Ethylene / α-olefin copolymer composition and film

Abstract

The present invention provides an ethylene / α-olefin copolymer composition comprising at least two distinguishable ethylene / α-olefin copolymer components with defined structural features. The ethylene / α-olefin copolymer composition has a melt index I2 of about 2.5 to about 6 dg / min and a density of about 0.860 to about 0.910 g / cm3. The ethylene / α-olefin copolymer composition has a zero shear viscosity η0 at 190°C, a VICAT softening temperature VSP, and a short-chain branching content SCB satisfying (I). The provided ethylene / α-olefin copolymer composition can be advantageously used in high-speed vertical and horizontal molding-filling-sealing processes and in film applications requiring sealing properties to block contaminants.

Description

Technology Field

[0001] The present disclosure generally relates to an ethylene / α-olefin copolymer composition and a film prepared therefrom. The ethylene / α-olefin copolymer composition comprises at least two distinguishable ethylene / α-olefin copolymer components having defined structural features. Background Technology

[0002] Devolatilization using stripping agents such as air, nitrogen, and gaseous hydrocarbons is a known technique for removing volatile hydrocarbon residues (e.g., unreacted monomers) from solid polymer particles in the finishing area of ​​a polymerization plant.

[0003] It is known to those with general experience that heating polymer particles is desirable to accelerate the desorption process of hydrocarbon residues and to reduce the residence time required to strip polymer particles from hydrocarbon residues. However, there is an upper limit to the devolatilization temperature for a given polymer composition, and above this temperature, polymer particles begin to soften and form aggregates, which can block the devolatilization device. Consequently, to accelerate the devolatilization rate, there is still a need to develop polymer compositions that delay softening and deformation under devolatilization conditions, thereby slowing down the initiation of polymer particle aggregate formation.

[0004] Existing approaches to addressing the requirements for polymer compositions with delayed softening generally involve sacrificing performance characteristics in end-use applications requiring melt fluidity and rapid self-diffusion, such as heat sealing applications requiring contaminant barrier sealing properties.

[0005] In a first aspect, an ethylene / α-olefin copolymer composition comprising the following is provided:

[0006] About 30 to about 50 weight% of a first ethylene / α-olefin copolymer, wherein the short-chain branching content is about 15 to about 40 branches per 1,000 carbon atoms, SCB 1 , weight average molecular weight of about 80 kg / mol to about 140 kg / mol, Mw 1 , and polyvariance indices of about 1.7 to about 2.3, M w 1 / M n 1 A first ethylene / α-olefin copolymer having; and

[0007] About 50 to about 70 weight% of a second ethylene / α-olefin copolymer, wherein the short-chain branching content is about 10 to about 35 branches per 1,000 carbon atoms, SCB 2 , weight-average molecular weight of about 20 kg / mol to about 60 kg / mol Mw 2 , and polyvariance indices of about 1.7 to about 2.3, M w 2 / M n 2 A second ethylene / α-olefin copolymer having

[0008] Here, the short-chain branching content of the first ethylene / α-olefin copolymer, SCB 1 The short-chain branching content of the second ethylene / α-olefin copolymer, SCB 2 Greater than or equal to;

[0009] The ethylene / α-olefin copolymer composition has a melt index I2 of about 2.5 to about 6 dg / min, measured using a weight of 2.16 kg at 190°C according to ASTM D1238, and a density of about 0.860 to about 0.910 g / cm³, measured according to ASTM D792. 3 is;

[0010] The ethylene / α-olefin copolymer composition has a zero shear viscosity at 190°C satisfying (I) η 0, VICAT softening temperature measured according to ASTM D1525 VSP , and short-chain branch content measured according to ASTM D6645 SCB has:

[0011]

[0012] In some embodiments of the first aspect, the ethylene / α-olefin copolymer composition has a VSP of about 70°C to about 100°C or about 80°C to about 95°C.

[0013] In some embodiments of the first aspect, the ethylene / α-olefin copolymer composition has a density of about 0.885 to about 0.910 g / cm³ or about 0.900 to about 0.910 g / cm³.

[0014] In some embodiments of the first aspect, the ethylene / α-olefin copolymer composition has a melt index, I2, of about 3 to about 6 dg / min or about 4 to about 6 dg / min.

[0015] In some embodiments of the first aspect, the ethylene / α-olefin copolymer composition satisfies the following (II). η 0, VSP and SCB has:

[0016]

[0017] In some embodiments of the first aspect, the ethylene / α-olefin copolymer composition has a monomodified molecular weight distribution.

[0018] In some embodiments of the first aspect, the ethylene / α-olefin copolymer composition has a polydispersity index M w / M n It has a molecular weight distribution of about 2.1 to about 4.

[0019] In some embodiments of the first aspect, the first ethylene / α-olefin copolymer and the second ethylene / α-olefin copolymer are M w 1 big M w 2 The ratio is about 2 to about 3.

[0020] In some embodiments of the first aspect, the short-chain branching content of the first ethylene / α-olefin copolymer and the second ethylene / α-olefin copolymer, SCB 1 and SCB 2 Is SCB 1 > SCB 2 Satisfies.

[0021] In some embodiments of the first aspect, the short-chain branching content of the first ethylene / α-olefin copolymer and the second ethylene / α-olefin copolymer, SCB 1 and SCB 2 Is SCB 1 > SCB 2 Satisfying the above; the ethylene / α-olefin copolymer composition has a comonomer distribution profile in GPC-FTIR analysis, and this comonomer distribution profile has a secant slope from about +1 short chain branch per 1000 carbons to about +30 short chain branches per 1000 carbons, where the secant slope is defined as the value obtained by subtracting the number of short chain branches per 1000 carbons at a molecular weight of 30 kg / mol from the number of short chain branches per 1000 carbons at a molecular weight of 30 kg / mol.

[0022] In some embodiments of the first aspect, the short-chain branching content of the first ethylene / α-olefin copolymer and the second ethylene / α-olefin copolymer, SCB 1 and SCB 2 Is SCB 1 > SCB 2Satisfying the above; the ethylene / α-olefin copolymer composition has a reversed-phase comonomer distribution profile in GPC-FTIR analysis, and this comonomer distribution profile has a secant slope from about +1 short chain branch per 1000 carbons to about +30 short chain branches per 1000 carbons, where the secant slope is defined as the number of short chain branches per 1000 carbons at a molecular weight of 300 kg / mol minus the number of short chain branches per 1000 carbons at a molecular weight of 30 kg / mol.

[0023] In some embodiments of the first aspect, the ethylene / α-olefin copolymer composition comprises a fraction that elutes in a temperature range of 90°C to 105°C having an integrated area of ​​less than 1 weight% in CTREF analysis.

[0024] In some embodiments of the first aspect, the ethylene / α-olefin copolymer composition contains long chain branching at a detectable level of 0.001 or more, as measured by the long chain branching factor, LCBF.

[0025] In some embodiments of the first aspect, the ethylene / α-olefin copolymer composition is C3 to C 10 It includes at least one α-olefin selected from the group consisting of α-olefins.

[0026] In some embodiments of the first aspect, the ethylene / α-olefin copolymer composition comprises at least one α-olefin selected from the group consisting of hexene-1, octene-1, and mixtures thereof.

[0027] In some embodiments of the first aspect, the ethylene / α-olefin copolymer composition essentially consists of ethylene and octene-1.

[0028] In a second aspect, a film layer comprising an ethylene / α-olefin copolymer composition defined in a first aspect is provided.

[0029] In a third aspect, a multilayer film structure is provided, the film structure having at least one skin layer, wherein at least one skin layer comprises an ethylene / α-olefin copolymer composition defined in a first aspect.

[0030] In some embodiments of the third aspect, at least one outer layer is a sealant layer.

[0031] In some embodiments of the third aspect, the film structure has a sealing start temperature of about 70°C to 100°C, where the sealing start temperature is the minimum sealing temperature at which the film structure has a sealing strength greater than 8.8 N per sealing width of 25.4 mm.

[0032] In some embodiments of the third aspect, the film structure has a peak hot tack force greater than about 6 N.

[0033] In a fourth aspect, an ethylene / α-olefin copolymer composition comprising the following is provided:

[0034] About 30 to about 50 weight% of a first ethylene / α-olefin copolymer, wherein the first ethylene / α-olefin copolymer has a short-chain branching content of about 15 to about 40 branches per 1,000 carbon atoms, SCB 1 , weight average molecular weight of about 80 kg / mol to about 140 kg / mol, Mw 1 , and polyvariance indices of about 1.7 to about 2.3, Mw 1 / Mn 1 A first ethylene / α-olefin copolymer having

[0035] About 50 to about 70 weight% of a second ethylene / α-olefin copolymer, wherein the second ethylene / α-olefin copolymer has a short-chain branching content of about 10 to about 35 branches per 1,000 carbon atoms, SCB 2, weight average molecular weight of about 20 kg / mol to about 60 kg / mol, Mw 2 , and polyvariance indices of about 1.7 to about 2.3, Mw 2 / Mn 2 A second ethylene / α-olefin copolymer having

[0036] Here, the short-chain branching content of the first ethylene / α-olefin copolymer, SCB 1 The short-chain branching content of the second ethylene / α-olefin copolymer, SCB 2 Greater than or equal to;

[0037] The ethylene / α-olefin copolymer composition has a melt index I2 of about 2.5 to about 6 dg / min, measured using a weight of 2.16 kg at 190°C according to ASTM D1238, and a density of about 0.860 to about 0.910 g / cm³, measured according to ASTM D792. 3 is;

[0038] The ethylene / α-olefin copolymer composition includes a fraction that elutes at a temperature range of 90°C to 105°C, in which the integrated area in CTREF analysis is less than 1 weight%.

[0039] In some embodiments of the fourth aspect, the ethylene / α-olefin copolymer composition has a VSP of about 70°C to about 100°C or about 80°C to about 95°C.

[0040] In some embodiments of the fourth aspect, the ethylene / α-olefin copolymer composition has a density of about 0.885 to about 0.910 g / cm³ or about 0.900 to about 0.910 g / cm³.

[0041] In some embodiments of the fourth aspect, the ethylene / α-olefin copolymer composition has a melt index I2 of about 3 to about 6 dg / min or about 4 to about 6 dg / min.

[0042] In some embodiments of the fourth aspect, the ethylene / α-olefin copolymer composition has a zero shear viscosity at 190°C satisfying (I) below η 0, VICAT softening temperature measured according to ASTM D1525 VSP , and short-chain branch content measured according to ASTM D6645 SCB has:

[0043]

[0044] In some embodiments of the fourth aspect, the ethylene / α-olefin copolymer composition has a zero shear viscosity at 190°C satisfying (II), VSP and SCB has:

[0045]

[0046] In some embodiments of the first aspect, the ethylene / α-olefin copolymer composition has a monomodified molecular weight distribution.

[0047] In some embodiments of the fourth aspect, the ethylene / α-olefin copolymer composition has a polydispersity index M w / M n It has a molecular weight distribution of about 2.1 to about 4.

[0048] In some embodiments of the fourth aspect, the first ethylene / α-olefin copolymer and the second ethylene / α-olefin copolymer are M w 1 big M w 2 The ratio is about 2 to about 3.

[0049] In some embodiments of the fourth aspect, the short-chain branching content of the first ethylene / α-olefin copolymer and the second ethylene / α-olefin copolymer, SCB 1 and SCB 2 Is SCB 1 > SCB 2 Satisfies.

[0050] In some embodiments of the fourth aspect, the short-chain branching content of the first ethylene / α-olefin copolymer and the second ethylene / α-olefin copolymer, SCB 1 and SCB 2 Is SCB 1 > SCB 2 Satisfying the above; the ethylene / α-olefin copolymer composition has a comonomer distribution profile in GPC-FTIR analysis, and this comonomer distribution profile has a secant slope from about +1 short chain branch per 1000 carbons to about +30 short chain branches per 1000 carbons, where the secant slope is defined as the value obtained by subtracting the number of short chain branches per 1000 carbons at a molecular weight of 30 kg / mol from the number of short chain branches per 1000 carbons at a molecular weight of 30 kg / mol.

[0051] In some embodiments of the fourth aspect, the short-chain branching content of the first ethylene / α-olefin copolymer and the second ethylene / α-olefin copolymer, SCB 1 and SCB 2 Is SCB 1 > SCB 2 Satisfying the above; the ethylene / α-olefin copolymer composition has a reversed-phase comonomer distribution profile in GPC-FTIR analysis, and this comonomer distribution profile has a secant slope ranging from about +1 short-chain branch per 1000 carbons to about +30 short-chain branches per 1000 carbons, where the secant slope is defined as the number of short-chain branches per 1000 carbons at a molecular weight of 300 kg / mol minus the number of short-chain branches per 1000 carbons at a molecular weight of 30 kg / mol.

[0052] In some embodiments of the fourth aspect, the ethylene / α-olefin copolymer composition contains a detectable level of long chain branching of 0.001 or more when measured according to the long chain branching factor, LCBF.

[0053] In some embodiments of the fourth aspect, the ethylene / α-olefin copolymer composition is C3 to C 10 It includes at least one α-olefin selected from the group consisting of α-olefins.

[0054] In some embodiments of the fourth aspect, the ethylene / α-olefin copolymer composition comprises at least one α-olefin selected from the group consisting of hexene-1, octene-1, and mixtures thereof.

[0055] In some embodiments of the fourth aspect, the ethylene / α-olefin copolymer composition essentially consists of ethylene and octene-1.

[0056] In a fifth aspect, a film layer comprising an ethylene / α-olefin copolymer composition defined in a fourth aspect is provided.

[0057] In a sixth aspect, a multilayer film structure is provided, the film structure comprising at least one outer layer, and at least one outer layer comprises an ethylene / α-olefin copolymer composition defined in a fourth aspect.

[0058] In some embodiments of the sixth aspect, at least one outer layer is a sealant layer.

[0059] In some embodiments of the sixth aspect, the film structure has a sealing start temperature of about 70°C to 100°C, where the sealing start temperature is the minimum sealing temperature at which the film structure has a sealing strength greater than 8.8 N per sealing width of 25.4 mm.

[0060] In some embodiments of the sixth aspect, the film structure has a peak hot tack force greater than about 6 N.

[0061] Definition of Terms

[0062] Except in the examples or as otherwise specified, any number or expression referring to the amount of ingredients, extrusion conditions, etc. used in the specification and claims shall be understood as being modified in all cases by the term "about."

[0063] Accordingly, unless otherwise specified, the numerical parameters set forth in the following specification and appended claims are approximations that may vary depending on the desired characteristics that various embodiments seek to obtain.

[0064] At a minimum, and not in an attempt to limit the scope of the doctrine of equivalents to the scope of the claim, each numeric parameter must be interpreted by applying the reported number of significant figures and general rounding techniques.

[0065] The numerical values ​​presented in specific embodiments are reported as accurately as possible. However, any numerical value contains a certain error that inevitably arises due to the standard deviation found in the corresponding test measurement.

[0066] Any numerical range specified herein should be understood to include all sub-ranges contained therein. For example, the range “1 to 10” should be interpreted to include all sub-ranges between the listed minimum value 1 and the listed maximum value 10; that is, the minimum value is 1 or greater and the maximum value is 10 or less. Since the disclosed numerical ranges are continuous, they include all values ​​between the minimum and maximum values. Unless expressly otherwise indicated, the various numerical ranges specified in this application are approximations.

[0067] All composition ranges specified herein are limited to a total amount of 100% (volume percentage or weight percentage) and do not actually exceed 100%. Where multiple components may be present in the composition, the sum of the maximum amounts of each component may exceed 100%, but it is assumed that, as will be readily understood by those skilled in the art, the amount of the component actually used complies with a maximum of 100%.

[0068] To ensure a more complete understanding of the present disclosure, the following terms are defined and should be used in conjunction with the description of various embodiments.

[0069] As used herein, the term "monomer" refers to a small molecule capable of chemically reacting with itself or other monomers to form a polymer. As used herein, the terms "α-olefin" or "alpha-olefin" refer to a molecule having a double bond at one end of a chain. n = Contains 3 to 20 carbon atoms and has a chemical formula C n H 2n It is used to describe monomers having linear hydrocarbon chains; the equivalent term is "linear α-olefin".

[0070] As used herein, the terms “polyethylene,” “polyethylene polymer,” or “ethylene polymer” refer to macromolecules formed from ethylene monomers and optionally at least one α-olefin monomer; regardless of the specific catalyst or specific process used to produce the ethylene polymer. The polymerized form of the ethylene polymer will contain more than 50 weight percent (based on the weight of the ethylene polymer) of ethylene monomers. Common polyethylenes include high-density polyethylene (HDPE), medium-density polyethylene (MDPE), linear low-density polyethylene (LLDPE), very low-density polyethylene (VLDPE), very low-density polyethylene (ULDPE), plastomers, and elastomers. The term polyethylene also includes combinations or blends of the polyethylenes described above.

[0071] The term "ethylene homopolymer" as used herein refers to a subset of polymers within the group of "ethylene polymers" produced using only ethylene as a polymerizable monomer.

[0072] The term "ethylene / α-olefin copolymer" refers to a subset of polymers within the group of "ethylene polymers" produced from ethylene and at least one α-olefin. Accordingly, as used herein, the term "ethylene / α-olefin copolymer" includes ethylene polymers produced from two polymerizable monomer units (i.e., ethylene and one α-olefin) and ethylene polymers produced from more than two polymerizable monomer units (i.e., ethylene and two or more α-olefins).

[0073] The term "heterogeneous branched ethylene / α-olefin copolymer" refers to a subset of ethylene copolymers produced using heterogeneous catalytic systems; non-limiting examples include Ziegler-Natta catalysts or chromium catalysts, both of which are well known in the art.

[0074] The term “homogeneous branched ethylene / α-olefin copolymer” refers to a subset of the group of ethylene copolymers produced using monosite catalysts; non-limiting examples include metallocene catalysts, phosphineimine catalysts, and catalysts with limited geometry, all of which are well known in the art.

[0075] Typically, homogeneous branched ethylene copolymers have a narrow molecular weight distribution, for example, gel permeation chromatography (GPC) M w / M n The value is less than approximately 2.8, specifically less than approximately 2.3, but exceptions may exist; where M w and M n refer to the weight-average molecular weight and the number-average molecular weight, respectively. On the other hand, M of the heterogeneous branched ethylene copolymer w / M n is typically M of a homogeneous branched ethylene copolymer w / M n It is larger than

[0076] Generally, homogeneous branched ethylene / α-olefin copolymers also have a narrow compositional distribution, that is, each macromolecule within the molecular weight distribution has a similar α-olefin comonomer content.

[0077] Weight-average molecular weight (M w A blend of two or more homogeneous branched ethylene / α-olefin copolymers with different characteristics is M w / M n This can be 2.8 or higher.

[0078] The term “thermoplastic polymer” refers to a polymer that becomes liquid when heated, flows when pressure is applied, and solidifies when cooled. Thermoplastic polymers include not only ethylene polymers but also other polymers used in the plastics industry; non-limiting examples of other polymers commonly used for film applications include barrier resins (e.g., EVOH), adhesive resins, polyethylene terephthalate (PET), polyamides, ethylene-vinyl acetate copolymer (EVA), etc.

[0079] The term "single-layer film" as used herein refers to a film containing a single layer of one or more thermoplastic polymers.

[0080] As used herein, the terms “multilayer film” or “multilayer film structure” refer to a film composed of one or more thermoplastic layers or optionally non-thermoplastic layers. Non-limiting examples of non-thermoplastic materials include metal (foil) or cellulose (paper) products. One or more thermoplastic layers within the multilayer film (or film structure) may be composed of one or more thermoplastic resins.

[0081] The term "adhesive resin" as used herein refers to a thermoplastic resin that promotes adhesion between adjacent film layers of different chemical compositions when formed as an intermediate layer or "adhesive layer" within a multilayer film structure.

[0082] The term "sealing layer" as used herein refers to a thermoplastic film layer that can be attached to a second substrate to form a leak-proof seal. The "sealing layer" may be an outer layer or an innermost layer of a multilayer film structure.

[0083] The terms “adhesive lamination” and “extrusion lamination” as used herein describe a continuous process in which two or more substrates or material webs are combined to form a multilayer product or sheet; wherein the two or more webs are each bonded using an adhesive or a molten thermoplastic film.

[0084] As used herein, the term “extrusion coating” describes a continuous process in which a molten thermoplastic layer is combined with or deposited upon a moving solid web or substrate. Non-limiting examples of substrates include paper, cardboard, foil, single-layer plastic film, multi-layer plastic film, or fabric. The molten thermoplastic layer may be single-layer or multi-layer.

[0085] As used herein, the terms “hydrocarbon,” “hydrocarbon radical,” or “hydrocarbon group” refer to linear or cyclic, aliphatic, olefinic, acetyleneic, and aryl (aromatic) radicals comprising hydrogen and a carbon lacking one hydrogen.

[0086] As used herein, the term “alkyl radical” includes linear, branched, and cyclic paraffin radicals lacking one hydrogen radical; non-limiting examples include methyl (-CH3) and ethyl (-CH2CH3) radicals. The term “alkenyl radical” refers to linear, branched, and cyclic hydrocarbons containing at least one carbon-carbon double bond lacking one hydrogen radical.

[0087] As used herein, the term “aryl” group includes phenyl, naphthyl, pyridyl, and other radicals having molecules with an aromatic ring structure; non-limiting examples include naphthylene, phenanthrene, and anthracene. The “arylalkyl” group is an alkyl group with an aryl group attached; non-limiting examples include benzyl, phenethyl, and tolylmethyl; and the “alkylaryl” is an aryl group with one or more alkyl groups attached; non-limiting examples include tolyl, xylyl, mesithyl, and cumyl.

[0088] As used herein, the term “heteroatom” includes carbon and any other atom other than hydrogen that can be bonded to carbon. “Heteroatom-containing group” is a hydrocarbon radical containing a heteroatom and may contain one or more of the same or different heteroatoms. In one embodiment, the heteroatom-containing group is a hydrocarbon group containing one to three atoms selected from the group consisting of boron, aluminum, silicon, germanium, nitrogen, phosphorus, oxygen, and sulfur. Non-limiting examples of heteroatom-containing groups include radicals such as imines, amines, oxides, phosphines, ethers, ketones, oxoazoline heterocyclic compounds, oxazolines, and thioethers. The term “heterocyclic” refers to a ring system having a carbon main chain containing one to three atoms selected from the group consisting of boron, aluminum, silicon, germanium, nitrogen, phosphorus, oxygen, and sulfur.

[0089] As used herein, the term “non-substituted” means that a hydrogen radical is bonded to the molecular group following the term “non-substituted.” The term “substituted” means that the group following this term possesses one or more moietyes (non-hydrogen radicals) that have replaced one or more hydrogen radicals at any position within this group; non-limiting examples of moietyes include halogen radicals (F, Cl, Br), hydroxyl groups, carbonyl groups, carboxyl groups, silyl groups, amine groups, phosphine groups, alkoxy groups, phenyl groups, naphthyl groups, C1 to C130 Alkyl group, C2 to C 30 It includes alkenyl groups and combinations thereof. Non-limiting examples of substituted alkyl and aryl include acyl radicals, alkyl silyl radicals, alkylamino radicals, alkoxy radicals, aryloxy radicals, alkylthio radicals, dialkylamino radicals, alkoxycarbonyl radicals, aryloxycarbonyl radicals, carbomoyl radicals, alkyl- and dialkyl-carbamoyl radicals, acyloxy radicals, acylamino radicals, arylamino radicals, and combinations thereof. Specific details for implementing the invention

[0090] In the present disclosure, the ethylene / α-olefin copolymer composition comprises at least two identifiable components, namely, a defined weight average molecular weight M w , defined short-chain branching content and defined polydispersity index M w / M n A first ethylene / α-olefin copolymer having; and a defined weight average molecular weight M w , defined short-chain branching content and defined polydispersity index M w / M n It includes a second ethylene / α-olefin copolymer having

[0091] The first ethylene / α-olefin copolymer and the second ethylene / α-olefin copolymer can be identified using known analytical methods such as chromatography and fractionation techniques and / or deconvolution through reaction simulation. Each of the first ethylene / α-olefin copolymer, the second ethylene / α-olefin copolymer, and the ethylene / α-olefin copolymer compositions in which they are part are described in more detail below.

[0092] 1st ethylene / α-olefin copolymer

[0093] The first ethylene / α-olefin copolymer comprises ethylene and at least one α-olefin. In an embodiment of the present disclosure, the at least one α-olefin polymerized with ethylene to produce the first ethylene / α-olefin copolymer may be selected from the group comprising propene-1, butene-1, pentene-1, hexene-1, and octene-1, and mixtures thereof.

[0094] In one embodiment of the present disclosure, the first ethylene / α-olefin copolymer is the first ethylene / octene-1 copolymer.

[0095] In one embodiment of the present disclosure, the first ethylene / α-olefin copolymer is a first homogeneous branched ethylene / α-olefin copolymer.

[0096] In one embodiment of the present disclosure, the ethylene / α-olefin copolymer is prepared using a first homogeneous catalyst, and non-limiting examples thereof include cross-linked metallocene catalysts well known in the art.

[0097] In one embodiment of the present disclosure, a first ethylene / α-olefin copolymer is prepared using a first homogeneous catalyst (i.e., the catalyst is a hafnocene catalyst) having hafnium, Hf as the active metal center.

[0098] In one embodiment of the present disclosure, the first ethylene / α-olefin copolymer is prepared using a cross-linked metallocene catalyst.

[0099] In one embodiment of the present disclosure, the first ethylene / α-olefin copolymer is prepared using a cross-linked metallocene catalyst having the following formula (I):

[0100]

[0101] In chemical formula (I), M is a Group 4 metal selected from titanium, zirconium, or hafnium; G is a Group 14 element selected from carbon, silicon, germanium, tin, or lead; and R1 is a hydrogen atom, C 1-20 Hydrocarbon radical, C 1-20 Alkoxy radical or C6-10 It is an aryl oxide radical; R2 and R3 are hydrogen atoms, C 1-20 Hydrocarbon radical, C 1-20 Alkoxy radical or C 6-10 Independently selected from aryl oxide radicals; R4 and R5 are hydrogen atoms, unsubstituted C 1-20 Hydrocarbon radical, substituted C 1-20 Hydrocarbon radical, C 1-20 Alkoxy radical or C 6-10 It is independently selected from aryl oxide radicals; Q is an independently activable leaving group ligand.

[0102] In one embodiment, R4 and R5 are independently aryl groups.

[0103] In one embodiment, R4 and R5 are independently phenyl groups or substituted phenyl groups.

[0104] In one embodiment, R4 and R5 are phenyl groups.

[0105] In one embodiment, R4 and R5 are independently substituted phenyl groups.

[0106] In one embodiment, R4 and R5 are substituted phenyl groups, where the phenyl groups are substituted with substituted silyl groups.

[0107] In one embodiment, R4 and R5 are substituted phenyl groups, where the phenyl groups are substituted with trialkyl silyl groups.

[0108] In one embodiment, R4 and R5 are substituted phenyl groups, wherein the phenyl groups are substituted with trialkylsilyl groups at the para position. In one embodiment, R 1 and R 2 is a substituted phenyl group, where the phenyl group is substituted with a trimethylsilyl group at the para position. In one embodiment, R 1 and R 2 is a substituted phenyl group, where the phenyl group is substituted with a triethylsilyl group at the para position.

[0109] In one embodiment, R4 and R5 are independently alkyl groups.

[0110] In one embodiment, R4 and R5 are independently alkenyl groups.

[0111] In one embodiment, R1 is hydrogen.

[0112] In one embodiment, R1 is an alkyl group.

[0113] In one embodiment, R1 is an aryl group.

[0114] In one embodiment, R1 is an alkenyl group.

[0115] In one embodiment, R2 and R3 are independently hydrocarbon groups having 1 to 30 carbon atoms.

[0116] In one embodiment, R2 and R3 are independently aryl groups.

[0117] In one embodiment, R2 and R3 are independently alkyl groups.

[0118] In one embodiment, R2 and R3 are independently alkyl groups having 1 to 20 carbon atoms.

[0119] In one embodiment, R2 and R3 are independently phenyl groups or substituted phenyl groups.

[0120] In one embodiment, R2 and R3 are tert-butyl groups.

[0121] In one embodiment, R2 and R3 are hydrogen.

[0122] In one embodiment, M is hafnium, Hf.

[0123] In one embodiment of the present disclosure, the first ethylene / α-olefin copolymer is prepared using a cross-linked metallocene catalyst having the formula (Ia):

[0124]

[0125] In chemical formula (Ia), G is a Group 14 element selected from carbon, silicon, germanium, tin, or lead; R1 is a hydrogen atom, C 1-20Hydrocarbon radical, C 1-20 Alkoxy radical or C 6-10 It is an aryl oxide radical; R2 and R3 are hydrogen atoms, C 1-20 Hydrocarbon radical, C 1-20 Alkoxy radical or C 6-10 Independently selected from aryl oxide radicals; R4 and R5 are independently hydrogen atoms, unsubstituted C 1-20 Hydrocarbon radical, substitution C 1-20 Hydrocarbon radical, C 1-20 Alkoxy radical or C 6-10 It is independently selected from aryl oxide radicals; Q is an independently activable leaving group ligand.

[0126] In the present disclosure, the term “activable” means that ligand Q can be cleaved from the metal center M via a protonation reaction or extracted from the metal center M by a suitable acidic or electrophilic catalytic activator compound (also known as a “co-catalyst” compound), examples of which are described below. The activable ligand Q can also be converted into other ligands that are cleaved or extracted from the metal center M (e.g., halides can be converted into alkyl groups). Without being bound by any single theory, the protonation or extraction reaction produces an active “cationic” metal center capable of polymerizing olefins.

[0127] In an embodiment of the present disclosure, the activable ligand Q is a hydrogen atom; a halogen atom; C 1-20 Hydrocarbon radical, C 1-20 Alkoxy radicals, and C 6-10 A radical as an aryl or aryloxy radical, wherein each hydrocarbon, alkoxy, aryl, or aryl oxide radical may be unsubstituted or additionally substituted with one or more halogens or other groups; C 1-8 Alkyl; C 1-8 Alkoxy; C 6-10Q is independently selected from the group consisting of aryl or aryloxy; and amido or phosphido radicals, provided that Q is not cyclopentadienyl. Two Q ligands may also conjugate to each other to 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 acetamidinate group. In a convenient embodiment of the present disclosure, each Q is a halogen atom, C 1-4 It is independently selected from the group consisting of alkyl radicals and benzyl radicals. Particularly suitable activating ligand Q is a single anion such as a halide (e.g., chloride) or a hydrocarbon (e.g., methyl, benzyl).

[0128] In one embodiment of the present disclosure, the first homogeneous catalyst used to produce the first ethylene / α-olefin copolymer is diphenylmethylene(cyclopentadienyl)(2,7-di-t-butylfluorenyl)hafnium dichloride having the following molecular formula:

[0129] [(2,7-tBu2Flu)Ph2C(Cp)HfCl2].

[0130] In one embodiment of the present disclosure, the first homogeneous catalyst used to produce the first ethylene / α-olefin copolymer is diphenylmethylene(cyclopentadienyl)(2,7-di-t-butylfluorenyl)hafnium dimethyl having the following molecular formula:

[0131] [(2,7-tBu2Flu)Ph2C(Cp)HfMe2].

[0132] In addition to the first homogeneous catalyst molecule itself, the active homogeneous catalyst system may further include one or more of an alkylaluminoxane co-catalyst and an ionic activator. Additionally, the homogeneous catalyst system may optionally include a sterically hindered phenol.

[0133] Although the exact structure of alkylaluminoxane is uncertain, experts in the field generally agree that alkylaluminoxane is an oligomeric species containing repeating units of the following general formula:

[0134] (R)2AlO-(Al(R)-O) n -Al(R)2

[0135] Here, the R group may be the same or different linear, branched, or cyclic hydrocarbon radicals containing 1 to 20 carbon atoms, and n is 0 to about 50. A non-limiting example of an alkylaluminoxane is methylaluminoxane (or MAO) in which each R group is a methyl radical.

[0136] In one embodiment of the present disclosure, R of the alkylaluminoxane is a methyl radical and m is 10 to 40.

[0137] In one embodiment of the present disclosure, the co-catalyst is modified methylaluminoxane (MMAO).

[0138] In the relevant technical field, it is well known that alkylaluminoxanes can play a dual role as both alkylating agents and activators. Therefore, alkylaluminoxane co-catalysts are frequently used with activable ligands such as halogens.

[0139] Generally, ionic activators consist of a cation and a bulky anion; the latter is substantially non-coordinate. A non-limiting example of an ionic activator is a tetracoordinate boron ionic activator in which four ligands are bonded to a boron atom. Non-limiting examples of boron ionic activators include the following formulas presented below:

[0140] [R 5 ] + [B(R 7 )4] -

[0141] Here, B represents a boron atom, and R 5 is an aromatic hydrocarbon (e.g., triphenylmethyl cation), and each R 7 C is a fluorine atom, unsubstituted or substituted with a fluorine atom. 1-4 A phenyl radical substituted or unsubstituted with 3 to 5 substituents selected from alkyl or alkoxy radicals; and the formula -Si(R 9It is a silyl radical of )3, but each R 9 hydrogen atoms and C 1-4 Independently selected from silyl radicals independently selected from alkyl radicals, and

[0142] [(R 8 ) t ZH] + [B(R 7 )4] -

[0143] Here, 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 C 1-8 Alkyl radical, unsubstituted or up to 3 C 1-4 Selected from phenyl radicals substituted with alkyl radicals, or one R 8 It can form an anilinium radical with this nitrogen atom and R 7 is as defined above.

[0144] R in both equations 7A non-limiting example is a pentafluorophenyl radical. Generally, boron ionic activators can be described as salts of tetra(perfluorophenyl)boron; non-limiting examples include anilinium, carbonium, oxonium, phosphonium, and sulfonium salts of tetra(perfluorophenyl)boron, including anilinium and trityl (or triphenylmethylium).Additional non-limiting examples of ionic active agents include triethylammonium tetra(phenyl)boron, tripropylammonium tetra(phenyl)boron, tri(n-butyl)ammonium tetra(phenyl)boron, trimethylammonium tetra(p-tolyl)boron, trimethylammonium tetra(o-tolyl)boron, tributylammonium tetra(pentafluorophenyl)boron, tripropylammonium tetra(o,p-dimethylphenyl)boron, tributylammonium tetra(m,m-dimethylphenyl)boron, tributylammonium tetra(p-trifluoromethylphenyl)boron, tributylammonium tetra(pentafluorophenyl)boron, tri(n-butyl)ammonium tetra(o-tolyl)boron, N,N-dimethylanilinium tetra(phenyl)boron, N,N-diethylanilinium tetra(phenyl)boron, and N,N-diethylanilinium Tetra(phenyl)n-butylboron, N,N-2,4,6-pentamethylanilinium 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, tropylium tetrakispentafluorophenyl borate, triphenylmethylium tetrakispentafluorophenyl borate, benzene(diazonium)tetrakispentafluorophenyl borate, tropylium tetrakis(2,3,5,6-tetrafluorophenyl)boron, triphenylmethylium tetrakis(2,3,5,6-tetrafluorophenyl)boron, benzene(diazonium)tetrakis(3,4,5-trifluorophenyl)boron, It includes tropium tetrakis(3,4,5-trifluorophenyl)borate, benzene(diazonium) tetrakis(3,4,5-trifluorophenyl)borate, tropium tetrakis(1,2,2-trifluoroethenyl)borate, triphenylmethylium tetrakis(1,2,2-trifluoroethenyl)borate, benzene(diazonium) tetrakis(1,2,2-trifluoroethenyl)borate, tropium tetrakis(2,3,4,5-tetrafluorophenyl)borate, triphenylmethylium tetrakis(2,3,4,5-tetrafluorophenyl)borate, and benzene(diazonium) tetrakis(2,3,4,5-tetrafluorophenyl)borate.Commercially available ionic activators include N,N-dimethylanilinium tetrakispentafluorophenyl borate and triphenylmethylium tetrakispentafluorophenyl borate.

[0145] Non-limiting examples of sterically hindered phenols include butylated phenolic antioxidants, butylated hydroxytoluene, 2,6-di-tert-butyl-4-ethylphenol, 4,4'-methylenebis(2,6-di-tert-butylphenol), 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, and octadecyl-3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate.

[0146] To produce an active homogeneous catalyst system, the amounts and molar ratios of three or four components, namely the first homogeneous catalyst, alkylaluminoxan, ionic activator, and selective sterically hindered phenol, are optimized.

[0147] In one embodiment of the present disclosure, the first homogeneous catalyst used to produce the first ethylene / α-olefin copolymer does not produce long-chain branches and / or the first ethylene / α-olefin copolymer contains an undetectable amount of long-chain branches.

[0148] In an embodiment of the present disclosure, the first homogeneous catalyst used to produce the first ethylene / α-olefin copolymer produces long-chain branches, and the first ethylene / α-olefin copolymer will contain detectable levels of long-chain branches, hereinafter referred to as "LCB". LCB is a structural phenomenon of ethylene polymers well known to those skilled in the art.

[0149] In one embodiment of the present disclosure, the first ethylene / α-olefin copolymer may contain long-chain branches characterized by the LCBF disclosed herein.

[0150] In one embodiment of the present disclosure, the upper limit for the LCBF of the first ethylene / α-olefin copolymer may be about 0.5, in another case about 0.4, and in yet another case about 0.3 (dimensionless). In an embodiment of the present disclosure, the lower limit for the LCBF of the first ethylene / α-olefin copolymer may be about 0.001, in another case about 0.0015, and in yet another case about 0.002 (dimensionless).

[0151] In some embodiments of the present disclosure, the molecular weight distribution (M) of the first ethylene / α-olefin copolymer w / M n The upper limit of ) is about 2.3, about 2.2, about 2.1, or about 2.0. In some embodiments of the present disclosure, the molecular weight distribution (M of the first ethylene / α-olefin copolymer w / M n The lower limit of ) is approximately 1.7, approximately 1.8, or approximately 1.9.

[0152] In some embodiments of the present disclosure, the first ethylene / α-olefin copolymer has a molecular weight distribution (M w / M n ) is ≤ 2.3, or < 2.3, or ≤ 2.2, or < 2.2, or ≤ 2.1, or < 2.1.

[0153] In some embodiments of the present disclosure, the first ethylene / α-olefin copolymer has a molecular weight distribution (M w / M n ) is about 1.7 to about 2.3, or about 1.8 to about 2.3, or about 1.8 to about 2.2.

[0154] In one embodiment, the first ethylene / α-olefin copolymer has 10 to 50 short-chain branches per 1,000 carbon atoms. In another embodiment, the first ethylene / α-olefin copolymer has more than 10 to 50 short-chain branches per 1,000 carbon atoms, or 20 to 45 short-chain branches per 1,000 carbon atoms, or more than 20 to 45 short-chain branches per 1,000 carbon atoms, or 15 to 40 short-chain branches per 1,000 carbon atoms, or more than 15 to 40 short-chain branches per 1,000 carbon atoms, or 25 to 35 short-chain branches per 1,000 carbon atoms.

[0155] In one embodiment, the first ethylene / α-olefin copolymer has about 10 to 50 short-chain branches per 1,000 carbon atoms, or about 20 to about 45 short-chain branches per 1,000 carbon atoms, or about 15 to about 40 short-chain branches per 1,000 carbon atoms, or about 25 to about 35 short-chain branches per 1,000 carbon atoms.

[0156] Short chain branches (i.e., short chain branches per 1,000 carbon atoms) are branches resulting from the presence of at least one α-olefin in the first ethylene / α-olefin copolymer, having, for example, 2 carbon atoms in the case of butene-1, 4 carbon atoms in the case of hexene-1, or 6 carbon atoms in the case of octene-1, etc.

[0157] In one embodiment of the present disclosure, the first ethylene / α-olefin copolymer has a weight average molecular weight M of about 70 kg / mol to about 160 kg / mol, or about 70 kg / mol to about 155 kg / mol, or about 70 kg / mol to about 150 kg / mol, or about 70 kg / mol to about 140 kg / mol, or about 80 kg / mol to about 140 kg / mol, or about 80 kg / mol to about 135 kg / mol, or about 80 kg / mol to about 130 kg / mol, or about 80 kg / mol to about 120 kg / mol, or about 90 kg / mol to about 115 kg / mol. w has

[0158] In some embodiments of the present disclosure, the upper limit of the weight percentage of the first ethylene / α-olefin copolymer in the ethylene / α-olefin copolymer composition (i.e., the weight percentage of the first ethylene / α-olefin copolymer based on the total weight of the ethylene / α-olefin copolymer composition) is about 70 weight%, or about 65 weight%, or about 60 weight%, or about 55 weight%, or about 52 weight%, or about 50 weight%. In some embodiments of the present disclosure, the lower limit of the weight percentage of the first ethylene / α-olefin copolymer in the ethylene / α-olefin copolymer composition is about 30 weight%, or about 35 weight%, or about 40 weight%, or about 45 weight%, or about 50 weight%. In one embodiment, the first ethylene / α-olefin copolymer is present in an amount of about 30 to about 60 weight% in the ethylene / α-olefin copolymer composition. In another embodiment, the first ethylene / α-olefin copolymer is present in an amount of about 30 to about 50 weight% in the ethylene / α-olefin copolymer composition. In yet another embodiment, the first ethylene / α-olefin copolymer is present in an amount of about 30 to about 50 weight% (<) in the ethylene / α-olefin copolymer composition.

[0159] Second ethylene / α-olefin copolymer

[0160] The second ethylene / α-olefin copolymer comprises ethylene and at least one α-olefin. In embodiments of the present disclosure, the at least one α-olefin polymerized with ethylene to produce the second ethylene / α-olefin may be selected from the group comprising propene-1, butene-1, pentene-1, hexene-1 and octene-1 and mixtures thereof.

[0161] In one embodiment of the present disclosure, the second ethylene / α-olefin copolymer is a second ethylene / octene-1 copolymer.

[0162] In one embodiment of the present disclosure, the second ethylene / α-olefin copolymer is a second homogeneously branched ethylene / α-olefin copolymer.

[0163] In one embodiment of the present disclosure, the second ethylene / α-olefin copolymer is prepared using a second homogeneous catalyst, and non-limiting examples thereof include cross-linked metallocene catalysts well known in the art.

[0164] In one embodiment of the present disclosure, the second ethylene / α-olefin copolymer is prepared using a second homogeneous catalyst (i.e., the catalyst is a hafnocene catalyst) having hafnium, Hf as the active metal center.

[0165] In one embodiment of the present disclosure, the second ethylene / α-olefin copolymer is prepared using a cross-linked metallocene catalyst.

[0166] In one embodiment of the present disclosure, the second ethylene / α-olefin copolymer is prepared using a cross-linked metallocene catalyst having the formula (I):

[0167]

[0168] In chemical formula (I): M is a Group 4 metal selected from titanium, zirconium, or hafnium; G is a Group 14 element selected from carbon, silicon, germanium, tin, or lead; R1 is a hydrogen atom, C 1-20 Hydrocarbon radical, C 1-20Alkoxy radical or C 6-10 It is an aryl oxide radical; R2 and R3 are independently hydrogen atoms, C 1-20 Hydrocarbon radical, C 1-20 Alkoxy radical or C 6-10 Independently selected from aryl oxide radicals; R4 and R5 are independently hydrogen atoms, unsubstituted C 1-20 Hydrocarbon radical, substituted C 1-20 Hydrocarbon radical, C 1-20 Alkoxy radical or C 6-10 It is independently selected from aryl oxide radicals; Q is an independently activable leaving group ligand.

[0169] In one embodiment, R4 and R5 are independently aryl groups.

[0170] In one embodiment, R4 and R5 are independently phenyl groups or substituted phenyl groups.

[0171] In one embodiment, R4 and R5 are phenyl groups.

[0172] In one embodiment, R4 and R5 are independently substituted phenyl groups.

[0173] In one embodiment, R4 and R5 are substituted phenyl groups, where the phenyl groups are substituted with substituted silyl groups.

[0174] In one embodiment, R4 and R5 are substituted phenyl groups, where the phenyl groups are substituted with trialkylsilyl groups.

[0175] In one embodiment, R4 and R5 are substituted phenyl groups, wherein the phenyl groups are substituted with trialkylsilyl groups at the para position. In one embodiment, R 1 and R 2 is a substituted phenyl group, where the phenyl group is substituted with a trimethylsilyl group at the para position. In one embodiment, R 1 and R 2 is a substituted phenyl group, where the phenyl group is substituted with a triethylsilyl group at the para position.

[0176] In one embodiment, R4 and R5 are independently alkyl groups.

[0177] In one embodiment, R4 and R5 are independently alkenyl groups.

[0178] In one embodiment, R1 is hydrogen.

[0179] In one embodiment, R1 is an alkyl group.

[0180] In one embodiment, R1 is an aryl group.

[0181] In one embodiment, R1 is an alkenyl group.

[0182] In one embodiment, R2 and R3 are independently hydrocarbon groups having 1 to 30 carbon atoms.

[0183] In one embodiment, R2 and R3 are independently aryl groups.

[0184] In one embodiment, R2 and R3 are independently alkyl groups.

[0185] In one embodiment, R2 and R3 are independently alkyl groups having 1 to 20 carbon atoms.

[0186] In one embodiment, R2 and R3 are independently phenyl groups or substituted phenyl groups.

[0187] In one embodiment, R2 and R3 are tert-butyl groups.

[0188] In one embodiment, R2 and R3 are hydrogen.

[0189] In one embodiment, M is hafnium, Hf.

[0190] In one embodiment of the present disclosure, the second ethylene / α-olefin copolymer is prepared using a cross-linked metallocene catalyst having the formula (Ia):

[0191]

[0192] In chemical formula (Ia), G is a Group 14 element selected from carbon, silicon, germanium, tin, or lead; R1 is a hydrogen atom, C 1-20Hydrocarbon radical, C 1-20 Alkoxy radical or C 6-10 It is an aryl oxide radical; R2 and R3 are hydrogen atoms, C 1-20 Hydrocarbon radical, C 1-20 Alkoxy radical or C 6-10 Independently selected from aryl oxide radicals; R4 and R5 are hydrogen atoms, unsubstituted C 1-20 Hydrocarbon radical, substitution C 1-20 Hydrocarbon radical, C 1-20 Alkoxy radical or C 6-10 It is independently selected from aryl oxide radicals; Q is an independently activable leaving group ligand.

[0193] In the present disclosure, the term “activable” means that ligand Q can be cleaved from the metal center M via a protonation reaction or extracted from the metal center M by a suitable acidic or electrophilic catalytic activator compound (also known as a “co-catalyst” compound), examples of which are described below. The activable ligand Q can also be converted into other ligands that are cleaved or extracted from the metal center M (e.g., halides can be converted into alkyl groups). Without being bound by any single theory, the protonation or extraction reaction produces an active “cationic” metal center capable of polymerizing olefins.

[0194] In an embodiment of the present disclosure, the activable ligand Q is a hydrogen atom; a halogen atom; C 1-20 Hydrocarbon radical, C 1-20 Alkoxy radicals, and C 6-10 A radical that is an aryl or aryloxy radical, wherein each of the hydrocarbon, alkoxy, aryl, or aryl oxide radical may be unsubstituted or additionally substituted with one or more halogens or other groups; C 1-8 Alkyl; C 1-8 Alkoxy; C 6-10Q is independently selected from the group consisting of aryl or aryloxy; and amido or phosphido radicals, provided that Q is not cyclopentadienyl. Two Q ligands may also conjugate to each other to 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 acetamidinate group. In a convenient embodiment of the present disclosure, each Q is a halogen atom, C 1-4 It is independently selected from the group consisting of alkyl radicals and benzyl radicals. Particularly suitable activable ligand Q is a single anion such as a halide (e.g., chloride) or a hydrocarbon (e.g., methyl, benzyl).

[0195] In one embodiment of the present disclosure, the second homogeneous catalyst used to produce the second ethylene / α-olefin is diphenylmethylene(cyclopentadienyl)(2,7-di-t-butylfluorenyl)hafnium dichloride having the following molecular formula:

[0196] [(2,7-tBu2Flu)Ph2C(Cp)HfCl2].

[0197] In one embodiment of the present disclosure, the second homogeneous catalyst used to produce the second ethylene / α-olefin is diphenylmethylene(cyclopentadienyl)(2,7-di-t-butylfluorenyl)hafnium dimethyl having the following molecular formula:

[0198] [(2,7-tBu2Flu)Ph2C(Cp)HfMe2].

[0199] In addition to the second homogeneous catalyst molecule itself, the active homogeneous catalyst system may further include one or more of an alkylaluminoxane co-catalyst and an ionic activator. Additionally, the homogeneous catalyst system may optionally include a sterically hindered phenol.

[0200] Although the exact structure of alkylaluminoxane is uncertain, experts in the field generally agree that alkylaluminoxane is an oligomeric species containing repeating units of the following general formula:

[0201] (R)2AlO-(Al(R)-O) n -Al(R)2

[0202] Here, the R group may be the same or different linear, branched, or cyclic hydrocarbon radicals containing 1 to 20 carbon atoms, and n is 0 to about 50. A non-limiting example of an alkylaluminoxane is methylaluminoxane (or MAO) in which each R group is a methyl radical.

[0203] In one embodiment of the present disclosure, R of the alkylaluminoxane is a methyl radical and m is 10 to 40.

[0204] In one embodiment of the present disclosure, the co-catalyst is modified methylaluminoxane (MMAO).

[0205] It is well known in the relevant technical field that alkylaluminoxanes can play a dual role as both alkylating agents and activators. Therefore, alkylaluminoxane co-catalysts are frequently used with activable ligands such as halogens.

[0206] Generally, ionic activators consist of a cation and a bulky anion; the latter is substantially non-coordinate. A non-limiting example of an ionic activator is a tetracoordinate boron ionic activator in which four ligands are bonded to a boron atom. Non-limiting examples of boron ionic activators include the following formulas presented below:

[0207] [R 5 ] + [B(R 7 )4] -

[0208] Here, B represents a boron atom, and R 5 is an aromatic hydrocarbon (e.g., triphenylmethyl cation), and each R 7 C is a fluorine atom, unsubstituted or substituted with a fluorine atom. 1-4 A phenyl radical substituted or unsubstituted with 3 to 5 substituents selected from alkyl or alkoxy radicals; and the formula -Si(R 9It is a silyl radical of )3, but each R 9 hydrogen atoms and C 1-4 Independently selected from silyl radicals independently selected from alkyl radicals, and

[0209] [(R 8 ) t ZH] + [B(R 7 )4] -

[0210] Here, 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 C 1-8 Alkyl radical, unsubstituted or up to 3 C 1-4 Selected from phenyl radicals substituted with alkyl radicals, or one R 8 It can form an anilinium radical with this nitrogen atom and R 7 is as defined above.

[0211] R in both equations 7A non-limiting example is a pentafluorophenyl radical. Generally, boron ionic activators can be described as salts of tetra(perfluorophenyl)boron; non-limiting examples include anilinium, carbonium, oxonium, phosphonium, and sulfonium salts of tetra(perfluorophenyl)boron, including anilinium and trityl (or triphenylmethylium).Additional non-limiting examples of ionic active agents include triethylammonium tetra(phenyl)boron, tripropylammonium tetra(phenyl)boron, tri(n-butyl)ammonium tetra(phenyl)boron, trimethylammonium tetra(p-tolyl)boron, trimethylammonium tetra(o-tolyl)boron, tributylammonium tetra(pentafluorophenyl)boron, tripropylammonium tetra(o,p-dimethylphenyl)boron, tributylammonium tetra(m,m-dimethylphenyl)boron, tributylammonium tetra(p-trifluoromethylphenyl)boron, tributylammonium tetra(pentafluorophenyl)boron, tri(n-butyl)ammonium tetra(o-tolyl)boron, N,N-dimethylanilinium tetra(phenyl)boron, N,N-diethylanilinium tetra(phenyl)boron, and N,N-diethylanilinium Tetra(phenyl)n-butylboron, N,N-2,4,6-pentamethylanilinium 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, tropylium tetrakispentafluorophenyl borate, triphenylmethylium tetrakispentafluorophenyl borate, benzene(diazonium)tetrakispentafluorophenyl borate, tropylium tetrakis(2,3,5,6-tetrafluorophenyl)boron, triphenylmethylium tetrakis(2,3,5,6-tetrafluorophenyl)boron, benzene(diazonium)tetrakis(3,4,5-trifluorophenyl)boron, It includes tropium tetrakis(3,4,5-trifluorophenyl)borate, benzene(diazonium) tetrakis(3,4,5-trifluorophenyl)borate, tropium tetrakis(1,2,2-trifluoroethenyl)borate, triphenylmethylium tetrakis(1,2,2-trifluoroethenyl)borate, benzene(diazonium) tetrakis(1,2,2-trifluoroethenyl)borate, tropium tetrakis(2,3,4,5-tetrafluorophenyl)borate, triphenylmethylium tetrakis(2,3,4,5-tetrafluorophenyl)borate, and benzene(diazonium) tetrakis(2,3,4,5-tetrafluorophenyl)borate.Commercially available ionic activators include N,N-dimethylanilinium tetrakispentafluorophenyl borate and triphenylmethylium tetrakispentafluorophenyl borate.

[0212] Non-limiting examples of sterically hindered phenols include butylated phenolic antioxidants, butylated hydroxytoluene, 2,6-di-tert-butyl-4-ethylphenol, 4,4'-methylenebis(2,6-di-tert-butylphenol), 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, and octadecyl-3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate.

[0213] To produce an active homogeneous catalyst system, the amounts and molar ratios of three or four components, namely the first homogeneous catalyst, alkylaluminoxan, ionic activator, and selective sterically hindered phenol, are optimized.

[0214] In one embodiment of the present disclosure, the second homogeneous catalyst used to produce the second ethylene / α-olefin copolymer will not produce long-chain branches, and / or the second ethylene / α-olefin copolymer will contain an undetectable amount of long-chain branches.

[0215] In one embodiment of the present disclosure, the second homogeneous catalyst used to produce the second ethylene / α-olefin copolymer produces long-chain branches, and the second ethylene / α-olefin copolymer will contain long-chain branches, hereinafter referred to as “LCB”. LCB is a structural phenomenon of ethylene polymers well known to those skilled in the art.

[0216] In one embodiment of the present disclosure, the second ethylene / α-olefin copolymer contains a long-chain branch characterized by the LCBF disclosed herein. In an embodiment of the present disclosure, the upper limit for the LCBF of the second ethylene / α-olefin copolymer may be about 0.5, in another case about 0.4, and in yet another about 0.3 (dimensionless). In an embodiment of the present disclosure, the lower limit for the LCBF of the second ethylene / α-olefin copolymer may be about 0.001, in another case about 0.0015, and in yet another about 0.002 (dimensionless).

[0217] In some embodiments of the present disclosure, the molecular weight distribution (M of the second ethylene / α-olefin copolymer w / M n The upper limit of ) is about 2.3, or about 2.2, or about 2.1, or about 2.0. In some embodiments of the present disclosure, the molecular weight distribution (M of the second ethylene / α-olefin copolymer w / M n The lower limit of ) is about 1.7, or about 1.8, or about 1.9.

[0218] In some embodiments of the present disclosure, the second ethylene / α-olefin copolymer has a molecular weight distribution (M w / M n ) is ≤ 2.3, or < 2.3, or ≤ 2.2, or < 2.2, or ≤ 2.1, or < 2.1.

[0219] In some embodiments of the present disclosure, the second ethylene / α-olefin copolymer has a molecular weight distribution (M w / M n ) is about 1.7 to about 2.3, or about 1.8 to about 2.3, or about 1.8 to about 2.2.

[0220] In one embodiment, the second ethylene / α-olefin copolymer has about 10 to about 40 short-chain branches per 1,000 carbon atoms. In a further embodiment, the second ethylene / α-olefin has about 10 to about 35 short-chain branches per 1,000 carbon atoms, or about 10 to about 30 short-chain branches per 1,000 carbon atoms, or about 15 to about 40 short-chain branches per 1,000 carbon atoms, or about 15 to about 35 short-chain branches per 1,000 carbon atoms, or about 15 to about 30 short-chain branches per 1,000 carbon atoms, or about 15 to about 25 short-chain branches per 1,000 carbon atoms.

[0221] A person skilled in the art will know that the short-chain branch (i.e., the short-chain branch per 1,000 carbon atoms) is a branch resulting from the presence of at least one α-olefin in the second ethylene / α-olefin copolymer, having, for example, 2 carbon atoms in the case of butene-1, 4 carbon atoms in the case of hexene-1, 6 carbon atoms in the case of octene-1, etc.

[0222] Short-chain branching content of the first ethylene / α-olefin copolymer, SCB 1 The short-chain branching content of the second ethylene / α-olefin copolymer, SCB 2 Greater than or equal to - that is, SCB 1 ≥ SCB 2 .

[0223] In some embodiments, the short-chain branching content of the first ethylene / α-olefin copolymer, SCB 1 The short-chain branching content of the second ethylene / α-olefin copolymer, SCB 2 Greater than - that is, SCB 1 > SCB 2 .

[0224] In one embodiment of the present disclosure, the second ethylene / α-olefin copolymer has a weight average molecular weight M w The amount is about 20 kg / mol to about 65 kg / mol, or about 20 kg / mol to about 60 kg / mol, or about 30 kg / mol to about 65 kg / mol, or about 35 kg / mol to about 60 kg / mol, or about 30 kg / mol to about 55 kg / mol, or about 30 kg / mol to about 50 kg / mol.

[0225] In some embodiments, the ratio of the weight-average molecular weight of the first ethylene / α-olefin copolymer to the weight-average molecular weight of the second ethylene / α-olefin copolymer is about 1.5 to about 6. In some embodiments, the ratio of the weight-average molecular weight of the first ethylene / α-olefin copolymer to the weight-average molecular weight of the second ethylene / α-olefin copolymer is about 2 to about 4. In some embodiments, the ratio of the weight-average molecular weight of the first ethylene / α-olefin copolymer to the weight-average molecular weight of the second ethylene / α-olefin copolymer is about 2 to about 3.

[0226] In one embodiment of the present disclosure, the number average molecular weight M of the second ethylene / α-olefin copolymer n It is about 10 kg / mol to about 30 kg / mol, or about 15 kg / mol to about 30 kg / mol, or about 15 kg / mol to about 25 kg / mol.

[0227] In some embodiments of the present disclosure, the upper limit of the weight percentage of the second ethylene / α-olefin copolymer in the ethylene / α-olefin copolymer composition (i.e., the weight percentage of the second ethylene / α-olefin copolymer based on the total weight of the ethylene / α-olefin copolymer composition) is about 70 weight%, or about 65 weight%, or about 60 weight%, or about 55 weight%, or about 52 weight%, or about 50 weight%. In some embodiments of the present disclosure, the lower limit of the weight percentage of the second ethylene / α-olefin copolymer in the ethylene / α-olefin copolymer composition is about 30 weight%, or about 35 weight%, or about 40 weight%, or about 45 weight%, or about 50 weight%. In one embodiment, the second ethylene / α-olefin copolymer is present in the ethylene / α-olefin copolymer composition in an amount of about 50 to about 70 weight%. In another embodiment, the second ethylene / α-olefin copolymer is present in the ethylene / α-olefin copolymer composition in an amount of about 50 to about 65 weight%. In yet another embodiment, the second ethylene / α-olefin copolymer is present in the ethylene / α-olefin copolymer composition in an amount of more than about 50 to about 70 weight%.

[0228] Ethylene / α-olefin copolymer composition

[0229] In some embodiments, the ethylene / α-olefin copolymer composition disclosed herein is a reactor blend of a first ethylene / α-olefin copolymer and a second ethylene / α-olefin copolymer. The term "reactor blend" refers to a blend formed during the polymerization process.

[0230] In some embodiments, the ethylene / α-olefin copolymer composition disclosed herein is a post-reactor blend of a first ethylene / α-olefin copolymer and a second ethylene / α-olefin copolymer. The term “post-reactor blend” refers to a blend formed by combining two or more blend components that have each already been polymerized and are recovered from a polymerization process before being combined with other blend component(s), wherein the recovery operation may include catalyst deactivation, phase separation, devolatilization of unreacted monomers and / or process solvents, pelletization, etc.

[0231] In one embodiment, the ethylene / α-olefin copolymer composition of the present disclosure is prepared by providing a first ethylene / α-olefin copolymer using a first homogeneous catalyst in a first reactor and providing a second ethylene / α-olefin copolymer using a second homogeneous catalyst in a second reactor.

[0232] In one embodiment, the ethylene / α-olefin copolymer composition of the present disclosure is prepared by forming a first ethylene / α-olefin copolymer by polymerizing ethylene and at least one α-olefin in a first reactor using a first homogeneous catalyst; and forming a second ethylene / α-olefin copolymer by polymerizing ethylene and at least one α-olefin in a second reactor using a second homogeneous catalyst.

[0233] In one embodiment, the ethylene / α-olefin copolymer composition of the present disclosure is prepared by forming a first ethylene / α-olefin copolymer by polymerizing ethylene and at least one α-olefin in a first solution-phase polymerization reactor using a first homogeneous catalyst; and forming a second ethylene / α-olefin copolymer by polymerizing ethylene and at least one α-olefin in a second solution-phase polymerization reactor using a second homogeneous catalyst.

[0234] In one embodiment, the ethylene / α-olefin copolymer composition of the present disclosure is prepared by forming a first ethylene / α-olefin copolymer by polymerizing ethylene and at least one α-olefin in a first solution-phase polymerization reactor using a first homogeneous catalyst; and forming a second ethylene / α-olefin copolymer by polymerizing ethylene and at least one α-olefin in a second solution-phase polymerization reactor using a second homogeneous catalyst, wherein the first and second solution-phase polymerization reactors are configured in series with each other.

[0235] In one embodiment, the ethylene / α-olefin copolymer composition of the present disclosure is prepared by forming a first ethylene / α-olefin copolymer by polymerizing ethylene and at least one α-olefin in a first solution-phase polymerization reactor using a first homogeneous catalyst; and forming a second ethylene / α-olefin copolymer by polymerizing ethylene and at least one α-olefin in a second solution-phase polymerization reactor using a second homogeneous catalyst, wherein the first and second solution-phase polymerization reactors are configured in parallel with each other.

[0236] In one embodiment, the solution phase polymerization reactor used as the first solution phase reactor or the second solution phase reactor is a continuous stirred tank reactor or a tubular reactor.

[0237] In one embodiment, the solution phase polymerization reactor used as the first solution phase reactor or the second solution phase reactor is a continuous stirred tank reactor.

[0238] In one embodiment, the solution phase polymerization reactor used as the first solution phase reactor or the second solution phase reactor is a tubular reactor.

[0239] In one embodiment, the solution phase polymerization reactor used as the first solution phase reactor and the second solution phase reactor is a continuous stirred tank reactor.

[0240] In solution polymerization, the monomer is dissolved or dispersed in a solvent before being fed into the reactor (or, in the case of gaseous monomers, the monomer may be fed into the reactor to be dissolved in the reaction mixture). Before mixing, the solvent and monomer are generally purified to remove catalyst toxins such as water, oxygen, or metal impurities. Feedstock purification follows standard practices in the relevant art; for example, molecular sieves, alumina layers, and oxygen removal catalysts are used for monomer purification. It is also desirable to treat the solvent itself (e.g., methylpentane, cyclohexane, hexane, or toluene) in a similar manner.

[0241] The feedstock can be heated or cooled before being fed into the reactor.

[0242] Generally, catalyst components can be pre-mixed in the solvent for the reaction or fed into the reactor as a separate stream. In some cases, it may be desirable to pre-mix the catalyst components to provide reaction time before they enter the reaction. Such "inline mixing" techniques are described in several patents in the name of DuPont Canada Inc. (e.g., U.S. Patent No. 5,589,555, issued December 31, 1996).

[0243] Solution polymerization processes for the polymerization or copolymerization of ethylene are well known in the art (see, e.g., U.S. Patents No. 6,372,864 and 6,777,509). These processes are carried out in the presence of inert hydrocarbon solvents. Various solvents may be used as process solvents in solution-phase polymerization reactors, and non-limiting examples include linear, branched, or cyclic C5 to C6. 12 It includes alkanes. Non-limiting examples of α-olefins include propene-1, butene-1, pentene-1, hexene-1, and octene-1. Suitable catalyst component solvents include aliphatic and aromatic hydrocarbons. Non-limiting examples of aliphatic catalyst component solvents include linear, branched, or cyclic C5 to C 12Aliphatic hydrocarbons, for example, pentane, methylpentane, hexane, heptane, octane, cyclohexane, cyclopentane, methylcyclohexane, hydrogenated naphtha, or combinations 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), xylene isomer mixtures, hemelytene (1,2,3-trimethylbenzene), pseudocumene (1,2,4-trimethylbenzene), mesitylene (1,3,5-trimethylbenzene), trimethylbenzene isomer mixtures, prehenitene (1,2,3,4-tetramethylbenzene), durene (1,2,3,5-tetramethylbenzene), tetramethylbenzene isomer mixtures, pentamethylbenzene, hexamethylbenzene, and combinations thereof.

[0244] The polymerization temperature in a typical solution process may be about 80°C to about 300°C. In one embodiment of the present disclosure, the polymerization temperature in the solution process is about 120°C to about 250°C. The polymerization pressure in the solution process may be a “medium pressure process,” which means that the pressure inside the reactor is less than about 6,000 psi (about 42,000 kilopascals or kPa). In one embodiment of the present disclosure, the polymerization pressure in the solution process may be about 10,000 kPa to about 40,000 kPa, or about 14,000 kPa to about 22,000 kPa (i.e., about 2,000 psi to about 3,000 psi).

[0245] In one embodiment of the present disclosure, the ethylene / α-olefin copolymer composition has at least 1 mol% of at least one α-olefin.

[0246] In one embodiment of the present disclosure, the ethylene / α-olefin copolymer composition has at least 3 mol% of at least one α-olefin.

[0247] In one embodiment of the present disclosure, the ethylene / α-olefin copolymer composition has at least one α-olefin in an amount of about 1 to about 10 mole%.

[0248] In one embodiment of the present disclosure, the ethylene / α-olefin copolymer composition has at least one α-olefin in an amount of about 3 to about 10 mole%.

[0249] In one embodiment of the present disclosure, the ethylene / α-olefin copolymer composition has about 3 to about 8 mol% of at least one α-olefin.

[0250] In one embodiment of the present disclosure, the ethylene / α-olefin copolymer composition comprises ethylene and C3 to C 10 It includes at least one α-olefin selected from the group consisting of α-olefins.

[0251] In one embodiment of the present disclosure, the ethylene / α-olefin copolymer composition comprises ethylene and at least one α-olefin selected from the group consisting of butene-1, hexene-1, octene-1 and mixtures thereof.

[0252] In one embodiment of the present disclosure, the ethylene / α-olefin copolymer composition comprises ethylene and at least one α-olefin selected from the group consisting of hexene-1, octene-1 and mixtures thereof.

[0253] In one embodiment of the present disclosure, the ethylene / α-olefin copolymer composition comprises ethylene and octene-1.

[0254] In one embodiment of the present disclosure, the ethylene / α-olefin copolymer composition comprises ethylene and at least 1 mol% of octene-1.

[0255] In one embodiment of the present disclosure, the ethylene / α-olefin copolymer composition comprises ethylene and 1 to 10 mol% of octene-1.

[0256] In one embodiment of the present disclosure, the ethylene / α-olefin copolymer composition comprises ethylene and 3 to 8 mol% of octene-1.

[0257] In one embodiment of the present disclosure, the ethylene / α-olefin copolymer composition essentially consists of ethylene and octene-1.

[0258] In some embodiments of the present disclosure, the ethylene / α-olefin copolymer composition has a density of about 0.860 g / cm³ to about 0.910 g / cm³, or about 0.865 g / cm³ to about 0.910 g / cm³. In some preferred embodiments, the ethylene / α-olefin copolymer composition has a density of 0.885 to 0.910 g / cm³, preferably 0.890 to 0.910 g / cm³, preferably 0.895 to 0.910 g / cm³, preferably 0.900 to 0.910 g / cm³, preferably greater than 0.900 to less than 0.910 g / cm³, preferably 0.902 to 0.908 g / cm³.

[0259] In some embodiments of the present disclosure, the melt index (I2) of the ethylene / α-olefin copolymer composition is about 1.5 dg / min to about 10 dg / min, or about 2 dg / min to about 10 dg / min, or about 2.5 dg / min to about 8 dg / min, or about 2.5 dg / min to about 7.5 dg / min, or about 2.5 dg / min to about 7 dg / min, or about 2.5 dg / min to about 6 dg / min, or about 3 dg / min to about 6 dg / min, or 3.5 dg / min to about 6 dg / min, or about 4 dg / min to about 6 dg / min, or about 2.2 dg / min to about 8 dg / min, or about 2.3 dg / min to It is about 8 dg / min, or about 3.2 dg / min to about 7 dg / min, or about 3 dg / min to about 6.5 dg / min, or about 3.1 dg / min to about 6 dg / min, or about 4 dg / min to about 5.5 dg / min.

[0260] In some embodiments, the high-load melt index (I) of the ethylene / α-olefin copolymer composition 21 ) is about 10 dg / min to about 10,000 dg / min, or about 10 dg / min to about 1,000 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 g / 10min.

[0261] In some embodiments, the melt flow ratio (I) of the ethylene / α-olefin copolymer composition 21 / I2) is about 15 to about 1,000, or about 15 to about 100, or about 15 to about 75, or about 15 to about 50, or about 15 to about 40, or about 18 to about 50, or about 20 to about 75, or about 20 to about 50, or about 20 to about 45, or about 20 to about 40, or about 20 to about 38, or about 20 to about 35, or about 24 to about 48, or about 27 to about 45, or about 30 to about 42. In some embodiments, the melt flow ratio (I) of the ethylene / α-olefin copolymer composition 21 / I2) is 20 to 50. In some embodiments, the melt flow ratio (I) of the ethylene / α-olefin copolymer composition 21 / I2) is less than about 50, less than about 45, or less than about 40.

[0262] In some embodiments, the ethylene / α-olefin copolymer composition has a weight-average molecular weight (M w) is about 25 kg / mol to about 120 kg / mol, or about 30 kg / mol to about 100 kg / mol, or about 30 kg / mol to about 90 kg / mol, or about 35 kg / mol to about 90 kg / mol, or about 30 kg / mol to about 80 kg / mol, or about 30 kg / mol to about 75 kg / mol, or about 30 kg / mol to about 70 kg / mol.

[0263] In some embodiments, the ethylene / α-olefin copolymer composition has a number average molecular weight (M n ) is about 5 kg / mol to about 35 kg / mol, or about 10 kg / mol to about 35 kg / mol, or about 10 kg / mol to about 30 kg / mol, or about 15 kg / mol to about 30 kg / mol, or about 25 kg / mol to about 30 kg / mol.

[0264] In an embodiment of the present disclosure, the ethylene / α-olefin copolymer composition has a lower molecular weight distribution (M w / M n ) is about 2.0, or about 2.1, or about 2.2, or about 2.3. In an embodiment of the present disclosure, the ethylene / α-olefin copolymer composition has an upper molecular weight distribution (M w / M n ) is about 6.0, or about 5.5, or about 5.0, or about 4.5, or about 4.0, or about 3.75, or about 3.5.

[0265] In an embodiment of the present disclosure, the ethylene / α-olefin copolymer composition has a molecular weight distribution (M w / M n) is about 2.0 to about 6.0, or about 2.1 to about 6, or about 2.3 to about 6, or about 2.3 to about 5.5, or about 2.3 to about 4.5, or about 2.3 to about 4, or about 2.3 to about 3.75, or about 2.0 to about 5.5, or about 2.0 to about 5.0, or about 2.0 to about 4.5, or about 2.0 to about 4.0, or about 2.0 to about 3.75, or about 2.0 to about 3.5, or about 2.1 to about 5.5, or about 2.1 to about 5.0, or about 2.1 to about 4.5, or about 2.1 to about 4.0, or about 2.1 to about 3.75, or about 2.1 to about 3.5, Or it is about 2.1 to about 3.3.

[0266] In an embodiment of the present disclosure, the ethylene / α-olefin copolymer composition has a z-average molecular weight distribution M 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.

[0267] In an embodiment of the present disclosure, the ethylene / α-olefin copolymer composition has a z-average molecular weight distribution M z / M w The amount is about 1.5 to about 4.0, or about 1.5 to about 3.5, or about 1.75 to about 3.5, or about 1.75 to about 3.0, or about 1.75 to about 2.5, or about 2.0 to about 4.0, or about 2.0 to about 3.5, or about 2.0 to about 3.0, or about 2.0 to about 2.75.

[0268] In one embodiment of the present disclosure, an ethylene / α-olefin copolymer composition has a monomodal profile in a gel permeation chromatograph generated according to the ASTM D6474-99 method. The term “monomomodal” is defined herein to mean that there is only one distinct significant peak or maximum value in the GPC curve. A monomodal profile includes a broad monomodal profile. In contrast, the use of the term “bimodal” is intended to convey that there is a second peak or shoulder portion indicating a higher or lower molecular weight component in addition to the first peak (i.e., this molecular weight distribution can be said to have two maximum values ​​in the molecular weight distribution curve). Alternatively, the term “bimodal” means that there are two maximum values ​​in the molecular weight distribution curve generated according to the ASTM D6474-99 method. The term "multi-modal" means that there are two or more, typically more than two maximum values, in the molecular weight distribution curve generated according to the method of ASTM D6474-99.

[0269] In one embodiment of the present disclosure, the ethylene / α-olefin copolymer composition has a flat comonomer distribution profile when measured using GPC-FTIR. As used herein, if the amount of comonomer incorporated is approximately constant with respect to molecular weight when measured using GPC-FTIR, such a distribution is described as "flat" or "uniform."

[0270] In one embodiment of the present disclosure, the ethylene / α-olefin copolymer composition has a partially normal distribution profile when measured using GPC-FTIR. As used herein, when the amount of comonomer incorporated decreases with increasing molecular weight and then increases again with increasing molecular weight when measured using GPC-FTIR, such a distribution is described as "partially normal." A partially normal comonomer distribution exhibits a minimum value.

[0271] In one embodiment of the present disclosure, the ethylene / α-olefin copolymer composition has a reversed-phase comonomer distribution profile when measured using GPC-FTIR. As used herein, when the amount of comonomer incorporated increases with increasing molecular weight when measured using GPC-FTIR, this distribution is described as "reversed-phase."

[0272] In one embodiment of the present disclosure, the ethylene / α-olefin copolymer composition has a partially reversed phase comonomer distribution profile when measured by GPC-FTIR. As used herein, when the amount of comonomer incorporated increases with increasing molecular weight and then decreases with increasing molecular weight when measured by GPC-FTIR, such a distribution may also be described as "partially reversed phase." A partially reversed phase comonomer distribution exhibits a maximum value.

[0273] In one embodiment, the ethylene / α-olefin copolymer composition has a comonomer distribution profile in GPC-FTIR analysis, wherein the comonomer distribution profile has a secant slope from +1 short chain branch per 1,000 carbons to +30 short chain branches per 1,000 carbons. The secant slope is defined herein as the value obtained by subtracting the number of short chain branches per 1,000 carbons at a molecular weight of 30,000 g / mol from the number of short chain branches per 1,000 carbons at a molecular weight of 300,000 g / mol. In another embodiment of the present disclosure, the ethylene / α-olefin copolymer composition has a comonomer distribution profile in GPC-FTIR analysis, wherein the comonomer distribution profile has a secant slope of +1 short chain branch per 1,000 carbons to +20 short chain branches per 1,000 carbons, or +1 short chain branch per 1,000 carbons to +15 short chain branches per 1,000 carbons, or +1 short chain branch per 1,000 carbons to +10 short chain branches per 1,000 carbons.

[0274] In some embodiments, the ethylene / α-olefin copolymer composition has a dimensionless long chain branching factor (LCBF) of 0.001 or greater (≥).

[0275] In some embodiments, the ethylene / α-olefin copolymer composition has a dimensionless long chain branching factor (LCBF) of 0.001 or more (≥) and 0.01 or less (≤).

[0276] In some embodiments, the ethylene / α-olefin copolymer composition has a VICAT softening temperature measured according to ASTM D1525, VSP The temperature is about 70 to about 100°C, or about 70 to about 95°C, or 75 to about 95°C, or about 80 to about 95°C.

[0277] In some embodiments, the ethylene / α-olefin copolymer composition has a zero shear viscosity at 190°C satisfying (I), η 0, VICAT softening temperature measured according to ASTM D1525, VSP , and short-chain branch content measured according to ASTM D6645, SCB has:

[0278]

[0279] In some embodiments, the ethylene / α-olefin copolymer composition has a zero shear viscosity at 190°C satisfying (II), η 0, VICAT softening temperature measured according to ASTM D1525, VSP , and short-chain branch content measured according to ASTM D6645, SCB has:

[0280]

[0281] In some embodiments, the ethylene / α-olefin copolymer composition comprises a fraction eluted in a temperature range of 90°C to 105°C, having an integrated area of ​​less than 1 wt% in CTREF analysis. In some other embodiments, the ethylene / α-olefin copolymer composition comprises a fraction eluted in a temperature range of 90°C to 105°C, having an integrated area of ​​less than 0.5 wt% in CTREF analysis. In yet another embodiment, the ethylene / α-olefin copolymer composition comprises a fraction eluted in a temperature range of 90°C to 105°C, having an integrated area of ​​less than 0.1 wt% in CTREF analysis.

[0282] Song-seong manufactured goods

[0283] The ethylene / α-olefin copolymer composition disclosed herein can be converted into a flexible manufactured article such as a monolayer or multilayer film.

[0284] Non-limiting examples of processes for manufacturing single-layer or multilayer films include blown processes.

[0285] In the blown film extrusion process, the extruder heats, melts, mixes, and conveys the thermoplastic resin or thermoplastic resin blend. Immediately after melting, the thermoplastic resin is pressurized through an annular die to produce a thermoplastic tube. In the case of co-extrusion, multiple extruders are used to produce multilayer thermoplastic tubes. The temperature of the extrusion process is primarily determined by the thermoplastic resin or thermoplastic resin blend being processed, such as the melting temperature or glass transition temperature of the thermoplastic resin and the desired viscosity of the melt. For polyolefins, typical extrusion temperatures range from 330°F to 550°F (166°C to 288°C). Immediately after exiting the annular die, the thermoplastic tube is expanded with air, cooled, and solidified, after which it is pulled through a pair of nip rollers. The air expansion increases the diameter of the tube, forming a bubble of the desired size. Due to the pulling action of the nip rollers, the bubble is stretched in the direction of the machine. Accordingly, bubbles are stretched in two directions: the transverse direction (TD), where the diameter of the bubble increases due to expanding air; and the machine direction (MD), where the nip roller stretches the bubble. Consequently, the physical properties of the blown film are typically anisotropic, meaning that the physical properties differ from one another in the MD and TD directions; for example, the tear strength and tensile properties of the film typically differ from one another in MD and TD. Some prior art literature uses the terms "transverse direction" or "CD"; these terms are equivalent to the terms "transverse direction" or "TD" used in this disclosure.

[0286] In the blown film process, air is blown around the outer circumference of a bubble to cool the thermoplastic resin as it exits the annular die. The final width of the film is determined by adjusting the expansion air or internal pressure of the bubble, that is, by increasing or decreasing the bubble diameter. Film thickness is controlled primarily by increasing or decreasing the speed of the nip roller to regulate the draw-down rate. After exiting the nip roller, the bubble or tube can collapse and be slit in the direction of the machine to produce a sheet. Each sheet can be wound into a film roll. Each roll can be further slit to produce a film of the desired width. Each film roll is further processed into various consumer products as described below.

[0287] Another example of a process for manufacturing single-layer or multi-layer films includes the cast film process.

[0288] The cast film process is similar in that a single or multiple extruder(s) can be used, but various thermoplastic materials are metered onto a flat die and extruded into single-layer or multi-layer sheets rather than tubes. In the cast film process, the extruded sheets are solidified on cooling rolls.

[0289] In the cast film process, the film is extruded from a flattening die onto a cooling roll or nip roll, and a vacuum box and / or air knife are optionally used. The cast film can be a single-layer film or a co-extruded multilayer film obtained by various extrusions through a single or multiple dies. The resulting film can be used as is or laminated onto another film or substrate by thermal lamination, adhesive lamination, or direct extrusion onto a substrate. The resulting films and laminates may undergo other forming operations such as embossing, stretching, and thermoforming. Surface treatments such as corona can be applied, and the film can be printed.

[0290] Further examples of processes for manufacturing monolayer or multilayer films include lamination and coating, wherein the monolayer or multilayer film containing the ethylene / α-olefin copolymer composition disclosed herein is extrusion laminated, adhesive laminated, or extrusion coated. In extrusion lamination or adhesive lamination, two or more substrates are each bonded together with a thermoplastic resin or adhesive. In extrusion coating, a thermoplastic resin is applied to the surface of the substrate. These processes are well known to those skilled in the art. Adhesive lamination or extrusion lamination is often used to bond different materials, and non-limiting examples include bonding a paper web and a thermoplastic web, or bonding an aluminum foil-containing web and a thermoplastic web, or bonding two chemically incompatible thermoplastic webs, for example, bonding a web containing an ethylene / α-olefin copolymer product and a polyester or polyamide web. Prior to lamination, the disclosed ethylene / α-olefin copolymer product(s) containing web may be monolayer or multilayer. Prior to lamination, individual webs may be surface-treated to improve bonding, and a non-limiting example of surface treatment is corona treatment. A primary web or film may be laminated with a secondary web on its upper surface, its lower surface, or both its upper and lower surfaces. A secondary web and a tertiary web may be laminated with the primary web; wherein the secondary web and the tertiary web have different chemical compositions. As a non-limiting example, the secondary or tertiary web may comprise polyamide, polyester, and polypropylene, or may be a web containing a barrier resin layer such as EVOH. Such webs may also contain a deposited barrier layer, for example, a thin silicon dioxide (SiO₂) layer. x ) or aluminum oxide (AlO x It may contain layers. The multilayer web (or film) may contain 3, 5, 7, 9, 11 or more layers.

[0291] The disclosed ethylene / α-olefin copolymer composition can be converted into monolayer or multilayer films of various thicknesses depending on the end use. Non-limiting examples include food packaging films, wherein the thickness may range from about 0.5 mil to about 10 mil.

[0292] The ethylene / α-olefin copolymer composition disclosed herein may be used in a monolayer film, which may contain more than one ethylene / α-olefin copolymer composition and / or additional ethylene or non-ethylene polymers as described herein. The lower limit of the weight percentage of the ethylene / α-olefin copolymer composition in the monolayer film may be about 3 wt%, in other cases about 10 wt%, and in yet another case about 30 wt%. The upper limit of the weight percentage of the ethylene / α-olefin copolymer composition in the monolayer film may be 100 wt%, in other cases about 90 wt%, and in yet another case about 70 wt%.

[0293] The ethylene / α-olefin copolymer composition disclosed herein may be used in one or more layers of a multilayer film structure; non-limiting examples of the multilayer film include 3, 5, 7, 9, 11 or more layers. The thickness of a specific layer (layer containing the ethylene / α-olefin copolymer composition) within the multilayer film structure may be about 5% of the total multilayer film thickness, about 13.5% in other cases, about 15% in other cases, about 20% in other cases, and about 25% in yet another case. In other embodiments, the thickness of a specific layer (layer containing the ethylene / α-olefin copolymer composition) within the multilayer film structure may be about 95% of the total multilayer film structure thickness, about 80% in other cases, and about 65% in yet another case. Each individual layer of the multilayer film structure may contain more than one ethylene / α-olefin copolymer composition and / or additional ethylene or non-ethylene polymers.

[0294] A monolayer or multilayer film comprising the ethylene / α-olefin copolymer composition disclosed herein may be used in various packaging processes, and non-limiting examples thereof include a molding-filling-sealing process for packaging commercial products (e.g., liquids, solids, pastes, parts, etc.) into a pillow pouch or stand-up pouch structure.

[0295] Films used in the manufactured articles described in this section may optionally contain additives and auxiliary agents depending on their intended use. Non-limiting examples of additives and auxiliary agents include anti-blocking agents, antioxidants, heat stabilizers, lubricants, processing aids, antistatic additives, colorants, dyes, fillers, light stabilizers, light absorbers, lubricants, pigments, plasticizers, nucleating agents, and combinations thereof.

[0296] In some embodiments, the multilayer film structure has at least one outer layer, and at least one outer layer comprises the ethylene / α-olefin copolymer composition disclosed herein.

[0297] In some embodiments, the multilayer film structure has at least one outer layer, and at least one outer layer is a sealant layer.

[0298] In some embodiments, the film structure has a sealing start temperature of about 70°C to about 100°C, or about 80°C to about 100°C, or about 85°C to about 100°C, wherein the sealing start temperature is a minimum sealing temperature at which the film structure has a sealing strength greater than 8.8 N per sealing width of 25.4 mm.

[0299] In some embodiments, the film structure has a peak hot tack force greater than about 6 N, or greater than 6.5 N, or greater than 7 N, or greater than 6 N and less than 10 N, or greater than 7 N and less than 10 N.

[0300] Examples

[0301] General test procedures

[0302] Prior to testing, each specimen was conditioned at 23±2°C and 50±10% relative humidity for at least 24 hours, and subsequent testing was performed at 23±2°C and 50±10% relative humidity. Here, the term "ASTM conditions" refers to a laboratory maintained at 23±2°C and 50±10% relative humidity. ASTM refers to the American Society for Testing and Materials.

[0303] polymer density

[0304] The solid-state densities of the disclosed examples and comparative examples were measured using ASTM D792.

[0305] Melting index

[0306] The melt indices of the disclosed examples and comparative examples were measured using ASTM D1238. The melt index I2 was measured at 190°C using a weight of 2.16 kg.

[0307] VICAT softening temperature

[0308] The VICAT softening temperatures of the disclosed examples and comparative examples were measured according to ASTM 1525-17 (August 1, 2017) with a load of 10 ± 0.2 N and a heating rate of 120 ± 10°C / h. The initial temperature of the heat transfer medium (DOW Corning 710) was 20 to 23°C. Unless otherwise specified in this disclosure, VICAT softening temperature measurements were performed on compression-molded specimens formed at 140°C and cooled at a cooling rate of 15°C / min.

[0309] Comonomer content: Fourier Transform Infrared (FTIR) spectroscopy

[0310] In the disclosed examples and comparative examples, the amount of comonomer was measured by FTIR analysis, and was expressed in mol% (mol%), weight percentage (wt%), and CH 3 / 1000 C A short-chain branch having the dimension of (number of methyl branches per 1,000 carbon atoms) SCBIt was reported as the content. This test was completed using a compression-molded polymer plaque and a Thermo-Nicolet 750 Magna-IR spectrometer according to ASTM D6645-01 (2001). The polymer plaque was manufactured using a compression molding device (Wabash-Genesis Series press) according to ASTM D4703-16 (April 2016).

[0311] Zero shear viscosity

[0312] Linear viscoelastic functions were obtained by performing viscous shear measurements under small strain amplitudes at 190°C, in a nitrogen atmosphere, with a 10% strain amplitude, at five points per tenth, within a frequency range of 0.02 to 126 rad / s. Frequency sweep experiments were performed using a TA Instruments DHR3 stress-controlled rheometer with a cone-plate geometry having a cone angle of 5°, a truncated length of 137 μm, and a diameter of 25 mm. In these experiments, sinusoidal strain waves were applied, and the stress response was analyzed using linear viscoelastic functions. Zero shear rate viscosity based on frequency sweep results ( η 0) is It was determined by fitting a 4-parameter Carreau-Yasuda viscosity model to the complex viscosity defined by versus angular frequency, where | η * | is angular frequency ω It is a complex viscosity measured as a function of, a is the slope in a log-log plot n -1 is a parameter that determines the width of the transition from the Newtonian plateau region to the shear thinning region. In the present disclosure, the parameter n was set to a constant value of 2 / 11, and the remaining model parameters were fitted using the least squares method.

[0313] Conventional Size Exclusion Chromatography (SEC)

[0314] Polymer solutions (1 to 3 mg / mL) were prepared by placing the polymer in 1,2,4-trichlorobenzene (TCB), heating in an oven at 150°C for 4 hours, and rotating on a wheel. To stabilize the polymer against oxidative degradation, the antioxidant 2,6-di-tert-butyl-4-methylphenol (BHT) was added to the mixture. The concentration of BHT was 250 ppm. Chromatography of the polymer solutions was performed at 140°C using a PL 220 high-temperature chromatography system equipped with four Shodex columns (HT803, HT804, HT805, and HT806), with TCB as the mobile phase, a flow rate of 1.0 mL / min, and a differential refractive index (DRI) detector as the concentration detector. BHT at a concentration of 250 ppm was added to the mobile phase to prevent oxidative degradation of the GPC columns. The sample injection volume was 200 μL. The GPC column was calibrated with polystyrene standards having a narrow distribution. The polystyrene molecular weight was converted to the polyethylene molecular weight using the Mark-Houwink equation described in ASTM standard test method D6474-12 (December 2012). The raw GPC data were processed with Cirrus GPC software to obtain the average molar mass ( M n , M w , M z ) and molar mass distribution (e.g., polydispersity, M w / M n ...produced ). A term commonly used as a synonym for SEC in the field of polyethylene is GPC, or gel permeation chromatography.

[0315] GPC-FTIR

[0316] The polymer solution was prepared by adding 2 to 4 mg / mL of the polymer sample to 1,2,4-trichlorobenzene (TCB), heating in an oven at 150°C for 4 hours, and rotating. The antioxidant 2,6-di-tert-butyl-4-methylphenol (BHT) was added to the mixture to stabilize the polymer against oxidative degradation. The BHT concentration was 250 ppm. Chromatographic analysis of the sample solution was performed at 140°C using a Waters GPC 150C chromatography system equipped with four Shodex columns (HT803, HT804, HT805, and HT806). TCB was used as the mobile phase at a flow rate of 1.0 mL / min, and a heated FTIR flow-through cell connected to the chromatography system via a heated transfer line and an FTIR spectrometer served as the detection system. BHT at a concentration of 250 ppm was added to the mobile phase to prevent oxidative degradation of the SEC columns. The sample injection volume was 300 μL. Raw FTIR spectra were processed with OPUS FTIR software, and polymer concentration and methyl content were calculated in real time using chemimetric software (PLS technique) associated with OPUS. Then, polymer concentration and methyl content were acquired with Cirrus GPC software and baseline calibration was performed. The SEC column was calibrated with polystyrene standards having a narrow distribution. Polystyrene molecular weight was converted to polyethylene molecular weight using the Mark-Houwink equation described in ASTM standard test method D6474. Comonomer content was calculated based on polymer concentration and methyl content predicted by the PLS technique as described in Paul J. DesLauriers, Polymer 43, pages 159-170 (2002); the said literature is incorporated herein by reference.

[0317] The GPC-FTIR method measures the total methyl content, including methyl groups located at the ends of each macromolecular chain, i.e., methyl terminal groups. Therefore, raw GPC-FTIR data must be corrected by subtracting the contribution of methyl terminal groups. To be clear, raw GPC-FTIR data overestimates the amount of short-chain branches (SCBs), and this overestimation increases as molecular weight decreases. In this disclosure, raw GPC-FTIR data was corrected using 2-methyl correction. Given molecular weight ( M The number of methyl terminal groups (N) in ) E ) was calculated using the following equation: N E = 28000 / M , from raw GPC-FTIR data N E ( M SCB (2-methyl corrected) GPC-FTIR data per 1,000 carbon atoms was generated by subtracting the dependent)

[0318] The slope of the comonomer distribution is determined using GPC-FTIR and is defined as SCB per 1,000 carbons at a molecular weight of 300,000 (g / mol) - SCB per 1,000 carbons at a molecular weight of 30,000 g / mol, where "-" is a minus sign, and SCB per 1,000 carbons is the 2-methyl corrected comonomer content determined by the number of single-chain branches per 1,000 carbons at the corresponding molecular weight (i.e., absolute molecular weight) in the GPC-FTIR chromatograph.

[0319] Long-chain branching factor (LCBF)

[0320] LCBF (Dimensionless) was determined for the disclosed embodiments and comparative examples using the method described in U.S. Patent Application Publication No. 2018 / 0305531 incorporated herein by reference. Briefly, LCBF Is LCBF = ( S h x S v Calculated according to ) / 2; hereS h and S v - log on the horizontal axis is the log value of the polydispersity-corrected zero shear viscosity according to Equation (2) of U.S. Patent Application Publication No. 2018 / 0305531 - log ZSV C , and on the vertical axis, the log value of the short-chain branch (SCB) corrected intrinsic viscosity according to Equation (3) of U.S. Patent Application Publication No. 2018 / 0305531 - log( IV c These are the horizontal and vertical shift coefficients from the baseline for the non-long-chain branched ethylene polymer in the plot plotting ). Zero shear viscosity ( η 0) was measured according to the test procedure described in the section under the heading "Zero Shear Viscosity". Intrinsic viscosity ([ η ]) was measured using triple detection size exclusion chromatography (3D-SEC) according to the method described in U.S. Patent Application Publication No. 2018 / 0305531. Horizontal and vertical shift coefficients S h and S v It was calculated according to Equation (5) and Equation (6) of U.S. Patent Application Publication No. 2018 / 0305531.

[0321] CRYSTAF / TREF

[0322] The "Composition Distribution Width Index" (hereinafter CDBI) of the disclosed ethylene copolymer composition was measured using a CRYSTAF / TREF 200+ instrument equipped with an IR detector, hereinafter CTREF. The acronym "TREF" stands for Temperature Rising Elution Fractionation. The CTREF was supplied by PolymerChar SA (Valencia Technology Park, Gustave Eiffel, 8, Paterna, E-46980 Valencia, Spain). The CTREF was operated in TREF mode, which measures the elution temperature and the CDBI (Composition Distribution Width Index), i.e., CDBI 50 The chemical composition of the polymer sample is generated as a function of. A polymer sample (80 to 100 mg) was placed in a CTREF reactor vessel. 35 ml of 1,2,4-trichlorobenzene (TCB) was added to the reactor vessel, and the solution was heated to 150°C for 2 hours to dissolve the polymer. Then, an aliquot (1.5 mL) of the solution was loaded onto a CTREF column packed with stainless steel beads. The column loaded with the sample was stabilized at 110°C for 45 minutes. Subsequently, the temperature was lowered to 30°C at a cooling rate of 0.09°C / min to crystallize the polymer from the solution in the column. Then, the column was equilibrated at 30°C for 30 minutes. The crystallized polymer was then eluted by passing TCB through the column at a flow rate of 0.75 mL / min, while the column was slowly heated from 30°C to 120°C at a heating rate of 0.25°C / min. The raw CTREF data was processed using Polymer Char software, Excel spreadsheets, and our own developed CTREF software.

[0323] The CTREF procedure described above is also used to determine the weight percentage (wt.%) of test samples eluted in the temperature range of 90°C to 105°C (i.e., the integrated area of ​​the weight percentage of the polymer sample fraction eluted at 90°C to 105°C in the CTREF analysis).

[0324] Hot Tag

[0325] In this disclosure, the “Hot Tack Test” was performed as follows. Hot Tack data was generated using the J&B Hot Tack tester commercially available from Jbi Hot Tack (Belgium B-3630 Maëlëlen Geloslan 30). In the Hot Tack Test, seal strength is measured immediately after two film samples are heat-sealed together, i.e., when the macromolecule containing the film is in a semi-molten state, and the two film samples were cut from the same film roll. This test simulates the heat sealing of a film in a high-speed automatic packaging machine, such as a Vertical Forming, Filling, and Sealing (VFFS) machine. The following parameters were used for 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 / mm²; delay time 0.5 seconds; film peeling speed 7.9 inches / second (200 mm / second); test temperature range 131℉ to 293℉ (55℃ to 145℃); Temperature increment 9℉ (5℃); five film samples were tested at each temperature increment, and the average value at each temperature was calculated. In this way, a hot tack profile of tensile force versus sealing temperature was generated. From this hot tack profile, the following data can be calculated: "Hot tack start temperature at 1.0 N (℃)" or "HTOT" is the temperature at which a hot tack force of 1 N was observed (average value of five film samples); "Maximum hot tack strength (N)" is the maximum hot tack force observed in the test temperature range (average value of five film samples); "Temperature - Maximum hot tack (℃)" is the temperature at which the maximum hot tack force was observed.

[0326] Sealing strength

[0327] In this disclosure, the “heat seal strength test” (also known as the “cold seal test”) was performed as follows. Heat seal data was generated using a standard Instron tensile testing machine. In this test, two film samples were sealed at various temperature ranges—the two film samples were cut from the same film roll. The following parameters were used for the heat seal strength (or cold seal) test: film specimen width 1 inch (25.4 mm); film seal time 0.5 seconds; film seal pressure 40 psi (0.28 N / mm²); temperature range 212℉ to 302℉ (100℃ to 150℃); and temperature increment 9℉ (5℃). After aging for at least 24 hours under ASTM conditions, the seal strength was measured using the following tensile parameters: tensile (crosshead) speed 12 inches / min (2.54 cm / min); tensile direction, 90° relative to the sealing face; five film samples were tested at each temperature increment. The sealing start temperature, hereinafter "SIT", is defined as the temperature at which a sealing strength of more than 8.8 N per 25.4 mm of sealing width is achieved.

[0328] Continuous solution polymerization process

[0329] The ethylene / α-olefin copolymer compositions of Examples 1 to 11 and Comparative Examples 1 to 7 were each prepared using a pilot-scale “series” multiple reactor solution polymerization process, wherein the ethylene / α-olefin copolymer composition was prepared by forming a first ethylene / α-olefin copolymer in a first reactor (R1); and forming a second ethylene / α-olefin copolymer in a second reactor (R2); wherein R1 and R2 were configured in series with each other. A multiple reactor solution polymerization process operating in series is described in U.S. Patent Application Publications No. 2019 / 0135958 and No. 2018 / 0305531.

[0330] In a "series" reactor system, the outlet stream of the first polymerization reactor (R1) flows directly into the second polymerization reactor (R2). The pressure of R1 is between approximately 14 MPa and approximately 18 MPa; whereas R2 was operated at a lower pressure to facilitate the continuous flow from R1 to R2. Both R1 and R2 were continuous stirred reactors (CSTRs). The third reactor (R3) was configured in series with the second reactor (R2) (i.e., the contents of reactor 2 flowed into reactor 3). The third reactor (R3) was a tubular reactor. The process was operated continuously by supplying fresh process solvent, ethylene, octene-1, and hydrogen to the first and second reactors and removing the products. Methylpentane (a commercial blend of methylpentane isomers) was used as the process solvent. The volume of the first CSTR reactor (R1) was 3.2 gallons (12 L), and the volume of the second CSTR reactor (R2) was 5.8 gallons (22 L). The volume of the tubular reactor (R3) was 0.6 gallons (2.2 L). The monomer (ethylene) and comonomer (octene-1) were purified using a conventional feed preparation system (e.g., contact with various adsorption media to remove impurities such as water, oxygen, and polar contaminants) before being added to the reaction. The reactor feed was pumped into the reactors at the rates shown in Table 1.

[0331] Table 1 shows the reactor conditions used to prepare each ethylene / α-olefin copolymer composition in Examples 1 to 11 and Comparative Examples 1 to 7. Table 1 includes process parameters such as the splitting of ethylene and octene-1 between reactors (R1 and R2), reactor temperature, ethylene conversion rate, concentrations of hydrogen, ethylene, and octene-1 in the fresh feed supplied to the reactor, total solution ratio of the fresh feed, and stirring speed of the CSTR reactors (R1 and R2).

[0332] In Examples 1 to 11, the following crosslinked metallocene catalyst components were used to produce a first ethylene / α-olefin copolymer in a first CSTR reactor (R1) and a second ethylene / α-olefin copolymer in a second CSTR reactor (R2): Component A, diphenylmethylene(cyclopentadienyl)(2,7-di-t-butylfluorenyl)hafnium dimethide [(2,7-tBu2Flu)Ph2C(Cp)HfMe2]; Component M, methylaluminoxan (MMAO-07); Component B, trityltetrakis(pentafluorophenyl)borate (trityl borate); and Component P, 2,6-di-tert-butyl-4-ethylphenol (BHEB).methylaluminoxan (MMAO-07); and 2,6-di-tert-butyl-4-ethylphenol were pre-mixed in series and then combined with diphenylmethylene(cyclopentadienyl)(2,7-di-t-butylfluorenyl)hafnium dimethide and trityltetrakis(pentafluorophenyl)borate immediately before entering the polymerization reactors (R1 and R2). The following catalyst component solvents were used: methylpentane for components M and P; and xylene for components A and B. The efficiency of the cross-linked metallocene catalyst formulations was optimized by adjusting the amount of component A added to R1 and R2 [R1 catalyst (ppm) and R2 catalyst (ppm) listed in Table 1], the molar ratios of the catalyst components—i.e., [M] / [A], [P] / [M], and [B] / [A])—and the R1 and R2 catalyst injection temperatures listed in Table 1.

[0333] In Comparative Examples 1 to 7, a first ethylene / α-olefin copolymer was prepared in a first reactor (R1) using the following monosite catalyst components: component A, diphenylmethylene(cyclopentadienyl)(2,7-di-t-butylfluorenyl)hafnium dimethide [(2,7-tBu2Flu)Ph2C(Cp)HfMe2]; component M, methylaluminoxan (MMAO-07); component B, trityltetrakis(pentafluorophenyl)borate (trityl borate); and component P, 2,6-di-tert-butyl-4-ethylphenol (BHEB).methylaluminoxan (MMAO-07); and 2,6-di-tert-butyl-4-ethylphenol were pre-mixed in series and then combined with diphenylmethylene(cyclopentadienyl)(2,7-di-t-butylfluorenyl)hafnium dimethide and trityltetrakis(pentafluorophenyl)borate immediately before entering the polymerization reactor (R1). The following catalyst component solvents were used: methylpentane for components M and P; and xylene for components A and B. The efficiency of the single-site catalyst formulation was optimized by adjusting the amount of component A added to R1 [R1 catalyst (ppm) listed in Table 1], the molar ratios of the catalyst components—i.e., [M] / [A], [P] / [M], and [B] / [A]—and the R1 catalyst injection temperature listed in Table 1.

[0334] In Comparative Examples 1 to 7, an inline Ziegler-Natta catalyst formulation was used to produce a second ethylene / α-olefin copolymer in a second reactor (R2). The components of the inline Ziegler-Natta catalyst formulation are as follows: butyl ethyl magnesium [component v]; tert-butyl chloride [component vi]; titanium tetrachloride [component vii]; diethyl aluminum ethoxide [component viii]; and triethyl aluminum [component ix]. Methylpentane was used as the catalyst component solvent, and the inline Ziegler-Natta catalyst formulation was prepared according to the following steps and then injected into the second reactor (R2). In Step 1, a solution of triethyl aluminum and butyl ethyl magnesium (Mg:Al = 20, mol:mol) was mixed with a tert-butyl chloride solution and reacted for about 30 seconds to produce an MgCl2 support. In step 2, a titanium tetrachloride solution was added to the mixture produced in step 1 and reacted for about 14 seconds, after which it was injected into the second reactor (R2). The inline Ziegler-Natta catalyst was activated in the reactor by injecting a diethylaluminum ethoxide solution into R2. The efficiency of the inline Ziegler-Natta catalyst formulation was optimized by adjusting the amount of titanium tetrachloride added to the reactor (listed as R2 catalyst (ppm) in Table 1), the molar ratio of the catalyst components (i.e., [vi] / [v], [viii] / [vii], and [ix] / [vii]), and the R2 catalyst inlet temperature as listed in Table 1.

[0335] When operating the continuous solution polymerization process shown in Table 1, the total amount of ethylene supplied to the process was distributed or split among the three reactors R1 and R2. In Table 1, this operating variable was referred to as ethylene splitting (ES), i.e. ES R1 and ES R2 is referred to as the weight percentage of ethylene injected into R1 and R2, respectively; provided, ES R1 + ES R2= 100%. Octene-1 was also added to the continuous solution polymerization process and was distributed or split between R1 and R2. In Table 1, this operating variable was called Octene-1 Splitting (OS), i.e. OS R1 and OS R2 was referred to as the weight percentage of octene-1 comonomer injected into R1 and R2, respectively; provided, OS R1 + OS R2 = 100%.

[0336] In Examples 1 to 11 and Comparative Examples 1 to 7, new ethylene, octene-1, hydrogen, and catalyst were not pumped into the third reactor.

[0337] The total amount of ethylene converted in each reactor was monitored while operating the continuous solution polymerization process shown in Table 1. Terms Q R1 referred to the percentage of ethylene added to R1 converted into the first ethylene α / olefin copolymer by the catalytic formulation. Likewise, Q R2 represents the percentage of ethylene added to R2 converted into the second ethylene α / olefin copolymer.

[0338] In Table 1, terms Q T represented the total or total ethylene conversion rate along the entire continuous solution polymerization plant: that is, Q T = 100 × [Weight of ethylene in ethylene α / olefin copolymer composition] / ([Weight of ethylene in ethylene α / olefin copolymer composition] + [Weight of unreacted ethylene]).

[0339] In the continuous solution polymerization process, polymerization was terminated by adding a catalyst deactivator to the third outlet stream coming out of the tubular reactor (R3). The catalyst deactivator used was octanoic acid (caprylic acid) commercially available from P&G Chemicals in Cincinnati, Ohio, USA. The catalyst deactivator was added such that it was 50% of the total molar amount of catalyst metal and aluminum added to the polymerization process; to be clear, the molar amount of added octanoic acid = 0.5 × (molar of hafnium + molar of aluminum).

[0340] A two-stage devolatilization process was used to recover the ethylene / α-olefin copolymer composition from the process solvent; specifically, two gas-liquid separators were used, and the second bottom stream (derived from the second V / L separator) was passed through a gear pump / pelletizer combination. The gear pump was a VACOREX with a capacity of 191 liters per hour. ® It was a 45 / 45 pump, which was steam-jacketed with 270# steam. The ethylene / α-olefin copolymer composition exiting the gear pump was passed through a 4-inch diameter static mixer before entering the pelletizer, where the ethylene / α-olefin copolymer composition was forced from top to bottom through the holes in the die plate. The die had 32 holes with a diameter of 0.125 inches. The aspect ratio (i.e., length-to-diameter ratio) of each hole was 6.3:1, and the die thickness was 1.63 inches and the diameter was 12 inches. On the side of the die facing the cooling water system, there were six cutting edges with an 8.6878-inch OD sweep and a 6.2418-inch ID sweep. There were internal heating channels within the die plate, and the die body and plate were heated with 600# or 270# steam. The temperature range of the cooling water system was 10 to 80°C, and the flow rate was 7,500 to 9,500 kg / h. DHT supplied by Kyowa Chemical Industry Co., Ltd. of Tokyo, Japan. ®-4V (hydrotalcite) can be used as a passivating agent or acid scavenger in a continuous solution process. A slurry of DHT-4V in the process solvent can be added before being fed into the first V / L separator. Prior to pelletization, the ethylene / α-olefin copolymer composition contains 500 ppm of IRGANOX based on the weight of the ethylene / α-olefin copolymer composition. ® 1076 (primary antioxidant) and 500 ppm of IRGAFOS ® 168 (secondary antioxidant) was added to stabilize it. The antioxidant was dissolved in a process solvent and added between the first and second V / L separators.

[0341]

[0342]

[0343]

[0344]

[0345]

[0346]

[0347]

[0348] M of each component manufactured in R1 and R2 w , M n , M w / M n , weight percentage, and SCB per 1,000 carbon atoms were calculated through reactor model simulations using the injection conditions used in actual pilot-scale operations and are shown in Tables 2a to 2c. References for the relevant reactor modeling methods are "Copolymerization" by A. Hamielec, J. MacGregor, and A. Penlidis in Comprehensive Polymer Science and Supplements, volume 3, Chapter 2, page 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" by JBP Soares and AE Hamielec in Polymer Reaction Engineering See , 4(2&3), p153, 1996.

[0349] This model takes the flow rates of various reaction species (e.g., catalysts, monomers such as ethylene, comonomers such as octene-1, hydrogen, and solvents) entering each reactor as injection conditions, temperature (for each reactor), and monomer conversion rate (for each reactor), and calculates the polymer characteristics (polymers produced in each reaction zone) using a terminal kinetics model for a series-connected continuous stirred tank reactor (CSTR). The "terminal kinetics model" assumes that kinetics depend on the monomer units within the polymer chain where the active catalyst sites are located—"Copolymerization" by A. Hamielec, J. MacGregor, and A. Penlidis in Comprehensive Polymer Science and Supplements See Volume 3, Chapter 2, page 17, Elsevier, 1996. In this model, it is assumed that the molecular weight of the copolymer chain is significantly large, so that the statistics for insertion of monomer / comonomer units into the center of the active catalyst are valid, and that monomer / comonomers consumed in pathways other than propagation can be ignored. This is known as the "long chain" approximation.

[0350] The end-stage kinetics model for polymerization includes reaction rate equations for the activation, initiation, propagation, chain transfer, and inactivation pathways. This model solves steady-state conservation equations (e.g., total mass balance and thermal balance) for the reaction fluid containing the reactive species identified above. The total mass balance for a typical CSTR with a given number of inlets and outlets is as follows:

[0351]

[0352] Here, is an index representing the inlet and outlet streams i It represents the mass flow rate of individual streams having . Equation 1 can be further extended to represent individual species and reactions:

[0353]

[0354] Here, is a fluid inlet or outlet i It is the average molar weight of, and is a stream i My servant j It is the mass fraction of, and ρ 혼합물 is the molar density of the reactor mixture, and V is the reactor volume, and is the reaction rate of species j, and kmol / m 3 It has units of s. The total heat balance is interpreted for an adiabatic reactor and is provided as follows:

[0355]

[0356] Here, is a stream i It is the mass flow rate of (inlet or outlet), and stream relative to reference state i It is the enthalpy difference, and q Rx is the heat released by the reaction(s), and V is the reactor volume, and is the input work (i.e., the stirrer), and is the heat input / loss. The catalyst concentration input to each reactor is adjusted to match the experimentally determined ethylene conversion rate and reactor temperature values ​​to solve the kinetic model equations (e.g., propagation rate, heat balance, and mass balance). The H2 concentration input to each reactor can likewise be adjusted so that the calculated molecular weight distribution of the polymer produced in all reactors (and thus, the molecular weight of the polymer produced in each reactor) matches the experimentally observed value.

[0357] The reported weight percentage values ​​shown in Tables 2a to 2c are values ​​such that the sum of the weight percentages of the materials produced in R1 and R2 is 100%.

[0358] Degree of polymerization of the polymerization reaction ( dp n ) is provided as the ratio of the chain propagation reaction rate to the chain transfer / termination reaction rate:

[0359]

[0360] Here, k p 12 is the propagation rate constant for the addition of monomer 2 (octene-1) to a growing polymer chain ending in monomer 1 (ethylene), and [ m 1] is the molar concentration of monomer 1 in the reactor, and [ m 2] is the molar concentration of monomer 2 in the reactor, and k tm 12 is the termination rate constant for chain transfer to monomer 2 for a growing chain ending in monomer 1, and k ts 1 is the spontaneous chain termination rate constant for a chain ending in monomer 1, and k tH 1 is the rate constant for hydrogen chain termination for a chain ending in monomer 1. φ 1 and φ 2 is the fraction of catalytic sites occupied by chains ending in monomer 1 or monomer 2, respectively.

[0361] Number average molecular weight of the polymer (M n ) is derived from 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 for a monosite catalyst, the molecular weight distribution for the polymer is determined through the following relationship:

[0362]

[0363] Here, n is the number of monomer units in the polymer chain, and w ( n ) is the chain length n It is the mass fraction of the polymer chain, τ is calculated using the equation below:

[0364]

[0365] Here dp n is the degree of polymerization, and R p is the propagation speed, and R t is the termination rate. The Florey-Schultz distribution can be converted into a general log-scale gel permeation chromatography, GPC trace by applying the following.

[0366]

[0367] Here, is chain length n ( n = , where 28 is the differential weight fraction of the polymer having the molecular weight of the polymer segment corresponding to the C2H4 unit, and dp n is the degree of polymerization.

[0368] Assuming the Florey-Schultz model, different moments of the molecular weight distribution can be calculated using the following:

[0369]

[0370] in other words, , , and and therefore:

[0371]

[0372] Here, Mw 단량체 is the molecular weight of the polymer segment corresponding to the C2H4 unit of the monomer. Finally, when a single-site catalyst produces long-chain branches, the molecular weight distribution of the polymer is determined using the following relationship ("Polyolefins with Long Chain Branches Made with Single-Site Coordination Catalysts: A Review of Mathematical Modeling Techniques for Polymer Microstructure" by JBP Soares in Macromolecular Materials and Engineering , Volume 289, Issue 1, Pages 70-87, Wiley-VCH, 2004 and “Polyolefin Reaction Engineering” by JBP Soares and TFL McKenna Wiley-VCH, 2012).

[0373]

[0374] Here, n is the number of monomer units in the polymer chain, and w ( n ) is chain length n It is the weight fraction of a polymer chain having, τ B and α It is calculated using the formula below:

[0375]

[0376] Here, is the degree of polymerization, and R p is the propagation speed, R t is the termination speed, R LCB is the long-chain branching rate calculated using the formula below:

[0377]

[0378] Here, k p 13 is the propagation rate constant for the addition of monomer 3 (a macromonomer formed in the reactor) to a growing polymer chain ending in monomer 1, and [ m 3] is the molar concentration of the macromonomer in the reactor. The weight distribution can be converted into a GPC trace on a standard logarithmic scale by applying the following:

[0379]

[0380] Here, is chain length n ( n = , where 28 is the differential weight fraction of the polymer having the molecular weight of the polymer segment corresponding to the C2H4 unit. From the weight distribution, the different moments of the molecular weight distribution can be calculated using the following equation:

[0381]

[0382] Here, is the degree of polymerization, and α is calculated as explained.

[0383] Assuming that the addition of monomer 2 (octene-1) units to a chain ending in an octene terminal unit is not significant, the octene number after the ethylene step is equivalent to the ethylene number after the octene step. Branching content of the polymer produced per 1,000 main chain carbon atoms (500 monomer units), BrF is the ratio of the addition rate of monomer 1 (ethylene) to the addition rate of monomer 2 (octene-1).

[0384]

[0385] Here, k p 12is the propagation rate constant for adding monomer 2 (octene-1) to a growing polymer chain ending in monomer 1 (ethylene), and k p 11 is the propagation rate constant for adding monomer 1 (ethylene) to a growing polymer chain ending in monomer 1 (ethylene), and [ m 1] is the molar concentration of monomer 1 in the reactor, and [ m 2] is the molar concentration of monomer 2 in the reactor.

[0386] Referring to Tables 2a and 2b, Examples 1 to 11 have a weight-average molecular weight M w α is 80 to 140 kg / mol, the comonomer content is 15 to 40 branches per 1,000 carbon atoms, and the polydispersity index M w / M n This contained 30 to 50 weight% of a first ethylene / α-olefin copolymer having a molecular weight of 1.7 to 2.3. In addition, the example had a weight average molecular weight M w α is 20 to 60 kg / mol, the number of short-chain branches per 1,000 carbon atoms is 10 to 35, and the polydispersity index M w / M n This contained 50 to 70 weight% of a second ethylene / α-olefin copolymer with a molecular weight of 1.7 to 2.3. In addition, in Examples 1 to 11, it can be confirmed that the weight-average molecular weight of the second ethylene / α-olefin copolymer is smaller than the weight-average molecular weight of the first ethylene / α-olefin copolymer. In Examples 1 to 11, the ratio of the weight-average molecular weight of the first ethylene / α-olefin copolymer to the weight-average molecular weight of the second ethylene / α-olefin copolymer was 2 to 3. In Comparative Examples 1 to 3, low M w and the copolymer component having a low SCB content, namely the second ethylene / α-olefin copolymer, is M w / M n It can be seen that this exceeds 2.3.

[0387]

[0388]

[0389]

[0390] As summarized in Tables 3a to 3c, Examples 1 to 11 showed an improved (increased) VICAT softening temperature (indicated as VSP in Tables 3a to 3c) compared to Comparative Examples 1 to 7. As will be well known to those skilled in the art, ethylene / α-olefin copolymer compositions with an increased softening temperature allow the softening process to be delayed, thereby enabling the devolatilization of the resulting polymer to proceed at an accelerated rate at a higher temperature. As used herein, devolatilization is defined as the removal of volatile hydrocarbon residues (e.g., unreacted monomers or process solvents) from solid polymer particles using a stripping agent such as air or nitrogen as a finishing step of the polymerization plant (e.g., a process step after pelletization).

[0391] In addition, Examples 1 to 11 are A specific VSP- defined according to η It is noteworthy that it followed the 0-SCB relationship - experimentally measured VSP and predicted VSP( VSP pred Refer to the table value for the absolute value of the difference between ).

[0392]

[0393]

[0394]

[0395] Multilayer film

[0396] The multilayer film was produced on a commercially available 9-layer line at Brampton Engineering (Bramton, Ontario, Canada). The structure of the produced 9-layer film is shown in Table 4. The total thickness of the multilayer film was kept constant at 3.5 mil. The die technology consisted of a pancake die and a FLEX-STACK co-extrusion die (SCD), flow paths were machined on both sides of the plate, the die tooling diameter was 6.3 inches, the die gap was kept constant at 85 mil in the present disclosure, the film was produced at a blow-up rate (BUR) of 2.5, and the line output was kept constant at 200 pounds per hour. The specifications of the nine extruders are as follows: a screw diameter of 1.5 inches, a length-to-diameter ratio of 30 / 1, an 8-polyethylene screw with a single flight, a Maddox mixer, and a 1-Nylon screw; the extruders were air-cooled and equipped with 20-HP motors, and all extruders were fitted with gravimetric blenders. The nip and collapsing frames included Decatex horizontal vibrating pullers and pearl cooling slats directly below the nip. The lines were equipped with turret winders and vibrating slitter knives. Table 5 summarizes the temperature settings used. The temperatures of all dies—namely, the layer section, mandrel bottom, mandrel, inner lip, and outer lip—were maintained constant at 430°F.

[0397]

[0398]

[0399] Caulking test

[0400] This test allows for the evaluation of the caulkability of the sealant layer in a multilayer film, i.e., the sealing performance against contaminants. The definitions and descriptions of the caulkability tests are as follows: "Burst Test": Also known as the seal strength test, the package is connected to a machine with a needle, and the air pressure inside the package is increased until it bursts to measure the seal strength; if the package seal is strong, the film structure typically expands and ruptures instead of failing due to seal leakage; the burst test complies with ASTM F2054-13 (issued June 2013). "Leak Test": Also known as the pressure loss test, it is used to evaluate the integrity of the package, and the leak test complies with ASTM F2095-07 (issued September 2013); the package is connected to a machine with a needle, and the internal pressure of the package is set to 50% of the burst pressure; the test pressure and the pressure loss during the test can be used as a measure of package integrity; these results provide the theoretical "hole size" of the leak; This information can be used to calculate the leakage rate and average hole size, and this calculation complies with ASTM F2095; "hole length" is the seal width measured in millimeters used in the hole size calculation; "volume" is the value obtained by subtracting the volume of the product inside the package from the expanded volume of the package; and "caulking ability" is a term related to the ability of the sealant to encapsulate contaminants within the seal or to flow completely into the voids within the seal so that the package does not leak.

[0401] The test equipment consists of the following items: Mocon Lippke Package Test System 4500, 1 bar; needle (sharp 1B or blunt 2B); Septa Black 4 mm; ASTM compliant mounting plate; PC software version 1.2 with hole size calculation function; and impulse sealer.

[0402] The following describes the manufacture of a film package (or pouch) for a caulking test, wherein the film consists of the 9-layer film described in Table 4. Sixteen film specimens are cut to form a single-layer sheet (of the 9-layer film) 14 inches long and 7 inches wide (the 14-inch dimension is the transverse direction of the film, i.e., the transverse direction defined during film production on the blown film line); the film sheets are folded in half to form a 7-inch square double-layer sheet; a 3-styrofoam pack peanut is placed inside the pouch to maintain separation between the upper and lower film layers; the top of the double-layer sheet is impulse-sealed; the left edge of the double-layer sheet is impulse-sealed; a contaminant (a copper wire with a diameter of 0.01 inches) is placed between the double-layer sheets; and the remaining open end (bottom) of the pouch is heat-sealed using an SL5 sealer (120°C / 40 psi / 0.5 second hold time) so that the contaminant is trapped inside the heat seal. The resulting packaging has a volume of approximately 650 ml. Five pouches containing copper wire contaminants are prepared for leak testing; and five pouches without copper wire contaminants are prepared for burst testing. Using the burst test, the pouches (without contaminants) are inflated, and the average burst pressure of the five pouches is determined (assuming the average burst pressure is 8 psi). After inflating the pouches with contaminants to 50% of the average burst pressure (i.e., 4 psi), a leak test is performed, the pressure collapse and time are monitored, and the hole size (μm) is calculated.

[0403] To calculate the leakage rate (volumetric flow rate), the pressure loss ΔP and time Δt are required; these are measured in the leakage test. Volume is specified as a test parameter. The leakage rate according to ASTM F2095 is calculated as follows:

[0404]

[0405] For example, volume ( V A package of 1 liter (1000 cm³) is tested for 30 seconds, and after that time, 10 mbar (ΔP = 9.87×10 -3 (atm) is lost. A leakage rate of 0.329 sccs is resulted; to convert this leakage rate from sccs to mbar × cm³ / s, multiply by 1.01325.

[0406] The "hole size" is calculated using the Hagen-Poiseullie law; this requires the following: leakage rate (volumetric flow rate, cc / sec), path length (hole length, cm), differential pressure, and kinematic viscosity. The leakage rate is determined as described above (leakage test); the differential pressure is measured during the pressure loss test; the hole length is specified as part of the pressure loss test parameter set, and the viscosity is constant (the working fluid is air; air viscosity η 공기 = 1.827 × 10⁻⁶ -4 Pa·s, at 18℃).

[0407] The effective (average) "hole size" is calculated as follows using the Hagen-Poiseullie law:

[0408]

[0409] During the test, the pressure inside the package changes, and

[0410]

[0411] It results in the following:

[0412]

[0413] In the present disclosure, the diameter of the hole d is defined as "hole size" and is measured in microns (μm).

[0414]

[0415] Table 6 summarizes the hole size data obtained by measuring the caulkability test according to Equation 20 in μm units. The listed hole size values ​​are the average of 5 measurements. The values ​​in parentheses are the standard deviation values ​​calculated based on 5 measurements.

[0416] Table 6 shows the experimentally measured VSP and predicted VSP in Tables 3a to 3c ( VSP pred. It additionally includes the absolute value of the difference of ). As you can see, in the sealant layer | VSP - VSP pred. The 9-layer structure containing the example at 1.5℃ or lower is | VSP - VSP pred. It had an improved (reduced) pore size value compared to the comparative example exceeding 1.5℃. Softening temperature of Comparative Examples 2, 3, and 5 VSP Considering that is lower than the corresponding example among Examples 1 to 8, 10, and 11, the observation of improved caulking properties or contaminant-preventing sealing performance in the case of Examples 1 to 8, 10, and 11 is a result not particularly expected by those skilled in the art, and similar VSP pred. The sealing temperature T s = results in a larger difference between 120℃ and their experimentally measured softening temperatures. To be clear, the predicted softening temperature of Comparative Example 2 VSP pred. = 88.0, and the predicted softening temperature of Example 11 VSP pred. = was 88.1℃. Comparative Example 2 was experimentally measured VSP It was 85.4℃, and as a result T s - VSP was 34.6℃, and the experimentally measured VSP of Example 11 was 88.7℃, and as a result T s - VSP It was 31.3℃.

[0417]

[0418] Sealing strength and heat sealing performance

[0419] Table 7 summarizes the sealing characteristics of the manufactured 9-layer film structure, namely the hot tack onset temperature (HTOT) at 1.0 N, maximum hot tack strength, and the seal onset temperature at 8.8 N / 2.5 mm. The data provided in Table 7 demonstrated that the multilayer film manufactured with a 9-layer structure incorporating Examples 1 to 8, 10, and 11 exhibited similar or superior heat sealing characteristics compared to the structure incorporating Comparative Examples 2, 3, and 5.

[0420]

[0421] Molding-Filling-Sealing Process

[0422] The heat sealing performance of a 9-layer film containing the ethylene / α-olefin copolymer compositions prepared in Examples 1, 3, 5 to 7 and Comparative Examples 2 and 3 in the sealant layer, as described in Table 4, was characterized in a horizontal forming-filling-sealing (HFFS) process using an Effytech HB15 HFFS machine. As shown in Tables 8a and 8b, the HFFS machine had three sealing stations (sealing stations 1 to 3) that form the body of the stand-up pouch. Sealing stations 1 and 2 are plate sealers that form the horizontal and bottom seals of the pouch. The third sealing station is a point sealer that seals only a small area of ​​the joint where four film layers meet to form a gusset. Approximately 50 ml of room temperature water was partially filled into a manufactured stand-up pouch (height 190 mm × width 125 mm), sealed with a top heat sealer at 120°C, and then tested in a Haug vacuum leak tester at a pressure of 15 mmHg for 30 seconds. Pouches that produced bubbles in the water bath were considered defective. Pouches that did not produce bubbles were recorded as acceptable. A total of 20 bags were produced under each sealing condition. The results in Tables 8a-8b are recorded as the pass rate (%) out of the 20 bags. The pouch production speed was set to 60 bags per minute.

[0423] The seal integrity of pillow pouches produced from 9-layer films containing the ethylene / α-olefin copolymer compositions prepared in Examples 1, 3, 5, and 6 as described in Table 4 was characterized in a vertical forming-filling-sealing (VFFS) process using a ROVEMA VFFS machine. Pin-sealed pillow pouches measuring 200 mm × 150 mm filled with approximately 100 ml of room temperature water were produced at a fixed sealing bar temperature using the following four general conditions: low sealing time and low sealing bar pressure; low sealing time and high sealing bar pressure; high sealing time and low sealing bar pressure; and high sealing time and high sealing bar pressure (see Table 9a-b). A total of 20 bags were produced for each of the four conditions at a specific sealing bar temperature, and a Haug vacuum leak test was performed. The bags produced under each condition were tested for leakage (inspection for bubble formation in a water bath) for 30 seconds at a pressure of 15 mmHg. To be considered successful in this test procedure, at least 18 out of 20 bags tested under all four conditions at a specific sealing bar temperature must pass the Haug vacuum leak test (i.e., no leaks should be observed). In this procedure, the success or failure of the bags under each of the four conditions was evaluated using an initial horizontal sealing temperature of 95°C, and then the test was repeated to evaluate the success or failure of the bags under each of the four conditions while increasing the horizontal sealing temperature by 5°C. The vertical sealing temperature was maintained constant at 165°C.

[0424] Referring to the data summarized in Tables 8a to 8b and 9a to 9b, those skilled in the art understand that a nine-layer structure comprising the ethylene / α-olefin copolymer composition of the present disclosure provides desirable heat sealing properties for high-speed vertical and horizontal molding-filling-sealing processes for loading and sealing commercially available products (liquids, solids, pastes, parts, etc.) inside pouch-type packaging materials.

[0425]

[0426]

[0427]

[0428]

[0429] Example A: An ethylene / α-olefin copolymer composition comprising about 30 to about 50 weight% of a first ethylene / α-olefin copolymer, wherein the short-chain branching content comprises about 15 to about 40 branches per 1,000 carbon atoms, SCB 1 , weight average molecular weight of about 80 kg / mol to about 140 kg / mol, M w 1 , and polyvariance indices of about 1.7 to about 2.3, M w 1 / M n 1 A first ethylene / α-olefin copolymer having; and about 50 to about 70 weight% of a second ethylene / α-olefin copolymer, wherein the short-chain branching content has about 10 to about 35 branches per 1,000 carbon atoms, SCB 2 , weight average molecular weight of about 20 kg / mol to about 60 kg / mol, M w 2 , and polyvariance indices of about 1.7 to about 2.3, M w 2 / M n 2 Comprising a second ethylene / α-olefin copolymer having; wherein the short-chain branching content of the first ethylene / α-olefin copolymer, SCB 1 The short-chain branching content of the second ethylene / α-olefin copolymer, SCB 2Greater than or equal to; the ethylene / α-olefin copolymer composition has a melt index I2 of about 2.5 to about 6 dg / min, measured using a weight of 2.16 kg at 190°C according to ASTM D1238, and a density of about 0.860 to about 0.910 g / cm³, measured according to ASTM D792. 3 and; the ethylene / α-olefin copolymer composition has a zero shear viscosity at 190°C satisfying (I) below η 0, VICAT softening temperature measured according to ASTM D1525 VSP , and short-chain branch content measured according to ASTM D6645 SCB Ethylene / α-olefin copolymer composition having:

[0430]

[0431] Example B: In Example A, the ethylene / α-olefin copolymer composition at about 70°C to about 100°C VSP An ethylene / α-olefin copolymer composition having

[0432] Example C: In Example A, the ethylene / α-olefin copolymer composition at about 80°C to about 95°C VSP An ethylene / α-olefin copolymer composition having

[0433] Example D: An ethylene / α-olefin copolymer composition in Example A, B or C, wherein the ethylene / α-olefin copolymer composition has a density of about 0.885 to about 0.910 g / cm³.

[0434] Example E: An ethylene / α-olefin copolymer composition in Example A, B or C, wherein the ethylene / α-olefin copolymer composition has a density of about 0.900 to about 0.910 g / cm³.

[0435] Example F: The ethylene / α-olefin copolymer composition of Examples A, B, C, D or E, wherein the ethylene / α-olefin copolymer composition has a melt index I2 of about 3 to about 6 dg / min.

[0436] Example G: An ethylene / α-olefin copolymer composition in Example A, B, C, D or E, wherein the ethylene / α-olefin copolymer composition has a melt index I2 of about 4 to about 6 dg / min.

[0437] Example H: In Examples A, B, C, D, E, F or G, the ethylene / α-olefin copolymer composition satisfies the following (II). η 0, VSP and SCB Ethylene / α-olefin copolymer composition having:

[0438]

[0439] Example I: An ethylene / α-olefin copolymer composition having a monomodified molecular weight distribution, in accordance with Examples A, B, C, D, E, F, G, or H.

[0440] Example J: In Examples A, B, C, D, E, F, G, H or I, the ethylene / α-olefin copolymer composition has a polydispersity index M w / M n An ethylene / α-olefin copolymer composition having a molecular weight distribution of about 2.1 to about 4.

[0441] Example K: In Examples A, B, C, D, E, F, G, H, I, or J, the first ethylene / α-olefin copolymer and the second ethylene / α-olefin copolymer M w 1 big M w 2 An ethylene / α-olefin copolymer composition having a ratio of about 2 to about 3.

[0442] Example L: In Examples A, B, C, D, E, F, G, H, I, J or K, the short-chain branching content of the first ethylene / α-olefin copolymer and the second ethylene / α-olefin copolymer, SCB 1 and SCB 2 go SCB 1 > SCB 2 An ethylene / α-olefin copolymer composition satisfying [ ].

[0443] Example M: ​​An ethylene / α-olefin copolymer composition according to Example L, wherein the ethylene / α-olefin copolymer composition has a comonomer distribution profile in GPC-FTIR analysis, and the comonomer distribution profile has a secant slope of about +1 short chain branch per 1,000 carbons to about +30 short chain branches per 1,000 carbons, and the secant slope is defined as the value obtained by subtracting the number of short chain branches per 1,000 carbons at a molecular weight of 30 kg / mol from the number of short chain branches per 1,000 carbons at a molecular weight of 30 kg / mol.

[0444] Example N: An ethylene / α-olefin copolymer composition in Example L or M, wherein the ethylene / α-olefin copolymer composition has a reversed-phase comonomer distribution profile.

[0445] Example O: An ethylene / α-olefin copolymer composition according to Examples A, B, C, E, F, G, H, I, J, K, L, M or N, comprising a fraction eluted in a temperature range of 90°C to 105°C in which the integrated area in CTREF analysis is less than 1 weight%.

[0446] Example P: An ethylene / α-olefin copolymer composition in Example A, B, C, E, F, G, H, I, J, K, L, M, N or O, wherein the ethylene / α-olefin copolymer composition contains long chain branches determined according to the long chain branching factor, LCBF, at a detectable level of 0.001 or more.

[0447] Example Q: In Examples A, B, C, E, F, G, H, I, J, K, L, M, N, O, or P, the ethylene / α-olefin copolymer composition is C3 to C 10 An ethylene / α-olefin copolymer composition comprising at least one α-olefin selected from the group consisting of α-olefins.

[0448] Example R: An ethylene / α-olefin copolymer composition in Example A, B, C, E, F, G, H, I, J, K, L, M, N, O, or P, wherein the ethylene / α-olefin copolymer composition comprises at least one α-olefin selected from the group consisting of hexene-1, octene-1, and mixtures thereof.

[0449] Example S: In Examples A, B, C, E, F, G, H, I, J, K, L, M, N, O or P, the ethylene / α-olefin copolymer composition essentially comprises ethylene and octene-1.

[0450] Embodiment T: A film layer comprising an ethylene / α-olefin copolymer composition according to Embodiments A, B, C, E, F, G, H, I, J, K, L, M, N, O, P, Q, R, or S.

[0451] Embodiment U: A multilayer film structure, wherein the film structure has at least one outer layer, and at least one outer layer comprises an ethylene / α-olefin copolymer composition according to Embodiments A, B, C, E, F, G, H, I, J, K, L, M, N, O, P, Q, R, or S.

[0452] Embodiment V: A multilayer film structure in which, in Embodiment U, at least one outer layer is a sealant layer.

[0453] Embodiment W: A multilayer film structure in which, in Embodiment V, the film structure has a sealing start temperature of about 70°C to 100°C, and the sealing start temperature is a minimum sealing temperature in which the film structure has a sealing strength of more than 8.8 N per sealing width of 25.4 mm.

[0454] Embodiment X: In Embodiment V or W, a multilayer film structure having a peak hot tack force of more than about 6 N.

[0455] Example Y: An ethylene / α-olefin copolymer composition, wherein about 30 to about 50 weight% of a first ethylene / α-olefin copolymer, the content of short chain branches having about 15 to about 40 branches per 1,000 carbon atoms, SCB 1 , weight average molecular weight of about 80 kg / mol to about 140 kg / mol, M w 1 , and polyvariance indices of about 1.7 to about 2.3, M w 1 / M n 1 A first ethylene / α-olefin copolymer having; and about 50 to about 70 weight% of a second ethylene / α-olefin copolymer, wherein the short-chain branching content has about 10 to about 35 branches per 1,000 carbon atoms, SCB 2, weight average molecular weight of about 20 kg / mol to about 60 kg / mol, M w 2 , and polyvariance indices of about 1.7 to about 2.3, M w 2 / M n 2 Comprising a second ethylene / α-olefin copolymer having; wherein the short-chain branching content of the first ethylene / α-olefin copolymer, SCB 1 The short-chain branching content of the second ethylene / α-olefin copolymer, SCB 2 Greater than or equal to; the ethylene / α-olefin copolymer composition has a melt index I2 of about 2.5 to about 6 dg / min, measured using a weight of 2.16 kg at 190°C according to ASTM D1238, and a density of about 0.860 to about 0.910 g / cm³, measured according to ASTM D792. 3 The ethylene / α-olefin copolymer composition comprises a fraction eluted in a temperature range of 90°C to 105°C with an integrated area of ​​less than 1 weight% in CTREF analysis.

[0456] Example Z: An ethylene / α-olefin copolymer composition in Example Y, wherein the ethylene / α-olefin copolymer composition has a VSP of about 70°C to about 100°C, or about 80°C to about 95°C.

[0457] Example AA: An ethylene / α-olefin copolymer composition in Example Y, wherein the ethylene / α-olefin copolymer composition has a VSP of about 70°C to about 100°C.

[0458] Example BB: An ethylene / α-olefin copolymer composition in Example Y, Z or AA, wherein the ethylene / α-olefin copolymer composition has a density of about 0.885 to about 0.910 g / cm³.

[0459] Example CC: An ethylene / α-olefin copolymer composition in Example Y, Z or AA, wherein the ethylene / α-olefin copolymer composition has a density of about 0.900 to about 0.910 g / cm³.

[0460] Example DD: In Examples Y, Z, AA, BB or CC, the ethylene / α-olefin copolymer composition has a melt index I2 of about 3 to about 6 dg / min.

[0461] Example EE: In Examples Y, Z, AA, BB or CC, the ethylene / α-olefin copolymer composition has a melt index I2 of about 4 to about 6 dg / min.

[0462] Example FF: In Examples Y, Z, AA, BB, CC, or EE, the shear viscosity at 190°C of the ethylene / α-olefin copolymer composition satisfies (I) below. η 0, VICAT softening temperature measured according to ASTM D1525 VSP , and short-chain branch content measured according to ASTM D6645 SCB Ethylene / α-olefin copolymer composition having:

[0463]

[0464] Example GG: In Examples Y, Z, AA, BB, CC, or EE, the ethylene / α-olefin copolymer composition has a shear viscosity at 190°C that satisfies (II) below, VSP and SCB Ethylene / α-olefin copolymer composition having:

[0465]

[0466] Example HH: In Example Y, Z, AA, BB, CC, DD, EE, FF, or GG, the ethylene / α-olefin copolymer composition has a monomodified molecular weight distribution.

[0467] Example II: In Examples Y, Z, AA, BB, CC, DD, EE, FF, GG, or HH, the ethylene / α-olefin copolymer composition has a polydispersity index M w / M n An ethylene / α-olefin copolymer composition having a molecular weight distribution of about 2.1 to about 4.

[0468] Example JJ: In Examples Y, Z, AA, BB, CC, DD, EE, FF, GG, HH, or II, the first ethylene / α-olefin copolymer and the second ethylene / α-olefin copolymer M w 1 big M w 2 An ethylene / α-olefin copolymer composition having a ratio of about 2 to about 3.

[0469] Example KK: In Examples Y, Z, AA, BB, CC, DD, EE, FF, GG, HH, II, or JJ, the short-chain branching content of the first ethylene / α-olefin copolymer and the second ethylene / α-olefin copolymer, SCB 1 and SCB 2 go SCB 1 > SCB 2 An ethylene / α-olefin copolymer composition satisfying [ ].

[0470] Example LL: An ethylene / α-olefin copolymer composition in Example KK, wherein the ethylene / α-olefin copolymer composition has a comonomer distribution profile in GPC-FTIR analysis, and the comonomer distribution profile has a secant slope of about +1 short chain branch per 1,000 carbons to about +30 short chain branches per 1,000 carbons, and the secant slope is defined as the value obtained by subtracting the number of short chain branches per 1,000 carbons at a molecular weight of 30 kg / mol from the number of short chain branches per 1,000 carbons at a molecular weight of 30 kg / mol.

[0471] Example MM: An ethylene / α-olefin copolymer composition in Example KK or LL, wherein the ethylene / α-olefin copolymer composition has a reverse phase comonomer distribution.

[0472] Example NN: In Example Y, Z, AA, BB, CC, DD, EE, FF, GG, HH, II, JJ, KK, LL, or MM, the ethylene / α-olefin copolymer composition contains a long chain branch determined according to the long chain branch factor, LCBF, at a detectable level of 0.001 or more.

[0473] Example OO: In Examples Y, Z, AA, BB, CC, DD, EE, FF, GG, HH, II, JJ, KK, LL, MM, or NN, the ethylene / α-olefin copolymer composition is C3 to C 10 An ethylene / α-olefin copolymer composition comprising at least one α-olefin selected from the group consisting of α-olefins.

[0474] Example PP: In Example Y, Z, AA, BB, CC, DD, EE, FF, GG, HH, II, JJ, KK, LL, MM, or NN, the ethylene / α-olefin copolymer composition comprises at least one α-olefin selected from the group consisting of hexene-1, octene-1, and mixtures thereof.

[0475] Example QQ: In Example Y, Z, AA, BB, CC, DD, EE, FF, GG, HH, II, JJ, KK, LL, MM, or NN, the ethylene / α-olefin copolymer composition is essentially composed of ethylene and octene-1.

[0476] Embodiment RR: A film layer comprising an ethylene / α-olefin copolymer composition according to Embodiments Y, Z, AA, BB, CC, DD, EE, FF, GG, HH, II, JJ, KK, LL, MM, NN, or QQ.

[0477] Example SS: A multilayer film structure, wherein the film structure has at least one outer layer, and at least one outer layer comprises an ethylene / α-olefin copolymer according to Example Y, Z, AA, BB, CC, DD, EE, FF, GG, HH, II, JJ, KK, LL, MM, NN, or QQ.

[0478] Embodiment TT: In Embodiment SS, a film structure in which at least one outer layer is a sealant layer.

[0479] Embodiment UU: Embodiment TT, wherein the film structure has a sealing start temperature of about 70°C to 100°C, and the sealing start temperature is a minimum sealing temperature at which the film structure has a sealing strength of more than 8.8 N per sealing width of 25.4 mm.

[0480] Embodiment VV: In Embodiment TT or UU, the film structure has a peak hot tack force of more than about 6 N.

[0481] Industrial applicability

[0482] An ethylene / α-olefin copolymer composition is provided having a melt index I2 of about 2.5 to about 6 dg / min and a density of about 0.860 to about 0.910 g / cm³. This ethylene / α-olefin copolymer composition exhibits a softening delay property, thereby reducing the tendency for aggregation formation in the devolatilization zone of a polymerization plant. When converted into a film, this ethylene / α-olefin copolymer composition can be advantageously used for heat sealing applications requiring contaminant barrier sealing properties.

Claims

Claim 1 As an ethylene / α-olefin copolymer composition, about 30 to about 50 weight% of a first ethylene / α-olefin copolymer, wherein the short-chain branching content is about 15 to about 40 branches per 1,000 carbon atoms, SCB 1 , weight average molecular weight of about 80 kg / mol to about 140 kg / mol, M w 1 , and polyvariance indices of about 1.7 to about 2.3, M w 1 / M n 1 A first ethylene / α-olefin copolymer having; and about 50 to about 70 weight% of a second ethylene / α-olefin copolymer, wherein the short-chain branching content has about 10 to about 35 branches per 1,000 carbon atoms, SCB 2 , weight average molecular weight of about 20 kg / mol to about 60 kg / mol, M w 2 , and polyvariance indices of about 1.7 to about 2.3, M w 2 / M n 2 Comprising a second ethylene / α-olefin copolymer having; the short-chain branching content of the first ethylene / α-olefin copolymer, SCB 1 is the short-chain branching content of the second ethylene / α-olefin copolymer, SCB 2 Greater than or equal to; the ethylene / α-olefin copolymer composition has a melt index I2 of about 2.5 to about 6 dg / min, measured using a weight of 2.16 kg at 190°C according to ASTM D1238, and a density of about 0.860 to about 0.910 g / cm³, measured according to ASTM D792. 3 and; the ethylene / α-olefin copolymer composition has a zero shear viscosity at 190°C satisfying (I) below η 0, VICAT softening temperature measured according to ASTM D1525 VSP , and short-chain branch content measured according to ASTM D6645 SCB Ethylene / α-olefin copolymer composition having: Claim 2 The ethylene / α-olefin copolymer composition according to claim 1, wherein the VSP of the ethylene / α-olefin copolymer composition is about 70°C to about 100°C. Claim 3 The ethylene / α-olefin copolymer composition according to claim 1, wherein the VSP of the ethylene / α-olefin copolymer composition is about 80°C to about 95°C. Claim 4 An ethylene / α-olefin copolymer composition according to any one of claims 1 to 3, wherein the density of the ethylene / α-olefin copolymer composition is about 0.885 to about 0.910 g / cm³. Claim 5 An ethylene / α-olefin copolymer composition according to any one of claims 1 to 3, wherein the density of the ethylene / α-olefin copolymer composition is about 0.900 to about 0.910 g / cm³. Claim 6 An ethylene / α-olefin copolymer composition according to any one of claims 1 to 5, wherein the melt index I2 of the ethylene / α-olefin copolymer composition is about 3 to about 6 dg / min. Claim 7 In any one of paragraphs 1 through 6, η 0, VSP and SCB an ethylene / α-olefin copolymer composition satisfying the following (II): Claim 8 An ethylene / α-olefin copolymer composition according to any one of claims 1 to 7, wherein the ethylene / α-olefin copolymer composition has a monomodified molecular weight distribution. Claim 9 In any one of claims 1 to 8, the ethylene / α-olefin copolymer composition has a polydispersity index M w / M n An ethylene / α-olefin copolymer composition having a molecular weight distribution of about 2.1 to about 4. Claim 10 In any one of paragraphs 1 through 9, M w 1 big M w 2 An ethylene / α-olefin copolymer composition having a ratio of about 2 to about 3. Claim 11 In any one of claims 1 to 10, the short-chain branching content of the first ethylene / α-olefin copolymer, SCB 1 The short-chain branching content of the above-mentioned second ethylene / α-olefin copolymer, SCB 2 A larger ethylene / α-olefin copolymer composition. Claim 12 An ethylene / α-olefin copolymer composition according to claim 11, wherein the ethylene / α-olefin copolymer composition has a comonomer distribution profile in GPC-FTIR analysis, and the comonomer distribution profile has a secant slope of about +1 short chain branch per 1,000 carbons to about +30 short chain branches per 1,000 carbons, and the secant slope is defined as the value obtained by subtracting the number of short chain branches per 1,000 carbons at a molecular weight of 30 kg / mol from the number of short chain branches per 1,000 carbons at a molecular weight of 30 kg / mol. Claim 13 An ethylene / α-olefin copolymer composition according to claim 11 or 12, wherein the comonomer distribution profile is a reversed comonomer distribution profile. Claim 14 An ethylene / α-olefin copolymer composition according to any one of claims 1 to 13, comprising a fraction that is eluted in a temperature range of 90°C to 105°C in which the integrated area in CTREF analysis is less than 1 weight%. Claim 15 An ethylene / α-olefin copolymer composition according to any one of claims 1 to 14, wherein the ethylene / α-olefin copolymer composition contains long chain branches determined according to the long chain branching factor, LCBF, at a detectable level of 0.001 or more. Claim 16 In any one of claims 1 to 15, the ethylene / α-olefin copolymer composition is C3 to C 10 An ethylene / α-olefin copolymer composition comprising at least one α-olefin selected from the group consisting of α-olefins. Claim 17 An ethylene / α-olefin copolymer composition according to any one of claims 1 to 15, wherein the ethylene / α-olefin copolymer composition comprises at least one α-olefin selected from the group consisting of hexene-1, octene-1, and mixtures thereof. Claim 18 An ethylene / α-olefin copolymer composition according to any one of claims 1 to 15, wherein the ethylene / α-olefin copolymer composition is essentially composed of ethylene and octene-1. Claim 19 As an ethylene / α-olefin copolymer composition, About 30 to about 50 weight% of a first ethylene / α-olefin copolymer, wherein the short-chain branching content is about 15 to about 40 branches per 1,000 carbon atoms, SCB 1 , weight average molecular weight of about 80 kg / mol to about 140 kg / mol, M w 1 , and polyvariance indices of about 1.7 to about 2.3, M w 1 / M n 1 A first ethylene / α-olefin copolymer having; and About 50 to about 70 weight% of a second ethylene / α-olefin copolymer, wherein the short-chain branching content is about 10 to about 35 branches per 1,000 carbon atoms, SCB 2 , weight average molecular weight of about 20 kg / mol to about 60 kg / mol, M w 2 , and polyvariance indices of about 1.7 to about 2.3, M w 2 / M n 2 Comprising a second ethylene / α-olefin copolymer having; Here, the short-chain branching content of the first ethylene / α-olefin copolymer, SCB 1 is the short-chain branching content of the second ethylene / α-olefin copolymer, SCB 2 Greater than or equal to; The above ethylene / α-olefin copolymer composition has a melt index I2 of about 2.5 to about 6 dg / min, measured using a weight of 2.16 kg at 190°C according to ASTM D1238, and a density of about 0.860 to about 0.910 g / cm³, measured according to ASTM D792. 3 is; The above ethylene / α-olefin copolymer composition comprises a fraction eluted in a temperature range of 90°C to 105°C, in which the integrated area in CTREF analysis is less than 1 weight%. Claim 20 In claim 19, the short-chain branching content of the first ethylene / α-olefin copolymer, SCB 1 The short-chain branching content of the above-mentioned second ethylene / α-olefin copolymer, SCB 2 A larger ethylene / α-olefin copolymer composition. Claim 21 An ethylene / α-olefin copolymer composition according to claim 20, wherein the ethylene / α-olefin copolymer composition has a comonomer distribution profile in GPC-FTIR analysis, and the comonomer distribution profile has a secant slope of about +1 short chain branch per 1,000 carbons to about +30 short chain branches per 1,000 carbons, and the secant slope is defined as the value obtained by subtracting the number of short chain branches per 1,000 carbons at a molecular weight of 30 kg / mol from the number of short chain branches per 1,000 carbons at a molecular weight of 30 kg / mol. Claim 22 An ethylene / α-olefin copolymer composition according to claim 20 or 21, wherein the comonomer distribution profile is a reversed comonomer distribution profile. Claim 23 In any one of claims 19 to 22, the ethylene / α-olefin copolymer composition is C3 to C 10 An ethylene / α-olefin copolymer composition comprising at least one α-olefin selected from the group consisting of α-olefins. Claim 24 An ethylene / α-olefin copolymer composition according to any one of claims 19 to 22, wherein the ethylene / α-olefin copolymer composition comprises at least one α-olefin selected from the group consisting of hexene-1, octene-1, and mixtures thereof. Claim 25 An ethylene / α-olefin copolymer composition according to any one of claims 19 to 22, wherein the ethylene / α-olefin copolymer composition is essentially composed of ethylene and octene-1. Claim 26 A film layer comprising an ethylene / α-olefin copolymer composition according to any one of claims 1 to 25. Claim 27 A multilayer film structure, wherein the film structure has at least one outer layer, and the at least one outer layer comprises an ethylene / α-olefin copolymer composition according to any one of claims 1 to 25. Claim 28 In claim 27, a film structure in which at least one outer layer is a sealing layer. Claim 29 A film structure according to claim 28, wherein the film structure has a sealing start temperature of about 70°C to 100°C, and the sealing start temperature is a minimum sealing temperature at which the film structure has a sealing strength of more than 8.8 N per sealing width of 25.4 mm. Claim 30 A film structure according to claim 28 or 29, wherein the film structure has a peak hot tack force of more than about 6 N.

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