about 0.1 MPa or more, such as 2 MPa or more.
  • the upper pressure limit is not critically constrained but can be about 200 MPa or less, such as 120 MPa or less.
  • Temperature control in the reactor can generally be obtained by balancing the heat of polymerization and with reactor cooling by reactor jackets or cooling coils to cool the contents of the reactor, auto refrigeration, pre-chilled feeds, vaporization of liquid medium (diluent, monomers or solvent) or combinations of all three. Adiabatic reactors with pre-chilled feeds can also be used.
  • the purity, type, and amount of solvent can be optimized for the maximum catalyst productivity for a particular type of polymerization.
  • the solvent can be also introduced as a catalyst carrier.
  • the solvent can be introduced as a gas phase or as a liquid phase depending on the pressure and temperature.
  • the solvent can be kept in the liquid phase and introduced as a liquid.
  • Solvent can be introduced in the feed to the polymerization reactors.
  • compositions that can be produced by the methods of the present disclosure.
  • a process described herein produces ethylene homopolymers or ethylene copolymers, such as ethylene-alpha-olefin (such as C3 to C20) copolymers (such as ethylene-butene copolymers, ethylene-hexene and/or ethylene-octene copolymers).
  • ethylene-alpha-olefin such as C3 to C20
  • copolymers such as ethylene-butene copolymers, ethylene-hexene and/or ethylene-octene copolymers.
  • the copolymers produced herein have from 0 to 25 wt% (alternatively from 0.5 to 20 wt%, alternatively from 1 to 15 wt%, such as from 3 to 10 wt%) of one or more C3 to C20 olefin comonomer, such as a C3-C20 alpha-olefin, (such as C3 to C 12 alpha-olefin, such as propylene, butene, hexene, octene, decene, dodecene, such as propylene, butene, hexene, octene).
  • C3 to C20 olefin comonomer such as a C3-C20 alpha-olefin, (such as C3 to C 12 alpha-olefin, such as propylene, butene, hexene, octene).
  • an ethylene alpha-olefin copolymer has a density of from 0.880 g/cc to 1 g/cc, such as from 0.910 g/cc to 0.960 g/cc, such as from 0.920 g/cc to 0.940 g/cc, for example about 0.930 g/cc.
  • an ethylene alpha-olefin copolymer has a melt index from 0.5 to 5, such as from 1 to 2.
  • an ethylene alpha-olefin copolymer has a melt index ratio from 25 to 125, such as from 25 to 50, such as from 80 to 110.
  • an ethylene alpha-olefin copolymer has: 1) at least 50 mol% ethylene; and 2) a density of 0.910 g/cc or greater, such as 0.935 g/cc or greater (ASTM 1505).
  • the copolymer has higher comonomer (e.g., hexene) content in the higher molecular weight component of the resin as compared to the lower molecular weight component, as determined by GPC-4D.
  • the copolymer produced herein can have a composition distribution breadth T75- T25, as measured by TREF, which is greater than 20°C, such as greater than 30°C, such as greater than 40°C.
  • the T75-T25 value represents the homogeneity of the composition distribution as determined by temperature rising elution fractionation.
  • a TREF curve is produced as described below. Then the temperature at which 75% of the polymer is eluted is subtracted from the temperature at which 25% of the polymer is eluted, as determined by the integration of the area under the TREF curve.
  • the T75-T25 value represents the difference. The closer these temperatures come together, the narrower the composition distribution.
  • the polymers produced herein have an Mw of 5,000 to 1,000,000 g/mol (such as 25,000 to 750,000 g/mol, such as 50,000 to 500,000 g/mol, such as 75,000 to 200,000), and/or an Mw/Mn of greater than 1 to 40 (such as from 1.2 to 20, such as from 2 to 15, such as from 5 to 12, such as from 7 to 11, such as from 8 to 10) as determined by GPC- 4D.
  • Mw/Mn of greater than 1 to 40 (such as from 1.2 to 20, such as from 2 to 15, such as from 5 to 12, such as from 7 to 11, such as from 8 to 10) as determined by GPC- 4D.
  • the ratio of other average molecular weights can also be calculated to highlight how the molecular weight distribution is affected. For instance, a trace amount of very high molecular weight species in a polymer product can increase Mz more than Mw and, therefore, result in a significantly higher ratio of Mz/Mw.
  • Polymers of the present disclosure can have an Mz/Mw value of from 1 to 10, such as from 2 to 6, such as from 3 to 5.
  • Polymers of the present disclosure can have an Mz/Mn from about 1 to 10, such as from 2 to 6, such as from 3 to 5.
  • the polymer produced herein has a unimodal or multimodal molecular weight distribution as determined by Gel Permeation Chromatography (GPC).
  • GPC Gel Permeation Chromatography
  • unimodal is meant that the GPC trace has one peak or two inflection points.
  • multimodal is meant that the GPC trace has at least two peaks or more than 2 inflection points.
  • An inflection point is that point where the second derivative of the curve changes in sign (e.g., from negative to positive or vice versa).
  • the compound represented by formula (I) when: 1) the compound represented by formula (I) is run under the same polymerization conditions as a supported two catalyst composition described herein, except that the compound represented by formula (II) is absent, a polymer having a comonomer content (hexene) of 6.1 wt% and density of 0.92 g/cc is produced, and 2) the compound represented by formula (II) is run under the same polymerization conditions as step 1), except that the compound represented by formula (I) is absent, a polymer having a comonomer content (hexene) of about 0 wt% is produced.
  • an ethylene alpha-olefin copolymer has a comonomer content of from 1 wt% to 15 wt% comonomer (such as hexene), such as 7 wt% or greater, such as from 1 wt% to 10 wt%, such as from 6 wt% to 10 wt%.
  • a linear low density polyethylene may be produced by using the catalyst systems described herein (e.g., having activator and two catalysts represented by formula (I) and formula (II) supported on the same support) where the LDPE has: a) a melt index of 0.5 or greater, a density of 0.92 g/cm 3 or greater, a melt index ratio of 90 or greater, and a comonomer content (hexene) of 7 wt% or greater; or b) a melt index of 1.5 or less, a density of 0.92 g/cm 3 or greater, a melt index ratio of 50 or less, and a comonomer content (hexene) of 7 wt% or greater.
  • the catalyst systems described herein e.g., having activator and two catalysts represented by formula (I) and formula (II) supported on the same support
  • the LDPE has: a) a melt index of 0.5 or greater, a density of 0.92 g/cm 3 or greater,
  • the polymer produced herein has a bimodal molecular weight distribution as determined by Gel Permeation Chromatography (GPC).
  • GPC Gel Permeation Chromatography
  • the polymer produced herein has two peaks in the TREF measurement (see below).
  • Two peaks in the TREF measurement means the presence of two distinct normalized IR response peaks in a graph of normalized IR response (vertical or y axis) versus elution temperature (horizontal or x axis with temperature increasing from left to right) using the TREF method below.
  • A“peak” in this context means where the general slope of the graph changes from positive to negative with increasing temperature. Between the two peaks is a local minimum in which the general slope of the graph changes from negative to positive with increasing temperature. “General trend” of the graph is intended to exclude the multiple local minimums and maximums that can occur in intervals of 2°C or less.
  • the two distinct peaks are at least 3°C apart, such as at least 4°C apart, such as at least 5°C apart. Additionally, both of the distinct peaks occur at a temperature on the graph above 20°C and below l20°C where the elution temperature is run to 0°C or lower. This limitation avoids confusion with the apparent peak on the graph at low temperature is caused by material that remains soluble at the lowest elution temperature. Two peaks on such a graph indicate a bimodal composition distribution. An alternate method for TREF measurement can be used if the method below does not show two peaks, i.e., see B. Monrabal,“Crystallization Analysis Fractionation: A New Technique for the Analysis of Branching Distribution in Polyolefins,” Journal of Applied Polymer Science, Vol. 52, 491-499 (1994).
  • Temperature Rising Elution Fractionation (TREF) analysis is done using a Crystallization Elution Fractionation (CEF) instrument from Polymer Char, S.A., Valencia, Spain.
  • CEF Crystallization Elution Fractionation
  • tubing connected to the l l-o’clock port is connected to the 9-o’clock port and the tubing connected to the 9-o’clock port is connected to the l l-o’clock port.
  • Pertinent details of the analysis method and features of the apparatus to be used are as follows.
  • the solvent used for preparing the sample solution and for elution was 1,2- Dichlorobenzene (ODCB) which was stabilized by dissolving 1.6 g of 2,6-bis(l,l- dimethylethyl)-4-methylphenol (butylated hydroxy toluene) in a 4-L bottle of fresh solvent at ambient temperature. The stabilized solvent was then filtered using a 0.1 -pm Teflon filter (Millipore). The sample (6-10 mg) to be analyzed was dissolved in 8 ml of ODCB metered at ambient temperature by stirring (Medium setting) at l50°C for 90 min.
  • ODCB 1,2- Dichlorobenzene
  • a small volume of the polymer solution was first filtered by an inline filter (stainless steel, 10 pm), which is back- flushed after every filtration. The filtrate was then used to completely fill a 200-pl injection- valve loop. The volume in the loop was then introduced near the center of the CEF column (l5-cm long SS tubing, 3/8 " o.d., 7.8 mm i.d.) packed with an inert support (SS balls) at l40°C, and the column temperature was stabilized at l25°C for 20 min. The sample volume was then allowed to crystallize in the column by reducing the temperature to 0°C at a cooling rate of l°C/min.
  • the column was kept at 0°C for 10 min before injecting the ODCB flow (1 ml/min) into the column for 10 min to elute and measure the polymer that did not crystallize (soluble fraction).
  • the wide-band channel of the infrared detector used (Polymer Char IR5) generates an absorbance signal that is proportional to the concentration of polymer in the eluting flow.
  • a complete TREF curve was then generated by increasing the temperature of the column from 0 to l40°C at a rate of 2°C/min while maintaining the ODCB flow at 1 ml/min to elute and measure the concentration of the dissolving polymer.
  • the distribution and the moments of molecular weight (Mw, Mn, Mw/Mn, etc.), the comonomer content (C2, C3, Ce, etc.) and the branching index (g'vis) are determined by using a high temperature Gel Permeation Chromatography (Polymer Char GPC-IR) equipped with a multiple-channel band-filter based Infrared detector IR5, an 18-angle light scattering detector and a viscometer. Three Agilent PLgel l0-pm Mixed-B LS columns are used to provide polymer separation.
  • TCB Aldrich reagent grade 1, 2, 4-tri chlorobenzene
  • BHT butylated hydroxytoluene
  • the TCB mixture is filtered through a 0.1 -pm Teflon filter and degassed with an online degasser before entering the GPC instrument.
  • the nominal flow rate is 1.0 ml/min and the nominal injection volume is 200 pL.
  • the whole system including transfer lines, columns, and detectors are contained in an oven maintained at l45°C.
  • the polymer sample is weighed and sealed in a standard vial with 80-pL flow marker (Heptane) added to it.
  • polymer After loading the vial in the autosampler, polymer is automatically dissolved in the instrument with 8 ml added TCB solvent. The polymer is dissolved at l60°C with continuous shaking for about 1 hour for most PE samples or 2 hour for PP samples.
  • the TCB densities used in concentration calculation are 1.463 g/ml at room temperature and 1.284 g/ml at l45°C.
  • the sample solution concentration is from 0.2 to 2.0 mg/ml, with lower concentrations being used for higher molecular weight samples.
  • the mass recovery is calculated from the ratio of the integrated area of the concentration chromatography over elution volume and the injection mass which is equal to the pre-determined concentration multiplied by injection loop volume.
  • the conventional molecular weight (IR MW) is determined by combining universal calibration relationship with the column calibration which is performed with a series of monodispersed polystyrene (PS) standards ranging from 700 to lOM gm/mole.
  • PS monodispersed polystyrene
  • variables with subscript“PS” stand for polystyrene while those without a subscript are for the test samples.
  • a 0.695 and K is 0.000579*(l- 0.0087*w2b+0.0000l8*(w2b)
  • a 0.695 and K is 0.000579*(l-0.0075*w2b) for ethylene- hexene copolymer where w2b is a bulk weight percent of hexene comonomer
  • a 0.695 and K is 0.000579*(l-0.0077*w2b) for ethylene-octene copolymer where w2b is
  • the comonomer composition is determined by the ratio of the IR5 detector intensity corresponding to CFh and CFb channel calibrated with a series of PE and PP homo/copolymer standards whose nominal value are predetermined by NMR or FTIR. In particular, this provides the methyls per 1000 total carbons (CFE/1000TC) as a function of molecular weight.
  • the short-chain branch (SCB) content per 1000TC (SCB/1000TC) is then computed as a function of molecular weight by applying a chain-end correction to the CFE/1000TC function, assuming each chain to be linear and terminated by a methyl group at each end.
  • the weight % comonomer is then obtained from the following expression in which / is 0.3, 0.4, 0.6, 0.8, and so on for C3, C 4 , Ce, Ce, and so on co-monomers, respectively:
  • bulk SCB/1000TC bulk CH3/1000TC - bulk CH3end/1000TC and bulk SCB/1000TC is converted to bulk w2 in the same manner as described above.
  • the LS detector is the 18-angle Wyatt Technology High Temperature DAWN HELEOSII.
  • the LS molecular weight (M) at each point in the chromatogram is determined by analyzing the LS output using the Zimm model for static light scattering ( Light Scattering from Polymer Solutions, Huglin, M. B., Ed.; Academic Press, 1972.):
  • AR(0) is the measured excess Rayleigh scattering intensity at scattering angle Q
  • c is the polymer concentration determined from the IR5 analysis
  • a 2 is the second virial coefficient
  • R(q) is the form factor for a monodisperse random coil
  • K 0 is the optical constant for the system:
  • N A is Avogadro’s number
  • (dn/dc) is the refractive index increment for the system.
  • a high temperature Agilent (or Viscotek Corporation) viscometer which has four capillaries arranged in a Wheatstone bridge configuration with two pressure transducers, is used to determine specific viscosity.
  • One transducer measures the total pressure drop across the detector, and the other, positioned between the two sides of the bridge, measures a differential pressure.
  • the specific viscosity, %. for the solution flowing through the viscometer is calculated from their outputs.
  • the intrinsic viscosity, [h] %/c. where c is concentration and is determined from the IR5 broadband channel output.
  • the branching index (g' v is) is calculated using the output of the GPC-IR5-LS-VIS method as follows.
  • av g. of the sample is calculated by:
  • the reversed-co-monomer index (RCI,m) is computed from x2 (mol% co monomer C3, C4, C6, Ce, etc.), as a function of molecular weight, where x2 is obtained from the following expression in which n is the number of carbon atoms in the comonomer (3 for C3, 4 for C4, 6 for Ce, etc.):
  • M w r modified weight-average molecular weight
  • the RCI,m is then computed as
  • a reversed-co-monomer index (RCI,w) is also defined on the basis of the weight fraction co-monomer signal (w2/100) and is computed as follows:
  • w2(Mw) is the % weight co-monomer signal corresponding to a molecular weight of Mw
  • w2(Mz) is the % weight co-monomer signal corresponding to a molecular weight of Mz
  • w2[(Mw+Mn)/2)] is the % weight co-monomer signal corresponding to a molecular weight of (Mw+Mn)/2
  • w2[(Mz+Mw)/2] is the % weight co-monomer signal corresponding to a molecular weight of Mz+Mw/2
  • Mw is the weight-average molecular weight
  • Mn is the number-average molecular weight
  • Mz is the z-average molecular weight.
  • the co-monomer distribution ratios can be also defined utilizing the % mole co-monomer signal, CDR-l,m, CDR-2,m, CDR-3,m, as:
  • x2(Mw) is the % mole co-monomer signal corresponding to a molecular weight of Mw
  • x2(Mz) is the % mole co-monomer signal corresponding to a molecular weight of Mz
  • x2[(Mw+Mn)/2)] is the %mole co-monomer signal corresponding to a molecular weight of (Mw+Mn)/2
  • x2[(Mz+Mw)/2] is the % mole co-monomer signal corresponding to a molecular weight of Mz+Mw/2
  • Mw is the weight-average molecular weight
  • Mn is the number-average molecular weight
  • Mz is the z-average molecular weight.
  • An“in-situ polymer composition” (also referred to as an“in-situ blend” or a “reactor blend”) is the composition which is the product of a polymerization with two catalyst compounds in the same reactor described herein. Without wishing to be bound by theory it is thought that the two catalyst compounds produce a reactor blend (i.e., an interpenetrating network) of two (or more) components made in the same reactors (or reactions zones) with the two catalysts. These sorts of compositions may be referred to as reactor blends, although the term may not be strictly accurate since there may be polymer species comprising components produced by each catalyst compound that are not technically a blend.
  • An“ex-situ blend” is a blend which is a physical blend of two or more polymers synthesized independently and then subsequently blended together using a melt-mixing process, such as an extruder.
  • An ex-situ blend is distinguished by the fact that the polymer components are collected in solid form after exiting their respective synthesis processes, and then combined to form the blend; whereas for an in-situ polymer composition, the polymer components are prepared within a common synthesis process and only the combination is collected in solid form.
  • the polymer composition produced is an in-situ polymer composition.
  • the polymer produced is an in-situ polymer composition having an ethylene content of 70 wt% or more, such as 80 wt% or more, such as 90 wt% or more and/or a density of0.9l0 g/cc or more, alternatively 0.93 g/cc or more; alternatively 0.935 g/cc or more, alternatively 0.938 g/cc or more.
  • the polymer produced is an in- situ polymer composition having a density of 0.910 g/cc or more, alternatively from 0.935 to 0.960 g/cc.
  • a polymer produced comprises ethylene and one or more comonomers and the polymer has: an RCI,m greater than 30 (such as from 150 to 500, such as from 300 to 450, such as from 400 to 500, such as from 150 to 250), a CDR-2,m of from 1 to 4 (such as from 1.5 to 3.5), an Mw/Mn of greater than 3, and optionally a T75-T25 of from 15 to 50°C (such as from 25 to 45°C).
  • a polymer of the present disclosure has a PDI of from 1 to about 15, such as from 4 to 12, such as from 8 to 11.
  • a polymer of the present disclosure has a low degree of internal unsaturation.
  • a polymer has an internal unsaturation of less than 50% of the total unsaturations, such as less than 40% such as less than 30%.
  • Internal unsaturation can be decreased by increasing the amount of the catalyst represented by formula (I) (as compared the amount of the catalyst represented by formula (II)) in a catalyst system of the present disclosure.
  • Polymers having a high degree of internal unsaturation can provide a low g’vis of 0.95 or more. Internal unsaturation can disrupt the crystallization of ethylene chains and contribute to the amorphous phase of the PE resin which may contribute to increased impact strength of the polymer.
  • Polymers of the present disclosure can also have a high degree of terminal unsaturation, e.g. vinylogous end groups.
  • a polymer has a terminal unsaturation of 50% or more of the total unsaturations, such as 60% or more, such as 70% or more, alternately from 50 to 90%, from 60 to 85%, from 60 to 80%.
  • Terminal unsaturation can be promoted by increasing the amount of the catalyst represented by formula (II) (as compared to the amount of the catalyst represented by formula (I)) in a catalyst system of the present disclosure.
  • Terminal unsaturation can provide reactive end groups of polymers for functionalization.
  • a polymer of the present disclosure has a combination of internal and terminal unsaturation of 0.7 or greater unsaturations per 1000 carbon atoms, such as 0.8 or greater, such as 0.9 or greater.
  • a polymer of the present disclosure has a ratio of terminal unsaturation to internal unsaturation of from 1 :5 to 20: 1, such as from 1: 1 to 20: 1, such as from 5: 1 to 15: 1, such as from 8: 1 to 12: 1, such as about 9: 1.
  • Unsaturation (internal and terminal) in a polymer can be determined by 'H NMR with reference to Macromolecules 2014, 47, 3782 and Macromolecules 2005, 38, 6988, but in event of conflict Macromolecules 2014, 47, 3782 shall control. Peak assignments are determined referencing the solvent of tetrachloroethane-l,2 d 2 at 5.98 ppm. Specifically, percent internal unsaturation is determined by adding Vyl+Vy2+trisubstituted olefins then dividing by total unsaturation.
  • a polymer of the present disclosure has a g’vis of 0.9 or greater, such as 0.92 or greater, such as 0.95 or greater. In at least one embodiment, a polymer of the present disclosure has a g’vis of 0.95 or less, such as 0.9 or less, such as 0.88 or less.
  • a polymer of the present disclosure has a RCI,m of 50 kg/mol or greater, such as 55 kg/mol or greater, such as 60 or greater.
  • a polymer of the present disclosure has a melt temperature (Tm) of from about 250°F to about 600°F, such as from about 300°F to about 500°F, such as from about 350°F to about 450°F, such as from about 350°F to about 400°F.
  • Tm melt temperature
  • a melt temperature below 600°F for example, such as below 450°F can provide films formed using a lower die pressure (e.g., 3,000 psi or lower, such as 1,700 psi or lower), as compared to conventional films having a higher melt temperature.
  • Polymers and compositions of the present disclosure can include optional additives ⁇ see, for example, U.S. Publication No. 2016/0060430, paragraphs [0082]-[0093]) and/or may be used in a variety of end-use applications.
  • Such end uses may be produced by any suitable method.
  • End uses include polymer products and products having specific end-uses.
  • Exemplary end uses are films, film-based products, diaper backsheets, housewrap, wire and cable coating compositions, articles formed by molding techniques, e.g., injection or blow molding, extrusion coating, foaming, casting, and combinations thereof.
  • End uses also include products made from films, e.g., bags, packaging, and personal care films, pouches, medical products, such as for example, medical films and intravenous (IV) bags.
  • IV intravenous
  • Films include monolayer or multilayer films. Films include film structures and film applications. Specific end use films include, for example, blown films, cast films, stretch films, stretch/cast films, stretch cling films, stretch hand wrap films, machine stretch wrap, shrink films, shrink wrap films, green house films, laminates, and laminate films. Exemplary films are prepared by any suitable technique, such as for example, techniques utilized to prepare blown, extruded, and/or cast stretch and/or shrink films (including shrink-on-shrink applications). [00192] In one embodiment, multilayer films/multiple-layer films may be formed by any suitable method. The total thickness of multilayer films may vary based upon the application desired. A total film thickness of about 5-100 pm, such as about 10-50 pm, is suitable for most applications.
  • each layer may be coextruded through a coextrusion feedblock and die assembly to yield a film with two or more layers adhered together but differing in composition. Coextrusion can be adapted for use in both cast film or blown film processes.
  • Exemplary multilayer films have at least two, at least three, or at least four layers. In one embodiment the multilayer films are composed of five to ten layers.
  • Each layer of a film is denoted “A” or "B”.
  • a layer or B includes more than one A layer or more than one B layer
  • one or more prime symbols are appended to the A or B symbol to indicate layers of the same type that can be the same or can differ in one or more properties, such as chemical composition, density, melt index, thickness, etc.
  • the symbols for adjacent layers are separated by a slash (/).
  • a three-layer film having an inner layer positioned between two adjacent layers would be denoted A/B/A'.
  • a five-layer film of alternating layers would be denoted A/B/A7B7A".
  • each film layer is similarly denoted, with the thickness of each layer relative to a total film thickness of 100 (dimensionless) indicated numerically and separated by slashes; e.g., the relative thickness of an A/B/A' film having A and A' layers of 10 pm each and a B layer of 30 pm is denoted as 20/60/20.
  • each layer of the film, and of the overall film is not particularly limited, but is determined according to the desired properties of the film.
  • Suitable film layers have a thickness of from about 1 pm to about 1000 pm, such as from about 5 pm to about 100 pm, and suitable films have an overall thickness of from about 10 pm to about 100 pm.
  • the present disclosure provides for multilayer films with any of the following exemplary structures: (a) two-layer films, such as A/B and B/B'; (b) three-layer films, such as A/B/A', A/A'/B, B/A/B' and B/B'/B"; (c) four-layer films, such as A/AVA7B, A/A'/B/A", A/A7B/B', A/B/A'/B', A/B/B'/A', B/A/A7B', A/B/B7B", B/A/B7B" and B/B7B7B'"; (d) five-layer films, such as A/A7A7A"7B, A/A7A'7B/A"', A/A7B/A7A'", A/A7A7B/B', A/A7B/A7B', A/A/A7B', A/A/A7B', A/A
  • one or more A layers can be replaced with a substrate layer, such as glass, plastic, paper, metal, etc., or the entire film can be coated or laminated onto a substrate.
  • a substrate layer such as glass, plastic, paper, metal, etc.
  • the films may also be used as coatings for substrates such as paper, metal, glass, plastic, and other materials capable of accepting a coating.
  • the films can further be embossed, or produced or processed according to other suitable processes.
  • the films can be tailored to specific applications by adjusting the thickness, materials and order of the various layers, as well as the additives in or modifiers applied to each layer.
  • a film made from the polyethylene composition as described above, may a have:
  • MD and TD moduli and density may be as follows:
  • the seal initiation temperature (see below for the test method) at 1 N may be ⁇ 99.0°C, ⁇ 98.0°C, ⁇ 97.0°C, ⁇ 96.0°C, ⁇ 95.0°C, or ⁇ 94.0°C.
  • the seal initiation temperature (see below for the test method) at 5 N is ⁇ l03.0°C, ⁇ l02.0°C, ⁇ 101.0°C, ⁇ l00.0°C, ⁇ 99.0°C, or ⁇ 98.0°C.
  • a film has an average of the MD and TD 1% secant moduli (see below for the test method) of 30,000 psi or greater, such as 35,000 psi or greater, such as 40,000 psi or greater, such as 45,000 psi or greater, such as from 50,000 psi to 100,000 psi, such as 60,000 psi to 90,000 psi, such as from 65,000 psi to 80,000 psi, such as from 68,000 psi to 77,000 psi.
  • a film of the present disclosure also has a Dart Drop Impact (or Dart F50 or Dart Drop Impact Strength (DIS), reported in grams (g) or grams per mil (g/mil), in accordance with ASTM D-1709, method A using a phenolic probe.
  • a film has a Dart Drop Impact of at least 100 g/mil, such as at least 150 g/mil, such as at least 200 g/mil, such as at least 250 g/mil, such as at least 300 g/mil, and such as at least 350 g/mil.
  • the Dart Drop Impact can be from 100 g/mil to 500 g/mil, such as 150 g/mil to 350 g/mil, such as 175 g/mil to 225 g/mil, or from 300 g/mil to 400 g/mil.
  • a film of the present disclosure also has a Tensile Strength (according to ASTM D- 882, 25.4 mm width strip), reported in pounds per square inch (psi).
  • a film has a tensile strength in the machine direction (MD) of from 3,000 psi to 12,000 psi, such as from 4,000 psi to 9,000 psi, such as from 6,000 psi to 9,000 psi, such as from 7,000 psi to 8,500 psi, such as from 7,500 psi to 8,500 psi.
  • MD machine direction
  • a film has a tensile strength in the transverse direction (TD) of from 3,000 psi to 12,000 psi, such as from 3,500 psi to 9,000 psi, such as from 4,000 psi to 8,000 psi, such as from 4,500 psi to 7,500 psi.
  • TD transverse direction
  • a film of the present disclosure also has a Tensile Strength at Yield (according to ASTM D-882 with a crosshead speed of 50 mm/min), reported in pounds per square inch (psi).
  • a film has a Tensile Strength at Yield in the machine direction (MD) of from 1,000 psi to 4,000 psi, such as 1,500 psi to 3,000 psi, such as 2,000 psi to 3,000 psi, such as 2,500 psi to 3,000 psi.
  • a film has a Tensile Strength at Yield in the transverse direction (TD) of from 1,000 psi to 4,000 psi, such as 1,500 psi to 3,000 psi, such as 2,000 psi to 3,000 psi, such as 2,500 psi to 3,000 psi.
  • TD transverse direction
  • a film of the present disclosure also has an Elongation at Break (according to ASTM D-882, 25.4 mm width strip), reported in percent (%).
  • a film has an Elongation at Break in the machine direction (MD) of from 200% to 600%, such as from 250% to 500%, such as from 300% to 450%, such as from 350% to 425%.
  • a film has an Elongation at Break in the transverse direction (TD) of from 400% to 800%, such as from 450% to 750%, such as from 500% to 700%, such as from 600% to 700%.
  • a film of the present disclosure also has an Elmendorf Tear value, in accordance with ASTM D- 1922.
  • afilm has an ElmendorfTear value in the machine direction (MD) of from 10 g/mil to 100 g/mil, such as from 15 g/mil to 75 g/mil, such as from 25 g/mil to 75 g/mil, such as from 30 g/mil to 40 g/mil or from 60 g/mil to 70 g/mil.
  • MD machine direction
  • a film has an Elmendorf Tear value in the transverse direction (TD) of from 300 g/mil to 1200 g/mil, such as from 500 g/mil to 1,100 g/mil, such as from 600 g/mil to 1,100 g/mil, such as from 900 g/mil to 1,050 g/mil or from 600 g/mil to 700 g/mil.
  • a film of the present disclosure has an Elmendorf TD/MD tear ratio of 5 or greater, such as 7 or greater, such as 10 or greater, such as 12 or greater, such as 15 or greater. Stretch Films
  • Stretch films are widely used in a variety of bundling and packaging applications.
  • the term “stretch film” indicates films capable of stretching and applying a bundling force, and includes films stretched at the time of application as well as "pre-stretched” films, i.e., films which are provided in a pre-stretched form for use without additional stretching.
  • Stretch films can be monolayer films or multilayer films, and can include conventional additives, such as cling-enhancing additives such as tackifiers, and non-cling or slip additives, to tailor the slip/ cling properties of the film.
  • shrink films also referred to as heat-shrinkable films
  • Such films are widely used in both industrial and retail bundling and packaging applications. Such films are capable of shrinking upon application of heat to release stress imparted to the film during or subsequent to extrusion.
  • the shrinkage can occur in one direction or in both longitudinal and transverse directions.
  • Conventional shrink films are described, for example, in WO 2004/022646.
  • Industrial shrink films are commonly used for bundling articles on pallets. Suitable industrial shrink films are formed in a single bubble blown extrusion process to a thickness of about 80 pm to 200 pm, and provide shrinkage in two directions, at a machine direction (MD) to transverse direction (TD) ratio of about 60:40.
  • MD machine direction
  • TD transverse direction
  • Retail films are commonly used for packaging and/or bundling articles for consumer use, such as, for example, in supermarket goods. Such films are formed in a single bubble blown extrusion process to a thickness of about 35 pm to 80 pm, with a suitable MD:TD shrink ratio of about 80:20.
  • Films may be used in“shrink-on-shrink” applications.“Shrink-on-shrink,” as used herein, refers to the process of applying an outer shrink wrap layer around one or more items that have already been individually shrink wrapped (herein, the“inner layer” of wrapping). In these processes, it is desired that the films used for wrapping the individual items have a higher melting (or shrinking) point than the film used for the outside layer. When such a configuration is used, it is possible to achieve the desired level of shrinking in the outer layer, while preventing the inner layer from melting, further shrinking, or otherwise distorting during shrinking of the outer layer. Some films described herein have been observed to have a sharp shrinking point when subjected to heat from a heat gun at a high heat setting, which indicates that they may be especially suited for use as the inner layer in a variety of shrink-on-shrink applications.
  • the polymers and compositions as described above may be utilized to prepare stretch to prepare greenhouse films.
  • Greenhouse films are generally heat retention films that, depending on climate requirements, retain different amounts of heat. Less demanding heat retention films are used in warmer regions or for spring time applications. More demanding heat retention films are used in the winter months and in colder regions.
  • Bags include those bag structures and bag applications. Exemplary bags include shipping sacks, trash bags and liners, industrial liners, produce bags, and heavy duty bags. Packaging
  • Packaging includes those packaging structures and packaging applications.
  • Exemplary packaging includes flexible packaging, food packaging, e.g., fresh cut produce packaging, frozen food packaging, bundling, packaging and unitizing a variety of products.
  • Applications for such packaging include various foodstuffs, rolls of carpet, liquid containers, and various like goods normally containerized and/or palletized for shipping, storage, and/or display.
  • the polymers and compositions described above may also be used in blow molding processes and applications. Such processes involve a process of inflating a hot, hollow thermoplastic preform (or parison) inside a closed mold. In this manner, the shape of the parison conforms to that of the mold cavity, enabling the production of a wide variety of hollow parts and containers.
  • a parison in a blow molding process, can be formed between mold halves and the mold can be closed around the parison, sealing one end of the parison and closing the parison around a mandrel at the other end. Air is then blown through the mandrel (or through a needle) to inflate the parison inside the mold. The mold is then cooled and the part formed inside the mold is solidified. Finally, the mold is opened and the molded part is ejected.
  • the process lends itself to any design having a hollow shape, including but not limited to bottles, tanks, toys, household goods, automobile parts, and other hollow containers and/or parts.
  • Blow molding processes may include extrusion and/or injection blow molding.
  • Suitable extrusion blow molding can be suited for the formation of items having a comparatively heavy weight, such as greater than about 12 ounces, including but not limited to food, laundry, or waste containers.
  • Suitable injection blow molding can be used to achieve accurate and uniform wall thickness, high quality neck finish, and to process polymers that cannot be extruded.
  • Suitable injection blow molding applications can include, but are not limited to, pharmaceutical, cosmetic, and single serving containers, such as weighing less than 12 ounces.
  • the polymers and compositions described above may also be used in injection molded applications.
  • Injection molding is a process that usually occurs in a cyclical fashion. Cycle times generally range from 10 to 100 seconds and are controlled by the cooling time of the polymer or polymer blend used.
  • polymer pellets or powder can be fed from a hopper and melted in a reciprocating screw type injection molding machine.
  • the screw in the machine rotates forward, filling a mold with melt and holding the melt under high pressure.
  • the melt cools in the mold and contracts, the machine adds more melt to the mold to compensate.
  • the mold is isolated from the injection unit and the melt cools and solidifies.
  • the solidified part is ejected from the mold and the mold is then closed to prepare for the next injection of melt from the injection unit.
  • Injection molding processes offer high production rates, good repeatability, minimum scrap losses, and little to no need for finishing of parts. Injection molding is suitable for a wide variety of applications, including containers, household goods, automobile components, electronic parts, and many other solid articles.
  • Extrusion coating is a plastic fabrication process in which molten polymer is extruded and applied onto a non-plastic support or substrate, such as paper or aluminum in order to obtain a multi-material complex structure.
  • This complex structure combines toughness, sealing and resistance properties of the polymer formulation with barrier, stiffness or aesthetics attributes of the non-polymer substrate.
  • the substrate can be fed from a roll into a molten polymer as the polymer is extruded from a slot die, which is similar to a cast film process.
  • the resultant structure is cooled with a chill roll or rolls, and wound into finished rolls.
  • Suitable extrusion coating materials can be used in food and non-food packaging, pharmaceutical packaging, and manufacturing of goods for the construction (insulation elements) and photographic industries (paper).
  • the polymers and compositions described above may be foamed articles.
  • a blowing agent such as, for example, carbon dioxide, nitrogen, or a compound that decomposes to form carbon dioxide or nitrogen
  • a blowing agent is injected into a polymer melt by means of a metering unit.
  • the blowing agent is then dissolved in the polymer in an extruder, and pressure is maintained throughout the extruder.
  • a rapid pressure drop rate upon exiting the extruder creates a foamed polymer having a homogenous cell structure.
  • the resulting foamed product can be light, strong, and suitable for use in a wide range of applications in industries such as packaging, automotive, aerospace, transportation, electric and electronics, and manufacturing.
  • electrical articles and devices including one or more layers formed of or comprising the polymers and compositions described above.
  • Such devices include, for example, electronic cables, computer and computer-related equipment, marine cables, power cables, telecommunications cables or data transmission cables, and combined power/telecommunications cables.
  • Electrical devices described herein can be formed by any suitable method, such as by one or more extrusion coating steps in a reactor/extruder equipped with a cable die.
  • a cable extrusion apparatus and processes are well known.
  • an optionally heated conducting core can be pulled through a heated extrusion die, such as a cross-head die, in which a layer of melted polymer composition can be applied.
  • Multiple layers can be applied by consecutive extrusion steps in which additional layers are added, or, with the proper type of die, multiple layers can be added simultaneously.
  • the cable can be placed in a moisture curing environment, or allowed to cure under ambient conditions.
  • the multi-modal polyolefin produced by the processes of the present disclosure and blends thereof are useful in such forming operations as film, sheet, and fiber extrusion and co extrusion as well as blow molding, injection molding, and rotary molding.
  • Films include blown or cast films formed by co-extrusion or by lamination useful as shrink film, cling film, stretch film, sealing films, oriented films, snack packaging, heavy duty bags, grocery sacks, baked and frozen food packaging, medical packaging, industrial liners, membranes, etc., in food-contact and non-food contact applications.
  • Fibers include melt spinning, solution spinning and melt blown fiber operations for use in woven or non-woven form to make filters, diaper fabrics, medical garments, geotextiles, etc.
  • Extruded articles include medical tubing, wire and cable coatings, pipe, geomembranes, and pond liners. Molded articles include single and multi layered constructions in the form of bottles, tanks, large hollow articles, rigid food containers and toys, etc.
  • any of the foregoing polymers such as the foregoing ethylene copolymers or blends thereof, may be used in mono- or multi-layer blown, extruded, and/or shrink films.
  • These films may be formed by any suitable extrusion or coextrusion technique, such as a blown bubble film processing technique, wherein the composition can be extruded in a molten state through an annular die and then expanded to form a uni-axial or biaxial orientation melt prior to being cooled to form a tubular, blown film, which can then be axially slit and unfolded to form a flat film. Films may be subsequently unoriented, uniaxially oriented, or biaxially oriented to the same or different extents.
  • the polymers and compositions of the present disclosure may be further blended with additional ethylene polymers (referred to as“second ethylene polymers” or“second ethylene copolymers”) and used in film, molded parts and other suitable polyethylene applications.
  • additional ethylene polymers referred to as“second ethylene polymers” or“second ethylene copolymers”
  • the second ethylene polymer is selected from ethylene homopolymer, ethylene copolymers, and blends thereof.
  • Useful second ethylene copolymers can comprise one or more comonomers in addition to ethylene and can be a random copolymer, a statistical copolymer, a block copolymer, and/or blends thereof.
  • the method of making the second ethylene polymer is not critical, as it can be made by slurry, solution, gas phase, high pressure or other suitable processes, and by using catalyst systems appropriate for the polymerization of polyethylenes, such as Ziegler-Natta-type catalysts, chromium catalysts, metallocene-type catalysts, other appropriate catalyst systems or combinations thereof, or by free-radical polymerization.
  • the second ethylene polymers are made by the catalysts, activators and processes described in U.S. Patent Nos. 6,342,566; 6,384,142; 5,741,563; PCT Publication Nos. WO 03/040201; and WO 97/19991.
  • Such catalysts are described in, for example, ZIEGLER CATALYSTS (Gerhard Fink, Rolf Miilhaupt and Hans H. Brintzinger, eds., Springer-Verlag 1995); Resconi et al; and I, II METALLOCENE- BASED POLYOLEFINS (Wiley & Sons 2000). Additional useful second ethylene polymers and copolymers are described at paragraph [00118] to [00126] at pages 30 to 34 of PCT/US2016/028271, filed April 19, 2016.
  • TREF-LS data reported herein were measured using an analytical size TREF instrument (Polymerchar, Spain), with a column of the following dimension: inner diameter (ID) 7.8 mm and outer diameter (OD) 9.53 mm and a column length of 150 mm.
  • the column was filled with steel beads.
  • 0.5 mL of a 6.4% (w/v) polymer solution in orthodichlorobenzene (ODCB) containing 6 g BHT/4 L were charged onto the column and cooled from l40°C to 25°C at a constant cooling rate of l.0°C/min.
  • the ODCB was pumped through the column at a flow rate of 1.0 ml/min and the column temperature was increased at a constant heating rate of 2°C/min to elute the polymer.
  • the polymer concentration in the eluted liquid was detected by means of measuring the absorption at a wavenumber of 2857 cnT 1 using an infrared detector.
  • the concentration of the ethylene-a- olefin copolymer in the eluted liquid was calculated from the absorption and plotted as a function of temperature.
  • the molecular weight of the ethylene-a-olefm copolymer in the eluted liquid was measured by light scattering using a Minidawn Tristar light scattering detector (Wyatt, Calif., USA). The molecular weight was also plotted as a function of temperature.
  • Cross-Fractionation Chromatography CFC
  • CFC Cross-fractionation chromatography
  • the solvent used for preparing the sample solution and for elution was 1,2- Dichlorobenzene (ODCB) which was stabilized by dissolving 2 g of 2,6-bis(l,l- dimethylethyl)-4-methylphenol (butylated hydroxy toluene) in a 4-L bottle of fresh solvent at ambient temperature.
  • ODCB 1,2- Dichlorobenzene
  • the sample to be analyzed 25-125 mg
  • a small volume (0.5 ml) of the solution was introduced into a TREF column (stainless steel; o.d., 3/8"; length, 15 cm; packing, non-porous stainless steel micro-balls) at l50°C, and the column temperature was stabilized for 30 min at a temperature (l20-l25°C) approximately 20°C higher than the highest-temperature fraction for which the GPC analysis was included in obtaining the final bivariate distribution.
  • the sample volume was then allowed to crystallize in the column by reducing the temperature to an appropriate low temperature (30, 0, or -l5°C) at a cooling rate of 0.2°C/min.
  • the low temperature was held for 10 min before injecting the solvent flow (1 ml/min) into the TREF column to elute the soluble fraction (SF) into the GPC columns (3 x PLgel 10 pm Mixed-B 300 x 7.5 mm, Agilent Technologies, Inc.); the GPC oven was held at high temperature (l40°C).
  • the SF was eluted for 5 min from the TREF column and then the injection valve was put in the“load” position for 40 min to completely elute all of the SF through the GPC columns (standard GPC injections).
  • the universal calibration method was used for determining the molecular weight distribution (MWD) and molecular-weight averages (M n , M w , etc.) of eluting polymer fractions. Thirteen narrow molecular- weight distribution polystyrene standards (obtained from Agilent Technologies, Inc.) within the range of 1.5-8200 kg/mol were used to generate a universal calibration curve. Mark-Houwink parameters were obtained from Appendix I of Mori, S.; Barth, H. G. Size Exclusion Chromatography, Springer, 1999.
  • a polymer fraction, which eluted at a temperature step, that has a weight fraction (wt% recovery) of less than 0.5% the MWD and the molecular- weight averages were not computed; additionally, such polymer fractions were not included in computing the MWD and the molecular-weight averages of aggregates of fractions.
  • Additional test methods include the following.
  • n-Butyl lithium (2.5 M solution in hexane), dimethylsilyl dichloride (NtoSiCh) and methylmagnesium bromide (3.0 M solution in diethyl ether) were purchased from Sigma-Aldrich.
  • Hafnium tetrachloride (HfCL) 99+% and (trimethylsilyl)methyl trifluoromethanesulfonate were procured from Strem Chemicals and TCI America, respectively, and used as received.
  • n-Butyl lithium (2.5 M solution in hexane), iodomethane, indene and methyllithium (1.6 M solution in diethyl ether) were purchased from Sigma-Aldrich. The 'H NMR measurements were recorded on a 400 MHz Bruker spectrometer.
  • SMAO is methylalumoxane supported on silica ES-70 (PQ Corporation, Conshohocken, Pennsylvania) that has been calcined at 875°C and was prepared as follows: [00245] In a Celestir vessel in the drybox 55 grams methylaluminoxane (MAO) (30 wt% in toluene) was added along with 100 mL of toluene. ES-70 silica (44.0 g) that has been calcined at 875°C was then added to the vessel and stirred for 2 hours.
  • MAO methylaluminoxane
  • FIG. 1 is a graph illustrating a temperature rising elution fractionation curve of a mixed catalyst system having Catalyst 5 and Catalyst 1 under Run 1 conditions. (Y-axis on the left side of the graph corresponds to the cumulative and the Y-axis on the right side of the graph corresponds to the derivative).
  • FIG. 2 is a graph illustrating a temperature rising elution fractionation curve of a mixed catalyst system having Catalyst 5 and Catalyst 1 under Run 2 conditions. (Y-axis on the left side of the graph corresponds to the cumulative and the Y-axis on the right side of the graph corresponds to the derivative).
  • Catalyst 1 provides a bimodal polyethylene composition. Furthermore, under Run 1 conditions, MI values were high (1.5 and trending up) and the polymer density was 0.9343 g/cm 3 . Under Run 2 conditions (which had increased hexene concentration), negligible changes in polymer density were observed as compared to polymer formed under Run 1 conditions. However, increasing hexene (Run 2) provided an increased
  • MIR value of 102 as compared to an MIR value of 36 of the polymer formed under Run 1 conditions.
  • the reduced MIR value of 36 is coupled with a reduced split between the high and low density components (as shown in FIG. 2) as compared to the TREF spectrum of FIG. 1.
  • FIG. 3A is a graph illustrating MIR and C6/C2 flow ratio versus time (hours).
  • MIR is shown by circles and C6/C2 flow ratio is shown by a solid line.
  • FIG. 3B is a graph illustrating C6/C2 flow ratio and density versus time (hours). (Density is shown by squares and C6/C2 flow ratio is shown by a solid line).
  • FIG. 3A and FIG. 3B illustrate the influence of hexene on MIR and its limited impact on density. In a conventional polymerization, an increase in C6/C2 flow ratio can lead to lower polymer density, unlike polymerizations according to at least one embodiment of the present disclosure.
  • FIG. 4 is a gel permeation chromatography spectrum of the ethylene hexene copolymer formed by a catalyst system under Run 2 conditions.
  • FIG. 5 is a gel permeation chromatography spectrum of the ethylene hexene copolymer formed by a catalyst system under Run 1 conditions.
  • the PDI (Mw/Mn) value of the polymer compositions increased from Run 1 to Run 2 conditions but the overall comonomer content (hexene wt%) was negligibly affected (7.46 wt% to 7.58 wt%).
  • Catalyst 5 alone when run under the same conditions as Run 1 and Run 2 produces a polymer having a hexene content of 6.1 wt% and a density of 0.920 g/cm 3 .
  • 'H NMR data was collected at 393K in a 10 mm probe using a Bruker spectrometer with a 'H frequency of at least 400 MHz (available from Agilent Technologies, Santa Clara, CA). Data was recorded using a maximum pulse width of 45°C, 5 seconds between pulses and signal averaging 512 transients. Spectral signals were integrated and the number of unsaturation types per 1000 carbons was calculated by multiplying the different groups by 1000 and dividing the result by the total number of carbons. The number average molecular weight (Mn) was calculated by dividing the total number of unsaturated species into 14,000, and has units of g/mol.
  • Comparative films were formed from ExceedTM Polyethylene 1018.
  • ExceedTM Polyethylene 1018 (“Exceed PE 1018”), is an mLLDPE (metallocene ethylene/hexene copolymer) available from ExxonMobil Chemical Company (Houston, Texas), having an MI of 1.0 g/ 10 min, MIR of 16, and a density of 0.918 g/cm 3 .
  • mLLDPE metalocene ethylene/hexene copolymer
  • TDA is the total defect area. It is a measure of defects in a film specimen, and reported as the accumulated area of defects in square millimeters (mm 2 ) normalized by the area of film in square meters (m 2 ) examined, thus having a unit of (mm 2 /m 2 ) or“ppm”. In Table 5, only defects with a dimension above 200 microns are reported.
  • TDA is obtained by an Optical Control System (OCS).
  • OCS Optical Control System
  • ME20 2800 small extruder
  • Cast film die cast film die
  • chill roll unit Model CR-9
  • winding system with good film tension control chill roll unit
  • FSA-100 on-line camera system
  • Extruder temperature setting (°C): Feed throat/Zone l/Zone 2/Zone 3/Zone 4/Die: 70/190/200/210/215/215
  • the PE resin was pelletized and film was blown at 4 different film gauges. It is particularly noteworthy to mention that the rates for film blowing were maxed out on the instrument with no signs of bubble instability. This observation indicates a promising processability.
  • compositions (resins) formed by Run 1 and Run2 are extruded with lower melt temperature (37l°F and 377°F) (l88°C and l92°C) and die pressure (1603 psi and 2759 psi) as compared to Exceed PE 1018.
  • melt temperature 37l°F and 377°F
  • die pressure 1603 psi and 2759 psi
  • the melt temperature is 387°F with a die pressure of 3545 psi.
  • films of the present disclosure can have a combination of good Dart (e.g., 320 g/mil (Dart method A)) and high stiffness (e.g. 70,000 psi avg.). Films of the present disclosure can be obtained from polyethylene compositions having a density of 0.93 g/cm 3 .
  • Polyethylene compositions of the present disclosure can be formed by catalyst systems and processes of the present disclosure to provide ethylene polymers having medium density with comonomer content. The density can provide a stiff polymer (like a high density material) but is tougher because of the comonomer content.
  • Catalyst systems and processes of the present disclosure can provide ethylene polymers having the unique properties of high stiffness, high toughness and good processability.
  • Polyethylene compositions can be obtained from catalyst systems comprising catalyst 1: catalyst 5 and can have an MIR of from about 20 to about 110 with the MIR being tunable based on the amount of hexene in a gas phase reactor.
  • compositions, an element or a group of elements are preceded with the transitional phrase “comprising,” it is understood that we also contemplate the same composition or group of elements with transitional phrases “consisting essentially of,” “consisting of,”“selected from the group of consisting of,” or“I”” preceding the recitation of the composition, element, or elements and vice versa, e.g., the terms“comprising,”“consisting essentially of,”“consisting of’ also include the product of the combinations of elements listed after the term.

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Abstract

La présente divulgation concerne des films à base de compositions de polyéthylène (PE). Dans au moins un mode de réalisation, le film comprend un polyéthylène contenant au moins 50 % en poids de motifs dérivés de l'éthylène et de 0 à 50 % en poids d'un comonomère d'oléfine en C3-C40, sur la base du poids total de la composition de polyéthylène. La composition de polyéthylène peut avoir une température de fusion de 250 à 600 °C et le film peut avoir une moyenne de modules sécants à 1 % dans le sens MD et TD de 30 000 psi ou plus, et une résistance au choc au mouton de 100 à 500 g/mil. Des procédés de fabrication d'un film selon au moins un mode de réalisation de la présente divulgation sont en outre décrits.
PCT/US2018/057638 2017-12-01 2018-10-26 Films comprenant une composition de polyéthylène Ceased WO2019108327A1 (fr)

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EP3826833A1 (fr) * 2018-07-26 2021-06-02 ExxonMobil Chemical Patents Inc. Films de mousse multicouches et leurs procédés de fabrication
WO2021119152A1 (fr) * 2019-12-09 2021-06-17 Exxonmobil Chemical Patents Inc. Films de polyéthylène orientés dans le sens machine
WO2021222016A2 (fr) 2020-05-01 2021-11-04 Exxonmobil Chemical Patents Inc. Polyéthylène linéaire basse densité pour applications de film
WO2021222280A2 (fr) 2020-05-01 2021-11-04 Exxonmobil Chemical Patents Inc. Polyéthylène linéaire de faible densité pour applications de film
US12344686B2 (en) 2019-12-17 2025-07-01 Exxonmobil Chemical Patents Inc. Broad orthogonal distribution polyethylenes for films

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WO2021119152A1 (fr) * 2019-12-09 2021-06-17 Exxonmobil Chemical Patents Inc. Films de polyéthylène orientés dans le sens machine
US12344686B2 (en) 2019-12-17 2025-07-01 Exxonmobil Chemical Patents Inc. Broad orthogonal distribution polyethylenes for films
WO2021222016A2 (fr) 2020-05-01 2021-11-04 Exxonmobil Chemical Patents Inc. Polyéthylène linéaire basse densité pour applications de film
WO2021222280A2 (fr) 2020-05-01 2021-11-04 Exxonmobil Chemical Patents Inc. Polyéthylène linéaire de faible densité pour applications de film
WO2021222280A3 (fr) * 2020-05-01 2022-02-10 Exxonmobil Chemical Patents Inc. Polyéthylène linéaire de faible densité pour applications de film

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