Plastomers with fast crystallization rates

Abstract

Density is 0.902 g / cm 3 Ethylene copolymer compositions having a density of 0.902 g / cm or less exhibit fast crystallization behavior. The ethylene copolymer compositions include a first ethylene copolymer, a second ethylene copolymer, and optionally a third ethylene copolymer, wherein the first ethylene copolymer has a number average molecular weight greater than the number average molecular weight of the second ethylene copolymer. The ethylene copolymer compositions can be used to form monolayer and multilayer films.

Description

Technical Field

[0001] Density: 0.902 g / cm 3 The ethylene copolymer composition of 100% or less comprises a first ethylene copolymer, a second ethylene copolymer and optionally a third ethylene copolymer. The ethylene copolymer composition has a high crystallization rate and has good sealing properties and a balance of toughness and rigidity when blown into a film. Background Art

[0002] Multicomponent polyethylene compositions are well known in the art. One method of obtaining a multicomponent polyethylene composition is to use a polymerization catalyst in two or more separate polymerization reactors. For example, it is known to use a single-site catalyst in at least two different solution polymerization reactors. Such reactors can be connected in series or in parallel or in a combination thereof.

[0003] Solution polymerization processes are generally conducted at temperatures above the melting point of the ethylene homopolymer or copolymer product being produced.In a typical solution polymerization process, catalyst components, solvent, monomers and hydrogen are fed under pressure to one or more reactors.

[0004] For solution phase ethylene polymerization or ethylene copolymerization, reactor temperature can be in the range of about 80 ℃ to about 300 ℃, and pressure is usually in the range of about 3MPag to about 45MPag.Under reactor conditions, the ethylene homopolymer or copolymer produced remains dissolved in the solvent.The residence time of the solvent in the reactor is relatively short, for example, about 1 second to about 20 minutes.The solution process can operate under the method conditions of the wide range of allowing the production of multiple ethylene polymers.After the reactor, the polymerization reaction is quenched by adding a catalyst deactivator to prevent further polymerization, and optionally passivated by adding an acid scavenger.Once deactivated (and optionally passivated), the polymer solution is sent to a polymer recovery operation (devolatilization system), wherein ethylene homopolymer or copolymer is separated from method solvent, unreacted residual ethylene and unreacted optional one or more alpha-olefins.

[0005] Regardless of the method of production, there remains a need to improve the performance of multicomponent polyethylene compositions in film applications. Summary of the invention

[0006] One embodiment is an ethylene copolymer composition comprising:

[0007] (i) 15 to 80 weight percent of a first ethylene copolymer having a density of 0.855 to 0.913 g / cm 3 ; Molecular weight distribution M w / M n is 1.7-2.7; and the melt index I2 is 0.1-10g / 10min;

[0008] (ii) 85 to 20 weight percent of a second ethylene copolymer having a density of 0.865 to 0.926 g / cm 3 ; Molecular weight distribution M w / M n is 1.7-2.7; and a melt index I2 is 0.1-10 g / 10 min; and

[0009] (iii) 0 to 40 wt% of a third ethylene copolymer having a density of 0.855 to 0.930 g / cm 3 ; Molecular weight distribution M w / M n is 1.7-6.0; and the melt index I2 is 0.1-100g / 10min;

[0010] The density of the ethylene copolymer composition is 0.860-0.902 g / cm 3 ; a melt index I2 of 0.5-10 g / 10 min; and at least 0.0015 parts per million (ppm) of hafnium;

[0011] The number average molecular weight Mn of the first ethylene copolymer is 1 Greater than the number average molecular weight Mn of the second ethylene copolymer 2 ;and

[0012] The weight percent of the first, second or third ethylene copolymer is defined as the weight of the first, second or third ethylene copolymer divided by the sum of the weight of (i) the first ethylene copolymer, (ii) the second ethylene copolymer and (iii) the third ethylene copolymer, multiplied by 100%.

[0013] One embodiment is a film or film layer comprising an ethylene copolymer composition comprising:

[0014] (i) 15 to 80 weight percent of a first ethylene copolymer having a density of 0.855 to 0.913 g / cm 3 ; Molecular weight distribution M w / M n is 1.7-2.7; and the melt index I2 is 0.1-10g / 10min;

[0015] (ii) 85 to 20 weight percent of a second ethylene copolymer having a density of 0.865 to 0.926 g / cm 3 ; Molecular weight distribution M w / M n is 1.7-2.7; and a melt index I2 is 0.1-10 g / 10 min; and

[0016] (iii) 0 to 40 wt% of a third ethylene copolymer having a density of 0.855 to 0.930 g / cm 3 ; Molecular weight distribution M w / M n is 1.7-6.0; and the melt index I2 is 0.1-100g / 10min;

[0017] The density of the ethylene copolymer composition is 0.860-0.902 g / cm 3 ; a melt index I2 of 0.5-10 g / 10 min; and at least 0.0015 parts per million (ppm) of hafnium;

[0018] The number average molecular weight Mn of the first ethylene copolymer is 1 Greater than the number average molecular weight Mn of the second ethylene copolymer 2 ;and

[0019] The weight percent of the first, second or third ethylene copolymer is defined as the weight of the first, second or third ethylene copolymer divided by the sum of the weight of (i) the first ethylene copolymer, (ii) the second ethylene copolymer and (iii) the third ethylene copolymer, multiplied by 100%.

[0020] One embodiment is a multilayer film structure comprising at least one film layer, the film layer comprising an ethylene copolymer composition comprising:

[0021] (i) 15 to 80 weight percent of a first ethylene copolymer having a density of 0.855 to 0.913 g / cm 3 ; Molecular weight distribution M w / M n is 1.7-2.7; and the melt index I2 is 0.1-10g / 10min;

[0022] (ii) 85 to 20 weight percent of a second ethylene copolymer having a density of 0.865 to 0.926 g / cm 3 ; Molecular weight distribution M w / M n is 1.7-2.7; and a melt index I2 is 0.1-10 g / 10 min; and

[0023] (iii) 0 to 40 wt% of a third ethylene copolymer having a density of 0.855 to 0.930 g / cm 3 ; Molecular weight distribution M w / M n is 1.7-6.0; and the melt index I2 is 0.1-100g / 10min;

[0024] The density of the ethylene copolymer composition is 0.860-0.902 g / cm 3 ; a melt index I2 of 0.5-10 g / 10 min; and at least 0.0015 parts per million (ppm) of hafnium;

[0025] The number average molecular weight Mn of the first ethylene copolymer is 1 Greater than the number average molecular weight Mn of the second ethylene copolymer 2 ;and

[0026] The weight percent of the first, second or third ethylene copolymer is defined as the weight of the first, second or third ethylene copolymer divided by the sum of the weight of (i) the first ethylene copolymer, (ii) the second ethylene copolymer and (iii) the third ethylene copolymer, multiplied by 100%.

[0027] One embodiment is a film or film layer comprising a polymer blend comprising:

[0028] (a) 5 to 50 wt% of an ethylene copolymer composition; and

[0029] (b) 95-50 wt. % linear low density polyethylene;

[0030] wherein the ethylene copolymer composition comprises:

[0031] (i) 15 to 80 weight percent of a first ethylene copolymer having a density of 0.855 to 0.913 g / cm 3 ; Molecular weight distribution M w / M n is 1.7-2.7; and the melt index I2 is 0.1-10g / 10min;

[0032] (ii) 85 to 20 weight percent of a second ethylene copolymer having a density of 0.865 to 0.926 g / cm 3 ; Molecular weight distribution M w / M n is 1.7-2.7; and a melt index I2 is 0.1-10 g / 10 min; and

[0033] (iii) 0 to 40 wt% of a third ethylene copolymer having a density of 0.855 to 0.930 g / cm 3 ; Molecular weight distribution M w / M n is 1.7-6.0; and the melt index I2 is 0.1-100g / 10min;

[0034] The density of the ethylene copolymer composition is 0.860-0.902 g / cm3 ; a melt index I2 of 0.5-10 g / 10 min; and at least 0.0015 parts per million (ppm) of hafnium;

[0035] The number average molecular weight Mn of the first ethylene copolymer is 1 Greater than the number average molecular weight Mn of the second ethylene copolymer 2 ;and

[0036] The weight percent of the first, second or third ethylene copolymer is defined as the weight of the first, second or third ethylene copolymer divided by the sum of the weight of (i) the first ethylene copolymer, (ii) the second ethylene copolymer and (iii) the third ethylene copolymer, multiplied by 100%.

[0037] One embodiment is a multilayer film structure comprising at least one film layer, the film layer comprising a polymer blend comprising:

[0038] (a) 5 to 50 wt% of an ethylene copolymer composition; and

[0039] (b) 95-50 wt. % linear low density polyethylene;

[0040] wherein the ethylene copolymer composition comprises:

[0041] (i) 15 to 80 weight percent of a first ethylene copolymer having a density of 0.855 to 0.913 g / cm 3 ; Molecular weight distribution M w / M n is 1.7-2.7; and the melt index I2 is 0.1-10g / 10min;

[0042] (ii) 85 to 20 weight percent of a second ethylene copolymer having a density of 0.865 to 0.926 g / cm 3 ; Molecular weight distribution M w / M n is 1.7-2.7; and a melt index I2 is 0.1-10 g / 10 min; and

[0043] (iii) 0 to 40 wt% of a third ethylene copolymer having a density of 0.855 to 0.930 g / cm 3 ; Molecular weight distribution M w / M n is 1.7-6.0; and the melt index I2 is 0.1-100g / 10min;

[0044] The density of the ethylene copolymer composition is 0.860-0.902 g / cm 3; a melt index I2 of 0.5-10 g / 10 min; and at least 0.0015 parts per million (ppm) of hafnium;

[0045] The number average molecular weight Mn of the first ethylene copolymer is 1 Greater than the number average molecular weight Mn of the second ethylene copolymer 2 ;and

[0046] The weight percent of the first, second or third ethylene copolymer is defined as the weight of the first, second or third ethylene copolymer divided by the sum of the weight of (i) the first ethylene copolymer, (ii) the second ethylene copolymer and (iii) the third ethylene copolymer, multiplied by 100%. BRIEF DESCRIPTION OF THE DRAWINGS

[0047] Figure 1 The non-isothermal crystallization (cooling) characteristics of the disclosed ethylene copolymer compositions as well as comparative resins at a cooling rate of 10°C / min are shown.

[0048] Figure 2 The maximum crystallization temperature (T max ) varies linearly with its variation as a function of the logarithm of the cooling rate (β).

[0049] Figure 3 Representative graph showing how the activation energy is calculated based on the Kissinger method describing the non-isothermal crystallization method of Inventive Example 1.

[0050] Figure 4 The hot tack properties of multilayer film structures are shown, wherein the sealant layer is prepared from 100 wt. % of the ethylene copolymer composition of the present disclosure or from a comparative resin.

[0051] Figure 5 The cold seal properties of multilayer film structures are shown, wherein the sealant layer is prepared from 100 wt. % of the ethylene copolymer composition of the present disclosure or from a comparative resin.

[0052] Figure 6 Shown is the relationship between dart drop impact (in grams per mil) and machine direction 1% secant modulus (in MPa) for monolayer blown films prepared from blends comprising the disclosed ethylene copolymer composition and an LLDPE resin or a comparative resin and an LLDPE resin.

[0053] definition

[0054] In order to form a more complete understanding of the present disclosure, the following terms are defined and should be used in conjunction with the drawings and description of the various embodiments throughout.

[0055] As used herein, the term "monomer" refers to a small molecule that can chemically react with itself or other monomers and chemically bond with them to form a polymer.

[0056] As used herein, the term "α-olefin" or "α(alpha)-olefin" is used to describe a monomer having a linear hydrocarbon chain containing 3-20 carbon atoms, which has a double bond at one end of the chain; the equivalent term is "linear α-olefin". As used herein, the term "polyethylene" or "ethylene polymer" refers to a macromolecule produced from ethylene monomer and optionally one or more additional monomers; regardless of the specific catalyst or specific process used to prepare the ethylene polymer. In the polyethylene field, the one or more additional monomers are called "comonomers" and generally include α-olefins. The term "homopolymer" refers to a polymer containing only one type of monomer. "Ethylene homopolymers" are prepared using only ethylene as a polymerizable monomer. The term "copolymer" refers to a polymer containing two or more types of monomers. "Ethylene copolymers" are prepared using ethylene and one or more other types of polymerizable monomers (e.g., α-olefins).

[0057] Common polyethylene includes high density polyethylene (HDPE), medium density polyethylene (MDPE), linear low density polyethylene (LLDPE), very low density polyethylene (VLDPE), ultra low density polyethylene (ULDPE), plastomers and elastomers. The term polyethylene also includes polyethylene terpolymers, which may also include two or more comonomers (e.g., α-olefins) in addition to ethylene. The term polyethylene also includes combinations or blends of the above polyethylenes.

[0058] As used herein, the terms "linear low density polyethylene" and "LLDPE" refer to polyethylene homopolymers, or more preferably, having a density of about 0.910 g / cm 3 To about 0.945g / cm 3 Ethylene copolymers.

[0059] The term "heterogeneously branched polyethylene" refers to a subset of polymers in the group of ethylene polymers produced using heterogeneous catalyst systems; non-limiting examples of which include Ziegler-Natta or chromium catalysts, both of which are well known in the art.

[0060] The term "homogeneously branched polyethylene" refers to a subset of the group of ethylene polymers produced using single-site catalysts; non-limiting examples of which include metallocene catalysts, phosphinimine catalysts, and constrained geometry catalysts, all of which are well known in the art.

[0061] Typically, homogeneously branched polyethylene has a narrow molecular weight distribution, for example, as measured by gel permeation chromatography (GPC). w / M nValues ​​less than about 2.8, especially less than about 2.3, although exceptions may occur; M w and M n Refers to the weight average molecular weight and number average molecular weight, respectively. In contrast, the M of heterogeneously branched ethylene polymers is w / M n Usually greater than the M of homogeneous polyethylene w / M n Typically, homogeneously branched ethylene polymers also have a narrow composition distribution, i.e., each macromolecule within the molecular weight distribution has a relatively similar comonomer content when normalized with respect to the number of carbon atoms in the macromolecular chain. Typically, the composition distribution breadth index "CDBI" is used to quantify how the comonomer is distributed within an ethylene polymer, as well as to differentiate between ethylene polymers produced with different catalysts or processes. The "CDBI 50 "CDBI" is defined as the percentage of ethylene polymer whose composition is within 50 weight percent (wt%) of the median comonomer composition; this definition is consistent with that described in WO 93 / 03093 assigned to Exxon Chemical Patents Inc. The CDBI of ethylene copolymers 50 It can be calculated from the TREF curve (temperature rising elution fractionation); the TREF method is described in Wild et al., J. Polym. Sci., Part B, Polym. Phys., Vol. 20(3), pp. 441-455. In general, the CDBI of a homogeneously branched ethylene polymer is 50 In contrast, the CDBI of heterogeneously branched ethylene polymers containing α-olefins is greater than about 70% or greater than about 75%. 50 Usually lower than the CDBI of homogeneous ethylene polymers 50 For example, the CDBI of a heterogeneously branched ethylene polymer is 50 It may be less than about 75%, or less than about 70%.

[0062] It is well known to those skilled in the art that homogeneously branched ethylene polymers are generally further subdivided into "linear homogeneous ethylene polymers" and "substantially linear homogeneous ethylene polymers". The two subgroups differ in the amount of long chain branching: more specifically, linear homogeneous ethylene polymers have less than about 0.01 long chain branches per 1000 carbon atoms; whereas substantially linear homogeneous ethylene polymers have greater than about 0.01 to about 3.0 long chain branches per 1000 carbon atoms. The long chain branches are macromolecular in nature, i.e., similar in length to the macromolecule to which the long chain branches are attached. Hereinafter, in the present disclosure, the term "homogeneously branched polyethylene" or "homogeneously branched ethylene polymer" refers to both linear homogeneous ethylene polymers and substantially linear homogeneous ethylene polymers.

[0063] The term "thermoplastic" refers to a polymer that becomes liquid when heated, flows under pressure, and solidifies when cooled. Thermoplastic polymers include ethylene polymers as well as other polymers used in the plastics industry; non-limiting examples of other polymers commonly used in film applications include barrier resins (EVOH), bonding resins, polyethylene terephthalate (PET), polyamides, etc.

[0064] As used herein, the term "monolayer film" refers to a film containing a single layer of one or more thermoplastics.

[0065] As used herein, the term "multilayer film" or "multilayer film structure" refers to a film composed of more than one thermoplastic layer or optional non-thermoplastic layer. Non-limiting examples of non-thermoplastic materials include metal (foil) or cellulose (paper) products. One or more thermoplastic layers within a multilayer film (or film structure) can be composed of more than one thermoplastic material.

[0066] As used herein, the term "tie resin" refers to a thermoplastic that, when formed as an interlayer or "tie layer" within a multi-layer film structure, promotes adhesion between adjacent film layers of differing chemical composition.

[0067] As used herein, the term "sealant layer" refers to a layer of a thermoplastic film that is capable of being attached to a second substrate to form a leakproof seal. The "sealant layer" may be a skin layer or the innermost layer in a multi-layer film structure.

[0068] As used herein, the term "adhesive lamination" and the term "extrusion lamination" describe a continuous process by which two or more substrates or webs of material are combined to form a multilayer product or sheet; wherein the two or more webs are joined using an adhesive or molten thermoplastic film, respectively.

[0069] As used herein, the term "extrusion coating" describes a continuous process by which a molten thermoplastic layer is combined with or deposited on a moving solid web or substrate. Non-limiting examples of substrates include paper, paperboard, foil, a single-layer plastic film, a multi-layer plastic film, or fabric. The molten thermoplastic layer can be a single layer or multiple layers.

[0070] As used herein, the term "hydrocarbyl," "radical," or "hydrocarbyl group" refers to straight chain or cyclic, aliphatic, olefinic, acetylenic, and aryl (aromatic) radicals comprising hydrogen and carbon lacking one hydrogen.

[0071] As used herein, "alkyl" includes straight chain, branched, and cyclic alkane groups lacking one hydrogen group; non-limiting examples include methyl (-CH3) and ethyl (-CH2CH3). The term "alkenyl" refers to straight chain, branched, and cyclic hydrocarbons lacking one hydrogen group and containing at least one carbon-carbon double bond.

[0072] As used herein, the term "aryl" includes phenyl, naphthyl, pyridyl, and other groups whose molecules have an aromatic ring structure; non-limiting examples include naphthalene, phenanthrene, and anthracene. "Arylalkyl" is an alkyl group having an aryl group pendant therefrom; non-limiting examples include benzyl, phenethyl, and tolylmethyl. "Alkylaryl" is an aryl group having one or more alkyl groups pendant therefrom; non-limiting examples include tolyl, xylyl, mesityl, and cumyl.

[0073] An "alkoxy group" is an oxy group having an alkyl group pendant therefrom, and includes, for example, methoxy, ethoxy, isopropoxy, and the like.

[0074] An "aryloxy" or "aryloxide" group is an oxy group having an aryl group pendant therefrom, and includes, for example, phenoxy and the like.

[0075] As used herein, phrase "heteroatom" includes any atom other than carbon and hydrogen that can be bonded to carbon." heteroatom-containing group " is a hydrocarbon group containing heteroatom and can contain one or more identical or different heteroatoms. In one embodiment, the heteroatom-containing group is a hydrocarbon group containing 1-3 atoms selected from boron, aluminum, silicon, germanium, nitrogen, phosphorus, oxygen and sulfur. The non-limiting examples of heteroatom-containing groups include groups of imines, amines, oxides, phosphines, ethers, ketones, oxazoline heterocycles, oxazoline, thioethers, etc. The term "heterocycle" refers to a ring system with a carbon backbone, and the carbon backbone comprises 1-3 atoms selected from boron, aluminum, silicon, germanium, nitrogen, phosphorus, oxygen and sulfur.

[0076] As used herein, the term "unsubstituted" refers to a hydrogen radical bonded to the molecular group following the term unsubstituted. The term "substituted" refers to a group following the term having one or more moieties (non-hydrogen radicals) that have replaced one or more hydrogen radicals at any position within the group; non-limiting examples of such moieties include halogen groups (F, Cl, Br), hydroxyl, carbonyl, carboxyl, silyl, amine, phosphino, alkoxy, phenyl, naphthyl, C1-C 30 Alkyl, C2-C 30 Non-limiting examples of substituted alkyl and aryl groups include acyl, alkylsilyl, alkylamino, alkoxy, aryloxy, alkylthio, dialkylamino, alkoxycarbonyl, aryloxycarbonyl, carbamoyl, alkyl- and dialkyl-carbamoyl, acyloxy, acylamino, arylamino, and combinations thereof. DETAILED DESCRIPTION

[0077] In the present disclosure, the density of the ethylene copolymer composition is 0.902 g / cm 3 or less, and will comprise a first ethylene copolymer, a second ethylene copolymer, and optionally a third ethylene copolymer. Each of these ethylene copolymer components and the ethylene copolymer compositions of which they are a part are further described below.

[0078] In some embodiments of the present disclosure, the ethylene copolymer composition is used in a polymer blend comprising: (a) 5-50 wt% of the ethylene copolymer composition and (b) 95-50 wt% of a linear low density polyethylene (LLDPE).

[0079] In some embodiments of the present disclosure, the ethylene copolymer composition is used in a polymer blend comprising: (a) 5-35 wt% of the ethylene copolymer composition and (b) 95-65 wt% of a linear low density polyethylene (LLDPE).

[0080] In some embodiments of the present disclosure, the ethylene copolymer composition is used in a polymer blend comprising: (a) 5-30 wt% of the ethylene copolymer composition and (b) 95-70 wt% of a linear low density polyethylene (LLDPE).

[0081] In some embodiments of the present disclosure, the ethylene copolymer composition is used in a polymer blend comprising: (a) 10-30 wt% of the ethylene copolymer composition and (b) 90-70 wt% of a linear low density polyethylene (LLDPE).

[0082] In some embodiments of the present disclosure, the ethylene copolymer composition is used in a polymer blend comprising: (a) 15-25 wt% of the ethylene copolymer composition and (b) 85-75 wt% of a linear low density polyethylene (LLDPE).

[0083] The first ethylene copolymer

[0084] In an embodiment of the present disclosure, the first ethylene copolymer is prepared by a single site catalyst, non-limiting examples of which include phosphinimine catalysts, metallocene catalysts, and constrained geometry catalysts, all of which are well known in the art.

[0085] In an embodiment of the present disclosure, the first ethylene copolymer is prepared from a single site catalyst, having hafnium Hf as the active metal center.

[0086] In an embodiment of the present disclosure, the α-olefin that may be copolymerized with ethylene to prepare the first ethylene copolymer may be selected from the group consisting of 1-propylene, 1-butene, 1-pentene, 1-hexene, and 1-octene, and mixtures thereof.

[0087] In an embodiment of the present disclosure, the first ethylene copolymer is a homogeneously branched ethylene copolymer.

[0088] In an embodiment of the present disclosure, the first ethylene copolymer is an ethylene / 1-octene copolymer.

[0089] In an embodiment of the present disclosure, the first ethylene copolymer is produced by a metallocene catalyst.

[0090] In an embodiment of the present disclosure, the first ethylene copolymer is produced by a bridged metallocene catalyst.

[0091] In an embodiment of the present disclosure, the first ethylene copolymer is prepared from a bridged metallocene catalyst having Formula I:

[0092]

[0093] wherein G is a Group 14 element selected from carbon, silicon, germanium, tin or lead; R1 is a hydrogen atom, C 1-20 Hydrocarbon, C 1-20 Alkoxy or C 6-10 Aryl oxide group; R2 and R3 are independently selected from hydrogen atoms, C 1-20 Hydrocarbon, C 1-20 Alkoxy or C 6-10 Aryl oxide group; R4 and R5 are independently selected from hydrogen atoms, unsubstituted C 1-20 Hydrocarbon, substituted C 1-20 Hydrocarbon, C 1-20 Alkoxy or C 6-10 an aryl oxide group; and Q is independently an activatable leaving group ligand.

[0094] In an embodiment, R4 and R5 are independently aryl.

[0095] In an embodiment, R4 and R5 are independently phenyl or substituted phenyl.

[0096] In an embodiment, R4 and R5 are phenyl.

[0097] In an embodiment, R4 and R5 are independently substituted phenyl.

[0098] In an embodiment, R4 and R5 are substituted phenyl, wherein the phenyl is substituted with substituted silyl.

[0099] In an embodiment, R4 and R5 are substituted phenyl, wherein the phenyl is substituted with a trialkylsilyl group.

[0100] In an embodiment, R4 and R5 are substituted phenyl, wherein the phenyl is substituted in the para position by trialkylsilyl. In an embodiment, R4 and R5 are substituted phenyl, wherein the phenyl is substituted in the para position by trimethylsilyl. In an embodiment, R4 and R5 are substituted phenyl, wherein the phenyl is substituted in the para position by triethylsilyl.

[0101] In an embodiment, R4 and R5 are independently alkyl.

[0102] In an embodiment, R4 and R5 are independently alkenyl.

[0103] In an embodiment, R1 is hydrogen.

[0104] In an embodiment, R1 is alkyl.

[0105] In an embodiment, R1 is aryl.

[0106] In an embodiment, R1 is alkenyl.

[0107] In an embodiment, R2 and R3 are independently a hydrocarbyl group having 1 to 30 carbon atoms.

[0108] In an embodiment, R2 and R3 are independently aryl.

[0109] In an embodiment, R2 and R3 are independently alkyl.

[0110] In an embodiment, R2 and R3 are independently alkyl groups having 1 to 20 carbon atoms.

[0111] In an embodiment, R2 and R3 are independently phenyl or substituted phenyl.

[0112] In an embodiment, R2 and R3 are tert-butyl.

[0113] In an embodiment, R2 and R3 are hydrogen.

[0114] In an embodiment of the present disclosure, the first ethylene copolymer is prepared from a bridged metallocene catalyst having Formula II:

[0115]

[0116] wherein Q is independently an activatable leaving group ligand.

[0117] In the present disclosure, the term "activatable" means that the ligand Q can be cleaved from the metal center M via a protolysis reaction, or abstracted from the metal center M by a suitable acidic or electrophilic catalyst activator compound (also referred to as a "co-catalyst" compound), examples of which are described below. The activatable ligand Q can also be converted to another ligand that is cleaved or abstracted from the metal center M (e.g., a halide can be converted to an alkyl). Without wishing to be bound by any single theory, the protolysis or abstraction reaction produces an active "cationic" metal center that can polymerize olefins.

[0118] In embodiments of the present disclosure, the activatable ligand Q is independently selected from a hydrogen atom; a halogen atom; 1-20 Hydrocarbon, C 1-20 Alkoxy and C 6-10Aryl or aryloxy, wherein each of the hydrocarbyl, alkoxy, aryl or aryloxide groups may be unsubstituted or further substituted by one or more of the following groups: halogen or other groups; C 1-8 Alkyl; C 1-8 Alkoxy; C 6-10 Aryl or aryloxy; amido or phosphino, but wherein Q is not cyclopentadienyl. Two Q ligands can also be linked to each other and form, for example, a substituted or unsubstituted diene ligand (e.g., 1,3-butadiene); or a delocalized heteroatom-containing group, such as an acetate or acetamidine group.

[0119] In the embodiments of the present disclosure, each Q is independently selected from a halogen atom, C 1-4 Alkyl and benzyl.

[0120] In embodiments, suitable activatable ligands Q are monoanionic, such as halides (eg, chloride) or hydrocarbyl groups (eg, methyl, benzyl).

[0121] In an embodiment, each activatable ligand Q is a methyl group.

[0122] In an embodiment, each activatable ligand Q is benzyl.

[0123] In an embodiment, each activatable ligand Q is a chloride group.

[0124] In an embodiment of the present disclosure, the single site catalyst used to prepare the first ethylene copolymer is diphenylmethylene(cyclopentadienyl)(2,7-di-tert-butylfluorenyl)hafnium dichloride, which has the molecular formula: [(2,7-tBu2Flu)Ph2C(Cp)HfCl2].

[0125] In an embodiment of the present disclosure, the single site catalyst used to prepare the first ethylene copolymer is diphenylmethylene(cyclopentadienyl)(2,7-di-tert-butylfluorenyl)hafnium dimethyl, which has the molecular formula: [(2,7-tBu2Flu)Ph2C(Cp)HfMe2].

[0126] In addition to the single-site catalyst molecule itself, an active single-site catalyst system typically further comprises a catalyst activator.

[0127] In an embodiment of the present disclosure, the catalyst activator comprises an alkylaluminoxane and / or an ionic activator.

[0128] The catalyst activator may also optionally include a hindered phenol compound.

[0129] In an embodiment of the present disclosure, the catalyst activator comprises an aluminum alkyl, an ionic activator, and a hindered phenol compound.

[0130] Although the exact structure of an alkylaluminoxane is uncertain, subject matter experts generally agree that it is an oligomeric species containing repeating units of the general formula:

[0131] (R)2AlO-(Al(R)-O) n -Al(R)2

[0132] wherein the R groups can be the same or different linear, branched or cyclic hydrocarbon groups containing 1 to 20 carbon atoms, and n is from 0 to about 50. A non-limiting example of an alkylaluminoxane is methylaluminoxane (or MAO), wherein each R group is methyl.

[0133] In an embodiment of the present disclosure, R of the alkylaluminoxane is methyl, and m is 10-40.

[0134] In an embodiment of the present disclosure, the alkylaluminoxane is modified methylaluminoxane (MMAO).

[0135] It is well known in the art that alkylaluminoxanes can play a dual role as both an alkylating agent and an activator. Therefore, alkylaluminoxane catalyst activators are often used in combination with an activatable ligand (e.g., a halogen).

[0136] Typically, the ionic activator consists of a cation and a bulky anion; wherein the latter is substantially non-coordinating. A non-limiting example of an ionic activator is a boron ionic activator that is tetra-coordinated with four ligands bonded to a boron atom. Non-limiting examples of boron ionic activators include the following formula shown below:

[0137] [R 5 ] + [B(R 7 )4] -

[0138] Where B represents a boron atom, R 5 is an aromatic hydrocarbon group (e.g., a triphenylmethyl cation), and each R 7 independently selected from unsubstituted or substituted with 3-5 fluorine atoms, unsubstituted or substituted with fluorine atoms, 1-4 Phenyl substituted with an alkyl or alkoxy substituent; and -Si(R 9 )3 silyl group, wherein each R 9 are independently selected from hydrogen atoms and C 1-4 Alkyl, and

[0139] [(R 8 ) t [EN] + [B(R 7 )4] +

[0140] Where B is a boron atom, H is a hydrogen atom, Z is a nitrogen or phosphorus atom, t is 2 or 3, and R 8 Selected from C 1-8 Alkyl, unsubstituted or substituted with up to three C 1-4 Alkyl-substituted phenyl, or one R 8 Together with the nitrogen atom, it can form an aniline group, and R 7 As defined above.

[0141] In both formulas, R 7 A non-limiting example of is pentafluorophenyl. In general, the boron ion activator can be described as a salt of tetrakis(perfluorophenyl)boron; non-limiting examples include aniline salts, carbon salts, oxygen salts, phosphonium salts and sulfonium salts of tetrakis(perfluorophenyl)boron with aniline and trityl (or triphenylmethyl)boron. Additional non-limiting examples of ionic activators include: triethylammonium tetrakis(phenyl)boron, tripropylammonium tetrakis(phenyl)boron, tri(n-butyl)ammonium tetrakis(phenyl)boron, trimethylammonium tetrakis(p-tolyl)boron, trimethylammonium tetrakis(o-tolyl)boron, tributylammonium tetrakis(pentafluorophenyl)boron, tripropylammonium tetrakis(o,p-dimethylphenyl)boron, tributylammonium tetrakis(m,m-dimethylphenyl)boron, tributylammonium tetrakis(p-trifluoromethylphenyl)boron, tributylammonium tetrakis(pentafluorophenyl)boron Boron, tri(n-butyl)ammonium tetra(o-tolyl)boron, N,N-dimethylaniline tetra(phenyl)boron, N,N-diethylaniline tetra(phenyl)boron, N,N-diethylaniline tetra(phenyl)boron, N,N-diethylaniline tetra(phenyl)boron, N,N-2,4,6-pentamethylaniline tetra(phenyl)boron, di(isopropyl)ammonium tetra(pentafluorophenyl)boron, dicyclohexylammonium tetra(phenyl)boron, triphenylphosphonium tetra(phenyl)boron, tri(methylphenyl)phosphonium tetra(phenyl)boron, tri(dimethylphenyl) Phosphonium tetra(phenyl)boron, tropine tetra(pentafluorophenyl)borate, triphenylmethylium tetra(pentafluorophenyl)borate, benzene(diazonium)tetra(pentafluorophenyl)borate, tropine tetra(2,3,5,6-tetrafluorophenyl)borate, triphenylmethylium tetra(2,3,5,6-tetrafluorophenyl)borate, benzene(diazonium)tetra(3,4,5-trifluorophenyl)borate, tropine tetra(3,4,5-trifluorophenyl)borate, benzene(diazonium)tetra(3

[0013] Commercially available ionic activators include N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate and triphenylmethylium tetrakis(pentafluorophenyl)borate.

[0142] In an embodiment of the present disclosure, the catalyst activator comprises an ionic activator selected from the group consisting of: N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate ("[Me2NHPh][B(C6F5)4]"); triphenylmethylonium tetrakis(pentafluorophenyl)borate ("[Ph3C][B(C6F5)4]", also known as "trityl borate"); and tris(pentafluorophenyl)boron.

[0143] In an embodiment of the present disclosure, the catalyst activator comprises triphenylmethylonium tetrakis(pentafluorophenyl)borate "tritylborate".

[0144] In an embodiment of the present disclosure, the catalyst activator comprises a hindered phenol compound selected from the group consisting of butylated phenol antioxidant, butylated hydroxytoluene, 2,6-di-tert-butyl-4-ethylphenol (BHEB), 4,4′-methylenebis(2,6-di-tert-butylphenol), 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)hydroxy, and octadecyl-3-(3′,5′-di-tert-butyl-4′-hydroxyphenyl) propionate.

[0145] In an embodiment of the present disclosure, the catalyst activator comprises the hindered phenol compound 2,6-di-tert-butyl-4-ethylphenol (BHEB).

[0146] Optionally, in embodiments of the present disclosure, a mixture of an alkylaluminoxane and an ionic activator may be used as a catalyst activator, optionally together with a hindered phenol compound.

[0147] To produce an active single site catalyst system, the amounts and molar ratios of the above components (single site catalyst, alkylaluminoxane, ionic activator, and optional hindered phenol) are optimized.

[0148] In embodiments of the present disclosure, the ionic activator compound may be used in an amount to provide a molar ratio of hafnium Hf to boron (of a single site catalyst molecule) of 1:1 to 1:10, or 1:1 to 1:6, or 1:1 to 1:2.

[0149] In embodiments of the present disclosure, the molar ratio of aluminum contained in the alkylaluminoxane to hafnium Hf (of the single-site catalyst molecule) is from 5:1 to 1000:1, including narrower ranges within this range.

[0150] In an embodiment of the present disclosure, the molar ratio of aluminum contained in the alkylaluminoxane to the hindered phenol (eg, BHEB) is from 1:1 to 1:0.1, including narrower ranges within this range.

[0151] To produce an active single site catalyst system, the amounts and molar ratios of the three or four components (single site catalyst, alkylaluminoxane, ionic activator, and optional hindered phenol) are optimized.

[0152] In an embodiment of the present disclosure, the single-site catalyst used to prepare the first ethylene copolymer produces long chain branches, and the first ethylene copolymer will contain long chain branches, hereinafter referred to as 'LCB'. LCB is a well-known structural phenomenon in ethylene copolymers and is well known to those of ordinary skill in the art. Traditionally, there are three methods for LCB analysis, namely nuclear magnetic resonance spectroscopy (NMR), see, for example, JC Randall, J Macromol. Sci., Rev. Macromol. Chem. Phys. 1989, 29, 201; triple detection SEC, which is equipped with DRI, viscometer and low-angle laser scattering detector, see, for example, WW Yau and DR Hill, Int. J. Polym. Anal. Charact. 1996; 2: 151; and rheology, see, for example, WW Graessley, Acc. Chem. Res. 1977, 10, 332-339 J.C. In the present disclosure, long chain branches are macromolecular in nature, ie, long enough to be visible in NMR spectroscopy, triple detector SEC experiments, or rheology experiments.

[0153] In embodiments of the present disclosure, the first ethylene copolymer contains long chain branching characterized by the LCBF disclosed herein. In embodiments of the present disclosure, the upper limit of the LCBF of the first ethylene copolymer can be about 0.5, about 0.4 in other cases, and about 0.3 in still other cases (dimensionless). In embodiments of the present disclosure, the lower limit of the LCBF of the first ethylene copolymer can be about 0.001, about 0.0015 in other cases, and about 0.002 in still other cases (dimensionless).

[0154] The first ethylene copolymer can contain catalyst residues reflecting the chemical composition of the catalyst preparation for preparing it. It will be appreciated by those skilled in the art that catalyst residues are usually quantified by parts / million of metals in, for example, the first ethylene copolymer (or ethylene copolymer composition; vide infra), wherein the metal present is derived from the metal in the catalyst preparation for preparing it. The non-limiting examples of metal residues that may be present include Group 4 metals titanium, zirconium and hafnium. In embodiments of the present disclosure, the upper limit of the ppm of the metal in the first ethylene copolymer can be about 3.0ppm, about 2.0ppm in other cases, and about 1.5ppm in other cases. In embodiments of the present disclosure, the lower limit of the ppm of the metal in the first ethylene copolymer can be about 0.03ppm, about 0.09ppm in other cases, and about 0.15ppm in other cases.

[0155] In an embodiment of the present disclosure, the density of the first ethylene copolymer is 0.855-0.913 g / cm 3, molecular weight distribution M w / M n The melt index I2 is 1.7-2.7 and the melt index I2 is 0.1-10 g / 10 min.

[0156] In an embodiment of the present disclosure, the density of the first ethylene copolymer is 0.855-0.913 g / cm 3 , molecular weight distribution M w / M n The melt index I2 is 1.7-2.3, and the melt index I2 is 0.1-10 g / 10 min.

[0157] In an embodiment of the present disclosure, the molecular weight distribution M of the first ethylene copolymer is w / M n The upper limit of can be about 2.8, or about 2.6, or about 2.5, or about 2.4, or about 2.3, or about 2.2. In an embodiment of the present disclosure, the molecular weight distribution M of the first ethylene copolymer is w / M n The lower limit of may be about 1.6, or about 1.7, or about 1.8, or about 1.9.

[0158] In an embodiment of the present disclosure, the molecular weight distribution M of the first ethylene copolymer is w / M n <2.6, or <2.3, or ≤2.3, or <2.1, or ≤2.1, or <2.0, or ≤2.0, or about 2.0. In an embodiment of the present disclosure, the molecular weight distribution M of the first ethylene copolymer is w / M n From about 1.7 to about 2.3, or from about 1.8 to about 2.3, or from about 1.8 to about 2.2.

[0159] In an embodiment of the present disclosure, the first ethylene copolymer has 10-150 short chain branches (SCB1) per thousand carbon atoms. In a further embodiment, the first ethylene copolymer has 15-100 short chain branches (SCB1) per thousand carbon atoms, or 20-100 short chain branches (SCB1) per thousand carbon atoms, or 25-100 short chain branches (SCB1) per thousand carbon atoms, or 10-75 short chain branches (SCB1) per thousand carbon atoms, or 15-75 short chain branches (SCB1) per thousand carbon atoms, or 20-75 short chain branches (SCB1) per thousand carbon atoms, or 25-75 short chain branches (SCB1) per thousand carbon atoms. In yet further embodiments, the first ethylene copolymer has 15-70 short chain branches (SCB1) per thousand carbon atoms, or 20-70 short chain branches (SCB1) per thousand carbon atoms, or 20-60 short chain branches (SCB1) per thousand carbon atoms, or 15-60 short chain branches (SCB1) per thousand carbon atoms, or 15-55 short chain branches (SCB1) per thousand carbon atoms, or 20-55 short chain branches (SCB1) per thousand carbon atoms, or 25-50 short chain branches (SCB1) per thousand carbon atoms, or 20-50 short chain branches (SCB1) per thousand carbon atoms.

[0160] Short chain branching (i.e. short chain branching per thousand backbone carbon atoms, SCB1) is branching due to the presence of α-olefin comonomers in the ethylene copolymer and will, for example, have two carbon atoms for a 1-butene comonomer, or four carbon atoms for a 1-hexene comonomer, or six carbon atoms for a 1-octene comonomer, and so on.

[0161] In an embodiment of the present disclosure, the number of short chain branches per thousand carbon atoms in the first ethylene copolymer (SCB1) and the number of short chain branches per thousand carbon atoms in the second ethylene copolymer (SCB2) satisfy the following condition: SCB1 / SCB2>0.8.

[0162] In embodiments of the present disclosure, the number of short chain branches per thousand carbon atoms (SCB1) in the first ethylene copolymer is greater than the number of short chain branches per thousand carbon atoms (SCB2) in the second ethylene copolymer.

[0163] In embodiments of the present disclosure, the number of short chain branches per thousand carbon atoms (SCB1) in the first ethylene copolymer is greater than the number of short chain branches per thousand carbon atoms (SCB3) in the third ethylene copolymer.

[0164] In embodiments of the present disclosure, the number of short chain branches per thousand carbon atoms (SCB1) in the first ethylene copolymer is greater than the number of short chain branches per thousand carbon atoms (SCB2) and (SCB3) in the second and third ethylene copolymers, respectively.

[0165] In an embodiment of the present disclosure, the upper limit of the density d1 of the first ethylene copolymer may be about 0.915 g / cm 3 ; in some cases about 0.912 g / cm 3 ; in other cases about 0.910g / cm 3 , in other cases about 0.906 g / cm 3 , in other cases about 0.902 g / cm 3 , in other cases about 0.900 g / cm 3 In an embodiment of the present disclosure, the lower limit of the density d1 of the first ethylene copolymer may be about 0.855 g / cm 3 , in some cases about 0.865 g / cm 3 ; and in other cases about 0.875 g / cm 3 .

[0166] In an embodiment of the present disclosure, the density d1 of the first ethylene copolymer may be about 0.855 g / cm 3 To about 0.915g / cm 3 , or about 0.855g / cm 3 to about 0.912g / cm 3 , or about 0.855g / cm 3 To about 0.910g / cm 3 , or about 0.855g / cm 3 to about 0.906g / cm 3 , or about 0.855g / cm 3 to about 0.902g / cm 3 , or about 0.855g / cm 3 To about 0.900g / cm 3 , or 0.865g / cm 3 to about 0.915g / cm 3 , or about 0.865g / cm 3 to about 0.912g / cm 3 , or about 0.865g / cm 3 To about 0.910g / cm 3 , or about 0.865g / cm 3 to about 0.906g / cm 3 , or about 0.865g / cm 3to about 0.902g / cm 3 , or about 0.865g / cm 3 To about 0.900g / cm 3 , or 0.875g / cm 3 to about 0.915g / cm 3 , or about 0.875g / cm 3 to about 0.912g / cm 3 , or about 0.875g / cm 3 To about 0.910g / cm 3 , or about 0.875g / cm 3 to about 0.906g / cm 3 , or about 0.875g / cm 3 to about 0.902g / cm 3 , or about 0.875g / cm 3 To about 0.900g / cm 3 .

[0167] In an embodiment of the present disclosure, the density d1 of the first ethylene copolymer is equal to or less than the density d2 of the second ethylene copolymer.

[0168] In an embodiment of the present disclosure, the density d1 of the first ethylene copolymer is less than the density d2 of the second ethylene copolymer.

[0169] In an embodiment of the present disclosure, the CDBI of the first ethylene copolymer is 50 The upper limit of may be about 98 weight percent, in other cases about 95 weight percent, and in still other cases about 90 weight percent. In embodiments of the present disclosure, the CDBI of the first ethylene copolymer is 50 The lower limit may be about 70 weight percent, in other cases about 75 weight percent, and in still other cases about 80 weight percent.

[0170] In an embodiment of the present disclosure, the melt index I2 of the first ethylene copolymer is 1It can be about 0.01 g / 10min to about 100 g / 10min, or about 0.01 g / 10min to about 75 g / 10min, or about 0.1 g / 10min to about 100 g / 10min, or about 0.1 g / 10min to about 70 g / 10min, or about 0.01 g / 10min to about 50 g / 10min, or about 0.1 g / 10min to about 50 g / 10min, or about 0.1 g / 10min to about 25g / 10min, or about 0.1g / 10min to about 20g / 10min, or about 0.1g / 10min to about 15g / 10min, or about 0.1 to about 10g / 10min, or about 0.1 to about 5g / 10min, or about 0.1-2.5g / 10min, or less than about 5g / 10min, or less than about 3g / 10min, or less than about 1.0g / 10min, or less than about 0.75g / 10min.

[0171] In an embodiment of the present disclosure, the weight average molecular weight M of the first ethylene copolymer is w From about 50,000 to about 300,000 g / mol, or from about 50,000 to about 250,000 g / mol, or from about 60,000 to about 250,000 g / mol, or from about 70,000 to about 250,000 g / mol, or from about 75,000 to about 200,000 g / mol, or from about 75,000 to about 175,000 g / mol, or from about 70,000 to about 175,000 g / mol, or from about 100,000 to about 200,000 g / mol, or from about 100,000 to about 175,000 g / mol.

[0172] In an embodiment of the present disclosure, the weight average molecular weight M of the first ethylene copolymer is w Greater than the weight average molecular weight M of the second ethylene copolymer w .

[0173] In an embodiment of the present disclosure, the number average molecular weight M of the first ethylene copolymer is n From about 25,000 to about 100,000 g / mol, or from about 30,000 to about 90,000 g / mol, or from about 40,000 to about 80,000 g / mol.

[0174] In an embodiment of the present disclosure, the number average molecular weight M of the first ethylene copolymer is n Greater than the number average molecular weight M of the second ethylene copolymer n .

[0175] In embodiments of the present disclosure, the upper limit of the weight percent (wt%) of the first ethylene copolymer in the ethylene copolymer composition (i.e., the wt% of the first ethylene copolymer based on the total weight of the first, second, and third ethylene copolymers) can be about 80 wt%, or about 75 wt%, or about 70 wt%, or about 65 wt%, or about 60 wt%, or about 55 wt%, or about 50 wt%, or about 45 wt%, or about 40 wt%. In embodiments of the present disclosure, the lower limit of the wt% of the first ethylene copolymer in the ethylene copolymer composition can be about 5 wt%, or about 10 wt%, or about 15 wt%, or about 20 wt%, or about 25 wt%, or about 30 wt%, or about 35 wt% in other cases.

[0176] The second ethylene copolymer

[0177] In an embodiment of the present disclosure, the second ethylene copolymer is prepared by a single site catalyst, non-limiting examples of which include phosphinimine catalysts, metallocene catalysts, and constrained geometry catalysts, all of which are well known in the art.

[0178] In an embodiment of the present disclosure, the second ethylene copolymer is prepared from a single site catalyst, having hafnium Hf as the active metal center.

[0179] In an embodiment of the present disclosure, the α-olefin that may be copolymerized with ethylene to prepare the second ethylene copolymer may be selected from the group consisting of 1-propylene, 1-butene, 1-pentene, 1-hexene, and 1-octene, and mixtures thereof.

[0180] In an embodiment of the present disclosure, the second ethylene copolymer is a homogeneously branched ethylene copolymer.

[0181] In an embodiment of the present disclosure, the second ethylene copolymer is an ethylene / 1-octene copolymer.

[0182] In an embodiment of the present disclosure, the second ethylene copolymer is produced by a metallocene catalyst.

[0183] In an embodiment of the present disclosure, the second ethylene copolymer is produced by a bridged metallocene catalyst.

[0184] In an embodiment of the present disclosure, the second ethylene copolymer is prepared from a bridged metallocene catalyst having Formula I:

[0185]

[0186] wherein G is a Group 14 element selected from carbon, silicon, germanium, tin or lead; R1 is a hydrogen atom, C 1-20 Hydrocarbon, C 1-20 Alkoxy or C 6-10 Aryl oxide group; R2 and R3 are independently selected from hydrogen atoms, C1-20 Hydrocarbon, C 1-20 Alkoxy or C 6-10 Aryl oxide group; R4 and R5 are independently selected from hydrogen atoms, unsubstituted C 1-20 Hydrocarbon, substituted C 1-20 Hydrocarbon, C 1-20 Alkoxy or C 6-10 an aryl oxide group; and Q is independently an activatable leaving group ligand.

[0187] In an embodiment, R4 and R5 are independently aryl.

[0188] In an embodiment, R4 and R5 are independently phenyl or substituted phenyl.

[0189] In an embodiment, R4 and R5 are phenyl.

[0190] In an embodiment, R4 and R5 are independently substituted phenyl.

[0191] In an embodiment, R4 and R5 are substituted phenyl, wherein the phenyl is substituted with substituted silyl.

[0192] In an embodiment, R4 and R5 are substituted phenyl, wherein the phenyl is substituted with a trialkylsilyl group.

[0193] In an embodiment, R4 and R5 are substituted phenyl, wherein the phenyl is substituted in the para position by trialkylsilyl. In an embodiment, R4 and R5 are substituted phenyl, wherein the phenyl is substituted in the para position by trimethylsilyl. In an embodiment, R4 and R5 are substituted phenyl, wherein the phenyl is substituted in the para position by triethylsilyl.

[0194] In an embodiment, R4 and R5 are independently alkyl.

[0195] In an embodiment, R4 and R5 are independently alkenyl.

[0196] In an embodiment, R1 is hydrogen.

[0197] In an embodiment, R1 is alkyl.

[0198] In an embodiment, R1 is aryl.

[0199] In an embodiment, R1 is alkenyl.

[0200] In an embodiment, R2 and R3 are independently a hydrocarbyl group having 1 to 30 carbon atoms.

[0201] In an embodiment, R2 and R3 are independently aryl.

[0202] In an embodiment, R2 and R3 are independently alkyl.

[0203] In an embodiment, R2 and R3 are independently alkyl groups having 1 to 20 carbon atoms.

[0204] In an embodiment, R2 and R3 are independently phenyl or substituted phenyl.

[0205] In an embodiment, R2 and R3 are tert-butyl.

[0206] In an embodiment, R2 and R3 are hydrogen.

[0207] In an embodiment of the present disclosure, the second ethylene copolymer is prepared from a bridged metallocene catalyst having Formula II:

[0208]

[0209] wherein Q is independently an activatable leaving group ligand.

[0210] In the present disclosure, the term "activatable" means that the ligand Q can be cleaved from the metal center M via a protolysis reaction, or abstracted from the metal center M by a suitable acidic or electrophilic catalyst activator compound (also referred to as a "co-catalyst" compound), examples of which are described below. The activatable ligand Q can also be converted to another ligand that is cleaved or abstracted from the metal center M (e.g., a halide can be converted to an alkyl). Without wishing to be bound by any single theory, the protolysis or abstraction reaction produces an active "cationic" metal center that can polymerize olefins.

[0211] In embodiments of the present disclosure, the activatable ligand Q is independently selected from a hydrogen atom; a halogen atom; 1-20 Hydrocarbon, C 1-20 Alkoxy and C 6-10 Aryl or aryloxy, wherein each of the hydrocarbyl, alkoxy, aryl or aryloxide groups may be unsubstituted or further substituted by one or more of the following groups: halogen or other groups; C 1-8 Alkyl; C 1-8 Alkoxy; C 6-10 Aryl or aryloxy; amido or phosphino, but wherein Q is not cyclopentadienyl. Two Q ligands can also be linked to each other and form, for example, a substituted or unsubstituted diene ligand (e.g., 1,3-butadiene); or a delocalized heteroatom-containing group, such as an acetate or acetamidine group.

[0212] In the embodiments of the present disclosure, each Q is independently selected from a halogen atom, C 1-4 Alkyl and benzyl.

[0213] In embodiments, suitable activatable ligands Q are monoanionic, such as halides (eg, chloride) or hydrocarbyl groups (eg, methyl, benzyl).

[0214] In an embodiment, each activatable ligand Q is a methyl group.

[0215] In an embodiment, each activatable ligand Q is benzyl.

[0216] In an embodiment, each activatable ligand Q is a chloride group.

[0217] In an embodiment of the present disclosure, the single site catalyst used to prepare the second ethylene copolymer is diphenylmethylene(cyclopentadienyl)(2,7-di-tert-butylfluorenyl)hafnium dichloride, which has the molecular formula: [(2,7-tBu2Flu)Ph2C(Cp)HfCl2].

[0218] In an embodiment of the present disclosure, the single site catalyst used to prepare the second ethylene copolymer is diphenylmethylene(cyclopentadienyl)(2,7-di-tert-butylfluorenyl)hafnium dimethyl, which has the molecular formula: [(2,7-tBu2Flu)Ph2C(Cp)HfMe2].

[0219] In addition to the single-site catalyst molecule itself, an active single-site catalyst system typically further comprises a catalyst activator.

[0220] In an embodiment of the present disclosure, the catalyst activator comprises an alkylaluminoxane and / or an ionic activator.

[0221] The catalyst activator may also optionally include a hindered phenol compound.

[0222] In an embodiment of the present disclosure, the catalyst activator comprises an aluminum alkyl, an ionic activator, and a hindered phenol compound.

[0223] Although the exact structure of an alkylaluminoxane is uncertain, subject matter experts generally agree that it is an oligomeric species containing repeating units of the general formula:

[0224] (R)2AlO-(Al(R)-O) n -Al(R)2

[0225] wherein the R groups can be the same or different linear, branched or cyclic hydrocarbon groups containing 1 to 20 carbon atoms, and n is from 0 to about 50. A non-limiting example of an alkylaluminoxane is methylaluminoxane (or MAO), wherein each R group is methyl.

[0226] In an embodiment of the present disclosure, R of the alkylaluminoxane is methyl, and m is 10-40.

[0227] In an embodiment of the present disclosure, the alkylaluminoxane is modified methylaluminoxane (MMAO).

[0228] It is well known in the art that alkylaluminoxanes can play a dual role as both an alkylating agent and an activator. Therefore, alkylaluminoxane catalyst activators are often used in combination with an activatable ligand (e.g., a halogen).

[0229] Typically, the ionic activator consists of a cation and a bulky anion; wherein the latter is substantially non-coordinating. A non-limiting example of an ionic activator is a boron ionic activator that is tetra-coordinated with four ligands bonded to a boron atom. Non-limiting examples of boron ionic activators include the following formula shown below:

[0230] [R 5 ] + [B(R 7 )4] -

[0231] Where B represents a boron atom, R 5 is an aromatic hydrocarbon group (e.g., a triphenylmethyl cation), and each R 7 independently selected from unsubstituted or substituted with 3-5 fluorine atoms, unsubstituted or substituted with fluorine atoms, 1-4 Phenyl substituted with an alkyl or alkoxy substituent; and -Si(R 9 )3 silyl group, wherein each R 9 are independently selected from hydrogen atoms and C 1-4 Alkyl, and

[0232] [(R 8 ) t [EN] + [B(R 7 )4] -

[0233] Where B is a boron atom, H is a hydrogen atom, Z is a nitrogen or phosphorus atom, t is 2 or 3, and R 8 Selected from C 1-8 Alkyl, unsubstituted or substituted with up to three C 1-4 Alkyl-substituted phenyl, or one R 8 Together with the nitrogen atom, it can form an aniline group, and R 7 As defined above.

[0234] In both formulas, R 7A non-limiting example of is pentafluorophenyl. In general, the boron ion activator can be described as a salt of tetrakis(perfluorophenyl)boron; non-limiting examples include aniline salts, carbon salts, oxygen salts, phosphonium salts and sulfonium salts of tetrakis(perfluorophenyl)boron with aniline and trityl (or triphenylmethyl)boron. Additional non-limiting examples of ionic activators include: triethylammonium tetrakis(phenyl)boron, tripropylammonium tetrakis(phenyl)boron, tri(n-butyl)ammonium tetrakis(phenyl)boron, trimethylammonium tetrakis(p-tolyl)boron, trimethylammonium tetrakis(o-tolyl)boron, tributylammonium tetrakis(pentafluorophenyl)boron, tripropylammonium tetrakis(o,p-dimethylphenyl)boron, tributylammonium tetrakis(m,m-dimethylphenyl)boron, tributylammonium tetrakis(p-trifluoromethylphenyl)boron, tributylammonium tetrakis(pentafluorophenyl)boron Boron, tri(n-butyl)ammonium tetra(o-tolyl)boron, N,N-dimethylaniline tetra(phenyl)boron, N,N-diethylaniline tetra(phenyl)boron, N,N-diethylaniline tetra(phenyl)boron, N,N-diethylaniline tetra(phenyl)boron, N,N-2,4,6-pentamethylaniline tetra(phenyl)boron, di(isopropyl)ammonium tetra(pentafluorophenyl)boron, dicyclohexylammonium tetra(phenyl)boron, triphenylphosphonium tetra(phenyl)boron, tri(methylphenyl)phosphonium tetra(phenyl)boron, tri(dimethylphenyl) Phosphonium tetra(phenyl)boron, tropine tetra(pentafluorophenyl)borate, triphenylmethylium tetra(pentafluorophenyl)borate, benzene(diazonium)tetra(pentafluorophenyl)borate, tropine tetra(2,3,5,6-tetrafluorophenyl)borate, triphenylmethylium tetra(2,3,5,6-tetrafluorophenyl)borate, benzene(diazonium)tetra(3,4,5-trifluorophenyl)borate, tropine tetra(3,4,5-trifluorophenyl)borate, benzene(diazonium)tetra(3

[0013] Commercially available ionic activators include N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate and triphenylmethylium tetrakis(pentafluorophenyl)borate.

[0235] In an embodiment of the present disclosure, the catalyst activator comprises an ionic activator selected from the group consisting of: N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate ("[Me2NHPh][B(C6F5)4]"); triphenylmethylonium tetrakis(pentafluorophenyl)borate ("[Ph3C][B(C6F5)4]", also known as "trityl borate"); and tris(pentafluorophenyl)boron.

[0236] In an embodiment of the present disclosure, the catalyst activator comprises triphenylmethylonium tetrakis(pentafluorophenyl)borate "tritylborate".

[0237] In an embodiment of the present disclosure, the catalyst activator comprises a hindered phenol compound selected from the group consisting of butylated phenol antioxidant, butylated hydroxytoluene, 2,6-di-tert-butyl-4-ethylphenol (BHEB), 4,4′-methylenebis(2,6-di-tert-butylphenol), 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)hydroxy, and octadecyl-3-(3′,5′-di-tert-butyl-4′-hydroxyphenyl) propionate.

[0238] In an embodiment of the present disclosure, the catalyst activator comprises the hindered phenol compound 2,6-di-tert-butyl-4-ethylphenol (BHEB).

[0239] Optionally, in embodiments of the present disclosure, a mixture of an alkylaluminoxane and an ionic activator may be used as a catalyst activator, optionally together with a hindered phenol compound.

[0240] To produce an active single site catalyst system, the amounts and molar ratios of the above components (single site catalyst, alkylaluminoxane, ionic activator, and optional hindered phenol) are optimized.

[0241] In embodiments of the present disclosure, the ionic activator compound may be used in an amount to provide a molar ratio of hafnium Hf to boron (of a single site catalyst molecule) of 1:1 to 1:10, or 1:1 to 1:6, or 1:1 to 1:2.

[0242] In embodiments of the present disclosure, the molar ratio of aluminum contained in the alkylaluminoxane to hafnium Hf (of the single-site catalyst molecule) is from 5:1 to 1000:1, including narrower ranges within this range.

[0243] In an embodiment of the present disclosure, the molar ratio of aluminum contained in the alkylaluminoxane to the hindered phenol (eg, BHEB) is from 1:1 to 1:0.1, including narrower ranges within this range.

[0244] To produce an active single site catalyst system, the amounts and molar ratios of the three or four components (single site catalyst, alkylaluminoxane, ionic activator, and optional hindered phenol) are optimized.

[0245] In an embodiment of the present disclosure, the single-site catalyst used to prepare the second ethylene copolymer produces long chain branches, and the second ethylene copolymer will contain long chain branches, hereinafter referred to as 'LCB'. LCB is a well-known structural phenomenon in ethylene copolymers and is well known to those of ordinary skill in the art. Traditionally, there are three methods for LCB analysis, namely nuclear magnetic resonance spectroscopy (NMR), see, for example, JC Randall, J Macromol. Sci., Rev. Macromol. Chem. Phys. 1989, 29, 201; triple detection SEC, which is equipped with DRI, viscometer and low-angle laser scattering detector, see, for example, WW Yau and DR Hill, Int. J. Polym. Anal. Charact. 1996; 2: 151; and rheology, see, for example, WW Graessley, Acc. Chem. Res. 1977, 10, 332-339 J.C. In the present disclosure, long chain branches are macromolecular in nature, ie, long enough to be visible in NMR spectroscopy, triple detector SEC experiments, or rheology experiments.

[0246] In embodiments of the present disclosure, the second ethylene copolymer contains long chain branching characterized by the LCBF disclosed herein. In embodiments of the present disclosure, the upper limit of the LCBF of the second ethylene copolymer can be about 0.5, about 0.4 in other cases, and about 0.3 in still other cases (dimensionless). In embodiments of the present disclosure, the lower limit of the LCBF of the second ethylene copolymer can be about 0.001, about 0.0015 in other cases, and about 0.002 in still other cases (dimensionless).

[0247] The second ethylene copolymer can contain catalyst residues reflecting the chemical composition of the catalyst preparation for preparing it. It will be appreciated by those skilled in the art that catalyst residues are usually quantified by parts / million of metals in, for example, the second ethylene copolymer (or ethylene copolymer composition; vide infra), wherein the metal present is derived from the metal in the catalyst preparation for preparing it. The non-limiting examples of metal residues that may be present include Group 4 metals titanium, zirconium and hafnium. In embodiments of the present disclosure, the upper limit of the ppm of the metal in the second ethylene copolymer can be about 3.0ppm, about 2.0ppm in other cases, and about 1.5ppm in other cases. In embodiments of the present disclosure, the lower limit of the ppm of the metal in the second ethylene copolymer can be about 0.03ppm, about 0.09ppm in other cases, and about 0.15ppm in other cases.

[0248] In an embodiment of the present disclosure, the density of the second ethylene copolymer is 0.865-0.926 g / cm 3 , molecular weight distribution Mw / M n The melt index I2 is 1.7-2.7 and the melt index I2 is 0.1-10 g / 10 min.

[0249] In an embodiment of the present disclosure, the density of the second ethylene copolymer is 0.865-0.926 g / cm 3 , molecular weight distribution M w / M n The melt index I2 is 1.7-2.3, and the melt index I2 is 0.1-10 g / 10 min.

[0250] In an embodiment of the present disclosure, the molecular weight distribution M of the second ethylene copolymer is w / M n The upper limit of can be about 2.8, or about 2.6, or about 2.5, or about 2.4, or about 2.3, or about 2.2. In an embodiment of the present disclosure, the molecular weight distribution M of the second ethylene copolymer is w / M n The lower limit of may be about 1.6, or about 1.7, or about 1.8, or about 1.9.

[0251] In an embodiment of the present disclosure, the molecular weight distribution M of the second ethylene copolymer is w / M n <2.6, or <2.3, or ≤2.3, or <2.1, or ≤2.1, or <2.0, or ≤2.0, or about 2.0. In an embodiment of the present disclosure, the molecular weight distribution M of the second ethylene copolymer is w / M n From about 1.7 to about 2.3, or from about 1.8 to about 2.3, or from about 1.8 to about 2.2.

[0252] In an embodiment of the present disclosure, the second ethylene copolymer has 10-150 short chain branches (SCB2) per thousand carbon atoms. In a further embodiment, the second ethylene copolymer has 15-100 short chain branches (SCB2) per thousand carbon atoms, or 20-100 short chain branches (SCB2) per thousand carbon atoms, or 25-100 short chain branches (SCB2) per thousand carbon atoms, or 10-75 short chain branches (SCB2) per thousand carbon atoms, or 15-75 short chain branches (SCB2) per thousand carbon atoms, or 20-75 short chain branches (SCB2) per thousand carbon atoms, or 25-75 short chain branches (SCB2) per thousand carbon atoms. In yet further embodiments, the second ethylene copolymer has 15-70 short chain branches (SCB2) per thousand carbon atoms, or 20-70 short chain branches (SCB2) per thousand carbon atoms, or 20-60 short chain branches (SCB2) per thousand carbon atoms, or 15-60 short chain branches (SCB2) per thousand carbon atoms, or 15-55 short chain branches (SCB2) per thousand carbon atoms, or 20-55 short chain branches (SCB2) per thousand carbon atoms, or 25-50 short chain branches (SCB2) per thousand carbon atoms, or 20-50 short chain branches (SCB2) per thousand carbon atoms.

[0253] Short chain branching (i.e., short chain branching per thousand backbone carbon atoms, SCB2) is branching due to the presence of α-olefin comonomers in the ethylene copolymer and will, for example, have two carbon atoms for a 1-butene comonomer, or four carbon atoms for a 1-hexene comonomer, or six carbon atoms for a 1-octene comonomer, and so on.

[0254] In embodiments of the present disclosure, the upper limit of the density d2 of the second ethylene copolymer may be about 0.926 g / cm 3 ; in some cases about 0.921 g / cm 3 ; in other cases about 0.916g / cm 3 , in other cases about 0.912 g / cm 3 , in other cases about 0.906 g / cm 3 , in other cases about 0.902 g / cm 3 In an embodiment of the present disclosure, the lower limit of the density d2 of the second ethylene copolymer may be about 0.855 g / cm 3 , in some cases about 0.865 g / cm 3 ; and in other cases about 0.875 g / cm 3 , or about 0.885g / cm 3 .

[0255] In embodiments of the present disclosure, the density d2 of the second ethylene copolymer may be about 0.855 g / cm 3 to about 0.926 g / cm 3 , or about 0.855g / cm 3 to about 0.921g / cm 3 , or about 0.855g / cm 3 to about 0.916 g / cm 3 , or about 0.855g / cm 3 to about 0.912g / cm 3 , or about 0.855g / cm 3 to about 0.906g / cm 3 , or about 0.855g / cm 3 to about 0.902g / cm 3 , or about 0.865g / cm 3 to about 0.926 g / cm 3 , or about 0.865g / cm 3 to about 0.921g / cm 3 , or about 0.865g / cm 3 to about 0.916 g / cm 3 , or about 0.865g / cm 3 to about 0.912g / cm 3 , or about 0.865g / cm 3 to about 0.906g / cm 3 , or about 0.865g / cm 3 to about 0.902g / cm 3 , or about 0.875g / cm 3 to about 0.926 g / cm 3 , or about 0.875g / cm 3 to about 0.921g / cm 3 , or about 0.875g / cm 3 to about 0.916 g / cm 3 , or about 0.875g / cm 3 to about 0.912g / cm 3 , or about 0.875g / cm 3 to about 0.906g / cm 3 , or about 0.875g / cm 3 to about 0.902g / cm 3 , about 0.885g / cm 3 to about 0.926 g / cm 3 , or about 0.885g / cm 3 to about 0.921g / cm 3, or about 0.885g / cm 3 to about 0.916 g / cm 3 , or about 0.885g / cm 3 to about 0.912g / cm 3 , or about 0.885g / cm 3 to about 0.906g / cm 3 , or about 0.885g / cm 3 to about 0.902g / cm 3 .

[0256] In an embodiment of the present disclosure, the difference between the density d1 of the first ethylene copolymer and the density d2 of the second ethylene copolymer is less than 0.030 g / cm 3 In another embodiment of the present disclosure, the difference between the density d1 of the first ethylene copolymer and the density d2 of the second ethylene copolymer is less than 0.020 g / cm 3 In yet another embodiment of the present disclosure, the difference between the density d1 of the first ethylene copolymer and the density d2 of the second ethylene copolymer is less than 0.015 g / cm 3 In yet another embodiment of the present disclosure, the difference between the density d1 of the first ethylene copolymer and the density d2 of the second ethylene copolymer is less than 0.010 g / cm 3 .

[0257] In embodiments, the density of the second ethylene copolymer is equal to or greater than the density of the first ethylene copolymer.

[0258] In embodiments, the second ethylene copolymer has a higher density than the first ethylene copolymer.

[0259] In an embodiment of the present disclosure, the CDBI of the second ethylene copolymer is 50 The upper limit of may be about 98 weight percent, in other cases about 95 weight percent, and in still other cases about 90 weight percent. In embodiments of the present disclosure, the CDBI of the second ethylene copolymer is 50 The lower limit may be about 70 weight percent, in other cases about 75 weight percent, and in still other cases about 80 weight percent.

[0260] In an embodiment of the present disclosure, the melt index I2 of the second ethylene copolymer is 2It can be about 0.01 g / 10min to about 100 g / 10min, or about 0.01 g / 10min to about 75 g / 10min, or about 0.1 g / 10min to about 100 g / 10min, or about 0.1 g / 10min to about 70 g / 10min, or about 0.01 g / 10min to about 50 g / 10min, or about 0.1 g / 10min to about 50 g / 10min, or about 0.1 g / 10min to about 25g / 10min, or about 0.1g / 10min to about 20g / 10min, or about 0.1g / 10min to about 15g / 10min, or about 0.1 to about 10g / 10min, or about 0.1 to about 5g / 10min, or about 0.1-2.5g / 10min, or less than about 5g / 10min, or less than about 3g / 10min, or less than about 1.0g / 10min, or less than about 0.75g / 10min.

[0261] In an embodiment of the present disclosure, the weight average molecular weight M of the second ethylene copolymer is w From about 15,000 to about 175,000 g / mol, or from about 25,000 to about 150,000 g / mol, or from about 25,000 to about 100,000 g / mol, or from about 25,000 to about 75,000 g / mol, or from about 30,000 to about 75,000 g / mol, or from about 20,000 to about 75,000 g / mol, or from about 25,000 to about 80,000 g / mol, or from about 20,000 to about 80,000 g / mol.

[0262] In an embodiment of the present disclosure, the number average molecular weight M of the second ethylene copolymer is n From about 5,000 to about 75,000 g / mol, or from about 10,000 to about 50,000 g / mol, or from about 10,000 to about 40,000 g / mol.

[0263] In embodiments of the present disclosure, the upper limit of the weight percent (wt%) of the second ethylene copolymer in the ethylene copolymer composition (i.e., the wt% of the second ethylene copolymer based on the total weight of the first, second, and third ethylene copolymers) can be about 80 wt%, or about 75 wt%, or about 70 wt%, or about 65 wt%, or about 60 wt%, or about 55 wt%, or about 50 wt%, or about 45 wt%, or about 40 wt%. In embodiments of the present disclosure, the lower limit of the wt% of the second ethylene copolymer in the ethylene copolymer composition can be about 5 wt%, or about 10 wt%, or about 15 wt%, or about 20 wt%, or about 25 wt%, or about 30 wt%, or about 35 wt% in other cases.

[0264] The third ethylene copolymer

[0265] In embodiments of the present disclosure, a third ethylene copolymer is present in the ethylene copolymer composition.

[0266] In an embodiment of the present disclosure, the third ethylene copolymer is prepared by a single site catalyst, non-limiting examples of which include phosphinimine catalysts, metallocene catalysts, and constrained geometry catalysts, all of which are well known in the art.

[0267] In an embodiment of the present disclosure, the third ethylene copolymer is prepared by a multi-site catalyst system, non-limiting examples of which include Ziegler-Natta catalysts and chromium catalysts, both of which are well known in the art.

[0268] In an embodiment of the present disclosure, the α-olefin that may be copolymerized with ethylene to prepare the third ethylene copolymer may be selected from the group consisting of 1-propylene, 1-butene, 1-pentene, 1-hexene, and 1-octene, and mixtures thereof.

[0269] In an embodiment of the present disclosure, the third ethylene copolymer is a homogeneously branched ethylene copolymer.

[0270] In an embodiment of the present disclosure, the third ethylene copolymer is an ethylene / 1-octene copolymer.

[0271] In an embodiment of the present disclosure, the third ethylene copolymer is produced by a metallocene catalyst.

[0272] In an embodiment of the present disclosure, the third ethylene copolymer is produced by a Ziegler-Natta catalyst.

[0273] In an embodiment of the present disclosure, the third ethylene copolymer is a heterogeneously branched ethylene copolymer.

[0274] In an embodiment of the present disclosure, the third ethylene copolymer is produced by a metallocene catalyst.

[0275] In an embodiment of the present disclosure, the third ethylene copolymer is produced by a bridged metallocene catalyst.

[0276] In an embodiment of the present disclosure, the third ethylene copolymer is prepared from a bridged metallocene catalyst having Formula I:

[0277]

[0278] wherein G is a Group 14 element selected from carbon, silicon, germanium, tin or lead; R1 is a hydrogen atom, C 1-20 Hydrocarbon, C 1-20 Alkoxy or C 6-10 Aryl oxide group; R2 and R3 are independently selected from hydrogen atoms, C 1-20 Hydrocarbon, C 1-20Alkoxy or C 6-10 Aryl oxide group; R4 and R5 are independently selected from hydrogen atoms, unsubstituted C 1-20 Hydrocarbon, substituted C 1-20 Hydrocarbon, C 1-20 Alkoxy or C 6-10 an aryl oxide group; and Q is independently an activatable leaving group ligand.

[0279] In an embodiment, R4 and R5 are independently aryl.

[0280] In an embodiment, R4 and R5 are independently phenyl or substituted phenyl.

[0281] In an embodiment, R4 and R5 are phenyl.

[0282] In an embodiment, R4 and R5 are independently substituted phenyl.

[0283] In an embodiment, R4 and R5 are substituted phenyl, wherein the phenyl is substituted with substituted silyl.

[0284] In an embodiment, R4 and R5 are substituted phenyl, wherein the phenyl is substituted with a trialkylsilyl group.

[0285] In an embodiment, R4 and R5 are substituted phenyl, wherein the phenyl is substituted in the para position by trialkylsilyl. In an embodiment, R4 and R5 are substituted phenyl, wherein the phenyl is substituted in the para position by trimethylsilyl. In an embodiment, R4 and R5 are substituted phenyl, wherein the phenyl is substituted in the para position by triethylsilyl.

[0286] In an embodiment, R4 and R5 are independently alkyl.

[0287] In an embodiment, R4 and R5 are independently alkenyl.

[0288] In an embodiment, R1 is hydrogen.

[0289] In an embodiment, R1 is alkyl.

[0290] In an embodiment, R1 is aryl.

[0291] In an embodiment, R1 is alkenyl.

[0292] In an embodiment, R2 and R3 are independently a hydrocarbyl group having 1 to 30 carbon atoms.

[0293] In an embodiment, R2 and R3 are independently aryl.

[0294] In an embodiment, R2 and R3 are independently alkyl.

[0295] In an embodiment, R2 and R3 are independently alkyl groups having 1 to 20 carbon atoms.

[0296] In an embodiment, R2 and R3 are independently phenyl or substituted phenyl.

[0297] In an embodiment, R2 and R3 are tert-butyl.

[0298] In an embodiment, R2 and R3 are hydrogen.

[0299] In an embodiment of the present disclosure, the third ethylene copolymer is prepared from a bridged metallocene catalyst having Formula II:

[0300]

[0301] wherein Q is independently an activatable leaving group ligand.

[0302] In the present disclosure, the term "activatable" means that the ligand Q can be cleaved from the metal center M via a protolysis reaction, or abstracted from the metal center M by a suitable acidic or electrophilic catalyst activator compound (also referred to as a "co-catalyst" compound), examples of which are described below. The activatable ligand Q can also be converted to another ligand that is cleaved or abstracted from the metal center M (e.g., a halide can be converted to an alkyl). Without wishing to be bound by any single theory, the protolysis or abstraction reaction produces an active "cationic" metal center that can polymerize olefins.

[0303] In embodiments of the present disclosure, the activatable ligand Q is independently selected from a hydrogen atom; a halogen atom; 1-20 Hydrocarbon, C 1-20 Alkoxy and C 6-10 Aryl or aryloxy, wherein each of the hydrocarbyl, alkoxy, aryl or aryloxide groups may be unsubstituted or further substituted by one or more of the following groups: halogen or other groups; C 1-8 Alkyl; C 1-8 Alkoxy; C 6-10 Aryl or aryloxy; amido or phosphino, but wherein Q is not cyclopentadienyl. Two Q ligands can also be linked to each other and form, for example, a substituted or unsubstituted diene ligand (e.g., 1,3-butadiene); or a delocalized heteroatom-containing group, such as an acetate or acetamidine group.

[0304] In the embodiments of the present disclosure, each Q is independently selected from a halogen atom, C 1-4 Alkyl and benzyl.

[0305] In embodiments, suitable activatable ligands Q are monoanionic, such as halides (eg, chloride) or hydrocarbyl groups (eg, methyl, benzyl).

[0306] In an embodiment, each activatable ligand Q is a methyl group.

[0307] In an embodiment, each activatable ligand Q is benzyl.

[0308] In an embodiment, each activatable ligand Q is a chloride group.

[0309] In an embodiment of the present disclosure, the single site catalyst used to prepare the third ethylene copolymer is diphenylmethylene(cyclopentadienyl)(2,7-di-tert-butylfluorenyl)hafnium dichloride, which has the molecular formula: [(2,7-tBu2Flu)Ph2C(Cp)HfCl2].

[0310] In an embodiment of the present disclosure, the single site catalyst used to prepare the third ethylene copolymer is diphenylmethylene(cyclopentadienyl)(2,7-di-tert-butylfluorenyl)hafnium dimethyl, which has the molecular formula: [(2,7-tBu2Flu)Ph2C(Cp)HfMe2].

[0311] In addition to the single-site catalyst molecule itself, an active single-site catalyst system typically further comprises a catalyst activator.

[0312] In an embodiment of the present disclosure, the catalyst activator comprises an alkylaluminoxane and / or an ionic activator.

[0313] The catalyst activator may also optionally include a hindered phenol compound.

[0314] In an embodiment of the present disclosure, the catalyst activator comprises an aluminum alkyl, an ionic activator, and a hindered phenol compound.

[0315] Although the exact structure of an alkylaluminoxane is uncertain, subject matter experts generally agree that it is an oligomeric species containing repeating units of the general formula:

[0316] (R)2AlO-(Al(R)-O) n -Al(R)2

[0317] wherein the R groups can be the same or different linear, branched or cyclic hydrocarbon groups containing 1 to 20 carbon atoms, and n is from 0 to about 50. A non-limiting example of an alkylaluminoxane is methylaluminoxane (or MAO), wherein each R group is methyl.

[0318] In an embodiment of the present disclosure, R of the alkylaluminoxane is methyl, and m is 10-40.

[0319] In an embodiment of the present disclosure, the alkylaluminoxane is modified methylaluminoxane (MMAO).

[0320] It is well known in the art that alkylaluminoxanes can play a dual role as both an alkylating agent and an activator. Therefore, alkylaluminoxane catalyst activators are often used in combination with an activatable ligand (e.g., a halogen).

[0321] Typically, the ionic activator consists of a cation and a bulky anion; wherein the latter is substantially non-coordinating. A non-limiting example of an ionic activator is a boron ionic activator that is tetra-coordinated with four ligands bonded to a boron atom. Non-limiting examples of boron ionic activators include the following formula shown below:

[0322] [R 5 ] + [B(R 7 )4] -

[0323] Where B represents a boron atom, R 5 is an aromatic hydrocarbon group (e.g., a triphenylmethyl cation), and each R 7 independently selected from unsubstituted or substituted with 3-5 fluorine atoms, unsubstituted or substituted with fluorine atoms, 1-4 Phenyl substituted with an alkyl or alkoxy substituent; and -Si(R 9 )3 silyl group, wherein each R 9 are independently selected from hydrogen atoms and C 1-4 Alkyl, and

[0324] [(R 8 ) t [EN] + [B(R 7 )4] -

[0325] Where B is a boron atom, H is a hydrogen atom, Z is a nitrogen or phosphorus atom, t is 2 or 3, and R 8 Selected from C 1-8 Alkyl, unsubstituted or substituted with up to three C 1-4 Alkyl-substituted phenyl, or one R 8 Together with the nitrogen atom, it can form an aniline group, and R 7 As defined above.

[0326] In both formulas, R 7A non-limiting example of is pentafluorophenyl. In general, the boron ion activator can be described as a salt of tetrakis(perfluorophenyl)boron; non-limiting examples include aniline salts, carbon salts, oxygen salts, phosphonium salts and sulfonium salts of tetrakis(perfluorophenyl)boron with aniline and trityl (or triphenylmethyl)boron. Additional non-limiting examples of ionic activators include: triethylammonium tetrakis(phenyl)boron, tripropylammonium tetrakis(phenyl)boron, tri(n-butyl)ammonium tetrakis(phenyl)boron, trimethylammonium tetrakis(p-tolyl)boron, trimethylammonium tetrakis(o-tolyl)boron, tributylammonium tetrakis(pentafluorophenyl)boron, tripropylammonium tetrakis(o,p-dimethylphenyl)boron, tributylammonium tetrakis(m,m-dimethylphenyl)boron, tributylammonium tetrakis(p-trifluoromethylphenyl)boron, tributylammonium tetrakis(pentafluorophenyl)boron Boron, tri(n-butyl)ammonium tetra(o-tolyl)boron, N,N-dimethylaniline tetra(phenyl)boron, N,N-diethylaniline tetra(phenyl)boron, N,N-diethylaniline tetra(phenyl)boron, N,N-diethylaniline tetra(phenyl)boron, N,N-2,4,6-pentamethylaniline tetra(phenyl)boron, di(isopropyl)ammonium tetra(pentafluorophenyl)boron, dicyclohexylammonium tetra(phenyl)boron, triphenylphosphonium tetra(phenyl)boron, tri(methylphenyl)phosphonium tetra(phenyl)boron, tri(dimethylphenyl) Phosphonium tetra(phenyl)boron, tropine tetra(pentafluorophenyl)borate, triphenylmethylium tetra(pentafluorophenyl)borate, benzene(diazonium)tetra(pentafluorophenyl)borate, tropine tetra(2,3,5,6-tetrafluorophenyl)borate, triphenylmethylium tetra(2,3,5,6-tetrafluorophenyl)borate, benzene(diazonium)tetra(3,4,5-trifluorophenyl)borate, tropine tetra(3,4,5-trifluorophenyl)borate, benzene(diazonium)tetra(3

[0013] Commercially available ionic activators include N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate and triphenylmethylium tetrakis(pentafluorophenyl)borate.

[0327] In an embodiment of the present disclosure, the catalyst activator comprises an ionic activator selected from the group consisting of: N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate ("[Me2NHPh][B(C6F5)4]"); triphenylmethylonium tetrakis(pentafluorophenyl)borate ("[Ph3C][B(C6F5)4]", also known as "trityl borate"); and tris(pentafluorophenyl)boron.

[0328] In an embodiment of the present disclosure, the catalyst activator comprises triphenylmethylonium tetrakis(pentafluorophenyl)borate "tritylborate".

[0329] In an embodiment of the present disclosure, the catalyst activator comprises a hindered phenol compound selected from the group consisting of butylated phenol antioxidant, butylated hydroxytoluene, 2,6-di-tert-butyl-4-ethylphenol (BHEB), 4,4′-methylenebis(2,6-di-tert-butylphenol), 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)hydroxy, and octadecyl-3-(3′,5′-di-tert-butyl-4′-hydroxyphenyl) propionate.

[0330] In an embodiment of the present disclosure, the catalyst activator comprises the hindered phenol compound 2,6-di-tert-butyl-4-ethylphenol (BHEB).

[0331] Optionally, in embodiments of the present disclosure, a mixture of an alkylaluminoxane and an ionic activator may be used as a catalyst activator, optionally together with a hindered phenol compound.

[0332] To produce an active single site catalyst system, the amounts and molar ratios of the above components (single site catalyst, alkylaluminoxane, ionic activator, and optional hindered phenol) are optimized.

[0333] In embodiments of the present disclosure, the ionic activator compound may be used in an amount to provide a molar ratio of hafnium Hf to boron (of a single site catalyst molecule) of 1:1 to 1:10, or 1:1 to 1:6, or 1:1 to 1:2.

[0334] In embodiments of the present disclosure, the molar ratio of aluminum contained in the alkylaluminoxane to hafnium Hf (of the single-site catalyst molecule) is from 5:1 to 1000:1, including narrower ranges within this range.

[0335] In an embodiment of the present disclosure, the molar ratio of aluminum contained in the alkylaluminoxane to the hindered phenol (eg, BHEB) is from 1:1 to 1:0.1, including narrower ranges within this range.

[0336] To produce an active single site catalyst system, the amounts and molar ratios of the three or four components (single site catalyst, alkylaluminoxane, ionic activator, and optional hindered phenol) are optimized.

[0337] In embodiments of the present disclosure, the third ethylene copolymer is free of long chain branching or does not have any detectable level of long chain branching.

[0338] In embodiments of the present disclosure, the third ethylene copolymer will contain long chain branches, hereinafter referred to as 'LCB'. LCB is a well-known structural phenomenon in polyethylene and is well known to those of ordinary skill in the art. Traditionally, there are three methods for LCB analysis, namely nuclear magnetic resonance spectroscopy (NMR), see, for example, JC Randall, J Macromol. Sci., Rev. Macromol. Chem. Phys. 1989, 29, 201; triple detection SEC, which is equipped with DRI, viscometer and low angle laser light scattering detector, see, for example, WW Yau and DR Hill, Int. J. Polym. Anal. Charact. 1996; 2: 151; and rheology, see, for example, WW Graessley, Acc. Chem. Res. 1977, 10, 332-339 J.C. In the present disclosure, the long chain branches are macromolecular in nature, i.e., long enough to be visible in NMR spectroscopy, triple detector SEC experiments or rheology experiments.

[0339] In embodiments of the present disclosure, the third ethylene copolymer contains long chain branching characterized by the LCBF disclosed herein. In embodiments of the present disclosure, the upper limit of the LCBF of the third ethylene copolymer can be about 0.5, about 0.4 in other cases, and about 0.3 in still other cases (dimensionless). In embodiments of the present disclosure, the lower limit of the LCBF of the third ethylene copolymer can be about 0.001, about 0.0015 in other cases, and about 0.002 in still other cases (dimensionless).

[0340] In an embodiment of the present disclosure, the molecular weight distribution M of the third ethylene copolymer is w / M n The upper limit of can be about 2.8, or about 2.6, or about 2.5, or about 2.4, or about 2.3, or about 2.2. In an embodiment of the present disclosure, the molecular weight distribution M of the third ethylene copolymer is w / M n The lower limit of may be about 1.4, or about 1.6, or about 1.7, or about 1.8, or about 1.9.

[0341] In an embodiment of the present disclosure, the molecular weight distribution M of the third ethylene copolymer is w / M n <2.6, or <2.3, or ≤2.3, or <2.1, or ≤2.1, or <2.0, or ≤2.0, or about 2.0. In an embodiment of the present disclosure, the molecular weight distribution M of the third ethylene copolymer is w / M n From about 1.7 to about 2.3, or from about 1.8 to about 2.3, or from about 1.8-2.2.

[0342] In an embodiment of the present disclosure, the molecular weight distribution M of the third ethylene copolymer is w / M n ≥2.3, or >2.3, or ≥2.5, or >2.5, or ≥2.7, or >2.7, or ≥2.9, or >2.9, or ≥3.0, or 3.0. In an embodiment of the present disclosure, the molecular weight distribution M of the third ethylene copolymer is w / M n It is 2.3-6.5, or 2.3-6.0, or 2.3-5.5, or 2.3-5.0, or 2.3-4.5, or 2.3-4.0, or 2.3-3.5, or 2.3-3.0, or 2.5-5.0, or 2.5-4.5, or 2.5-4.0, or 2.5-3.5, or 2.7-5.0, or 2.7-4.5, or 2.7-4.0, or 2.7-3.5, or 2.9-5.0, or 2.9-4.5, or 2.9-4.0, or 2.9-3.5.

[0343] In an embodiment of the present disclosure, the molecular weight distribution M of the third ethylene copolymer is w / M n It is 2.0-6.5, or 2.3-6.5, or 2.3-6.0, or 2.0-6.0, or 2.0-5.5, or 2.0-5.0, or 2.0-4.5, or 2.0-4.0, or 2.0-3.5, or 2.0-3.0.

[0344] In an embodiment of the present disclosure, the third ethylene copolymer has 1-75 short chain branches (SCB3) per thousand carbon atoms. In a further embodiment, the second ethylene copolymer has 3-75 short chain branches (SCB3) per thousand carbon atoms, or 3-50 short chain branches (SCB3) per thousand carbon atoms, or 5-50 short chain branches (SCB3) per thousand carbon atoms, or 5-40 short chain branches (SCB3) per thousand carbon atoms, or 10-50 short chain branches (SCB3) per thousand carbon atoms, or 10-40 short chain branches (SCB3) per thousand carbon atoms, or 15-50 short chain branches (SCB3) per thousand carbon atoms, or 15-40 short chain branches (SCB3) per thousand carbon atoms.

[0345] In embodiments of the present disclosure, the upper limit of the density d3 of the third ethylene copolymer may be about 0.975 g / cm 3 ; in some cases about 0.965 g / cm 3 ; and in other cases about 0.955 g / cm 3 , in other cases about 0.945 g / cm 3 In an embodiment of the present disclosure, the lower limit of the density d3 of the third ethylene copolymer may be about 0.855 g / cm3 , in some cases about 0.865 g / cm 3 ; and in other cases about 0.875 g / cm 3 .

[0346] In embodiments of the present disclosure, the density d3 of the third ethylene copolymer may be about 0.875 g / cm 3 To about 0.965g / cm 3 , or about 0.875g / cm 3 To about 0.960g / cm 3 , or about 0.875g / cm 3 Up to 0.950g / cm 3 , about 0.865g / cm 3 To about 0.945g / cm 3 , or about 0.865g / cm 3 To about 0.940g / cm 3 , or about 0.865g / cm 3 to about 0.936 g / cm 3 , or about 0.865g / cm 3 to about 0.932g / cm 3 , or about 0.865g / cm 3 to about 0.926 g / cm 3 , or about 0.865g / cm 3 to about 0.921g / cm 3 , or about 0.865g / cm 3 to about 0.918 g / cm 3 , or about 0.875g / cm 3 to about 0.936 g / cm 3 , or about 0.875g / cm 3 to about 0.926 g / cm 3 , or about 0.875g / cm 3 to about 0.921g / cm 3 , or about 0.875g / cm 3 to about 0.918 g / cm 3 , or about 0.885g / cm 3 to about 0.936 g / cm 3 , or about 0.885g / cm 3 to about 0.932g / cm 3 , or about 0.885g / cm 3 to about 0.926 g / cm 3 , or about 0.885g / cm 3 to about 0.921g / cm 3, or about 0.885g / cm 3 to about 0.918 g / cm 3 .

[0347] In an embodiment, the third ethylene copolymer has a higher density than the first ethylene copolymer.

[0348] In an embodiment of the present disclosure, when a single-site catalyst is used to prepare the third ethylene copolymer, the CDBI of the third ethylene copolymer is 50 The upper limit of can be about 98 weight percent, about 95 weight percent in other cases, and about 90 weight percent in still other cases. In embodiments of the present disclosure, when a single-site catalyst is used to prepare the third ethylene copolymer, the CDBI of the third ethylene copolymer is 50 The lower limit may be about 70 weight percent, in other cases about 75 weight percent, and in still other cases about 80 weight percent.

[0349] In an embodiment of the present disclosure, when a multi-site catalyst is used to prepare the third ethylene copolymer, the third ethylene copolymer is a copolymer having a composition distribution breadth index CDBI of 50 Less than 75 wt%, or 70 wt% or less ethylene copolymer. In further embodiments of the present disclosure, when a multisite catalyst is used to prepare the third ethylene copolymer, the third ethylene copolymer is CDBI 50 65 wt% or less, or 60 wt% or less, or 55 wt% or less, or 50 wt% or less, or 45 wt% or less of ethylene copolymers.

[0350] In an embodiment of the present disclosure, the melt index I2 of the third ethylene copolymer is 3 It can be about 0.01 g / 10min to about 100 g / 10min, or about 0.01 g / 10min to about 75 g / 10min, or about 0.1 g / 10min to about 100 g / 10min, or about 0.1 g / 10min to about 70 g / 10min, or about 0.01 g / 10min to about 50 g / 10min, or about 0.1 g / 10min to about 50 g / 10min, or about 0.1 g / 10min to about 25g / 10min, or about 0.1g / 10min to about 20g / 10min, or about 0.1g / 10min to about 15g / 10min, or about 0.1 to about 10g / 10min, or about 0.1 to about 5g / 10min, or about 0.1-2.5g / 10min, or less than about 5g / 10min, or less than about 3g / 10min, or less than about 1.0g / 10min, or less than about 0.75g / 10min.

[0351] In an embodiment of the present disclosure, the weight average molecular weight M of the third ethylene copolymer is w From about 15,000 to about 175,000, or from about 25,000 to about 150,000 g / mol, or from about 35,000 to about 100,000 g / mol, or from about 45,000 to about 100,000 g / mol.

[0352] In an embodiment of the present disclosure, the number average molecular weight M of the third ethylene copolymer is n From about 5,000 to about 75,000 g / mol, or from about 10,000 to about 50,000 g / mol, or from about 10,000 to about 40,000 g / mol.

[0353] In embodiments of the present disclosure, the upper limit of the weight percent (wt%) of the third ethylene copolymer in the ethylene copolymer composition (i.e., the wt% of the third ethylene copolymer based on the total weight of the first, second, and third ethylene copolymers) can be about 60 wt%, or about 55 wt%, or 50 wt%, in other cases about 45 wt%, in other cases about 40 wt%, or about 35 wt%, or about 30 wt%, or about 25 wt%, or about 20 wt%. In embodiments of the present disclosure, the lower limit of the wt% of the third ethylene copolymer in the final ethylene copolymer composition can be 0 wt%, or about 1 wt%, or about 3 wt%, or about 5 wt%, or about 10 wt%, or about 15 wt%.

[0354] Ethylene copolymer composition

[0355] The polyethylene compositions disclosed herein may be prepared using any technique known in the art, including but not limited to melt blending, solution blending, or in-reactor reactor blending to bring together the first ethylene copolymer, the second ethylene copolymer, and the optional third ethylene copolymer.

[0356] In an embodiment, the ethylene copolymer compositions of the present disclosure are prepared using a single site catalyst in a first reactor to obtain a first ethylene copolymer and using a single site catalyst in a second reactor to obtain a second ethylene copolymer.

[0357] In an embodiment, the disclosed ethylene copolymer compositions are prepared using a single site catalyst in a first reactor to obtain a first ethylene copolymer, using a single site catalyst in a second reactor to obtain a second ethylene copolymer, and using a single site catalyst in a third reactor to obtain a third ethylene copolymer.

[0358] In an embodiment, the disclosed ethylene copolymer compositions are prepared using a single site catalyst in a first reactor to obtain a first ethylene copolymer, using a single site catalyst in a second reactor to obtain a second ethylene copolymer, and using a multisite catalyst in a third reactor to obtain a third ethylene copolymer.

[0359] In an embodiment, the disclosed ethylene copolymer compositions are prepared by forming a first ethylene copolymer by polymerizing ethylene and an alpha olefin with a single site catalyst in a first reactor; and forming a second ethylene copolymer by polymerizing ethylene and an alpha olefin with a single site catalyst in a second reactor.

[0360] In an embodiment, the ethylene copolymer composition of the present disclosure is prepared by forming a first ethylene copolymer by polymerizing ethylene and an alpha olefin with a single site catalyst in a first reactor; forming a second ethylene copolymer by polymerizing ethylene and an alpha olefin with a single site catalyst in a second reactor, and forming a third ethylene copolymer by polymerizing ethylene and an alpha olefin with a single site catalyst in a third reactor.

[0361] In an embodiment, the ethylene copolymer composition of the present disclosure is prepared by forming a first ethylene copolymer by polymerizing ethylene and an alpha olefin with a single site catalyst in a first reactor; forming a second ethylene copolymer by polymerizing ethylene and an alpha olefin with a single site catalyst in a second reactor, and forming a third ethylene copolymer by polymerizing ethylene and an alpha olefin with a multi-site catalyst in a third reactor.

[0362] In an embodiment, the ethylene copolymer composition of the present disclosure is prepared by forming a first ethylene copolymer by polymerizing ethylene and an alpha olefin with a single site catalyst in a first solution phase polymerization reactor; and forming a second ethylene copolymer by polymerizing ethylene and an alpha olefin with a single site catalyst in a second solution phase polymerization reactor.

[0363] In an embodiment, the ethylene copolymer composition of the present disclosure is prepared by forming a first ethylene copolymer by polymerizing ethylene and an alpha olefin with a single site catalyst in a first solution phase polymerization reactor; forming a second ethylene copolymer by polymerizing ethylene and an alpha olefin with a single catalyst in a second solution phase polymerization reactor, and forming a third ethylene copolymer by polymerizing ethylene and an alpha olefin with a single site catalyst in a third solution phase polymerization reactor.

[0364] In an embodiment, the ethylene copolymer composition of the present disclosure is prepared by forming a first ethylene copolymer by polymerizing ethylene and an alpha olefin with a single site catalyst in a first solution phase polymerization reactor; forming a second ethylene copolymer by polymerizing ethylene and an alpha olefin with a single catalyst in a second solution phase polymerization reactor, and forming a third ethylene copolymer by polymerizing ethylene and an alpha olefin with a multi-site catalyst in a third solution phase polymerization reactor.

[0365] In an embodiment, the ethylene copolymer composition of the present disclosure is prepared by forming a first ethylene copolymer by polymerizing ethylene and an alpha olefin with a single site catalyst in a first solution phase polymerization reactor; and forming a second ethylene copolymer by polymerizing ethylene and an alpha olefin with a single site catalyst in a second solution phase polymerization reactor; wherein the first and second solution phase polymerization reactors are configured in series with each other.

[0366] In an embodiment, the ethylene copolymer composition of the present disclosure is prepared by forming a first ethylene copolymer by polymerizing ethylene and an alpha olefin with a single site catalyst in a first solution phase polymerization reactor; and forming a second ethylene copolymer by polymerizing ethylene and an alpha olefin with a single site catalyst in a second solution phase polymerization reactor; wherein the first and second solution phase polymerization reactors are configured in parallel with each other.

[0367] In an embodiment, the ethylene copolymer composition of the present disclosure is prepared by forming a first ethylene copolymer by polymerizing ethylene and an alpha olefin with a single site catalyst in a first solution phase polymerization reactor; forming a second ethylene copolymer by polymerizing ethylene and an alpha olefin with a single catalyst in a second solution phase polymerization reactor, and forming a third ethylene copolymer by polymerizing ethylene and an alpha olefin with a single site catalyst in a third solution phase polymerization reactor; wherein the first, second, and third solution phase polymerization reactors are configured in series with each other.

[0368] In an embodiment, the ethylene copolymer composition of the present disclosure is prepared by forming a first ethylene copolymer by polymerizing ethylene and an alpha olefin with a single site catalyst in a first solution phase polymerization reactor; forming a second ethylene copolymer by polymerizing ethylene and an alpha olefin with a single catalyst in a second solution phase polymerization reactor, and forming a third ethylene copolymer by polymerizing ethylene and an alpha olefin with a single site catalyst in a third solution phase polymerization reactor; wherein the first, second, and third solution phase polymerization reactors are configured in parallel with each other.

[0369] In an embodiment, the ethylene copolymer composition of the present disclosure is prepared by forming a first ethylene copolymer by polymerizing ethylene and an alpha olefin with a single site catalyst in a first solution phase polymerization reactor; forming a second ethylene copolymer by polymerizing ethylene and an alpha olefin with a single catalyst in a second solution phase polymerization reactor, and forming a third ethylene copolymer by polymerizing ethylene and an alpha olefin with a single site catalyst in a third solution phase polymerization reactor; wherein the first and second solution phase reactors are configured in series with each other, and the third solution phase reactor is configured in parallel with the first and second reactors.

[0370] In an embodiment, the ethylene copolymer composition of the present disclosure is prepared by forming a first ethylene copolymer by polymerizing ethylene and an alpha olefin with a single site catalyst in a first solution phase polymerization reactor; forming a second ethylene copolymer by polymerizing ethylene and an alpha olefin with a single catalyst in a second solution phase polymerization reactor, and forming a third ethylene copolymer by polymerizing ethylene and an alpha olefin with a multi-site catalyst in a third solution phase polymerization reactor; wherein the first, second, and third solution phase polymerization reactors are configured in series with each other.

[0371] In an embodiment, the ethylene copolymer composition of the present disclosure is prepared by forming a first ethylene copolymer by polymerizing ethylene and an alpha olefin with a single site catalyst in a first solution phase polymerization reactor; forming a second ethylene copolymer by polymerizing ethylene and an alpha olefin with a single catalyst in a second solution phase polymerization reactor, and forming a third ethylene copolymer by polymerizing ethylene and an alpha olefin with a multi-site catalyst in a third solution phase polymerization reactor; wherein the first, second, and third solution phase polymerization reactors are configured in parallel with each other.

[0372] In an embodiment, the ethylene copolymer composition of the present disclosure is prepared by forming a first ethylene copolymer by polymerizing ethylene and an alpha olefin with a single site catalyst in a first solution phase polymerization reactor; forming a second ethylene copolymer by polymerizing ethylene and an alpha olefin with a single catalyst in a second solution phase polymerization reactor, and forming a third ethylene copolymer by polymerizing ethylene and an alpha olefin with a multi-site catalyst in a third solution phase polymerization reactor; wherein the first and second solution phase reactors are configured in series with each other, and the third solution phase reactor is configured in parallel with the first and second reactors.

[0373] In embodiments, the solution phase polymerization reactor used as the first solution phase reactor, the second solution phase reactor, or the third solution phase reactor is a continuous stirred tank reactor or a tubular reactor.

[0374] In embodiments, the solution phase polymerization reactor used as the first solution phase reactor, the second solution phase reactor, or the third solution phase reactor is a continuous stirred tank reactor.

[0375] In embodiments, the solution phase polymerization reactor used as the first solution phase reactor, the second solution phase reactor, or the third solution phase reactor is a tubular reactor.

[0376] In embodiments, the solution phase polymerization reactors used as the first solution phase reactor and the second solution phase reactor are continuous stirred tank reactors, and the solution phase polymerization reactor used as the third solution phase reactor is a tubular reactor.

[0377] In solution polymerization, the monomer is dissolved / dispersed in the solvent before being fed to the reactor (or for gaseous monomers, the monomer can be fed into the reactor so that it will dissolve in the reaction mixture). Prior to mixing, the solvent and monomer are usually purified to remove potential catalyst poisons, such as water, oxygen or metallic impurities. Raw material purification follows standard practice in the art, for example molecular sieves, alumina beds and deoxygenation catalysts are used for the purification of the monomers. The solvent itself (e.g. methylpentane, cyclohexane, hexane or toluene) is also preferably treated in a similar manner.

[0378] The feedstock may be heated or cooled before being fed to the reactor.

[0379] Typically, the catalyst component can be premixed in a reaction solvent or fed to the reactor as a separate stream. In some cases, premixing can be expected to provide reaction time for the catalyst component before it enters the reaction. Such "online mixing" technology is described in many patents under the name of DuPont Canada Inc (for example, U.S. Patent number 5,589,555, authorized on December 31, 1996).

[0380] Solution polymerization processes for the polymerization or copolymerization of ethylene are well known in the art (see, for example, U.S. Pat. Nos. 6,372,864 and 6,777,509). These processes are carried out in the presence of an inert hydrocarbon solvent. In a solution phase polymerization reactor, a variety of solvents can be used as process solvents; non-limiting examples include linear, branched or cyclic C5-C 12 Alkanes. Non-limiting examples of α-olefins include 1-propylene, 1-butene, 1-pentene, 1-hexene, and 1-octene. Suitable catalyst component solvents include aliphatic and aromatic hydrocarbons. Non-limiting examples of aliphatic catalyst component solvents include linear, branched, or cyclic C 5-12Aliphatic hydrocarbons, such as pentane, methylpentane, hexane, heptane, octane, cyclohexane, cyclopentane, methylcyclohexane, hydrogenated naphtha or a combination thereof. Non-limiting examples of aromatic catalyst component solvents include benzene, toluene (methylbenzene), ethylbenzene, o-xylene (1,2-dimethylbenzene), m-xylene (1,3-dimethylbenzene), p-xylene (1,4-dimethylbenzene), a mixture of xylene isomers, o-trimethylbenzene (1,2,3-trimethylbenzene), pseudocumene (1,2,4-trimethylbenzene), mesitylene (1,3,5-trimethylbenzene), a mixture of trimethylbenzene isomers, pre-nonene (1,2,3,4-tetramethylbenzene), durene (1,2,3,5-tetramethylbenzene), a mixture of tetramethylbenzene isomers, pentamethylbenzene, hexamethylbenzene and a combination thereof.

[0381] In conventional solution processes, the polymerization temperature may be from about 80°C to about 300°C. In embodiments of the present disclosure, the polymerization temperature in the solution process is from about 120°C to about 250°C. The polymerization pressure in the solution process may be a "medium pressure process," meaning that the pressure in the reactor is less than about 6,000 psi (about 42,000 kilopascals or kPa). In embodiments of the present disclosure, the polymerization pressure in the solution process may be from about 10,000 to about 40,000 kPa, or from about 14,000 to about 22,000 kPa (i.e., from about 2,000 psi to about 3,000 psi).

[0382] Suitable monomers for copolymerization with ethylene include C 3-20 Monoolefins and diolefins. Preferred comonomers include unsubstituted or substituted with up to two C 1-6 Alkyl substituted C 3-12 alpha olefins, unsubstituted or substituted with up to two selected from C 1-4 Alkyl substituents substituted C 8-12 Vinyl aromatic monomers, unsubstituted or substituted with C 1-4 Alkyl substituted C 4-12 Straight chain or cyclic dienes. Illustrative, non-limiting examples of such α-olefins are one or more of propylene, 1-butene, 1-pentene, 1-hexene, 1-octene and 1-decene, styrene, α-methylstyrene and constrained ring cyclic olefins such as cyclobutene, cyclopentene, dicyclopentadiene, norbornene, alkyl-substituted norbornene, alkenyl-substituted norbornene, etc. (e.g., 5-methylene-2-norbornene and 5-ethylidene-2-norbornene, bicyclo-(2,2,1)-hept-2,5-diene).

[0383] In an embodiment of the present disclosure, the ethylene copolymer composition has at least 1 mole % of one or more than one alpha olefin.

[0384] In an embodiment of the present disclosure, the ethylene copolymer composition has at least 3 mole % of one or more than one alpha olefin.

[0385] In embodiments of the present disclosure, the ethylene copolymer composition has from about 3 to about 12 mole percent of one or more than one α-olefin.

[0386] In embodiments of the present disclosure, the ethylene copolymer composition has from about 3 to about 10 mole percent of one or more than one α-olefin.

[0387] In embodiments of the present disclosure, the ethylene copolymer composition has from about 4 to about 10 mole percent of one or more than one alpha olefin.

[0388] In an embodiment of the present disclosure, the ethylene copolymer composition comprises ethylene and one or more than one alpha olefin selected from the group consisting of 1-butene, 1-hexene, 1-octene, and mixtures thereof.

[0389] In an embodiment of the present disclosure, the ethylene copolymer composition comprises ethylene and one or more than one alpha olefin selected from the group consisting of 1-hexene, 1-octene, and mixtures thereof.

[0390] In an embodiment of the present disclosure, the ethylene copolymer composition comprises ethylene and 1-octene.

[0391] In an embodiment of the present disclosure, the ethylene copolymer composition comprises ethylene and at least 1 mol % of 1-octene.

[0392] In an embodiment of the present disclosure, the ethylene copolymer composition comprises ethylene and at least 3 mol % 1-octene.

[0393] In an embodiment of the present disclosure, the ethylene copolymer composition comprises ethylene and 3 to 12 mol % of 1-octene.

[0394] In an embodiment of the present disclosure, the ethylene copolymer composition comprises ethylene and 3-10 mol% 1-octene.

[0395] In an embodiment of the present disclosure, the density of the ethylene copolymer composition of the present disclosure is 0.902 g / cm 3 In another embodiment of the present disclosure, the density of the ethylene copolymer composition of the present disclosure is less than 0.902 g / cm 3 In another embodiment of the present disclosure, the density of the ethylene copolymer composition of the present disclosure is less than 0.901 g / cm 3 In another embodiment of the present disclosure, the density of the ethylene copolymer composition of the present disclosure is less than 0.900 g / cm 3 .

[0396] In an embodiment of the present disclosure, the density of the ethylene copolymer composition of the present disclosure is 0.855 g / cm 3 To 0.902g / cm 3 , or 0.855g / cm 3 To less than 0.902g / cm 3 , or 0.855g / cm 3 To 0.901g / cm 3 , or 0.855g / cm 3 Up to 0.900g / cm 3 , or 0.865g / cm 3 To 0.902g / cm 3 , or 0.865g / cm 3 To less than 0.902g / cm 3 , or 0.865g / cm 3 To 0.901g / cm 3 , or 0.865g / cm 3 Up to 0.900g / cm 3 , or 0.875g / cm 3 To 0.902g / cm 3 , or 0.875g / cm 3 To less than 0.902g / cm 3 , or 0.875g / cm 3 To 0.901g / cm 3 , or 0.875g / cm 3 Up to 0.900g / cm 3 、0.880g / cm 3 To 0.902g / cm 3 , or 0.880g / cm 3 To less than 0.902g / cm 3 , or 0.880g / cm 3 To 0.901g / cm 3 , or 0.880g / cm 3 Up to 0.900g / cm 3 .

[0397] In embodiments of the present disclosure, the melt index I2 of the ethylene copolymer composition can be from about 0.01 g / 10 min to about 100 g / 10 min, or from about 0.01 g / 10 min to about 50 g / 10 min, or from about 0.01 g / 10 min to about 25 g / 10 min, or from about 0.01 g / 10 min to about 10 g / 10 min, or from about 0.01 g / 10 min to about 5 g / 10 min, or from about 0.01 g / 10 min to about 3 g / 10 min, or from about 0.01 g / 10 min to about 1 g / 10 min, or from about 0.1 g / 10 min to about 10 g / 10 min, or from about 0.1 g / 10 min to about 5 g / 10 min, or from about 0.01 g / 10 min to about 0. .1g / 10min to about 3g / 10min, or about 0.1g / 10min to about 2g / 10min, or about 0.1g / 10min to about 1.5g / 10min, or about 0.1g / 10min to about 1g / 10min, or about 0.5g / 10min to about 100g / 10min, or about 0.5g / 10min to about 50g / 10min, or about 0.5g / 10min to about 25g / 10min, or about 0.5g / 10min to about 10g / 10min, or about 0.5g / 10min to about 5g / 10min, or less than about 5g / 10min, or less than about 3g / 10min, or less than about 1.0g / 10min.

[0398] In an embodiment of the present disclosure, the high load melt index I of the ethylene copolymer composition is 21 It can be about 10 dg / min to about 10,000 dg / min, or about 10 dg / min to about 1000 dg / min, or about 10 dg / min to about 500 dg / min, or about 10 dg / min to about 250 dg / min, or about 10 dg / min to about 150 dg / min, or about 10 dg / min to about 100 dg / min.

[0399] In an embodiment of the present disclosure, the melt flow ratio of the ethylene copolymer composition is 21 / I2 can be from about 15 to about 1,000, or from about 18 to about 100, or from about 18 to about 75, or from about 18 to about 60, or from about 18 to about 50, or from about 18 to about 60, or from about 20 to about 75, or from about 20 to about 60, or from about 20 to about 55, or from about 25 to about 75, or from about 25 to about 60, or from about 25 to about 55.

[0400] In an embodiment of the present disclosure, the weight average molecular weight M of the ethylene copolymer composition is wFrom about 20,000 to about 300,000 g / mol, or from about 30,000 to about 300,000 g / mol, or from about 40,000 to about 300,000 g / mol, or from about 40,000 to about 250,000 g / mol, or from about 50,000 to about 250,000 g / mol, or from about 50,000 to about 225,000 g / mol, or from about 50,000 to about 200,000 g / mol, or from about 50,000 to about 175,000 g / mol, or from about 50,000 to about 150,000 g / mol, or from about 50,000 to about 125,000 g / mol.

[0401] In an embodiment of the present disclosure, the molecular weight distribution M of the ethylene copolymer composition is w / M n The lower limit of is 1.8, or 2.0, or 2.1, or 2.2, or 2.3. In an embodiment of the present disclosure, the molecular weight distribution M of the polyethylene composition is w / M n The upper limit is 6.0, or 5.5, or 5.0, or 4.5, or 4.0, or 3.75, or 3.5, or 3.0, or 2.5.

[0402] In an embodiment of the present disclosure, the molecular weight distribution M of the ethylene copolymer composition is w / M n It is 1.8-6.0, or 1.8-5.5, or 1.8-5.0, or 1.8-4.5, or 1.8-4.0, or 1.8-3.5, or 1.8-3.0, or 1.9-5.5, or 1.9-5.0, or 1.9-4.5, or 1.9-4.0, or 1.9-3.5, or 1.9-3.0.

[0403] In an embodiment of the present disclosure, the Z-average molecular weight distribution M of the ethylene copolymer composition is Z / M W ≤4.0, or <4.0, or ≤3.5, or <3.5, or ≤3.0, or <3.0, or ≤2.75, or <2.75, or ≤2.50, or <2.50, or ≤2.25, or <2.25, or ≤2.00, or <2.00. In embodiments of the present disclosure, the Z-average molecular weight distribution M of the polyethylene composition is Z / M W It is 1.5-4.0, or 1.5-3.5, or 1.5-3.0, or 1.5-2.5, or 1.7-3.5, or 1.7-3.0, or 1.7-2.5.

[0404] In an embodiment of the present disclosure, the ethylene copolymer composition has a unimodal distribution in a gel permeation chromatography produced according to the method of ASTM D6474-99. The term "unimodal" is defined herein as referring to the presence of only one obvious peak or maximum in a GPC curve. Unimodal distribution includes a wide unimodal distribution. On the contrary, the use of the term "bimodal" means to convey that in addition to the first peak, there will also be a second peak or shoulder (i.e., molecular weight distribution, it can be said that there are two maxima in the molecular weight distribution curve) representing a higher or lower molecular weight component. Alternatively, the term "bimodal" means that there are two maxima in the molecular weight distribution curve produced according to the method of ASTM D6474-99, and the term "multimodal" means that there are two or more (usually more than two) maxima in the molecular weight distribution curve produced according to the method of ASTM D6474-99.

[0405] In embodiments of the present disclosure, the ethylene copolymer composition will have a reverse or partially reversed comonomer distribution curve, as measured using GPC-FTIR. If comonomer introduction decreases with molecular weight, as measured using GPC-FTIR, the distribution is described as "normal". If comonomer introduction is approximately constant with molecular weight, as measured using GPC-FTIR, the comonomer distribution is described as "flat" or "uniform". The terms "reverse comonomer distribution" and "partially reverse comonomer distribution" refer to the presence of one or more higher molecular weight components in the GPC-FTIR data obtained for the copolymer, which have a higher comonomer introduction than one or more lower molecular weight components. The term "reverse (of) comonomer distribution" is used herein to refer to the fact that within the molecular weight range of the ethylene copolymer, the comonomer content of the various polymer fractions is substantially non-uniform, and its higher molecular weight fraction has a proportionally higher comonomer content (i.e., if comonomer introduction increases with molecular weight, the distribution is described as "reverse" or "reverse"). When comonomer incorporation increases and then decreases with increasing molecular weight, the comonomer distribution is still considered "reverse," but may also be described as "partially reverse." A partially reverse comonomer distribution will exhibit a peak or maximum.

[0406] In an embodiment of the present disclosure, the ethylene copolymer composition has a reverse comonomer distribution curve as measured using GPC-FTIR.

[0407] In an embodiment of the present disclosure, the ethylene copolymer composition has a partially reversed comonomer distribution curve as measured using GPC-FTIR.

[0408] In an embodiment of the present disclosure, the CDBI of the ethylene copolymer composition is 50 Greater than 75 wt%, or greater than 80 wt%, or greater than 85 wt%, or greater than 90 wt%.

[0409] In an embodiment of the present disclosure, the CDBI of the ethylene copolymer composition is 50 From about 60-99 weight %, or from about 70 to about 99 weight %, or from about 80 to about 99 weight %, or from about 85 to about 99 weight %, or from about 90 to about 99 weight %.

[0410] In embodiments of the present disclosure, the upper limit of hafnium parts per million (ppm) in the ethylene copolymer composition may be about 3.0 ppm, or about 2.5 ppm, or about 2.0 ppm, or about 1.5 ppm, or about 1.0 ppm, or about 0.75 ppm, or about 0.5 ppm. In embodiments of the present disclosure, the lower limit of hafnium parts per million (ppm) in the ethylene copolymer composition may be about 0.0015 ppm, or about 0.0050 ppm, or about 0.0075 ppm, or about 0.010 ppm, or about 0.015 ppm, or about 0.030 ppm, or about 0.050 ppm, or about 0.075 ppm, or about 0.100 ppm, or about 0.150 ppm, or about 0.175 ppm, or about 0.200 ppm.

[0411] In embodiments of the present disclosure, the ethylene copolymer composition has 0.0015-2.5 ppm hafnium, or 0.0050-2.5 ppm hafnium, or 0.0075-2.5 ppm hafnium, or 0.010-2.5 ppm hafnium, or 0.015-2.5 ppm hafnium, or 0.050-3.5 ppm, or 0.050-3.0 ppm hafnium, or 0.050-2.5 ppm, or 0.075-2.5 ppm hafnium, or 0.075-2.0 ppm hafnium, or 0.075-1.5 ppm hafnium, or 0.075-1.0 ppm hafnium, or 0.050-3.5 ppm, or 0.050-3.0 ppm hafnium, or 0.050-2.5 ppm, or 0.075-2.5 ppm hafnium, or 0.075-2.0 ppm hafnium, or 0.075-1.5 ppm hafnium, or 0.075-1.0 ppm hafnium. ppm of hafnium, or 0.100-2.0ppm, or 0.100-2.5ppm, or 0.100-2.0ppm of hafnium, or 0.200-3.0ppm of hafnium, or 0.200-2.5ppm, or 0.300-3.0ppm of hafnium, or 0.400-2.5ppm of hafnium, or 0.500-2.5ppm of hafnium, or 0.100-1.5ppm of hafnium, or 0.100-1.0ppm of hafnium, or 0.100-0.75ppm of hafnium, or 0.10-0.5ppm of hafnium, or 0.15-0.5ppm of hafnium, or 0.20-0.5ppm of hafnium.

[0412] In an embodiment of the present disclosure, the ethylene copolymer composition has at least 0.0015 ppm of hafnium, or at least 0.005 ppm of hafnium, or at least 0.0075 ppm of hafnium, or at least 0.015 ppm of hafnium, or at least 0.030 ppm of hafnium, or at least 0.050 ppm of hafnium, or at least 0.075 ppm of hafnium, or at least 0.100 ppm of hafnium, or at least 0.125 ppm of hafnium, or at least 0.150 ppm of hafnium, or at least 0.175 ppm of hafnium, or at least 0.200 ppm of hafnium.

[0413] In an embodiment of the present disclosure, the ethylene copolymer composition is defined as Log 10 [I6 / I2] / Log 10 The stress index of [6.48 / 2.16] is at least 1.30, or at least 1.35.

[0414] In a further embodiment of the present disclosure, the ethylene copolymer composition is defined as Log 10 [I6 / I2] / Log 10 The stress index of [6.48 / 2.16] is 1.35-1.70, or 1.38-1.70, or 1.40-1.70, or 1.38-1.65, or 1.40-1.65, or 1.38-1.60, or 1.40-1.60.

[0415] In an embodiment of the present disclosure, the ethylene copolymer composition has a dimensionless long chain branching factor LCBF ≥ 0.001.

[0416] Linear Low Density Polyethylene LLDPE

[0417] In an embodiment of the present disclosure, the linear low density polyethylene (LLDPE) comprises not less than 60 wt%, or not less than 75 wt% ethylene, with the balance being one or more than one alpha olefin selected from 1-butene, 1-hexene and 1-octene.

[0418] The linear low density polyethylene employed in some embodiments of the present disclosure has a density of about 0.910-0.940 g / cm 3 , or from about 0.910 to about 0.935 g / cm 3 .

[0419] In embodiments of the present disclosure, the density of the linear low density polyethylene is as low as about 0.910 g / cm 3 , or about 0.912g / cm 3 , or about 0.915g / cm 3 , or about 0.916g / cm 3 , or about 0.917g / cm 3Up to about 0.927g / cm 3 , or about 0.930g / cm 3 , or about 0.935g / cm 3 , or about 0.940g / cm 3 In the embodiment of the present disclosure, the density of the linear low-density polyethylene is 0.912 g / cm 3 Up to 0.940g / cm 3 , or 0.915g / cm 3 Up to 0.935g / cm 3 , or 0.915-0.930g / cm 3 , or 0.916-0.930g / cm 3 , or 0.915-0.925g / cm 3 , or 0.916-0.924g / cm 3 , or 0.917-0.923g / cm 3 , or 0.918 to about 0.922 g / cm 3 .

[0420] In an embodiment of the present disclosure, the molecular weight distribution (M w / M n ) is from about 1.5 to about 6.0. In an embodiment of the present disclosure, the molecular weight distribution (M w / M n ) ranges from as low as about 1.5, or about 1.7, or about 2.0, or about 2.5, or about 3.0, or about 3.5, or about 3.7, or about 4.0 to as high as about 5, or about 5.25, or about 5.5, or about 6.0. In embodiments of the present disclosure, the molecular weight distribution (M) of the linear low density polyethylene is w / M n ) is 1.7-5.0, or 1.5-4.0, or 1.8-3.5, or 2.0-3.0. Alternatively, in an embodiment of the present disclosure, the molecular weight distribution (M w / M n ) is 3.6-5.4, or 3.8-5.1, or 3.9-4.9.

[0421] In an embodiment of the present disclosure, the melt index (I2) of the linear low density polyethylene is 0.1 g / 10min to 20 g / 10min. In an embodiment of the present disclosure, the melt index (I2) of the linear low density polyethylene is in the range of 0.75 g / 10min to 15 g / 10min, or 0.85 g / 10min to 10 g / 10min, or 0.9 g / 10min to 8 g / 10min. In an embodiment of the present disclosure, the melt index (I2) of the linear low density polyethylene is in the range of as low as about 0.20 g / 10min, or 0.25 g / 10min, or about 0.5 g / 10min, or about 0.75 g / 10min, or about 1 g / 10min, or about 2 g / 10min to as high as about 3 g / 10min, or about 4 g / 10min, or about 5 g / 10min.

[0422] In an embodiment of the present disclosure, the linear low density polyethylene has a melt index (I2) of about 0.75 g / 10min to about 6 g / 10min, or about 1 g / 10min to about 8 g / 10min, or about 0.8 g / 10min to about 6 g / 10min, or about 1 g / 10min to about 4.5 g / 10min, or 0.20 g / 10min to 5.0 g / 10min, or 0.30 g / 10min to 5.0 g / 10min, or 0.40 g / 10min to 5.0 g / 10min, or 0.50 g / 10min to 5.0 g / 10min.

[0423] In an embodiment of the present disclosure, the melt flow ratio (I 21 / I2) is less than about 120, or less than about 100, or less than about 60, or less than about 50, or less than about 36, or less than 35, or less than 32, or less than 30.

[0424] In an embodiment of the present disclosure, the melt flow ratio (I 21 / I2) is 10-50, or 15-50, or 16-40, or 10-36, or 10-35, or 10-32, or 10-30, or 12-35, or 12-32, or 12-30, or 14-27, or 14-25, or 14-22, or 15-20.

[0425] In an embodiment of the present disclosure, the CBDI of the linear low density polyethylene is 50 ≥50 wt% or CBDI 50 ≤ 50 wt. % as determined by TREF analysis.

[0426] In an embodiment of the present disclosure, the composition distribution breadth index CDBI of the linear low density polyethylene is50 % by weight, or 35-90 wt %, or 40-85 wt %, or 40-80 wt % (as determined by Temperature Elution Fractionation (TREF)).

[0427] Manufactured products

[0428] The ethylene copolymer compositions disclosed herein or their polymer blends can be converted into flexible manufactured articles, such as monolayer or multilayer films. Non-limiting examples of methods for preparing such films include blown film processes, double bubble processes, triple bubble processes, cast film processes, tenter processes, and machine direction orientation (MDO) processes.

[0429] In the blown film extrusion process, the extruder is heated, melted, mixed and conveyed with thermoplastics or thermoplastic blends. Once melted, the thermoplastic is forced through an annular die to produce a thermoplastic tube. In the case of coextrusion, multiple extruders are used to produce multilayer thermoplastic tubes. The temperature of the extrusion process is mainly determined by the thermoplastic or thermoplastic blend being processed, such as the melting temperature or glass transition temperature of the thermoplastic and the desired viscosity of the melt. In the case of polyolefins, the typical extrusion temperature is 330°F to 550°F (166°C to 288°C). When coming out of the annular die, the thermoplastic tube is inflated, cooled, solidified and pulled through a pair of rollers by air. Due to the inflation, the diameter of the tube increases, forming bubbles of the desired size. Due to the pulling action of the rollers, the bubbles are stretched in the longitudinal direction. Therefore, the bubbles are stretched in two directions: transverse direction (TD) (at this transverse direction (TD), the air filled increases the diameter of the bubble) and longitudinal direction (MD) (in this longitudinal direction (MD), the roller stretches the bubble). As a result, the physical properties of blown films are generally anisotropic, that is, the physical properties are different in the MD and TD directions; for example, film tear strength and tensile properties are generally different in the MD and TD. In some prior art documents, the terms "cross direction" or "CD" are used; these terms are equivalent to the terms "transverse direction" or "TD" used in the present disclosure. In the blown film process, air is also blown on the outer circumference of the bubble to cool it when the thermoplastic leaves the annular die. The final width of the film is determined by controlling the air or internal bubble pressure filled; in other words, increasing or decreasing the bubble diameter. The film thickness is mainly controlled by increasing or decreasing the speed of the roller to control the drafting rate. After leaving the roller, the bubble or tube collapses and can be cut longitudinally, thus producing a sheet. Each sheet can be wound into a film roll. Each roll can be further cut to produce a film of desired width. Each film roll can be further processed into various consumer products.

[0430] The cast film process is similar in that single or multiple extruders may be used; however, various thermoplastic materials are metered into a flat die and extruded into a single or multi-layer sheet rather than a tube. In the cast film process, the extruded sheet solidifies on a chill roll.

[0431] In the double bubble process, a first blown film bubble is formed and cooled, then the first bubble is heated and re-inflated to form a second blown film bubble, which is then cooled. The ethylene copolymer compositions (or blends thereof) disclosed herein are also suitable for triple bubble blowing processes. Additional film conversion processes suitable for the disclosed ethylene copolymer compositions (or blends thereof) include processes involving a longitudinal orientation (MDO) step; for example, a blown film or cast film, a quenched film, and then subjecting the film tube or film sheet to an MDO process at any stretch ratio. In addition, the ethylene copolymer compositions (or blends thereof) films disclosed herein can be suitable for tenter frame processes and other methods that introduce biaxial orientation.

[0432] Depending on the end-use application, the disclosed ethylene copolymer compositions (or polymer blends thereof) can be converted into films spanning a wide range of thicknesses. Non-limiting examples include food packaging films, where the thickness can range from 0.5 mil (13 μm) to 4 mil (102 μm); and in heavy-duty bag applications, the film thickness can range from 2 mil (51 μm) to 10 mil (254 μm).

[0433] In a monolayer film, the monolayer may contain more than one ethylene copolymer composition and / or one or more additional polymers; non-limiting examples of additional polymers include ethylene polymers and propylene polymers. The lower limit of the weight percent of the ethylene copolymer composition in the monolayer film may be 3 weight percent, in other cases 10 weight percent, and in still other cases 30 weight percent. The upper limit of the weight percent of the ethylene copolymer composition in the monolayer film may be 100 weight percent, in other cases 90 weight percent, and in still other cases 70 weight percent.

[0434] The ethylene copolymer compositions (or polymer blends thereof) disclosed herein can also be used in one or more layers of a multilayer film; non-limiting examples of multilayer films include three layers, five layers, seven layers, nine layers, eleven layers or more. The disclosed ethylene copolymer compositions (or polymer blends thereof) can also be suitable for use in processes employing microlayered dies and / or feed blocks, such processes can produce films having many layers, non-limiting examples of which include 10-10,000 layers.

[0435] The thickness of a particular layer (containing an ethylene copolymer composition or its polymer blend) within a multilayer film may be 5%, in other cases 15%, and in still other cases 30% of the total thickness of the multilayer film. In other embodiments, the thickness of a particular layer (containing an ethylene copolymer composition or its polymer blend) within a multilayer film may be 95%, in other cases 80%, and in still other cases 65% of the total thickness of the multilayer film. Each single layer of the multilayer film may contain more than one ethylene copolymer composition and / or additional thermoplastics and blends thereof.

[0436] The film layer in the multilayer film structure can contain more than one ethylene copolymer composition and / or one or more additional polymers; Non-limiting examples of additional polymers include ethylene polymers and propylene polymers. The lower limit of the weight percentage of the ethylene copolymer composition in the film layer of the multilayer film structure can be 3 weight %, 10 weight % in other cases, and 30 weight % in other cases. The upper limit of the weight percentage of the ethylene copolymer composition in the film layer of the multilayer film structure can be 100 weight %, 90 weight % in other cases, and 70 weight % in other cases.

[0437] Other embodiments include lamination and coating, wherein the monolayer or multilayer film containing the disclosed ethylene copolymer composition (or its polymer blend) is extrusion lamination or adhesive lamination or extrusion coating. In extrusion lamination or adhesive lamination, two or more substrates are bonded together with thermoplastics or adhesives, respectively. In extrusion coating, thermoplastics are applied to the surface of the substrate. These methods are well known to those skilled in the art. Usually, adhesive lamination or extrusion lamination is used to bond different materials, and non-limiting examples include bonding a paper web to a thermoplastic web, or bonding a web containing aluminum foil to a thermoplastic web, or bonding two chemically incompatible thermoplastic webs, such as bonding a web containing an ethylene copolymer product to a polyester or polyamide web. Before lamination, the web containing the disclosed ethylene copolymer composition (or its polymer blend) can be monolayer or multilayer. Before lamination, a single web can be surface treated to improve bonding, and the non-limiting example of surface treatment is corona treatment. The primary web or film may be laminated to a secondary web on its upper surface, its lower surface, or both. A secondary web and a tertiary web may be laminated to the primary web; wherein the chemical composition of the secondary and tertiary webs is different. As non-limiting examples, the secondary or tertiary webs may include polyamide, polyester, and polypropylene, or a web containing a barrier resin layer (e.g., EVOH). Such webs may also contain a vapor deposited barrier layer; for example, a thin silicon oxide (SiO x ) or aluminum oxide (AlO x ) layers. The multilayer web (or film) may contain three, five, seven, nine, eleven or more layers.

[0438] The ethylene copolymer compositions (or polymer blends thereof) disclosed herein can be used in a wide range of manufactured articles comprising one or more films (monolayer or multilayer film structures). Non-limiting examples of such manufactured articles include: food packaging films (fresh and frozen foods, liquids and granular foods), stand-up pouches, retortable packaging and bag-in-box packaging; barrier films (oxygen, moisture, aroma, oil, etc.) and modified atmosphere packaging; light and heavy shrink films and packaging, collation shrink films, pallet shrink films, shrink bags, shrink strapping and shrink hoods; light and heavy stretch films, manual stretch wrap, machine stretch wrap and stretch hood films; high clarity films; heavy duty bags; household packaging, overwrap films and sandwich bags; industrial and institutional films, trash bags, can liners, magazine overwraps, newspapers Bags, mailers, bags and envelopes, bubble wrap, carpet films, furniture bags, garment bags, coin bags, automotive panel films; medical applications, such as gowns, drapes and surgical garments; architectural films and sheets, asphalt membranes, barrier bags, masking films, landscape films and bags; geomembrane liners for municipal waste management and mining applications; bulk wrap bags; agricultural films, turf films and greenhouse films; in-store packaging, self-service bags, boutique bags, grocery bags, take-out bags and T-shirt bags; functional film layers in oriented films, machine direction oriented (MDO) films, biaxially oriented films and oriented polypropylene (OPP) films, such as sealants and / or toughening layers. Additional manufactured articles comprising one or more films containing at least one ethylene copolymer composition (or polymer blends thereof) include laminates and / or multilayer films; sealants and tie layers in multilayer films and composites; laminations with paper; aluminum foil laminates or laminates containing vacuum deposited aluminum; polyamide laminates; polyester laminates; extrusion coated laminates; and hot melt adhesive formulations. The manufactured articles summarized in this paragraph contain at least one film (monolayer or multilayer) comprising at least one embodiment of the disclosed ethylene copolymer composition (or polymer blend thereof). Alternatively, the manufactured articles summarized in this paragraph contain a blend of at least one ethylene copolymer composition disclosed herein with at least one other thermoplastic.

[0439] The desired film physical properties (monolayer or multilayer) generally depend on the application of interest. Non-limiting examples of desired film properties include optical properties (gloss, haze and clarity), dart impact, Elmendorf tear, modulus (1% and 2% secant modulus), tensile properties (yield strength, breaking strength, elongation at break, toughness, etc.), heat seal properties (heat seal initiation temperature SIT and hot tack). In high-speed vertical and horizontal form-fill-seal processes for loading and sealing goods (liquids, solids, pastes, parts, etc.) into bag-like packages, specific hot tack and heat seal properties are desired.

[0440] In addition to the desired film physical properties, it is also expected that the disclosed ethylene copolymer composition (or its polymer blend) is easy to process on a film production line. Those skilled in the art often use the term "processability" to distinguish polymers with improved processability relative to polymers with poor processability. The commonly used measure of quantitative processability is extrusion pressure; More specifically, polymers with improved processability have lower extrusion pressure (on blown film or cast film extrusion lines) relative to polymers with poor processability. Alternatively, for the present ethylene copolymer composition, it is expected that they have good crystallization kinetics. For their use in films for form-fill-seal (e.g., VFFS and HFFS) packaging applications, it is particularly expected that the ethylene copolymer composition used in the film has a high crystallization rate for enhancing processability and packaging rate on related VFFS equipment. Slow crystallization rate can slow down packaging speed and can cause the sealant layer in VFFS packaging to fail, because when the article is added to the package, the sealant material can still be in a molten state, and therefore may not have enough sealing strength to withstand the bearing force of the article added to the package. This problem can be even more severe in packages made with all polyethylene film structures because polyethylene sealant layers generally require longer time to cool than non-polyethylene sealant layers.

[0441] The films used in the manufactured articles described in this section may optionally include additives and adjuvants, depending on their intended use. Non-limiting examples of additives and adjuvants include antiblocking agents, antioxidants, heat stabilizers, slip agents, processing aids, antistatic additives, colorants, dyes, filler materials, light stabilizers, light absorbers, lubricants, pigments, plasticizers, nucleating agents, and combinations thereof.

[0442] In an embodiment of the present disclosure, a film or film layer comprises the ethylene copolymer composition described herein.

[0443] In an embodiment of the present disclosure, the film or film layer comprises a blend of the ethylene copolymer composition described herein and at least one other thermoplastic.

[0444] In an embodiment of the present disclosure, the film or film layer comprises a polymer blend comprising (a) the ethylene copolymer composition described herein and (b) a linear low density polyethylene.

[0445] In an embodiment of the present disclosure, the film or film layer is a monolayer film and comprises the ethylene copolymer composition described herein.

[0446] In an embodiment of the present disclosure, the film or film layer is a monolayer film and comprises a blend of the ethylene copolymer composition described herein and at least one other thermoplastic.

[0447] In an embodiment of the present disclosure, the film or film layer is a monolayer film and comprises a polymer blend comprising (a) the ethylene copolymer composition described herein and (b) a linear low density polyethylene.

[0448] In an embodiment, the film or film layer is a blown film.

[0449] In embodiments, the film or film layer is a cast film.

[0450] In an embodiment of the present disclosure, the film or film layer comprises the ethylene copolymer composition described herein and has a thickness of 0.5 to 10 mils.

[0451] In an embodiment of the present disclosure, the film or film layer comprises a blend of the ethylene copolymer composition described herein with at least one other thermoplastic and has a thickness of 0.5 to 10 mils.

[0452] In an embodiment of the present disclosure, the film or film layer comprises a polymer blend comprising (a) the ethylene copolymer composition described herein; and (b) a linear low density polyethylene, and has a thickness of 0.5 to 10 mils.

[0453] In embodiments of the present disclosure, the film or film layer has a thickness of 0.5-10 mils.

[0454] In embodiments of the present disclosure, the multi-layer film structure has a thickness of 0.5-10 mils.

[0455] In an embodiment of the present disclosure, the multilayer film structure comprises at least one layer comprising the ethylene copolymer composition described herein, and the multilayer film structure has a thickness of 0.5 to 10 mils.

[0456] In an embodiment of the present disclosure, the multilayer film structure comprises at least one layer comprising a blend of the ethylene copolymer composition described herein and at least one other thermoplastic, and the multilayer film structure has a thickness of 0.5 to 10 mils.

[0457] In an embodiment of the present disclosure, the multilayer film structure comprises at least one layer comprising a polymer blend comprising: (a) the ethylene copolymer composition described herein; and (b) a linear low density polyethylene, and the multilayer film structure has a thickness of 0.5-10 mils.

[0458] An embodiment of the present disclosure is a multi-layer coextruded blown film structure.

[0459] An embodiment of the present disclosure is a multi-layer coextruded blown film structure having a thickness of 0.5-10 mils.

[0460] An embodiment of the present disclosure is a multilayer coextruded blown film structure comprising a film layer comprising the ethylene copolymer composition described herein.

[0461] An embodiment of the present disclosure is a multilayer coextruded blown film structure comprising a film layer comprising a blend of the ethylene copolymer composition described herein and at least one other thermoplastic.

[0462] An embodiment of the present disclosure is a multilayer coextruded blown film structure comprising a film layer comprising a polymer blend comprising: (a) the ethylene copolymer composition described herein and (b) a linear low density polyethylene.

[0463] An embodiment of the present disclosure is a multilayer coextruded blown film structure comprising a film layer comprising the ethylene copolymer composition described herein, and the multilayer film structure has a thickness of 0.5 to 10 mils.

[0464] An embodiment of the present disclosure is a multilayer coextruded blown film structure comprising a film layer comprising a blend of the ethylene copolymer composition described herein and at least one other thermoplastic, and the multilayer film structure has a thickness of 0.5 to 10 mils.

[0465] An embodiment of the present disclosure is a multilayer coextruded blown film structure comprising a film layer comprising a polymer blend comprising: (a) the ethylene copolymer composition described herein and (b) a linear low density polyethylene, and the multilayer film structure has a thickness of 0.5-10 mils.

[0466] An embodiment of the present disclosure is a multi-layer coextruded cast film structure.

[0467] An embodiment of the present disclosure is a multi-layer coextruded cast film structure having a thickness of 0.5-10 mils.

[0468] An embodiment of the present disclosure is a multi-layer coextruded cast film structure comprising a film layer comprising the ethylene copolymer composition described herein.

[0469] An embodiment of the present disclosure is a multi-layer coextruded cast film structure comprising a film layer comprising a blend of the ethylene copolymer composition described herein and at least one other thermoplastic.

[0470] An embodiment of the present disclosure is a multilayer coextruded cast film structure comprising a film layer comprising a polymer blend comprising: (a) the ethylene copolymer composition described herein and (b) a linear low density polyethylene.

[0471] An embodiment of the present disclosure is a multi-layer coextruded cast film structure comprising a film layer comprising the ethylene copolymer composition described herein, and the multi-layer film structure has a thickness of 0.5 to 10 mils.

[0472] An embodiment of the present disclosure is a multilayer coextruded cast film structure comprising a film layer comprising a blend of the ethylene copolymer composition described herein and at least one other thermoplastic, and the multilayer film structure has a thickness of 0.5 to 10 mils.

[0473] An embodiment of the present disclosure is a multilayer coextruded cast film structure comprising a film layer comprising a polymer blend comprising: (a) the ethylene copolymer composition described herein; and (b) a linear low density polyethylene, and the multilayer film structure has a thickness of 0.5-10 mils.

[0474] An embodiment of the present disclosure is a multilayer film structure comprising a film layer comprising the ethylene copolymer composition described herein.

[0475] An embodiment of the present disclosure is a multilayer film structure comprising a film layer comprising the ethylene copolymer composition described herein, wherein the multilayer film structure has at least 3 layers, or at least 5 layers, or at least 7 layers, or at least 9 layers.

[0476] An embodiment of the present disclosure is a multilayer film structure comprising a film layer comprising the ethylene copolymer composition described herein, wherein the multilayer film structure has 9 layers.

[0477] An embodiment of the present disclosure is a multi-layer film structure comprising at least one sealant layer comprising the ethylene copolymer composition described herein.

[0478] An embodiment of the present disclosure is a multi-layer film structure comprising a sealant layer comprising the ethylene copolymer composition described herein.

[0479] An embodiment of the present disclosure is a multi-layer film structure comprising a sealant layer comprising the ethylene copolymer composition described herein, and wherein the multi-layer film structure has at least 3 layers.

[0480] An embodiment of the present disclosure is a multi-layer film structure comprising a sealant layer comprising the ethylene copolymer composition described herein, and wherein the multi-layer film structure has at least 5 layers.

[0481] An embodiment of the present disclosure is a multi-layer film structure comprising a sealant layer comprising the ethylene copolymer composition described herein, and wherein the multi-layer film structure has at least 7 layers.

[0482] An embodiment of the present disclosure is a multi-layer film structure comprising a sealant layer comprising the ethylene copolymer composition described herein, and wherein the multi-layer film structure has at least 9 layers.

[0483] An embodiment of the present disclosure is a multi-layer film structure comprising a sealant layer comprising the ethylene copolymer composition described herein, and wherein the multi-layer film structure has 9 layers.

[0484] An embodiment of the present disclosure is a multilayer film structure comprising at least one film layer comprising a blend of the ethylene copolymer composition described herein and at least one other thermoplastic.

[0485] An embodiment of the present disclosure is a multilayer film structure comprising at least one film layer comprising a blend of the ethylene copolymer composition described herein and at least one other thermoplastic, wherein the multilayer film structure has at least 3 layers, or at least 5 layers, or at least 7 layers, or at least 9 layers.

[0486] An embodiment of the present disclosure is a multilayer film structure comprising at least one film layer comprising a blend of the ethylene copolymer composition described herein and at least one other thermoplastic, wherein the multilayer film structure has 9 layers.

[0487] An embodiment of the present disclosure is a multi-layer film structure comprising at least one sealant layer comprising a blend of the ethylene copolymer composition described herein and at least one other thermoplastic.

[0488] An embodiment of the present disclosure is a multi-layer film structure comprising a sealant layer comprising a blend of the ethylene copolymer composition described herein and at least one other thermoplastic.

[0489] An embodiment of the present disclosure is a multilayer film structure comprising a sealant layer comprising a blend of the ethylene copolymer composition described herein and at least one other thermoplastic, and wherein the multilayer film structure has at least 3 layers.

[0490] An embodiment of the present disclosure is a multilayer film structure comprising a sealant layer comprising a blend of the ethylene copolymer composition described herein and at least one other thermoplastic, and wherein the multilayer film structure has at least 5 layers.

[0491] An embodiment of the present disclosure is a multilayer film structure comprising a sealant layer comprising a blend of the ethylene copolymer composition described herein and at least one other thermoplastic, and wherein the multilayer film structure has at least 7 layers.

[0492] An embodiment of the present disclosure is a multilayer film structure comprising a sealant layer comprising a blend of the ethylene copolymer composition described herein and at least one other thermoplastic, and wherein the multilayer film structure has at least 9 layers.

[0493] An embodiment of the present disclosure is a multilayer film structure comprising a sealant layer comprising a blend of the ethylene copolymer composition described herein and at least one other thermoplastic, and wherein the multilayer film structure has 9 layers.

[0494] An embodiment of the present disclosure is a multilayer film structure comprising at least one film layer comprising a polymer blend comprising: (a) the ethylene copolymer composition described herein and (b) a linear low density polyethylene.

[0495] An embodiment of the present disclosure is a multilayer film structure comprising at least one film layer, the film layer comprising a polymer blend, the polymer blend comprising: (a) the ethylene copolymer composition described herein and (b) a linear low density polyethylene, and wherein the multilayer film structure has at least 3 layers, or at least 5 layers, or at least 7 layers, or at least 9 layers.

[0496] An embodiment of the present disclosure is a multilayer film structure comprising at least one film layer comprising a polymer blend comprising: (a) the ethylene copolymer composition described herein and (b) a linear low density polyethylene, and wherein the multilayer film structure has 9 layers.

[0497] An embodiment of the present disclosure is a multi-layer film structure comprising at least one sealant layer comprising a polymer blend comprising: (a) the ethylene copolymer composition described herein and (b) a linear low density polyethylene.

[0498] An embodiment of the present disclosure is a multi-layer film structure comprising a sealant layer comprising a polymer blend comprising: (a) the ethylene copolymer composition described herein and (b) a linear low density polyethylene.

[0499] An embodiment of the present disclosure is a multilayer film structure comprising a sealant layer comprising a polymer blend comprising: (a) an ethylene copolymer composition described herein and (b) a linear low density polyethylene, and wherein the multilayer film structure has at least 3 layers.

[0500] An embodiment of the present disclosure is a multilayer film structure comprising a sealant layer comprising a polymer blend comprising: (a) an ethylene copolymer composition described herein and (b) a linear low density polyethylene, and wherein the multilayer film structure has at least 5 layers.

[0501] An embodiment of the present disclosure is a multilayer film structure comprising a sealant layer comprising a polymer blend comprising: (a) an ethylene copolymer composition described herein and (b) a linear low density polyethylene, and wherein the multilayer film structure has at least 7 layers.

[0502] An embodiment of the present disclosure is a multilayer film structure comprising a sealant layer comprising a polymer blend comprising: (a) an ethylene copolymer composition described herein and (b) a linear low density polyethylene, and wherein the multilayer film structure has at least 9 layers.

[0503] An embodiment of the present disclosure is a multilayer film structure comprising a sealant layer comprising a polymer blend comprising: (a) an ethylene copolymer composition described herein and (b) a linear low density polyethylene, and wherein the multilayer film structure has 9 layers.

[0504] The following examples are presented for the purpose of illustrating selected embodiments of the present disclosure; it is understood that the presented examples do not limit the presented claims.

[0505] Example

[0506] General test procedures

[0507] Each polymer specimen was conditioned at 23±2°C and 50±10% relative humidity for at least 24 hours prior to testing and subsequently tested at 23±2°C and 50±10% relative humidity. As used herein, the term "ASTM conditions" refers to a laboratory maintained at 23±2°C and 50±10% relative humidity; and the specimens to be tested were conditioned in the laboratory for at least 24 hours prior to testing. ASTM refers to the American Society for Testing and Materials.

[0508] density

[0509] The density of the ethylene copolymer compositions was determined using ASTM D792-13 (November 1, 2013).

[0510] Melt Index

[0511] The melt index of the ethylene copolymer composition was determined using ASTM D1238 (August 1, 2013). Melt index I2, I6, I 10 and I 21Measured at 190°C using weights of 2.16 kg, 6.48 kg, 10 kg and 21.6 kg, respectively. As used herein, the term "stress index" or its acronym "S.Ex." is defined by the following relationship: S.Ex. = log (I6 / I2) / log (6480 / 2160), wherein I6 and I2 are melt flow rates measured at 190°C using loads of 6.48 kg and 2.16 kg, respectively.

[0512] Conventional size exclusion chromatography (SEC)

[0513] The ethylene copolymer composition sample (polymer) solution (1-3 mg / mL) was prepared by heating the polymer in 1,2,4-trichlorobenzene (TCB) and rotating on a wheel in an oven at 150°C for 4 hours. An antioxidant (2,6-di-tert-butyl-4-methylphenol (BHT)) was added to the mixture to stabilize the polymer from oxidative degradation. The BHT concentration was 250 ppm. The polymer solution was chromatographed at 140°C on a PL 220 high temperature chromatography unit equipped with four Shodex columns (HT803, HT804, HT805 and HT806) using TCB as the mobile phase, a flow rate of 1.0 mL / min, and a differential refractive index (DRI) as a concentration detector. BHT was added to the mobile phase at a concentration of 250 ppm to protect the GPC column from oxidative degradation. The sample injection volume was 200 μL. The GPC column was calibrated with narrow distribution polystyrene standards. Polystyrene molecular weights were converted to polyethylene molecular weights using the Mark-Houwink equation as described in ASTM Standard Test Method D6474-12 (December 2012). GPC raw data were processed with Cirrus GPC software to generate molar mass averages (M n 、M w 、M z ) and molar mass distribution (e.g. polydispersity M w / M n ). In the field of polyethylene, the commonly used term equivalent to SEC is GPC, which is gel permeation chromatography.

[0514] GPC-FTIR

[0515] Ethylene copolymer composition (polymer) solution (2-4 mg / mL) was prepared by heating the polymer in 1,2,4-trichlorobenzene (TCB) and rotating on a wheel in an oven at 150°C for 4 hours. Antioxidant 2,6-di-tert-butyl-4-methylphenol (BHT) was added to the mixture to stabilize the polymer from oxidative degradation. The BHT concentration was 250 ppm. At 140°C, TCB was used as the mobile phase on a Waters GPC 150C chromatography unit equipped with four Shodex columns (HT803, HT804, HT805 and HT806), with a flow rate of 1.0 mL / min, using an FTIR spectrometer and a heated FTIR flow cell coupled to the chromatography unit by a heated transmission line as a detection system, the sample solution was chromatographed. BHT was added to the mobile phase at a concentration of 250 ppm to protect the SEC column from oxidative degradation. The sample injection volume was 300 μL. The raw FTIR spectra were processed with OPUS FTIR software, and the polymer concentration and methyl content were calculated in real time with the chemometric software (PLS technology) associated with OPUS. The polymer concentration and methyl content were then obtained and baseline correction was performed with CIRRUS GPC software. The SEC column was calibrated with narrow distribution polystyrene standards. As described in ASTM standard test method D6474, the Mark-Houwink equation was used to convert polystyrene molecular weight into polyethylene molecular weight. Comonomer content was calculated based on polymer concentration and methyl content predicted by PLS technology, as described in Paul J. Deslalurers, Polymer 43, pp. 159-170 (2002); it is incorporated herein by reference.

[0516] The GPC-FTIR method measures the total methyl content, which includes the methyl groups at the ends of each macromolecular chain, i.e., the methyl end groups. Therefore, the raw GPC-FTIR data must be corrected by subtracting the contribution from the methyl end groups. More clearly, the raw GPC-FTIR data overestimates the amount of short chain branching (SCB), and this overestimation increases as the molecular weight (M) decreases. In the present disclosure, the 2-methyl correction is used to correct the raw GPC-FTIR data. At a given molecular weight (M), the methyl end groups (N) are calculated using the following equation E ) number; N E = 28000 / M, and N is subtracted from the raw GPC-FTIR data E (M dependence) to generate SCB / 1000C (2-methyl corrected) GPC-FTIR data.

[0517] CYTSAF / TREF(CTREF)

[0518] The "Composition Distribution Breadth Index", hereinafter referred to as CDBI, of the ethylene copolymer compositions (and comparative examples) was measured using a CRYSTAF / TREF 200+ unit (hereinafter referred to as CTREF) equipped with an IR detector. The acronym "TREF" refers to Temperature Rising Elution Fractionation. CTREF was supplied by PolymerChar SA (Valencia Technology Park, Gustave Eiffel, 8, Paterna, E-46980 Valencia, Spain). CTREF operates in TREF mode, which produces the chemical composition of the polymer sample as a function of elution temperature, Co / Ho ratio (copolymer / homopolymer ratio) and CDBI (Composition Distribution Breadth Index) (i.e., CDBI 50 and CDBI 25 ) function. A polymer sample (80-100 mg) is placed in a reactor vessel of CTREF. The reactor vessel is filled with 35 ml of 1,2,4-trichlorobenzene (TCB), and the polymer is dissolved by heating the solution to 150°C for 2 hours. An aliquot of the solution (1.5 mL) is then loaded into a CTREF column, which is filled with stainless steel beads. The column loaded with the sample is stabilized at 110°C for 45 minutes. The polymer is then crystallized from the solution in the column by lowering the temperature to 30°C at a cooling rate of 0.09°C / min. The column is then balanced at 30°C for 30 minutes. TCB is then passed through the column at 0.75 mL / min, the crystallized polymer is eluted from the column, and the column is slowly heated from 30°C to 120°C at a heating rate of 0.25°C / min. The original CTREF data is processed using Polymer ChAR software, Excel spreadsheets, and CTREF software developed in-house. CDBI 50 Defined as the percentage of polymers whose composition is within 50% of the median comonomer composition; CDBI is calculated from the composition distribution curve 50 , and the cumulative integral of the normalized composition distribution curve, as described in U.S. Pat. No. 5,376,439. One skilled in the art will appreciate that a calibration curve is required to convert the CTREF elution temperature into comonomer content, i.e., the amount of comonomer in the ethylene / α-olefin polymer fraction eluting at a particular temperature. The generation of such calibration curves is described in the prior art, for example, Wild et al., J. Polym. Sci., Part B, Polym. Phys., Vol. 20(3), pp. 441-455: which is hereby incorporated by reference in its entirety. CDBI is calculated in a similar manner 25 ;CDBI 25Defined as the percentage of polymers whose composition is within 25% of the median comonomer composition. At the end of each sample run, the CTREF column was cleaned for 30 minutes; specifically, the CTREF column temperature was 160°C and TCB (at 0.5 mL / min) was passed through the column for 30 minutes.

[0519] Neutron activation (elemental analysis)

[0520] Neutron Activation Analysis (hereinafter referred to as NAA) was used to determine the catalyst metal residues in the ethylene copolymer composition as follows. A radiation vial (composed of ultrapure polyethylene, 7 mL internal volume) was filled with the ethylene copolymer composition sample and the sample weight was recorded. Using a pneumatic delivery system, the sample was placed in a SLOWPOKE TM The irradiation time was 30-600 seconds for the short half-life elements (e.g., Ti, V, Al, Mg, and Cl) or 3-5 hours for the long half-life elements (e.g., Zr, Hf, Cr, Fe, and Ni) in a nuclear reactor (Atomic Energy of Canada Limited, Ottawa, Ontario, Canada). The average thermal neutron flux in the reactor was 5×10 11 / cm 2 / s. After irradiation, the sample is removed from the reactor and aged to allow the radioactivity to decay; short half-life elements are aged for 300 seconds or long half-life elements are aged for several days. After aging, the gamma-ray spectrum of the sample is recorded using a germanium semiconductor gamma-ray detector (Ortec model GEM55185, Advanced Measurement Technology Inc., Oak Ridge, TN, USA) and a multi-channel analyzer (Ortec model DSPEC Pro). The amount of each element in the sample is calculated from the gamma-ray spectrum and recorded in parts per million relative to the total weight of the ethylene copolymer composition sample. The NAA system is calibrated with Specpure standards (a solution of 1000ppm of the desired element (purity greater than 99%)). 1mL of the solution (element of interest) is pipetted onto a 15mm×800mm rectangular filter paper and air-dried. The filter paper is then placed in a 1.4mL polyethylene irradiation vial and analyzed by the NAA system. The standard is used to determine the sensitivity of the NAA procedure (in counts / μg).

[0521] Unsaturation

[0522] The amount of unsaturated groups (i.e., double bonds) in the ethylene copolymer compositions was determined according to ASTM D3124-98 (vinylidene unsaturation, published in March 2011) and ASTM D6248-98 (vinyl and trans unsaturation, published in July 2012). The ethylene copolymer composition samples were: a) first subjected to carbon disulfide extraction to remove additives that might interfere with the analysis; b) the samples (in pellet, film or granule form) were pressed to prepare plaques of uniform thickness (0.5 mm); and c) the plaques were analyzed by FTIR.

[0523] Comonomer content: Fourier transform infrared (FTIR) spectroscopy

[0524] The amount of comonomer in the ethylene copolymer composition was determined by FTIR and recorded as the short chain branching (SCB) content (number of methyl branches per 1000 carbon atoms) with the size of CH3# / 1000C. This test was completed according to ASTM D6645-01 (2001) using compression molded polymer plaques and a Thermo-Nicolet 750 Magna-IR spectrophotometer. Polymer plaques were prepared using a compression molding apparatus (Wabash-Genesis series press) according to ASTM D4703-16 (April 2016).

[0525] 13 C Nuclear Magnetic Resonance (NMR)

[0526] Between 0.21-0.30 g of polymer sample was weighed into a 10 mm NMR tube. The sample was then dissolved with deuterated o-dichlorobenzene (ODCB-d4) and heated to 125°C; a heat gun was used to assist the mixing process. The spectra were collected on a Bruker AVANCE IIIHD 400 MHz NMR spectrometer. 13 C NMR spectra (24,000 scans per spectrum) were obtained using a 10 mm PABBO probe maintained at 125°C. Chemical shifts were assigned a value of 30.0 ppm with reference to the polymer backbone resonance. The spectra were processed using the exponential multiplication method with a line broadening (LB) factor of 1.0 Hz. 13 C spectra. They were also processed using Gaussian multiplication with LB = -0.5 Hz and GB = 0.2 to enhance resolution.

[0527] Differential Scanning Calorimetry (DSC)

[0528] The main melting peak (°C), melting peak temperature (°C), heat of fusion (J / g), and crystallinity (%) were determined using differential scanning calorimetry (DSC) as follows: the instrument was first calibrated with indium; after calibration, the polymer sample was equilibrated at 0°C, then the temperature was raised to 200°C at a heating rate of 10°C / min; the melt was then held isothermally at 200°C for five minutes; the melt was then cooled to 0°C at a cooling rate of 10°C / min and held at 0°C for five minutes; the sample was then heated to 200°C at a heating rate of 10°C / min. DSC Tm, heat of fusion, and crystallinity were recorded from the second heating cycle.

[0529] Dynamic Mechanical Analysis (DMA)

[0530] Oscillatory shear measurements at small strain amplitudes were performed at 190°C under N2 atmosphere at 10% strain amplitude and in the frequency range of 0.02-126 rad / s at 5 points per decade to obtain a linear viscoelastic function. The frequency sweep experiments were performed with a TA Instruments DHR3 stress-controlled rheometer using a cone-plate geometry with a 5° cone angle, 137 μm truncated top and 25 mm diameter. In this experiment, a sinusoidal strain wave was applied and the stress response was analyzed based on a linear viscoelastic function. The zero shear rate viscosity (η0) based on the DMA frequency sweep results was predicted by the Ellis model (see RB Bird et al. "Dynamics of Polymer Liquids. Vol. 1: Fluid Mechanics" Wiley-Interscience Publications (1987) p. 228) or the Carreau-Yasuda model (see K. Yasuda (1979) PhD Thesis, IT Cambridge). In the present disclosure, LCBF (long chain branching factor) is determined using η0 determined by DMA.

[0531] Melt Strength

[0532] Melt strength was measured on a Rosand RH-7 capillary rheometer (barrel diameter = 15 mm) with a 2 mm diameter flat die, L / D ratio 10:1, at 190°C. Pressure sensor: 10,000 psi (68.95 MPa). Piston speed: 5.33 mm / min. Pull angle: 52°. Pull increment speed: 50-80 m / min 2 or 65±15m / min 2 A polymer melt is extruded through a capillary die at a constant rate and the polymer strand is then stretched at increasing pulling speeds until it breaks. The maximum steady-state value of the force in the plateau region of the force versus time curve is defined as the melt strength of the polymer.

[0533] Membrane dart impact

[0534] Film dart impact strength was determined using ASTM D1709-09 Method A (May 1, 2009). In the present disclosure, the dart impact test employs a 1.5 inch (38 mm) diameter hemispherical head dart.

[0535] Membrane puncture

[0536] The film "puncture" energy (J / mm) required to rupture the film was determined using ASTM D5748-95 (originally adopted in 1995 and reapproved in 2012).

[0537] Membrane lubricated puncture

[0538] The "lubricated puncture" test was performed as follows: a 0.75 inch (1.9 cm) diameter pear-shaped fluorocarbon coated probe was used to travel at a speed of 10 inches / minute (25.4 cm / minute) and the energy (J / mm) to puncture the film sample was determined. ASTM conditions were used. Before testing the sample, the probe was manually lubricated with Muko Lubricating Jelly to reduce friction. Muko Lubricating Jelly is a water-soluble personal lubricant available from Cardinal Health Inc., 1000 Tesma Way, Vaughan, ON L4K 5R8 Canada. The probe was mounted on an Instron Model 5 SL Universal Testing Machine and a 1000-N load cell was used. The film sample (1.0 mil (25 μm) thick, 5.5 inches (14 cm) wide and 6 inches (15 cm) long) was mounted in the Instron and punctured.

[0539] Film stretching

[0540] The following film tensile properties were determined using ASTM D882-12 (August 1, 2012): tensile strength at break (MPa), elongation at break (%), tensile strength at yield (MPa), tensile elongation at yield (%), and film toughness or total energy at break (ft·lb / in 3 ). The tensile properties were measured in both the machine direction (MD) and the transverse direction (TD) of the blown films.

[0541] Film secant modulus

[0542] Secant modulus is a measure of film rigidity. Secant modulus is the slope of a line (i.e., secant line) drawn between two points on a stress-strain curve. The first point on the stress-strain curve is the origin, i.e., the point corresponding to the origin (point of zero percent strain and zero stress); and the second point on the stress-strain curve is the point corresponding to 1% strain; given these two points, 1% secant modulus is calculated and expressed as force per unit area (MPa). 2% secant modulus is calculated similarly. This method is used to calculate film modulus, because the stress-strain relationship of polyethylene does not follow Hook's law, i.e., the stress-strain behavior of polyethylene is nonlinear due to its viscoelastic properties. Secant modulus is measured using a conventional Instron tensile tester equipped with a 200lbf load cell. The strips of the cut monolayer film sample are used for testing with the following dimensions: 14 inches long, 1 inch wide, and 1 mil thick; ensure that there are no notches or cuts on the edges of the sample. Film samples are cut and tested in both the longitudinal (MD) and transverse (TD) directions. ASTM conditions are used to adjust the sample. The thickness of each film was accurately measured with a handheld micrometer and entered into the Instron software along with the sample name. The sample was loaded into the Instron with a 10-inch grip spacing and stretched at a rate of 1 inch / minute to generate a strain-strain curve. The 1% and 2% secant moduli were calculated using the Instron software.

[0543] Membrane puncture-propagation tear

[0544] Puncture-propagation tear resistance of blown films was determined using ASTM D2582-09 (May 1, 2009). This test measures the resistance of blown films to blocking, or more precisely, the resistance to dynamic puncture and puncture propagation resulting in tearing. Puncture-propagation tear resistance was measured in the machine direction (MD) and transverse direction (TD) of the blown film.

[0545] Membrane Elmendorf tear

[0546] Film tear properties were determined by ASTM D1922-09 (May 1, 2009); the equivalent term for tear is "Film Elmendorf Tear." Film tear was measured in both the machine direction (MD) and the transverse direction (TD) of the blown film.

[0547] Film optics

[0548] Film optical properties were measured as follows: Haze, ASTM D1003-13 (November 15, 2013); and Gloss, ASTM D2457-13 (April 1, 2013).

[0549] Film drop hammer impact

[0550] Instrumented impact testing was performed on a machine called a drop dart impact tester purchased from Illinois Test Works Inc., Santa Barbara, CA, USA; those skilled in the art often refer to this test as a drop hammer impact test. The test was completed according to the following procedure. The test sample was prepared by cutting a strip of about 5 inches (12.7 cm) wide and about 6 inches (15.2 cm) long from a roll of blown film; the film was about 1 mil thick. Prior to testing, the thickness of each sample was accurately measured and recorded with a handheld micrometer. ASTM conditions were used. The test sample was mounted in a 9250 Dynatup Impact drop tower / testing machine using a pneumatic clamp. A 0.5 inch (1.3 cm) diameter drop dart impact hammer head #1 was attached to the crosshead using the supplied Allen bolts. Prior to testing, the crosshead was raised to a height that made the film impact velocity 10.9 ± 0.1 ft / s. Weights were added to the crosshead so that: 1) the crosshead deceleration or hammer deceleration did not exceed 20% from the start of the test to the peak load point; and 2) the hammer had to penetrate the sample. If the hammer did not penetrate the film, additional weight was added to the crosshead to increase the impact velocity. During each test, the Dynatup Impulse Data Acquisition System Software collected experimental data (load (lb) versus time). At least 5 film samples were tested, and the software recorded the following averages: "Maximum (Max) Load (lb) of Dart Impact", the highest load measured during the impact test; "Total Energy of Dart Impact (ft·lb)", the area under the load curve from the start of the test to the end of the test (sample penetration); and "Total Energy of Dart Impact at Maximum Load (ft·lb)", the area under the load curve from the start of the test to the maximum load point.

[0551] Membrane hexane extractable

[0552] Hexane extractables were determined according to Code of Federal Registration 21 CFR §177.1520 Para(c) 3.1 and 3.2; wherein the amount of hexane extractable material in the film was determined gravimetrically. In detail, 2.5 g of a 3.5 mil (89 μm) monolayer film was placed in a stainless steel basket, and the film and basket (w i ), while the membrane in the basket: extracted with n-hexane at 49.5°C for two hours; dried in a vacuum oven at 80°C for 2 hours; cooled in a desiccator for 30 minutes; and weighed (w f The weight loss percentage is the hexane extractable percentage (w C6 ): w C6 =100×(w i -w f ) / wi .

[0553] Film hot tack

[0554] In the present disclosure, the "Hot Tack Test" is performed as follows using ASTM conditions. Hot tack data are generated using a J&B Hot Tack Tester, which is available from Jbi Hot Tack, Geloeslaan 30, B-3630 Maamechelen, Belgium. In the hot tack test, the strength of the polyolefin-to-polyolefin seal is measured immediately after two film samples are heat sealed together (the two film samples are cut from the same roll of 2.0 mil (51 μm) thick film), that is, when the polyolefin macromolecules constituting the film are in a semi-molten state. This test simulates the heat sealing of polyethylene films on high-speed automatic packaging machines (such as vertical or horizontal form, fill and seal equipment). The following parameters are used in the J&B Hot Tack Test: film specimen width, 1 inch (25.4 mm); film sealing time, 0.5 seconds; film sealing pressure, 0.27 N / mm 2 ; Delay time, 0.5 seconds; Film peel speed, 7.9 inches / second (200 mm / second); Test temperature range, 131°F to 293°F (55°C to 145°C); Temperature increment, 9F (5°C); and Test five film samples at each temperature increment to calculate the average at each temperature. In this way, a hot tack distribution of tensile force relative to sealing temperature is generated. From this hot tack distribution, the following data can be calculated: "Hot tack initiation temperature (°C) at 1.0N" or "HTOT" is the temperature at which a hot tack force of 1N is observed (average of five film samples); "Maximum hot tack strength (N)" is the maximum hot tack force observed within the test temperature range (average of five film samples); "Maximum hot tack temperature (°C)" is the temperature at which the maximum hot tack force is observed. Finally, the hot tack (strength) window ("hot tack window" or "HTW") is defined as the temperature range spanned by the hot tack curve at a given seal strength (e.g., 5 Newtons), in °C. Those skilled in the art will recognize that the hot tack window can be determined for different defined seal strengths. Generally speaking, for a given seal strength, the larger the hot tack window, the larger the temperature window over which a high sealing force can be maintained or achieved.

[0555] Film heat seal strength

[0556] In the present disclosure, the "heat seal strength test" (also called "cold seal test") is performed as follows. ASTM conditions are used. Heat seal data is generated using a conventional Instron Tensile Tester. In this test, two film samples (two film samples are cut from the same roll of 2.0 mil (51 μm) thick film) are sealed over a range of temperatures. The following parameters are used in the heat seal strength (or cold seal strength) test: film test sample width, 1 inch (25.4 mm); film sealing time, 0.5 seconds; film sealing pressure, 40 psi (0.28 N / mm 2 ); temperature range 212°F to 302°F (100°C to 150°C), and temperature increments of 9°F (5°C). After aging for at least 24 hours under ASTM conditions, seal strength was determined using the following tensile parameters: pull (crosshead) speed, 12 in / min (2.54 cm / min); pull direction, 90° to seal; and 5 film samples were tested at each temperature increment. The seal initiation temperature (hereinafter referred to as "SIT") is defined as the temperature required to form a commercially viable seal; the seal strength of a commercially viable seal is 2.0 pounds / inch seal (8.8 N / 25.4 mm seal).

[0557] Ethylene copolymer composition

[0558] Each single-site catalyst system is used to prepare an ethylene copolymer composition in a "series" dual continuous stirred tank reactor "CSTR" reactor solution polymerization process. In this solution polymerization process, the first and second CSTR reactors are configured in series with each other, and each reactor receives a catalyst system component feed. However, the dual CSTR reactor system is followed by a downstream tubular reactor, which is also configured in series, which receives the outlet stream of the second CSTR reactor, but does not feed it with additional catalyst system components. As a result, depending on whether additional polymerizable monomers are added directly to the third reactor, the prepared ethylene copolymer compositions each contain the first and second ethylene copolymers prepared by the single-site catalyst and an optional third ethylene copolymer (also prepared by the single-site catalyst because the active single-site catalyst flows from the second reactor to the third reactor). The "series" "dual CSTR reactor" solution phase polymerization process is described in U.S. Patent Application Publication No. 2019 / 0135958.

[0559] Basically, in a "series" reactor system, the outlet stream from the first polymerization reactor (R1) flows directly into the second polymerization reactor (R2). The R1 pressure is about 14 MPa to about 18 MPa; while R2 operates at a lower pressure to facilitate continuous flow from R1 to R2. Both R1 and R2 are continuous stirred reactors (CSTRs) and are stirred to obtain conditions in which the reactor contents are fully mixed. A third reactor R3 is also used. The third reactor R3 is a tubular reactor configured in series with the second reactor R2 (i.e., the contents of reactor 2 flow into reactor 3). The process is continuously operated by feeding fresh process solvent, ethylene, 1-octene and hydrogen to at least the first and second reactors and removing the product. Methylpentane is used as a process solvent (a commercial blend of methylpentane isomers). The volume of the first CSTR reactor (R1) is 3.2 gallons (12L), while the volume of the second CSTR reactor (R2) is 5.8 gallons (22L). The volume of the tubular reactor (R3) is 0.58 gallons (2.2L). The monomer (ethylene) and comonomer (1-octene) were purified prior to addition to the reactor using conventional feed preparation systems (e.g., contact with various absorption media to remove impurities, such as water, oxygen, and polar contaminants). The reactor feeds were pumped into the reactor at the ratios shown in Table 1. The average reactor residence time was calculated by dividing the average flow rate by the reactor volume and was primarily affected by the amount of solvent flowing through each reactor and the total amount of solvent flowing through the solution process. For example, the average reactor residence time was: 61 seconds in R1, 73 seconds in R2, and 7.3 seconds for a volume of 0.58 gallons (2.2 L) of R3.

[0560] In a first CSTR reactor (R1) configured in series with a second CSTR reactor (R2), the following single site catalyst (SSC) components are used to prepare the first and second ethylene copolymers: diphenylmethylene (cyclopentadienyl) (2,7-di-tert-butylfluorenyl) dimethyl hafnium [(2,7-tBu2Flu)Ph2C(Cp)HfMe2]; methylaluminoxane (MMAO-07); trityl tetrakis(pentafluorophenyl)borate (trityl borate) and 2,6-di-tert-butyl-4-ethylphenol (BHEB). Methylaluminoxane (MMAO-07) and 2,6-di-tert-butyl-4-ethylphenol are premixed in-line and then combined with diphenylmethylene (cyclopentadienyl) (2,7-di-tert-butylfluorenyl) dimethyl hafnium and trityl tetrakis(pentafluorophenyl)borate immediately before entering the polymerization reactors (e.g., R1 and R2). The efficiency of the single-site catalyst preparation is optimized by adjusting the molar ratio of the catalyst components fed to R1 and R2 and the R1 and R2 catalyst component inlet temperatures. If ethylene is fed directly to the third reactor R3 (i.e., if ethylene is split, the "ES" entering R3 R3" is not zero), then due to the active polymerization catalyst flowing from the second CSTR reactor R2 to the third tubular reactor R3, a third ethylene copolymer is also formed. Alternatively, if no ethylene is directly fed to the third reactor R3 (i.e., if ethylene is split, then the "ES" entering R3 R3 ” is not zero), no significant amount of the third ethylene copolymer is formed.

[0561] The total amount of ethylene supplied to the solution polymerization process can be allocated or divided between the three reactors R1, R2 and R3. This operating variable is called ethylene split (ES), i.e. "ES R1 ”, “ES R2 ” and “ES R3 ” refers to the weight percentage of ethylene injected into R1, R2 and R3 respectively; provided that ES R1 +ES R2 +ES R3 = 100%. Similarly, the total amount of 1-octene supplied to the solution polymerization process can be allocated or divided between the three reactors R1, R2 and R3. This operating variable is called octene split (OS), i.e., "OS R1 ”, “OS R2 ” and “OS R3 ” refers to the weight percentage of ethylene injected into R1, R2 and R3 respectively; provided that OS R1 +OS R2 +OS R3 =100%. The term "Q R1 " refers to the percentage of ethylene added to R1 that is converted to ethylene copolymer by the catalyst formulation. Similarly, Q R2 and Q R3 represents the percentage of ethylene added to R2 and R3 that is converted into ethylene copolymer in the respective reactors. T " represents the total or overall ethylene conversion of the entire continuous solution polymerization unit, i.e., Q T =100×[weight of ethylene in copolymer product] / ([weight of ethylene in copolymer product]+[weight of unreacted ethylene]).

[0562] The polymerization in the continuous solution polymerization process is terminated by adding a catalyst deactivator to the third outlet stream leaving the tubular reactor (R3). The catalyst deactivator used is octanoic acid (octanoic acid), commercially available from P&G Chemicals, Cincinnati, OH, USA. The catalyst deactivator is added so that the number of moles of fatty acid added is 50% of the total moles of catalytic metal and aluminum added to the polymerization process; for clarity, the number of moles of octanoic acid added = 0.5 x (moles hafnium + moles aluminum).

[0563] The ethylene copolymer composition was recovered from the process solvent using a two-stage devolatilization process, i.e., using two vapor / liquid separators and passing the second bottoms stream (from the second V / L separator) through a gear pump / pelletizer combination.

[0564] DHT-4V (hydrotalcite) supplied by Kyowa Chemical Industry Co. Ltd., Tokyo, Japan can be used as a passivating agent or acid scavenger in the continuous solution process. A slurry of DHT-4V in the process solvent can be added before the first V / L separator.

[0565] Before pelletizing, the ethylene copolymer composition was prepared by adding 500 ppm of The ethylene copolymer composition was stabilized with 1076 (primary antioxidant) and 500 ppm of Irgafos 168 (secondary antioxidant). The antioxidants were dissolved in the process solvent and added between the first and second V / L separators.

[0566] Table 1 shows the reactor conditions used to prepare each of the inventive ethylene copolymer compositions. Table 1 includes process parameters such as the distribution of ethylene and 1-octene between reactors (R1, R2, and R3), reactor temperature, ethylene conversion, amount of hydrogen, etc.

[0567] The properties of the ethylene copolymer compositions of the invention (Inventive Examples 1, 6, 7, 8 and 12) and those for the comparative resin (Comparative Example 3) are shown in Table 2. Comparative Example 3 is a plastomer ethylene / 1-octene resin sold by Borealis AG. 8201LA. The density of Queo 8201LA is about 0.881 g / cm 3 , and the melt index is about 1.1 g / 10 min.

[0568] Details of the ethylene copolymer composition components (first ethylene copolymer, second ethylene copolymer and optional third ethylene copolymer) of the present invention are provided in Table 3. The ethylene copolymer composition component properties shown in Table 3 were determined using the Polymer Methods model equations (described further below).

[0569] Aggregation Method Model

[0570] For multicomponent (or bimodal) polyethylene polymers, the M for each component is calculated using the reactor model simulation using the input conditions w 、M n 、M w / M n, weight percent, branching frequency (i.e., BrF = SCB per 1000 carbons in the polymer backbone), density, and melt index I2, which are input conditions for actual pilot scale operating conditions (for reference to relevant reactor modeling methods, see "Copolymerization", A. Hamielec, J. MacGregor and A. Penlidis, Comprehensive Polymer Science and Supplements, Vol. 3, Chapter 2, p. 17, Elsevier, 1996 and "Copolymerization of Olefins in a Series of Continuous Stirred-Tank Slurry-Reactors using Heterogeneous Ziegler-Natta and Metallocene Catalysts. I. General Dynamic Mathematical Model", JBP Soares and AE Hamielec, Polymer Reaction Engineering, 4 (2&3), p153, 1996).

[0571] The model uses the input flow of several reactive materials (e.g., catalyst, monomer (e.g., ethylene), comonomer (e.g., 1-octene), hydrogen, and solvent) entering each reactor, the temperature (in each reactor), and the conversion of the monomer (in each reactor), and uses the terminal kinetic model for a series-connected continuous stirred tank reactor (CSTR) to calculate the polymer properties (of the polymer produced in each reactor, i.e., the first, second, and third ethylene copolymers). The "terminal kinetic model" assumes that the kinetics depend on the monomer units within the polymer chain, and the active catalyst sites are located on the monomer units (see "Copolymerization", A. Hamielec, J. MacGregor, and A. Penlidis, Comprehensive Polymer Science and Supplements, Vol. 3, Chapter 2, p. 17, Elsevier, 1996). In the model, it is assumed that the copolymer chain has a reasonably large molecular weight to ensure that the statistics of the monomer / comonomer unit insertion at the active catalyst center are valid, and the monomer / comonomer consumed in routes other than propagation is negligible. This is called the "long chain" approximation.

[0572] The terminal kinetic model of polymerization includes reaction rate equations for activation, initiation, propagation, chain transfer, and deactivation pathways.The model solves steady-state conservation equations (eg, overall mass balance and heat balance) for a reactive fluid containing the reactive species identified above.

[0573] The overall material balance for a typical CSTR with a given number of inlets and outlets is given by:

[0574]

[0575] in Represents the mass flow rate of an individual flow, with the index i indicating the inlet flow and the outlet flow.

[0576] Equation (1) can be further expanded to show the individual species and reactions:

[0577]

[0578] Among them, M i is the average molar weight of the fluid inlet or outlet (i), x ij is the mass fraction of species j in flow i, ρ mix is the molar density of the reactor mixture, V is the reactor volume, R j is the reaction rate of substance j, and its unit is kmol / m 3 s.

[0579] For the adiabatic reactor, the overall heat balance is solved and is given by:

[0580]

[0581] in is the mass flow rate of stream i (inlet or outlet), ΔH i is the enthalpy difference of flow i relative to the reference state, q Rx is the heat released by the reaction, V is the reactor volume, is the work input (i.e. the agitator), is the heat input / loss.

[0582] The catalyst concentration input to each reactor was adjusted to match experimentally determined values ​​of ethylene conversion and reactor temperature to solve the equations of the kinetic model (eg, propagation rates, heat balance, and mass balance).

[0583] The H2 concentration input to each reactor can likewise be adjusted so that the calculated molecular weight distribution of polymer produced in all reactors (and therefore the molecular weight of polymer produced in each reactor) matches the experimentally observed molecular weight distribution.

[0584] The weight fractions wt1, wt2 and wt3 of the material produced in each reactor R1, R2 and R3 are determined by the known mass flow rates of monomer and comonomer entering each reactor and the known conversion of monomer and comonomer in each reactor calculated based on the kinetic reactions.

[0585] The degree of polymerization (dp n ) is given by the ratio of the chain propagation reaction rate to the chain transfer / termination reaction rate:

[0586]

[0587] where k p12 is the propagation rate constant for the addition of monomer 2 (1-octene) to a growing polymer chain terminated by monomer 1 (ethylene), [m1] is the molar concentration of monomer 1 in the reactor, [m2] is the molar concentration of monomer 2 in the reactor, and k tm12 is the termination rate constant for the growing chain terminated by monomer 1 and transferred to monomer 2, k ts1 is the rate constant for spontaneous chain termination for a chain ending in monomer 1, k tH1 is the rate constant for hydrogen chain termination for chains ending in monomer 1. φ1 and φ2 are the fractions of catalyst sites occupied by chains ending in monomer 1 or monomer 2, respectively.

[0588] The number average molecular weight (Mn) of a polymer is determined by the degree of polymerization and the molecular weight of the monomer units. From the number average molecular weight of the polymer in a given reactor, and assuming a Flory-Schulz distribution of a single site catalyst, the molecular weight distribution of the polymer is determined using the following relationship.

[0589] (5)w(n)=nτ 2 e -τn

[0590] where n is the number of monomer units in the polymer chain, w(n) is the weight fraction of polymer chains with chain length n, and τ is calculated using the following equation:

[0591]

[0592] where dp n is the degree of polymerization, R p is the propagation rate, and R t is the termination rate.

[0593] The Flory-Schulz distribution can be converted to a commonly used logarithmic scale gel permeation chromatography (GPC) curve by applying the following formula:

[0594]

[0595] in is the differential weight fraction of polymers with chain length n (n = MW / 28, where 28 is the molecular weight of the polymer chain segment corresponding to the C2H4 unit), and dp n is the degree of polymerization.

[0596] Assuming the Flory-Schultz model, the different moments of the molecular weight distribution can be calculated using:

[0597]

[0598] therefore,

[0599] μ0=1,

[0600] μ1=dp n ,and

[0601] μ2=2dp n 2 ;

[0602] therefore,

[0603]

[0604]

[0605] Among them, Mw 单体 is the molecular weight of the polymer segment corresponding to the C2H4 unit of the monomer.

[0606] Finally, when a single-site catalyst produces long chain branching, the molecular weight distribution of the polymer is determined using the following relationship (see "Polyolefins with Long Chains Branches Made with Single-Site Coordination Catalysts: A Review of Mathematical Modeling Techniques for Polymer Microstructure", JBP Soares, Macromolecular Materials and Engineering, Vol. 289, No. 1, pp. 70-87, Wiley-VCH, 2004 and "Polyolefin Reaction Engineering", JBP Soares and TFL McKenna Wiley-VCH, 2012).

[0607]

[0608] where n is the number of monomer units in the polymer chain, w(n) is the weight fraction of polymer chains with chain length n, and τ B and α are calculated using the following equations:

[0609]

[0610]

[0611] in is the degree of polymerization, R p is the propagation rate, R t is the termination rate, and R LCB is the long chain branching formation rate calculated using the following equation:

[0612] R LCB =k p13 φ1[m3]

[0613] where k p13 is the propagation rate constant for the addition of monomer 3 (the macromonomer formed in the reactor) to the growing polymer chain terminated by monomer 1, and [m3] is the molar concentration of the macromonomer in the reactor.

[0614] The weight distribution can be converted to the commonly used logarithmic scale GPC curve by applying the following formula:

[0615]

[0616] in is the differential weight fraction of polymers having chain length n (n = MW / 28, where 28 is the molecular weight of the polymer chain segments corresponding to C2H4 units).

[0617] From the weight distribution, the different moments of the molecular weight distribution can be calculated using:

[0618]

[0619]

[0620] in is the degree of polymerization, and α is calculated as explained.

[0621] Assuming that the addition of monomer 2 (1-octene) units to the chain terminating in the octene terminal unit is negligible, the number of octenes after the ethylene step will be equal to the number of ethylene after the octene step. The branch content BrF of the resulting polymer per thousand backbone carbon atoms (500 monomer units) will be the ratio of the addition rate of monomer 1 (ethylene) to the addition rate of monomer 2 (1-octene).

[0622]

[0623] where k p12 is the propagation rate constant for the addition of monomer 2 (1-octene) to a growing polymer chain terminated by monomer 1 (ethylene), k p11 is the propagation rate constant for the addition of monomer 1 (ethylene) to a growing polymer chain terminated by monomer 1, [m1] is the molar concentration of monomer 1 in the reactor, and [m2] is the molar concentration of monomer 2 in the reactor.

[0624] The density of the polymer produced in each reactor is calculated based on the branching frequency, number average molecular weight, weight average molecular weight and the ratio of weight average molecular weight to number average molecular weight (determined as described above for the polymer produced in each reactor) using the following equation:

[0625]

[0626] Where a = 1.061, b = -5.434e -03 , c = 6.5268e -01 , d = 1.246e -09 , e = 1.453, f = -7.7458e -01 , g = 2.032e -02 , h = 8.434e -01 , and k = 1.565e -02 .

[0627] The melt index (I2, g / 10 min) of the polymer produced in each reactor is calculated based on the number average molecular weight and the weight average molecular weight (determined as described above for the polymer produced in each reactor) using the following equation:

[0628]

[0629] Table 1

[0630] Reactor operating conditions

[0631]

[0632]

[0633] a [(2,7-tBu2Flu)Ph2C(Cp)HfMe2]

[0634] b Methylaluminoxane (MMAO-7)

[0635] c 2,6-Di-tert-butyl-4-ethylphenol

[0636] d Triphenylmethyl tetrakis(pentafluorophenyl)borate

[0637] e Total solution rate (kg / h) = (R1 total solution rate (kg / h)) + (R2 total solution rate (kg / h) + (R3 total solution rate (kg / h))

[0638] Table 2

[0639] Polymer properties

[0640]

[0641]

[0642] Table 3

[0643] Polyethylene composition properties

[0644]

[0645]

[0646] Differential Scanning Calorimetry (DSC)

[0647] The main melting peak (C), melting peak temperature (C), heat of fusion (J / g) and crystallinity (%) listed in Table 2 were determined using differential scanning calorimetry (DSC) as follows: the instrument was first calibrated with indium; after calibration, the polymer sample was equilibrated at 0°C and then the temperature was raised to 200°C at a heating rate of 10°C / min; the melt was then held isothermally at 200°C for five minutes; the melt was then cooled to 0°C at a cooling rate of 10°C / min and held at 0°C for five minutes; the sample was then heated to 200°C at a heating rate of 10°C / min. The DSC main melting point / peak, secondary melting point / peak, heat of fusion and crystallinity were recorded from the second heating cycle.

[0648] Non-isothermal crystallization using differential scanning calorimetry (DSC)

[0649] The non-isothermal crystallization behavior of the inventive examples and comparative examples was studied by using differential scanning calorimetry (DSC) as follows: first calibrate the instrument with indium; after calibration, equilibrate the polymer sample at 0°C, then raise the temperature to 200°C at a desired heating rate of 1 or 5 or 10 or 20 or 40°C / min; then hold the melt isothermally at 200°C for five minutes; then cool the melt to 0°C at a desired cooling rate of 1 or 5 or 10 or 20 or 40°C / min and hold at 0°C for five minutes; then heat the sample to 200°C at a specific heating rate of 1 or 5 or 10 or 20 or 40°C / min. Crystallization onset temperature (T起始 ) and peak crystallization temperature (T max ) is reported from the cooling cycles performed at the corresponding cooling rates. The non-isothermal crystallization kinetics were analyzed according to the method of Seo (see: Seo Y; "Non-isothermal Crystallization Kinetics of Polytetrafluoroethylene", Polym. Eng. & Sci. 2000; Vol. 40, pp. 1293-7).

[0650] Table 4 provides parameters such as the crystallization onset (T) of the inventive examples and comparative examples measured at cooling rates of 1, 5, 10, 20 and 40 °C / min. 起始 ) and the maximum crystallization temperature (T max ).

[0651] Table 4

[0652] Non-isothermal crystallization parameters

[0653]

[0654] Table 4 (with Figure 1 The data given in the figure are shown at the start (T 起始 ) and peak value (T max ) crystallization temperature (related to the value of the associated enthalpy) and the peak broadening effect, the main differences between the inventive examples and the comparative examples are observed. It is obvious that the onset temperatures of all ethylene copolymer compositions of Inventive Examples 1, 6, 7, 8 and 12 at any given cooling rate are higher than those of the comparative resin of Comparative Example 3. This indicates that for the inventive examples, the supercooling required for crystallization to occur is less than that required for the comparative resins of similar density. Similarly, the data indicate that for each of the inventive examples, crystallization occurs at a faster rate relative to the comparative resins of similar density (because the onset of crystallization occurs at a higher temperature for each cooling rate examined).

[0655] Without wishing to be bound by theory, these differences may be attributed to nucleation, which is caused by the presence of a higher density fraction in the inventive ethylene copolymer compositions. The higher density fraction may be associated with the presence of the second or in some cases the third ethylene copolymer component in the inventive examples, which is absent in Comparative Example 3 (which is a single component plastic resin).

[0656] Figure 1 Shown are the exotherm curves of Inventive Examples 1, 6 and 12 and Comparative Example 3, each at a cooling rate of 10°C / min, as measured using DSC. Figure 1It is evident that the ethylene copolymer compositions of the inventive examples crystallize at a faster rate than the comparative resins at a given cooling rate of 10°C / min (because their onset and peak crystallization temperatures are higher than those of the comparative resins).

[0657] Figure 2 Displays the maximum crystallization temperature (T max ) varies linearly as a function of the logarithm of the cooling rate (β). The predicted behavior is observed in all cases, indicating that Seo's approach described above is quite satisfactory. Figure 2 shows that, because less time is available for crystallization at higher cooling rates, T max As expected, the T max decreases with increasing cooling rate (β). Figure 2 It is also shown that the T max Higher than the T of the comparative resin (Comparative Example 3) with similar density at the same cooling rate max (due to the faster crystallization rates associated with the inventive examples).

[0658] For non-isothermal crystallization methods, the activation energy of crystallization is derived from the Kissinger equation in the following form (see: Kissinger, Homer E. "Variation of Peak Temperature with Heating Rate in Differentiated Thermal Analysis", Journal of Research of the National Bureau of Standards, Vol. 57 (1956), p. 217; and Kim, Jihun et al. "Nonisothermal Crystallization Behaviors of Nanocomposites Prepared by In Situ Polymerization of High-Density Polyethylene on Multiwalled Carbon Nanotubes", Macromolecules Vol. 43 (2010), p. 10545):

[0659]

[0660] Where R is the ideal gas constant (8.3145 J mol -1 K -1 ), and E ais the activation energy (enthalpy change of crystallization), T max As above, and β is the cooling rate as above. For the non-isothermal crystallization method, by plotting Relative to d(1 / T max ), and multiply the slope of the line by the ideal gas constant to derive the activation energy of crystallization from the above Kissinger equation. Figure 3 A representative graph of activation energy calculated based on the Kissinger method for the non-isothermal crystallization method describing Inventive Example 1 is provided in .

[0661] The data in Table 6 represent the calculated activation energy values ​​(E ) for various ethylene copolymers of the present disclosure (Inventive Examples 1, 6, 7, 8, and 12) and a comparative resin of similar density (Comparative Example 3). a ). Those skilled in the art will recognize that the activation energy values ​​of Inventive Examples 1, 6, 7, 8, and 12 are lower than the activation energy value of Comparative Example 3.

[0662] Table 6

[0663] Activation energy (enthalpy change of crystallization, E a )

[0664] Example No. <![CDATA[I2(g / 10min)]]> <![CDATA[Density (g / cm 3 )]]> <![CDATA[E a (kJ / mol)]]> Invention 1 1.45 0.885 445 Invention 6 0.90 0.894 363 Invention 7 1.78 0.896 316 Invention 8 0.69 0.897 295 Invention 12 1.08 0.885 333 Contrast 3 1.10 0.881 485

[0665] Without wishing to be bound by theory, the lower activation energies found for the inventive examples indicate that the ethylene copolymer compositions of the present disclosure comprising a first, second, and optional third ethylene copolymer component (where the second and optional third ethylene copolymer components provide similar or higher density fractions relative to the first ethylene copolymer component) have significantly increased crystallization speed / kinetics relative to the single component comparative resin. The increased crystallization rate may be due to the fact that these second and / or third ethylene copolymer components can act as nucleation sites for crystallization.

[0666] Atomic Force Microscopy (AFM) Hot Stage

[0667] The crystallization kinetics and morphology of representative inventive embodiments and comparative embodiments were studied using atomic force microscopy (AFM) operated in tapping mode with phase imaging. The technique was performed using a Bruker multi-mode atomic force microscope equipped with a high temperature heater, which controlled the temperature within ± 0.25 ° C of the set point. A silicon probe (force constant 21-98 N / m) was used to operate the AFM in tapping mode. The scanning rate was 1 Hz, and the scanning area contained 512 × 512 lines. For each polymer sample, a compression molded plate was prepared, and a small square with a size of about 5 mm on each side was cut out and then directly mounted on a 1 cm diameter stainless steel sample disc without an adhesive. After the disc was mounted on the AFM stage (magnetically held in place), the stage temperature was rapidly increased to 200 ° C and maintained for five minutes to eliminate any thermal history; the melt was then rapidly cooled to 105 ° C. 2D height and 3D topography images of Inventive Example 1 and Comparative Example 3 were obtained at 25, 45 and 75 minutes, and using these images (note: the AFM program provides images of size 40 μm×40 μm for 3D topography format, which are enhanced in the so-called "line height" mode at a resolution of 256×256 pixels, not shown), the following surface roughness parameters are used to indicate the quantitative evaluation of surface roughness: surface area difference (%); average surface roughness (Ra); and root mean square surface roughness (Rq). Without wishing to be bound by theory, crystal growth (e.g., surface morphology) can be quantified by the above-mentioned surface roughness parameters, including surface area difference (%) (i.e., the difference between the three-dimensional surface area of ​​the analyzed area and its two-dimensional footprint area), average surface roughness (Ra) and root mean square surface roughness (Rq). The surface roughness parameters were analyzed with the "Nanoscope" software, and the resulting data are provided in Table 7.

[0668] Table 7

[0669] Surface difference percentage (%) measured at a hot stage temperature of 105°C

[0670]

[0671] The data in Table 7 show that Inventive Example 1 generally has a greater amount of crystal growth, as indicated by the higher % surface area difference, higher average surface roughness (Ra), and higher root mean square surface roughness (Rq) values, when compared to Comparative Example 3. The data presented in Table 7 also demonstrate that the crystal growth rate (an indicator of crystallization rate) for the ethylene copolymer compositions of the present disclosure is higher than that observed for a comparative plastic resin (Comparative 3) of similar density.

[0672] Blown film (multi-layer)

[0673] Multilayer blown films were produced on a 9-layer line commercially available from Brampton Engineering (Brampton ON, Canada). The structures of the 9-layer films produced are shown in Table 8. Layer 1 (sealant layer) contained the inventive ethylene copolymer composition prepared in accordance with the present disclosure, a blend thereof with an LLDPE material, a comparative plastomer resin, or a blend thereof with an LLDPE material. Layer 1 was typically formulated in the following manner: 91.5 wt % of the sealant resin examined, 2.5 wt % of an anti-blocking masterbatch, 3 wt % of a slip masterbatch, and 3 wt % of a processing aid masterbatch, such that sealant layer 1 contained 6250 ppm of anti-blocking (silicon dioxide (diatomaceous earth)), 1500 ppm of a slip agent (eurcamide), and 1500 ppm of a processing aid (fluoropolymer compound); the additive masterbatch carrier resin was LLDPE with a melt index (I2) of about 2 g / 10 min and a density of about 0.918 g / cm 3 Using the above details in hand, 91.5 wt% of Layer 1 contained one of the following resins as the sealant resin examined:

[0674] a) 100 wt % of Inventive Example 1;

[0675] b) Invention Example 1 and FP120-C blended at a weight ratio of 20%:80%;

[0676] c) 100 wt. % of Queo 8201LA, a comparative plastic resin having a density similar to that of Inventive Example 1 (Comparative Example 3); or

[0677] d) A blend of Queo 8201LA and SCLAIR FP120-C at a blending weight ratio of 20%:80%.

[0678] SCLAIR FP120-C is an ethylene / 1-octene copolymer resin available from NOVA Chemicals Corporation having a density of about 0.920 g / cm 3 , and the melt index I2 is about 1 g / 10 min.

[0679] Layer 1 is the inner layer, i.e., the inner bubble, because the multilayer film is produced on a blown film line. The total thickness of the 9-layer film was kept constant at 3.5 mils; the thickness of layer 1 was about 0.385 mil (9.8 μm), i.e., 11% of 3.5 mils (see Table 8). Layers 2, 3, and 7 contained FPs016-C, a LLDPE resin available from NOVA Chemicals Corporation, has a density of about 0.916 g / cm 3, and the melt index I2 is about 0.65 g / 10 min. Layers 4, 5, and 8 contain a bonding resin containing 80 wt% FPs016-C and 20 wt% 41E710, maleic anhydride grafted LLDPE, available from DuPont Packaging & Industrial Polymers, density 0.912 g / cm 3 , and the melt index (I2) is 2.7 g / 10 min. Layers 5 and 9 contain nylon resin, C40 L (polyamide 6 / 66), available from BASF Corporation, has a melt index (I2) of 1.1 g / 10 min.

[0680] Note: The resin blends were prepared by placing the target weight percentages of each component in a batch mixer and tumble blending for at least 15 minutes. The finished blends were fed directly into the extruder hopper as a dry blend for film layer formation, such as for layer number 1 (sealant layer) formation.

[0681] The multi-layer die technology consists of a flat die, a FLEX-STACK coextrusion die (SCD), where the flow path is machined onto both sides of the plate, the die tool diameter is 6.3 inches, and in the present disclosure, a die gap of 85 mils is used consistently to produce films with a blow-up ratio (BUR) of 2.5, and the output rate of the production line is kept constant at 250lb / hr. The specifications of the nine extruders are as follows: screw diameter 1.5 inches, 30 / 1 aspect ratio, 7 polyethylene screws with single threads and Maddock mixers, 2 nylon screws. All extruders are air cooled, equipped with 20-HP motors, and equipped with a weight blender. The roller gap and collapse frame include Decex horizontal oscillating traction and Pearl cooling strips just below the roller gap. The production line is equipped with a turret winder and an oscillating trimming knife. Table 9 summarizes the temperature settings used. All die temperatures are maintained at a constant 480°F, i.e., layer sections, mandrel bottom, mandrel, inner lip, and outer lip.

[0682] The sealing properties of the nine-layer blown film (3.5 mil thickness) prepared as described above are provided in Tables 10A and 10B. The hot tack and cold seal tests (hot tack and cold seal curves) of the nine-layer blown film are shown in Figure 4 and 5 middle.

[0683] Table 8

[0684] Multilayer blown film structure

[0685]

[0686] Table 9

[0687] Multilayer film manufacturing conditions

[0688]

[0689] Table 10A

[0690] Sealant properties of the inventive resin and comparative plastic resin when used as the sealant layer in a 9-layer all-PE film structure able

[0691]

[0692] ￥As determined in the "Vertical Form Fill and Seal" test as follows

[0693] Table 10 above and Figure 4 and 5 The data provided in is used to show that when used in the sealant layer of a multilayer film structure, Inventive Example 1 has comparable sealing properties (e.g., seal initiation temperature, cold seal strength, hot tack window, and maximum hot tack strength) relative to Comparative Example 3 (which is a resin with similar density and melt index I2). This trend is true for multilayer film structures when the sealant is composed of unblended plastic materials or plastic materials blended with LLDPE.

[0694] Vertical Form Fill and Seal (VFFS) Testing

[0695] This procedure describes how to determine the initial sealing temperature of bags made on a ROVEMA vertical form filling and sealing (VFFS) machine. This test is used as a comparative tool for evaluating sealant resins. Multilayer blown films produced on a 9-layer production line (as described above and in Table 8) are used to make the bags required for this evaluation. Bags with a size of 200 mm × 150 mm and filled with just enough water to produce a head space for the Haug vacuum pressure test (about 100 mils) are produced using the following four general conditions at a fixed sealing bar temperature: low sealing time and low pressure; low sealing time and high pressure; high sealing time and low pressure; and high sealing time and high pressure (see Table 10B below). A total of 20 bags were produced at each of the four conditions at a specific temperature for the Haug vacuum leak test. The bags produced under each condition were subjected to a 30-second leak test at a pressure of 15 mm Hg (by checking whether bubbles are generated in a water bath). In order to be considered successful in this test procedure, a minimum of 18 of the 20 bags tested must pass the Haug vacuum leak test (i.e., no observable leaks) for all four conditions at a specific seal bar temperature. Thus, the Haug test determines the so-called seal initiation temperature on the VFFS machine (VFFS initiation temperature in Table 10A). In this procedure, an initial suction seal temperature of 100°C is used to evaluate bag success / failure at each of the four conditions, then the seal temperature is increased by 5°C and the test is performed again to evaluate bag success / failure at each of the four conditions. The lowest seal temperature studied where 18 of the 20 bags tested remained sealed (no observable leaks) at all four conditions is the VFFS initiation temperature reported in Table 10A.

[0696] Table 10B

[0697] VFFS Test

[0698]

[0699] Blown film (single layer)

[0700] For the selected ethylene copolymer compositions of the present invention (Inventive Examples 6, 7 and 12) and comparative resins (Comparative Example 3) disclosed herein, blends were prepared from LLDPE materials (SCLAIR FP120-C, 30%:70% by weight). The resin blends were prepared by placing the target weight percentages of each component in a batch mixer and tumbling blending for at least 15 minutes. The resulting blends (the final blend was fed directly into the extruder hopper as a dry blend) were blown into monolayer films using a Gloucester blown film line with a single screw extruder having a 2.5 inch (6.45 cm) barrel diameter, 24 / 1 L / D (barrel length / barrel diameter), the single screw extruder being equipped with: a barrier screw; a 4 inch (10.16 cm) diameter low pressure die with a 35 mil (0.089 cm) die gap; and a Western Polymer Air ring. The die was coated with a polymer processing aid (PPA) to avoid melt fracture by doping the line with a high concentration of PPA masterbatch. The extruder was equipped with the following filter combination: 20 / 40 / 60 / 80 / 20 mesh. Blown films of approximately 1.0 mil (25.4 μm) thick and 2.0 mil (50.8 μm) thick were produced at a 2.5:1 blow ratio (BUR) at a constant output rate of 100 lb / hr (45.4 kg / hr) by adjusting the extruder screw speed; and the frost line height was maintained at 16-18 inches (40.64-45.72 cm) by adjusting the cooling air. The physical properties of the film were obtained using a single-layer 1 mil film produced with a blow ratio (BUR) of 2.5. Cold seal and hot tack curves were obtained using a single-layer 2 mil film (BUR=2.5). The sealing properties of the single-layer blown film prepared as described above are provided in Table 11. The physical properties of the monolayer blown films prepared as described above are provided in Table 12.

[0701] Table 11

[0702] Sealant properties for monolayer blown films

[0703]

[0704] The data provided in Table 11 above is used to show that when used as a blend component (with an LLDPE material) in a monolayer film, Inventive Examples 6, 7, and 12 provide comparable sealing properties (e.g., seal initiation temperature, cold seal strength, hot tack window, and maximum hot tack strength) relative to Comparative Example 3 (which is a resin with similar density and melt index I2).

[0705] Table 12

[0706] Physical properties of single layer blown film

[0707]

[0708] The data provided in Table 12 and Figure 6 It is shown that representative ethylene copolymer compositions of the present disclosure (Inventive Examples 6 and 12) provide a good balance of stiffness (eg 1% secant modulus in MD) and toughness (eg dart impact) properties when blended with LLDPE resin.

[0709] When considered together, all of the above data demonstrate that the ethylene copolymer compositions of the present disclosure have sealing properties comparable to commercially available plastic polyethylenes, while also providing a fast crystallization rate, and a good balance of stiffness and toughness properties.

[0710] Non-limiting embodiments of the present disclosure include the following:

[0711] Embodiment A. An ethylene copolymer composition comprising:

[0712] (i) 15 to 80 wt% of a first ethylene copolymer having a density d1 of 0.855 to 0.913 g / cm 3 ; Molecular weight distribution M w / M n is 1.7-2.7; and the melt index I2 is 0.1-10g / 10min;

[0713] (ii) 85 to 20 weight percent of a second ethylene copolymer having a density d2 of 0.865 to 0.926 g / cm 3 ; Molecular weight distribution M w / M n is 1.7-2.7; and a melt index I2 is 0.1-10 g / 10 min; and

[0714] (iii) 0 to 40 wt% of a third ethylene copolymer having a density d3 of 0.855 to 0.930 g / cm 3 ; Molecular weight distribution M w / M n is 1.7-6.0; and the melt index I2 is 0.1-100g / 10min;

[0715] The density of the ethylene copolymer composition is 0.860-0.902 g / cm 3 ; a melt index I2 of 0.5-10 g / 10 min; and at least 0.0015 parts per million (ppm) of hafnium;

[0716] The number average molecular weight Mn of the first ethylene copolymer is 1 Greater than the number average molecular weight Mn of the second ethylene copolymer 2 ;and

[0717] The weight percent of the first, second or third ethylene copolymer is defined as the weight of the first, second or third ethylene copolymer divided by the sum of the weight of (i) the first ethylene copolymer, (ii) the second ethylene copolymer and (iii) the third ethylene copolymer, multiplied by 100%.

[0718] Embodiment B. The ethylene copolymer composition described in Embodiment A, wherein the number of short chain branches per thousand carbon atoms in the first ethylene copolymer (SCB1) and the number of short chain branches per thousand carbon atoms in the second ethylene copolymer (SCB2) satisfy the following condition: SCB1 / SCB2>0.8.

[0719] Embodiment C. The ethylene copolymer composition of Embodiment A or B, wherein the density of the second ethylene copolymer is equal to or greater than the density of the first ethylene copolymer.

[0720] Embodiment D. The ethylene copolymer composition of Embodiment A, B or C, having a density of less than 0.902 g / cm 3 .

[0721] Embodiment E. The ethylene copolymer composition of Embodiment A, B, C or D, wherein the molecular weight distribution M of each of the first ethylene copolymer and the second ethylene copolymer is w / M n ≤2.3.

[0722] Embodiment F. The ethylene copolymer composition of Embodiment A, B, C, D or E, wherein the molecular weight distribution M of the third ethylene copolymer (if present) is w / M n >2.3.

[0723] Embodiment G. An ethylene copolymer composition according to Embodiment A, B, C, D, E or F, wherein the first ethylene copolymer and the second ethylene copolymer are each prepared by a single site catalyst system comprising a metallocene catalyst having formula (I):

[0724]

[0725] wherein G is a Group 14 element selected from carbon, silicon, germanium, tin or lead; R1 is a hydrogen atom, C 1-20 Hydrocarbon, C 1-20 Alkoxy or C 6-10 Aryl oxide group; R2 and R3 are independently selected from hydrogen atoms, C 1-20 Hydrocarbon, C 1-20 Alkoxy or C 6-10 Aryl oxide group; R4 and R5 are independently selected from hydrogen atoms, unsubstituted C 1-20Hydrocarbon, substituted C 1-20 Hydrocarbon, C 1-20 Alkoxy or C 6-10 an aryl oxide group; and Q is independently an activatable leaving group ligand.

[0726] Embodiment H. An ethylene copolymer composition according to Embodiment A, B, C, D, E, F or G, wherein the composition distribution breadth index CDBI of each of the first ethylene copolymer and the second ethylene copolymer is 50 At least 75% by weight.

[0727] Embodiment I. An ethylene copolymer composition according to Embodiment A, B, C, D, E, F, G or H, wherein the composition distribution breadth index CDBI of the third ethylene copolymer (if present) is 50 Less than 75% by weight.

[0728] Embodiment J. An ethylene copolymer composition according to Embodiment A, B, C, D, E, F, G, H or I having at least 3 mole percent of one or more than one α-olefin.

[0729] Embodiment K. An ethylene copolymer composition according to Embodiment A, B, C, D, E, F, G, H or I having 3 to 12 mole percent of one or more than one α-olefin.

[0730] Embodiment L. The ethylene copolymer composition of Embodiment A, B, C, D, E, F, G, H or I having 3 to 12 mole % 1-octene.

[0731] Embodiment M. An ethylene copolymer composition according to Embodiment A, B, C, D, E, F, G, H, I, J, K or L having 0.050 to 3.5 ppm of hafnium.

[0732] Embodiment N. The ethylene copolymer composition of Embodiment A, B, C, D, E, F, G, H, I, J, K, L or M, wherein the molecular weight distribution M w / M n It is 2.0-4.6.

[0733] Embodiment O. The ethylene copolymer composition of Embodiment A, B, C, D, E, F, G, H, I, J, K, L, M or N, wherein the difference between the density d1 of the first ethylene copolymer and the density d2 of the second ethylene copolymer is less than 0.030 g / cm 3 .

[0734] Embodiment P. The ethylene copolymer composition of Embodiment A, B, D, E, F, G, H, I, J, K, L, M, N or O, wherein the second ethylene copolymer has a higher density than the first ethylene copolymer.

[0735] Embodiment Q. The ethylene copolymer composition of Embodiment A, B, C, D, E, F, G, H, I, J, K, L, M, N, O or P, wherein the third ethylene copolymer has a higher density than the first ethylene copolymer.

[0736] Embodiment R. A film or film layer comprising an ethylene copolymer composition comprising:

[0737] (i) 15 to 80 weight percent of a first ethylene copolymer having a density of 0.855 to 0.913 g / cm 3 ; Molecular weight distribution M w / M n is 1.7-2.7; and the melt index I2 is 0.1-10g / 10min;

[0738] (ii) 85 to 20 weight percent of a second ethylene copolymer having a density of 0.865 to 0.926 g / cm 3 ; Molecular weight distribution M w / M n is 1.7-2.7; and a melt index I2 is 0.1-10 g / 10 min; and

[0739] (iii) 0 to 40 wt% of a third ethylene copolymer having a density of 0.855 to 0.930 g / cm 3 ; Molecular weight distribution M w / M n is 1.7-6.0; and the melt index I2 is 0.1-100g / 10min;

[0740] The density of the ethylene copolymer composition is 0.860-0.902 g / cm 3 ; a melt index I2 of 0.5-10 g / 10 min; and at least 0.0015 parts per million (ppm) of hafnium;

[0741] The number average molecular weight Mn of the first ethylene copolymer is 1 Greater than the number average molecular weight Mn of the second ethylene copolymer 2 ;and

[0742] The weight percent of the first, second or third ethylene copolymer is defined as the weight of the first, second or third ethylene copolymer divided by the sum of the weight of (i) the first ethylene copolymer, (ii) the second ethylene copolymer and (iii) the third ethylene copolymer, multiplied by 100%.

[0743] Embodiment S. A multilayer film structure comprising at least one film layer comprising an ethylene copolymer composition comprising:

[0744] (i) 15 to 80 weight percent of a first ethylene copolymer having a density of 0.855 to 0.913 g / cm 3 ; Molecular weight distribution M w / M n is 1.7-2.7; and the melt index I2 is 0.1-10g / 10min;

[0745] (ii) 85 to 20 weight percent of a second ethylene copolymer having a density of 0.865 to 0.926 g / cm 3 ; Molecular weight distribution M w / M n is 1.7-2.7; and a melt index I2 is 0.1-10 g / 10 min; and

[0746] (iii) 0 to 40 wt% of a third ethylene copolymer having a density of 0.855 to 0.930 g / cm 3 ; Molecular weight distribution M w / M n is 1.7-6.0; and the melt index I2 is 0.1-100g / 10min;

[0747] The density of the ethylene copolymer composition is 0.860-0.902 g / cm 3 ; a melt index I2 of 0.5-10 g / 10 min; and at least 0.0015 parts per million (ppm) of hafnium;

[0748] The number average molecular weight Mn of the first ethylene copolymer is 1 Greater than the number average molecular weight Mn of the second ethylene copolymer 2 ;and

[0749] The weight percent of the first, second or third ethylene copolymer is defined as the weight of the first, second or third ethylene copolymer divided by the sum of the weight of (i) the first ethylene copolymer, (ii) the second ethylene copolymer and (iii) the third ethylene copolymer, multiplied by 100%.

[0750] Embodiment T. A film or film layer comprising a polymer blend comprising:

[0751] (a) 5 to 50 wt% of an ethylene copolymer composition; and

[0752] (b) 95-50 wt. % linear low density polyethylene;

[0753] wherein the ethylene copolymer composition comprises:

[0754] (i) 15 to 80 weight percent of a first ethylene copolymer having a density of 0.855 to 0.913 g / cm 3 ; Molecular weight distribution M w / M n is 1.7-2.7; and the melt index I2 is 0.1-10g / 10min;

[0755] (ii) 85 to 20 weight percent of a second ethylene copolymer having a density of 0.865 to 0.926 g / cm 3 ; Molecular weight distribution M w / M n is 1.7-2.7; and a melt index I2 is 0.1-10 g / 10 min; and

[0756] (iii) 0 to 40 wt% of a third ethylene copolymer having a density of 0.855 to 0.930 g / cm 3 ; Molecular weight distribution M w / M n is 1.7-6.0; and the melt index I2 is 0.1-100g / 10min;

[0757] The density of the ethylene copolymer composition is 0.860-0.902 g / cm 3 ; a melt index I2 of 0.5-10 g / 10 min; and at least 0.0015 parts per million (ppm) of hafnium;

[0758] The number average molecular weight Mn of the first ethylene copolymer is 1 Greater than the number average molecular weight Mn of the second ethylene copolymer 2 ;and

[0759] The weight percent of the first, second or third ethylene copolymer is defined as the weight of the first, second or third ethylene copolymer divided by the sum of the weight of (i) the first ethylene copolymer, (ii) the second ethylene copolymer and (iii) the third ethylene copolymer, multiplied by 100%.

[0760] Embodiment U. A multilayer film structure comprising at least one film layer, the film layer comprising a polymer blend comprising:

[0761] (a) 5 to 50 wt% of an ethylene copolymer composition; and

[0762] (b) 95-50 wt. % linear low density polyethylene;

[0763] wherein the ethylene copolymer composition comprises:

[0764] (i) 15 to 80 weight percent of a first ethylene copolymer having a density of 0.855 to 0.913 g / cm 3 ; Molecular weight distribution M w / M n is 1.7-2.7; and the melt index I2 is 0.1-10g / 10min;

[0765] (ii) 85 to 20 weight percent of a second ethylene copolymer having a density of 0.865 to 0.926 g / cm 3 ; Molecular weight distribution M w / M n is 1.7-2.7; and a melt index I2 is 0.1-10 g / 10 min; and

[0766] (iii) 0 to 40 wt% of a third ethylene copolymer having a density of 0.855 to 0.930 g / cm 3 ; Molecular weight distribution M w / M n is 1.7-6.0; and the melt index I2 is 0.1-100g / 10min;

[0767] The density of the ethylene copolymer composition is 0.860-0.902 g / cm 3 ; a melt index I2 of 0.5-10 g / 10 min; and at least 0.0015 parts per million (ppm) of hafnium;

[0768] The number average molecular weight Mn of the first ethylene copolymer is 1 Greater than the number average molecular weight Mn of the second ethylene copolymer 2 ;and

[0769] The weight percent of the first, second or third ethylene copolymer is defined as the weight of the first, second or third ethylene copolymer divided by the sum of the weight of (i) the first ethylene copolymer, (ii) the second ethylene copolymer and (iii) the third ethylene copolymer, multiplied by 100%.

[0770] Industrial Applicability

[0771] An ethylene copolymer composition is provided having a density of 0.902 g / cm 3 or less, and it comprises a first ethylene copolymer, a second ethylene copolymer and optionally a third ethylene copolymer. The ethylene copolymer composition having a high crystallization rate can be converted into a blown film having good sealability and balanced toughness and stiffness.

Claims

1. An ethylene copolymer composition comprising: (i) 15 to 80 wt% of a first ethylene copolymer having a density d1 of 0.855 to 0.913 g / cm 3 ; Molecular weight distribution M w / M n is 1.7-2.7; and the melt index I2 is 0.1-10g / 10min; (ii) 85 to 20 weight percent of a second ethylene copolymer having a density d2 of 0.865 to 0.926 g / cm 3 ; Molecular weight distribution M w / M n is 1.7-2.7; and a melt index I2 is 0.1-10 g / 10 min; and (iii) 0 to 40 wt% of a third ethylene copolymer having a density d3 of 0.855 to 0.930 g / cm 3 ; Molecular weight distribution M w / M n is 1.7-6.0; and the melt index I2 is 0.1-100g / 10min; The density of the ethylene copolymer composition is 0.860-0.902 g / cm 3 ; a melt index I2 of 0.5-10 g / 10 min; and at least 0.0015 parts per million (ppm) of hafnium; The number average molecular weight Mn of the first ethylene copolymer is 1 Greater than the number average molecular weight Mn of the second ethylene copolymer 2 ; and The weight percent of the first, second or third ethylene copolymer is defined as the weight of the first, second or third ethylene copolymer divided by the sum of the weight of (i) the first ethylene copolymer, (ii) the second ethylene copolymer and (iii) the third ethylene copolymer, multiplied by 100%.

2. The ethylene copolymer composition of claim 1, wherein the number of short chain branches per thousand carbon atoms (SCB1) in the first ethylene copolymer and the number of short chain branches per thousand carbon atoms (SCB2) in the second ethylene copolymer satisfy the following condition: SCB1 / SCB2>0.

8.

3. The ethylene copolymer composition of claim 1, wherein the density of the second ethylene copolymer is equal to or greater than the density of the first ethylene copolymer.

4. The ethylene copolymer composition of claim 1, having a density lower than 0.902 g / cm 3 .

5. The ethylene copolymer composition of claim 1, wherein the molecular weight distribution M of each of the first ethylene copolymer and the second ethylene copolymer is w / M n ≤2.

3.

6. The ethylene copolymer composition according to claim 1, wherein The molecular weight distribution M of the third ethylene copolymer, if present, is w / M n >2.

3.

7. The ethylene copolymer composition of claim 1, wherein the first ethylene copolymer and the second ethylene copolymer are each prepared by a single site catalyst system comprising a metallocene catalyst having formula (I): wherein G is a Group 14 element selected from carbon, silicon, germanium, tin or lead; R1 is a hydrogen atom, C 1-20 Hydrocarbon, C 1-20 Alkoxy or C 6-10 Aryl oxide group; R2 and R3 are independently selected from hydrogen atoms, C 1-20 Hydrocarbon, C 1-20 Alkoxy or C 6-10 Aryl oxide group; R4 and R5 are independently selected from hydrogen atoms, unsubstituted C 1-20 Hydrocarbon, substituted C 1-20 Hydrocarbon, C 1-20 Alkoxy or C 6-10 an aryl oxide group; and Q is independently an activatable leaving group ligand.

8. The ethylene copolymer composition according to claim 1, wherein the composition distribution breadth index (CDBI) of each of the first ethylene copolymer and the second ethylene copolymer is 50 At least 75% by weight.

9. The ethylene copolymer composition according to claim 1, wherein The composition distribution breadth index CDBI of the third ethylene copolymer, if present, 50 Less than 75% by weight.

10. The ethylene copolymer composition of claim 1 having at least 3 mole % of one or more than one α-olefin.

11. The ethylene copolymer composition of claim 1 having 3-12 mol% of one or more than one α-olefin.

12. The ethylene copolymer composition of claim 1 having 3 to 12 mol% of 1-octene.

13. The ethylene copolymer composition of claim 1 having 0.050-3.5 ppm of hafnium.

14. The ethylene copolymer composition according to claim 1, wherein the molecular weight distribution M w / M n It is 2.0-4.

6.

15. The ethylene copolymer composition of claim 1, wherein the difference between the density d1 of the first ethylene copolymer and the density d2 of the second ethylene copolymer is less than 0.030 g / cm 3 .

16. The ethylene copolymer composition of claim 1, wherein the second ethylene copolymer has a higher density than the first ethylene copolymer.

17. The ethylene copolymer composition of claim 1, wherein the third ethylene copolymer has a higher density than the first ethylene copolymer.

18. A film or film layer comprising an ethylene copolymer composition comprising: (i) 15 to 80 weight percent of a first ethylene copolymer having a density of 0.855 to 0.913 g / cm 3 ; Molecular weight distribution M w / M n is 1.7-2.7; and the melt index I2 is 0.1-10g / 10min; (ii) 85 to 20 weight percent of a second ethylene copolymer having a density of 0.865 to 0.926 g / cm 3 ; Molecular weight distribution M w / M n is 1.7-2.7; and a melt index I2 is 0.1-10 g / 10 min; and (iii) 0 to 40 wt% of a third ethylene copolymer having a density of 0.855 to 0.930 g / cm 3 ; Molecular weight distribution M w / M n is 1.7-6.0; and the melt index I2 is 0.1-100g / 10min; The density of the ethylene copolymer composition is 0.860-0.902 g / cm 3 ; a melt index I2 of 0.5-10 g / 10 min; and at least 0.0015 parts per million (ppm) of hafnium; The number average molecular weight Mn of the first ethylene copolymer is 1 Greater than the number average molecular weight Mn of the second ethylene copolymer 2 ;and The weight percent of the first, second or third ethylene copolymer is defined as the weight of the first, second or third ethylene copolymer divided by the sum of the weight of (i) the first ethylene copolymer, (ii) the second ethylene copolymer and (iii) the third ethylene copolymer, multiplied by 100%.

19. A multilayer film structure comprising at least one film layer, said film layer comprising an ethylene copolymer composition comprising: (i) 15 to 80 weight percent of a first ethylene copolymer having a density of 0.855 to 0.913 g / cm 3 ; Molecular weight distribution M w / M n is 1.7-2.7; and the melt index I2 is 0.1-10g / 10min; (ii) 85 to 20 weight percent of a second ethylene copolymer having a density of 0.865 to 0.926 g / cm 3 ; Molecular weight distribution M w / M n is 1.7-2.7; and a melt index I2 is 0.1-10 g / 10 min; and (iii) 0 to 40 wt% of a third ethylene copolymer having a density of 0.855 to 0.930 g / cm 3 ; Molecular weight distribution M w / M n is 1.7-6.0; and the melt index I2 is 0.1-100g / 10min; The density of the ethylene copolymer composition is 0.860-0.902 g / cm 3 ; a melt index I2 of 0.5-10 g / 10 min; and at least 0.0015 parts per million (ppm) of hafnium; The number average molecular weight Mn of the first ethylene copolymer is 1 Greater than the number average molecular weight Mn of the second ethylene copolymer 2 ;and The weight percent of the first, second or third ethylene copolymer is defined as the weight of the first, second or third ethylene copolymer divided by the sum of the weight of (i) the first ethylene copolymer, (ii) the second ethylene copolymer and (iii) the third ethylene copolymer, multiplied by 100%.

20. A film or film layer comprising a polymer blend, the polymer blend comprising: (a) 5 to 50 wt% of an ethylene copolymer composition; and (b) 95-50 wt. % linear low density polyethylene; wherein the ethylene copolymer composition comprises: (i) 15 to 80 weight percent of a first ethylene copolymer having a density of 0.855 to 0.913 g / cm 3 ; Molecular weight distribution M w / M n is 1.7-2.7; and the melt index I2 is 0.1-10g / 10min; (ii) 85 to 20 weight percent of a second ethylene copolymer having a density of 0.865 to 0.926 g / cm 3 ; Molecular weight distribution M w / M n is 1.7-2.7; and a melt index I2 is 0.1-10 g / 10 min; and (iii) 0 to 40 wt% of a third ethylene copolymer having a density of 0.855 to 0.930 g / cm 3 ; Molecular weight distribution M w / M n is 1.7-6.0; and the melt index I2 is 0.1-100g / 10min; The density of the ethylene copolymer composition is 0.860-0.902 g / cm 3 ; a melt index I2 of 0.5-10 g / 10 min; and at least 0.0015 parts per million (ppm) of hafnium; The number average molecular weight Mn of the first ethylene copolymer is 1 Greater than the number average molecular weight Mn of the second ethylene copolymer 2 ;and The weight percent of the first, second or third ethylene copolymer is defined as the weight of the first, second or third ethylene copolymer divided by the sum of the weight of (i) the first ethylene copolymer, (ii) the second ethylene copolymer and (iii) the third ethylene copolymer, multiplied by 100%.

21. A multilayer film structure comprising at least one film layer, the film layer comprising a polymer blend, the polymer blend comprising: (a) 5 to 50 wt% of an ethylene copolymer composition; and (b) 95-50 wt. % linear low density polyethylene; wherein the ethylene copolymer composition comprises: (i) 15 to 80 weight percent of a first ethylene copolymer having a density of 0.855 to 0.913 g / cm 3 ; Molecular weight distribution M w / M n is 1.7-2.7; and the melt index I2 is 0.1-10g / 10min; (ii) 85 to 20 weight percent of a second ethylene copolymer having a density of 0.865 to 0.926 g / cm 3 ; Molecular weight distribution M w / M n is 1.7-2.7; and a melt index I2 is 0.1-10 g / 10 min; and (iii) 0 to 40 wt% of a third ethylene copolymer having a density of 0.855 to 0.930 g / cm 3 ; Molecular weight distribution M w / M n is 1.7-6.0; and the melt index I2 is 0.1-100g / 10min; The density of the ethylene copolymer composition is 0.860-0.902 g / cm 3 ; a melt index I2 of 0.5-10 g / 10 min; and at least 0.0015 parts per million (ppm) of hafnium; The number average molecular weight Mn of the first ethylene copolymer is 1 Greater than the number average molecular weight Mn of the second ethylene copolymer 2 ;and The weight percent of the first, second or third ethylene copolymer is defined as the weight of the first, second or third ethylene copolymer divided by the sum of the weight of (i) the first ethylene copolymer, (ii) the second ethylene copolymer and (iii) the third ethylene copolymer, multiplied by 100%.

Images