Ethylene interpolymer products and films

Abstract

An ethylene interpolymer product having defined branching and unsaturation characteristics. The ethylene interpolymer product has a molecular weight distribution index M of 1.8 to 4.0. w / M n and a first fraction having a molecular weight distribution index M of 2.0 to 6.0. w / M n and a second fraction having

Description

[Technical Field]

[0001] The present disclosure relates generally to multicomponent ethylene interpolymer products, and more particularly to multicomponent ethylene interpolymer products with defined branching and unsaturation characteristics that have advantageous performance properties for film applications. [Background technology]

[0002] Multicomponent ethylene-based polymer compositions are well known in the art. One method for accessing multicomponent polyethylene compositions is to use two or more separate polymerization catalysts in one or more polymerization reactors. For example, it is known to use a single-site polymerization catalyst and a Ziegler-Natta polymerization catalyst in at least two separate solution polymerization reactors. Such reactors may be configured in series or in parallel.

[0003] Solution polymerization processes are generally carried out at temperatures above the melting point of the ethylene homopolymer or copolymer product being produced. In a typical solution polymerization process, catalyst components, solvent, monomers, and hydrogen are fed under pressure to one or more reactors. In solution polymerization processes, reactor temperatures can range from about 80°C to about 300°C, and pressures can generally range from about 3 MPag to about 45 MPag. The ethylene homopolymer or copolymer produced remains dissolved in the solvent under reactor conditions. The residence time of the solvent in the reactor is relatively short, for example, from about 1 second to about 20 minutes. Solution processes can be operated under a wide range of process conditions, allowing for the production of a wide variety of ethylene polymers. After the reactor, the polymerization reaction is stopped to prevent further polymerization by adding a catalyst deactivator, and optionally passivated by adding an acid scavenger. Once inactivated (and optionally passivated), the polymer solution is sent to a polymer recovery operation (devolatilization system) where the ethylene homopolymer or copolymer is separated from the process solvent, residual unreacted ethylene, and any unreacted α-olefin.

[0004] Regardless of the method of production, there remains a need to improve the performance of multicomponent ethylene-based polymer compositions in film applications. Summary of the Invention

[0005] In a first aspect, provided is an ethylene interpolymer product having a molecular weight distribution index M of 1.8 to 4.0. w / M n and a molecular weight distribution index M of 2.0 to 6.0. w / M n and 55 to 70 weight percent of a second fraction having a formula: u is 0.047 or greater, and the weight percent and molecular weight distribution index of the first and second fractions are obtained by deconvoluting the experimentally measured molecular weight distribution of the ethylene interpolymer product, and the weight percent of the first fraction or the second fraction is defined as the weight of the first fraction or the second fraction divided by the combined weight of the first fraction and the second fraction multiplied by 100.

[0006] A second fraction of the ethylene interpolymer product has Formula (1a) and Formula (1b):

number

number

number

number

[0007] In some embodiments, the first fraction is a first semi-logarithmic derivative d(NCID i 1 ) / dlogM i The non-comonomer exponential distribution NCID is characterized by i 1 M i is the incremental molar mass characterizing the molecular weight distribution of the first fraction, and NCID i 1 is obtained by deconvoluting the experimentally measured non-comonomer index distribution of the ethylene interpolymer product.

[0008] In some embodiments, the second fraction has a weight average molecular weight that is less than the weight average molecular weight of the first fraction.

[0009] In some embodiments, the ethylene interpolymer product has a viscosity of 0.910 g / cm 3 ~0.930g / cm 3 It has a density of In some embodiments, the ethylene interpolymer product has a melt index, I2, from 0.5 dg / min to 1.5 dg / min. In some embodiments, the ethylene interpolymer product has a composition distribution breadth index (CDBI) of 50 to 75 weight percent. 50 It has. In some embodiments, the ethylene interpolymer product has a dimensionless long chain branching factor LCBF≦0.04. In some embodiments, the ethylene interpolymer product has a dimensionless long chain branching factor LCBF≧0.01. In some embodiments, the ethylene interpolymer product has a total of less than or equal to 0.07 unsaturations per 100 carbons. In some embodiments, the ethylene interpolymer product has a molecular weight distribution index M of 2.5 to 5.0. w / M n It has.

[0010] In some embodiments, the ethylene copolymer product comprises 1 to 10 mole percent of one or more α-olefins. In some embodiments, the ethylene copolymer product comprises 1 to 8 mole percent of one or more α-olefins.

[0011] In some embodiments, the one or more α-olefins are selected from the group including 1-hexene, 1-octene, and mixtures thereof.

[0012] In a second aspect, provided is a film layer comprising the ethylene interpolymer product defined in the first aspect.

[0013] In some embodiments, the film layer is a blown film.

[0014] In a third aspect, provided is a multilayer film structure comprising at least one layer comprising the ethylene interpolymer product defined in the first aspect.

[0015] In some embodiments, at least one film layer is a blown film.

[0016] In some embodiments, the multilayer film structure comprises 3 layers. In some embodiments, the multilayer film structure comprises at least 3 layers. In some embodiments, the multilayer film structure comprises 5 layers. In some embodiments, the multilayer film structure comprises 7 layers. In some embodiments, the multilayer film structure comprises 9 layers.

[0017] At least one layer defined in the third aspect may be a core layer in a multilayer film structure. The core layer may be between, e.g., sandwiched between, at least two other layers.

[0018] In a fourth aspect, provided is a multilayer film structure comprising a sealant layer, the sealant layer comprising the ethylene interpolymer product defined in the first aspect.

[0019] In some embodiments, the multilayer film structure comprises one sealant layer. In some embodiments, the multilayer film structure comprises two sealant layers. [Brief explanation of the drawings]

[0020] [Figure 1] 1 shows a comparison of the non-comonomer index distributions of the second fraction NCIDi 2 in Examples 1 to 13. [Figure 2]1 compares the first semi-log derivative of the non-comonomer exponential distribution of the second fractions in Examples 1-13. DETAILED DESCRIPTION OF THE INVENTION

[0021] <Terminology> Unless otherwise indicated in the examples or otherwise, all numbers or expressions relating to ingredient quantities, extrusion conditions, and the like used in the specification and claims are understood to be modified in all instances by the term "about." Accordingly, unless otherwise indicated, the numerical parameters set forth in the following specification and appended claims are approximations that may vary depending upon the desired properties desired to be obtained by various embodiments. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques. The numerical values ​​set forth in the specific examples are reported as precisely as possible. However, any numerical value inherently contains errors necessarily resulting from the standard deviation found in their respective testing measurements.

[0022] It should be understood that any numerical range recited herein is intended to include all subranges encompassed therein. For example, a range of "1 to 10" is intended to include all subranges therebetween, including the stated minimum value of 1 and the stated maximum value of 10, i.e., the minimum value is equal to or greater than 1 and the maximum value is equal to or less than 10. The disclosed numerical ranges are continuous, and therefore include all values ​​between the minimum and maximum values. Unless otherwise specified, the various numerical ranges specified in this application are approximations.

[0023] All composition ranges expressed herein are limited to and do not actually exceed 100 percent (volume percent or weight percent) in total. Where multiple components may be present in a composition, the sum of the maximum amounts of each component may exceed 100 percent, with the understanding that the amounts of the components actually used will meet the 100 percent maximum, as one of ordinary skill in the art will readily understand.

[0024] To form a more complete understanding of the present disclosure, the following terms should be defined and used in conjunction with the accompanying drawings and the description of various embodiments throughout.

[0025] As used herein, the term "monomer" refers to a small molecule that can chemically react and chemically bond with itself or other monomers to form a polymer.

[0026] As used herein, the term "α-olefin" or "alpha-olefin" is used to describe a monomer having a linear hydrocarbon chain containing 3 to 20 carbon atoms with a double bond at one end of the chain; an equivalent term is "linear α-olefin."

[0027] As used herein, the terms "polyethylene," "polyethylene polymer," or "ethylene polymer" refer to a polymer made from ethylene monomer and, optionally, one or more additional monomers, regardless of the specific catalyst or process used to make the ethylene polymer. In the polyethylene art, the one or more additional monomers are called "comonomers" and often include α-olefins. The term "homopolymer" refers to a polymer containing only one type of monomer. "Ethylene homopolymer" is made using only ethylene as the polymerizable monomer. 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 above polyethylenes.

[0028] The term "ethylene interpolymer" refers to a subset of polymers within the "ethylene polymer" group, excluding those produced by high-pressure polymerization processes, non-limiting examples of which include LDPE and EVA (the latter a copolymer of ethylene and vinyl acetate).

[0029] The term "heterogeneously branched ethylene interpolymer" refers to a subset of polymers in the ethylene interpolymer group that are produced using heterogeneous catalyst systems, non-limiting examples of which include Ziegler-Natta or chromium catalysts, both of which are well known in the art.

[0030] The term "homogeneously branched ethylene interpolymer" refers to a subset of polymers of the ethylene interpolymer group produced using single-site catalysts, non-limiting examples of which include metallocene catalysts, phosphinimine catalysts, and constrained geometry catalysts, all of which are well known in the art.

[0031] Typically, homogeneously branched ethylene interpolymers have narrow molecular weight distributions, e.g., M w / M n Values ​​are less than about 2.8, especially less than about 2.3, although exceptions may occur, and M w and M n refers to the weight average molecular weight and number average molecular weight, respectively. In contrast, the M w / M n is typically the M of homogeneous polyethylene w / M n Generally, homogeneously branched ethylene interpolymers also have a narrow composition distribution, i.e., each polymer within the molecular weight distribution has a similar comonomer content.

[0032] The composition distribution breadth index (CDBI) is often used to quantify how the comonomer is distributed within an ethylene interpolymer and to distinguish between ethylene interpolymers produced with different catalysts or processes. 50 " is defined as the percent of ethylene interpolymers whose composition is within 50 weight percent (wt.%) of the median comonomer composition, which is consistent with the definition set forth in WO 93 / 03093, assigned to Exxon Chemical Patents Inc. CDBI of ethylene interpolymers 50 can be calculated from the TREF (Temperature Rising Elution Fractionation) curve, and the TREF method is described in Wild et al., J. Polym. Sci., Part B, Polym. Phys., Vol. 20(3), pp. 441-455. Typically, the CDBI of a homogeneously branched ethylene interpolymer is 50 is greater than about 70% or greater than about 75%. In contrast, the CDBI of the α-olefin-containing heterogeneously branched ethylene interpolymers is 50 is generally a CDBI of a homogeneous ethylene interpolymer. 50For example, the CDBI of heterogeneously branched ethylene interpolymers is 50 The comonomer content of a blend of two or more homogeneous ethylene interpolymers may be less than about 75%, or less than about 70%. 50 In some cases, the weight average molecular weight (M w A blend of two or more homogeneous ethylene interpolymers having different M w / M n may be 2.8 or greater, and in this disclosure such blends are defined as homogeneous blends or homogeneous compositions.

[0033] The term "thermoplastic" refers to a polymer that becomes liquid when heated, flows under pressure, and solidifies when cooled. Thermoplastic polymers include ethylene polymers as well as other polymers used in the plastics industry. Non-limiting examples of other polymers commonly used in film applications include barrier resins (EVOH), tie resins, polyethylene terephthalate (PET), polyamides, etc.

[0034] As used herein, the term "monolayer film" refers to a film that includes one or more monolayers of thermoplastic.

[0035] As used herein, the terms "multilayer film" or "multilayer film structure" refer to a film composed of multiple thermoplastic layers, or optionally non-thermoplastic layers. Non-limiting examples of non-thermoplastic materials include metal (foil) or cellulosic (paper) products. One or more thermoplastic layers within a multilayer film (or film structure) may be composed of multiple thermoplastic plastics.

[0036] As used herein, the term "tie resin" refers to a thermoplastic plastic that, when formed into an intermediate layer or "tie layer" in a multilayer film structure, promotes adhesion between adjacent film layers of different chemical composition.

[0037] As used herein, the term "sealant layer" refers to a layer of a thermoplastic film that can be attached to a second substrate to form a leak-proof seal. A "sealant layer" may be a skin layer or the innermost layer in a multilayer film structure.

[0038] As used herein, the terms "adhesive lamination" and "extrusion lamination" describe a continuous process in which two or more substrates or webs of material are combined to form a multilayer product or sheet, wherein the two or more webs are bonded together using an adhesive or a molten thermoplastic film, respectively.

[0039] As used herein, the term "extrusion coating" describes a continuous process in which a molten thermoplastic layer is combined with or deposited onto a moving solid web or substrate. Non-limiting examples of substrates include paper, paperboard, foil, single-layer plastic film, multi-layer plastic film, or fabric. The molten thermoplastic layer may be single-layer or multi-layer.

[0040] As used herein, the terms "hydrocarbyl," "hydrocarbyl radical," or "hydrocarbyl group" refer to linear or cyclic aliphatic, olefinic, acetylenic, and aryl (aromatic) radicals that contain hydrogen and one carbon that is deficient in one hydrogen.

[0041] As used herein, "alkyl radical" includes straight-chain, branched, and cyclic paraffin radicals that are deficient in one hydrogen radical, non-limiting examples of which include methyl (-CH3) and ethyl (-CH2CH3) radicals. The term "alkenyl radical" refers to straight-chain, branched, and cyclic hydrocarbons containing at least one carbon-carbon double bond that is deficient in one hydrogen radical.

[0042] As used herein, the term "aryl" group includes phenyl, naphthyl, pyridyl, and other radicals in which the molecule has an aromatic ring structure; non-limiting examples include naphthylene, phenanthrene, and anthracene. "Arylalkyl" groups are alkyl groups pendant on an aryl group; non-limiting examples include benzyl, phenethyl, and tolylmethyl. "Alkylaryl" is an aryl group pendant on one or more alkyl groups; non-limiting examples include tolyl, xylyl, mesityl, and cumyl.

[0043] As used herein, the phrase "heteroatom" includes any atom other than carbon and hydrogen that can be bonded to carbon. A "heteroatom-containing group" is a hydrocarbon radical that contains a heteroatom and may contain one or more heteroatoms, the same or different. In one embodiment, the heteroatom-containing group is a hydrocarbyl group containing 1 to 3 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 heterocycles, oxazolines, and thioethers. The term "heterocyclic" refers to a ring system having a carbon skeleton containing 1 to 3 atoms selected from the group consisting of boron, aluminum, silicon, germanium, nitrogen, phosphorus, oxygen, and sulfur.

[0044] As used herein, the term "unsubstituted" means that a hydrogen radical is attached to the molecular group that follows the term unsubstituted. The term "substituted" means that the group that follows the term has one or more moieties (non-hydrogen radicals) replacing one or more hydrogen radicals anywhere within the group. Non-limiting examples of moieties 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-C6 30 Alkyl groups, C2-C 30 Non-limiting examples of substituted alkyl and aryl include acyl radicals, alkylsilyl radicals, alkylamino radicals, alkoxy radicals, aryloxy radicals, alkylthio radicals, dialkylamino radicals, alkoxycarbonyl radicals, aryloxycarbonyl radicals, carbamoyl radicals, alkyl- and dialkyl-carbamoyl radicals, acyloxy radicals, acylamino radicals, arylamino radicals, and combinations thereof.

[0045] <Description of the embodiment> In this disclosure, the ethylene interpolymer product has a molecular weight distribution index M of 1.8 to 4.0. w / M n and a distinguishable first fraction having a molecular weight distribution index M of 2.0 to 6.0. w / M n and a distinguishable second fraction having a weight percent of 1000 to 15000. The weight percent and molecular weight distribution index of the first and second fractions are obtained by deconvoluting the experimentally measured molecular weight distribution of the ethylene interpolymer product. Each of these fractions and the ethylene interpolymer products containing them are further described below.

[0046] <The First Fraction> In some embodiments, the first fraction is the first semi-logarithmic derivative dNCID i 1 / dlogM iNon-comonomer exponential distribution NCID characterized by a value greater than -0.0001 i 1 NCID i 1 is obtained by deconvoluting the experimentally determined non-comonomer index of the ethylene interpolymer product.

[0047] In some embodiments, the first fraction is a first semi-logarithmic derivative dNCID having a value of zero i 1 / dlogM i The non-comonomer exponential distribution NCID is characterized by i 1 NCID i 1 is obtained by deconvoluting the experimentally determined non-comonomer index of the ethylene interpolymer product.

[0048] In some embodiments, the first fraction has a first non-comonomer exponential distribution NCID that satisfies the inequalities of Equation (1a') and Equation (1b'), defined as follows: i 1 Has:

number

number

[0049] In an embodiment of the present disclosure, the molecular weight distribution M of the first fraction w / Mn The upper limit of the molecular weight distribution M of the first fraction may be about 4.0, or about 3.8, or about 3.7, or about 3.6, or about 3.5. w / M n The lower limit may be about 1.6, or about 1.7, or about 1.8, or about 1.9.

[0050] In an embodiment of the present disclosure, the first fraction has a molecular weight distribution M w / M n In an embodiment of the present disclosure, the first fraction has a molecular weight distribution M w / M n is about 1.8 to about 4.0, or about 1.9 to about 4.0, or about 2.0 to about 4.0.

[0051] In one embodiment of the present disclosure, the first fraction has a weight average molecular weight M w is about 50 kg / mol to about 300 kg / mol, or about 50 kg / mol to about 250 kg / mol, or about 60 kg / mol to about 250 kg / mol, or about 70 kg / mol to about 250 kg / mol, or about 75 kg / mol to about 200 kg / mol, or about 75 kg / mol to about 175 kg / mol, or about 70 kg / mol to about 175 kg / mol, or about 75 kg / mol to about 150 kg / mol.

[0052] In one embodiment of the present disclosure, the first fraction has a weight average molecular weight M w Weight average molecular weight M is greater than w It has.

[0053] In embodiments of the present disclosure, the upper limit of the weight percent (wt.%) of the first fraction in the ethylene interpolymer product (i.e., the weight percent of the first fraction based on the total weight of the first fraction and the second fraction) may be about 45 wt.%, or about 43 wt.%, or about 41 wt.%, or about 40 wt.%, or about 39 wt.%. In embodiments of the present disclosure, the lower limit of the wt.% of the first fraction in the ethylene interpolymer product may be about 35 wt.%, or about 37 wt.%, or about 39 wt.%, or about 40 wt.%.

[0054] <The Second Fraction> The second fraction has a second non-comonomer exponential distribution NCID having values ​​characterized by Equation (1a) and Equation (1b): i 2 Has:

number

number

number

number

[0055] In an embodiment of the present disclosure, the second fraction has a molecular weight distribution M w / M n is 2.0 or greater, or greater than 2.0, or 2.1 or greater, or greater than 2.1, or 2.2 or greater, or greater than 2.2, or 2.5 or greater, or greater than 2.5, or 3.0 or greater, or 3.0. In an embodiment of the present disclosure, the second fraction has a molecular weight distribution M w / M n is 2.0 to 6.0, or 2.0 to 5.5, or 2.0 to 5.0, or 2.1 to 4.5, or 2.1 to 4.0, or 2.1 to 3.5, or 2.1 to 3.0, or 2.1 to 2.9, or 2.1 to 2.7, or 2.1 to 2.5.

[0056] In one embodiment of the present disclosure, the second fraction has a weight average molecular weight M w is about 25 kg / mol to about 250 kg / mol, or about 25 kg / mol to about 200 kg / mol, or about 30 kg / mol to about 150 kg / mol, or about 40 kg / mol to about 150 kg / mol, or about 50 kg / mol to about 130 kg / mol, or about 50 kg / mol to about 110 kg / mol.

[0057] In one embodiment of the present disclosure, the second fraction has a weight average molecular weight M w Weight average molecular weight M smaller than w It has.

[0058] In embodiments of the present disclosure, the upper limit for the weight percent (wt.%) of the second fraction in the ethylene interpolymer product (i.e., the weight percent of the second fraction based on the total weight of the first and second fractions) may be about 70 wt%, or about 68 wt%, or about 66 wt%, or about 64 wt%, or about 62 wt%, or about 60 wt%. In some embodiments of the present disclosure, the lower limit for the wt.% of the second fraction in the ethylene copolymer composition is about 55 wt%, or about 57 wt%, or about 59 wt%, or about 61 wt%, or about 63 wt%, or about 65 wt%.

[0059] <Ethylene interpolymer product> The ethylene interpolymer products disclosed herein can be made using any technique known in the art.

[0060] In one embodiment, the ethylene interpolymer product of the present disclosure is prepared by forming a first ethylene interpolymer in a first reactor; and forming a second ethylene interpolymer in a second reactor.

[0061] In one embodiment, the ethylene interpolymer products of the present disclosure are made by forming a first ethylene interpolymer in a first reactor; forming a second ethylene interpolymer in a second reactor; and forming a third ethylene interpolymer in a third reactor.

[0062] In one embodiment, the ethylene interpolymer products of the present disclosure are made by forming a first ethylene interpolymer in a first reactor by polymerizing ethylene and an α-olefin using a single-site catalyst; and forming a second ethylene interpolymer in a second reactor by polymerizing ethylene and an α-olefin using a multi-site catalyst.

[0063] In one embodiment, the ethylene interpolymer products of the present disclosure are made by forming a first ethylene interpolymer in a first reactor by polymerizing ethylene and an α-olefin using a single-site catalyst; forming a second ethylene interpolymer in a second reactor by polymerizing ethylene and an α-olefin using a multi-site catalyst; and forming a third ethylene interpolymer in a third reactor by polymerizing ethylene and an α-olefin using a multi-site catalyst.

[0064] In one embodiment, the ethylene interpolymer products of the present disclosure are made by forming a first ethylene interpolymer in a first reactor by polymerizing ethylene and an α-olefin using a single-site catalyst; forming a second ethylene interpolymer in a second reactor by polymerizing ethylene and an α-olefin using a multi-site catalyst; and forming a third ethylene interpolymer in a third reactor by polymerizing ethylene and an α-olefin using a single-site catalyst.

[0065] In one embodiment, the ethylene interpolymer products of the present disclosure are made by forming a first ethylene interpolymer in a first solution phase polymerization reactor by polymerizing ethylene and an α-olefin using a single-site catalyst; and forming a second ethylene interpolymer in a second solution phase polymerization reactor by polymerizing ethylene and an α-olefin using a multi-site catalyst.

[0066] In one embodiment, the ethylene interpolymer products of the present disclosure are made by forming a first ethylene interpolymer in a first solution phase polymerization reactor by polymerizing ethylene and an α-olefin using a single-site catalyst; forming a second ethylene interpolymer in a second reactor by polymerizing ethylene and an α-olefin using a multi-site catalyst; and forming a third ethylene interpolymer in a third solution phase polymerization reactor by polymerizing ethylene and an α-olefin using a multi-site catalyst.

[0067] In one embodiment, the ethylene interpolymer products of the present disclosure are made by forming a first ethylene interpolymer in a first solution phase polymerization reactor by polymerizing ethylene and an α-olefin with a single-site catalyst; forming a second ethylene interpolymer in a second solution phase polymerization reactor by polymerizing ethylene and an α-olefin with a multi-site catalyst; and forming a third ethylene interpolymer in a third solution phase polymerization reactor by polymerizing ethylene and an α-olefin with a single-site catalyst.

[0068] In one embodiment, the ethylene interpolymer products of the present disclosure are made by polymerizing ethylene and an α-olefin with a single-site catalyst to form a first ethylene interpolymer in a first solution phase polymerization reactor; and polymerizing ethylene and an α-olefin with a multi-site catalyst to form a second ethylene interpolymer in a second solution phase polymerization reactor, wherein the first and second solution phase polymerization reactors are configured in series with each other.

[0069] In one embodiment, the ethylene interpolymer products of the present disclosure are made by forming a first ethylene interpolymer in a first solution phase polymerization reactor by polymerizing ethylene and an α-olefin with a single-site catalyst; and forming a second ethylene interpolymer in a second solution phase polymerization reactor by polymerizing ethylene and an α-olefin with a multi-site catalyst, wherein the first and second solution phase polymerization reactors are configured in parallel with one another.

[0070] In one embodiment, the ethylene interpolymer products of the present disclosure are made by forming a first ethylene interpolymer in a first solution phase polymerization reactor by polymerizing ethylene and an α-olefin with a single-site catalyst; forming a second ethylene interpolymer in a second solution phase polymerization reactor by polymerizing ethylene and an α-olefin with a multi-site catalyst; and forming a third ethylene interpolymer in a third solution phase polymerization reactor by polymerizing ethylene and an α-olefin with a multi-site catalyst, wherein the first and second solution phase polymerization reactors are configured in series with each other.

[0071] In one embodiment, the ethylene interpolymer products of the present disclosure are made by forming a first ethylene interpolymer in a first solution phase polymerization reactor by polymerizing ethylene and an α-olefin with a single-site catalyst; forming a second ethylene interpolymer in a second solution phase polymerization reactor by polymerizing ethylene and an α-olefin with a multi-site catalyst; and forming a third ethylene interpolymer in a third solution phase polymerization reactor by polymerizing ethylene and an α-olefin with a multi-site catalyst, wherein at least the first and second solution phase polymerization reactors are configured in series with each other.

[0072] In one embodiment, the ethylene interpolymer products of the present disclosure are made by forming a first ethylene interpolymer in a first solution phase polymerization reactor by polymerizing ethylene and an α-olefin with a single-site catalyst; forming a second ethylene interpolymer in a second solution phase polymerization reactor by polymerizing ethylene and an α-olefin with a multi-site catalyst; and forming a third ethylene interpolymer in a third solution phase polymerization reactor by polymerizing ethylene and an α-olefin with a multi-site catalyst, wherein the first, second, and third solution phase polymerization reactors are configured in series with one another.

[0073] In one embodiment, the ethylene interpolymer products of the present disclosure are made by forming a first ethylene interpolymer in a first solution phase polymerization reactor by polymerizing ethylene and an α-olefin with a single-site catalyst; forming a second ethylene interpolymer in a second solution phase polymerization reactor by polymerizing ethylene and an α-olefin with a multi-site catalyst; and forming a third ethylene interpolymer in a third solution phase polymerization reactor by polymerizing ethylene and an α-olefin with a multi-site catalyst, wherein each of the first, second, and third solution phase polymerization reactors are configured in parallel with one another.

[0074] In one embodiment, the ethylene interpolymer products of the present disclosure are made by forming a first ethylene interpolymer in a first solution phase polymerization reactor by polymerizing ethylene and an α-olefin with a single-site catalyst; forming a second ethylene interpolymer in a second solution phase polymerization reactor by polymerizing ethylene and an α-olefin with a multi-site catalyst; and forming a third ethylene interpolymer in a third solution phase polymerization reactor by polymerizing ethylene and an α-olefin with a multi-site catalyst, wherein the first and second solution phase reactors are configured in series with each other and the third solution phase reactor is configured in parallel with the first and second reactors.

[0075] In one embodiment, the ethylene interpolymer products of the present disclosure are made by forming a first ethylene interpolymer in a first solution phase polymerization reactor by polymerizing ethylene and an α-olefin with a single-site catalyst; forming a second ethylene interpolymer in a second solution phase polymerization reactor by polymerizing ethylene and an α-olefin with a multi-site catalyst; and forming a third ethylene interpolymer in a third solution phase polymerization reactor by polymerizing ethylene and an α-olefin with a single-site catalyst, wherein at least the first and second solution phase polymerization reactors are configured in series with one another.

[0076] In one embodiment, the ethylene interpolymer products of the present disclosure are made by forming a first ethylene interpolymer in a first solution phase polymerization reactor by polymerizing ethylene and an α-olefin with a single-site catalyst; forming a second ethylene interpolymer in a second solution phase polymerization reactor by polymerizing ethylene and an α-olefin with a multi-site catalyst; and forming a third ethylene interpolymer in a third solution phase polymerization reactor by polymerizing ethylene and an α-olefin with a single-site catalyst, wherein the first, second, and third solution phase polymerization reactors are configured in series with one another.

[0077] In one embodiment, the ethylene interpolymer product of the present disclosure is made by forming a first ethylene interpolymer in a first solution phase polymerization reactor by polymerizing ethylene and an α-olefin with a single-site catalyst; forming a second ethylene interpolymer in a second solution phase polymerization reactor by polymerizing ethylene and an α-olefin with a multi-site catalyst; and forming a third ethylene interpolymer in a third solution phase polymerization reactor by polymerizing ethylene and an α-olefin with a single-site catalyst, wherein each of the first, second, and third solution phase polymerization reactors are configured in parallel with one another.

[0078] In one embodiment, the ethylene interpolymer products of the present disclosure are made by forming a first ethylene interpolymer in a first solution phase polymerization reactor by polymerizing ethylene and an α-olefin with a single-site catalyst; forming a second ethylene interpolymer in a second solution phase polymerization reactor by polymerizing ethylene and an α-olefin with a multi-site catalyst; and forming a third ethylene interpolymer in a third solution phase polymerization reactor by polymerizing ethylene and an α-olefin with a single-site catalyst, wherein the first and second solution phase reactors are configured in series with each other and the third solution phase reactor is configured in parallel with the first and second reactors.

[0079] In one embodiment, the solution phase polymerization reactor used as the first solution phase reactor, the second solution phase reactor, or the third solution phase reactor is a continuous stirred tank reactor or a tubular reactor. In one embodiment, the solution phase polymerization reactor used as the first solution phase reactor, the second solution phase reactor, or the third solution phase reactor is a continuous stirred tank reactor. In one embodiment, the solution phase polymerization reactor used as the first solution phase reactor, the second solution phase reactor, or the third solution phase reactor is a tubular reactor.

[0080] In one embodiment, the solution phase polymerization reactors used as the first solution phase reactor and the second solution phase reactor are continuous stirred tank reactors, and the solution phase polymerization reactor used as the third solution phase reactor is a tubular reactor.

[0081] In one embodiment of the present disclosure, the single-site catalyst has hafnium (Hf) as the active metal center.

[0082] In one embodiment of the present disclosure, the single-site catalyst is a metallocene catalyst. In one embodiment of the present disclosure, the single-site catalyst is a bridged metallocene catalyst.

[0083] In one embodiment of the present disclosure, the single-site catalyst is a bridged metallocene catalyst having Formula I: [ka]

[0084] In 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; R is a hydrogen atom, C 1-20 Hydrocarbyl radical, C 1-20 Alkoxy radical, or C 6-10 is an aryloxide radical; R2 and R3 are hydrogen atoms, C 1-20 Hydrocarbyl radical, C 1-20 Alkoxy radical or C 6-10 aryloxide radicals; R and R are independently selected from hydrogen atoms, unsubstituted C 1-20 Hydrocarbyl radical, substituted C 1-20 Hydrocarbyl radical, C 1-20 Alkoxy radical or C 6-10 aryloxide radicals; and Q is independently an activatable leaving group ligand.

[0085] In one embodiment, R4 and R5 are independently an aryl group. In one embodiment, R4 and R5 are independently a phenyl group or a substituted phenyl group. In one embodiment, R4 and R5 are phenyl groups. In one embodiment, R4 and R5 are independently a substituted phenyl group. In one embodiment, R4 and R5 are substituted phenyl groups, where the phenyl group is substituted with a substituted silyl group. In one embodiment, R4 and R5 are substituted phenyl groups, where the phenyl group is substituted with a trialkylsilyl group.

[0086] In one embodiment, R4 and R5 are substituted phenyl groups, where the phenyl group is substituted at the para position with a trialkylsilyl group. In one embodiment, R1 and R2 are substituted phenyl groups, where the phenyl group is substituted at the para position with a trimethylsilyl group. In one embodiment, R1 and R2 are substituted phenyl groups, where the phenyl group is substituted at the para position with a triethylsilyl group.

[0087] In one embodiment, R4 and R5 are independently an alkyl group. In one embodiment, R4 and R5 are independently an alkenyl group. In one embodiment, R1 is hydrogen. In one embodiment, R1 is an alkyl group. In one embodiment, R1 is an aryl group. In one embodiment, R1 is an alkenyl group. In one embodiment, R2 and R3 are independently a hydrocarbyl group having from 1 to 30 carbon atoms. In one embodiment, R2 and R3 are independently an aryl group. In one embodiment, R2 and R3 are independently an alkyl group. In one embodiment, R2 and R3 are independently an alkyl group having from 1 to 20 carbon atoms. In one embodiment, R2 and R3 are independently a phenyl group or a substituted phenyl group. In one embodiment, R2 and R3 are tert-butyl groups. In one embodiment, R2 and R3 are hydrogen.

[0088] In one embodiment of the present disclosure, the single-site catalyst is a bridged metallocene catalyst having formula II. [ka]

[0089] In formula (II), G is a Group 14 element selected from carbon, silicon, germanium, tin, or lead; R is a hydrogen atom, C 1-20 Hydrocarbyl radical, C 1-20 Alkoxy radical, or C 6-10 is an aryloxide radical; R2 and R3 are hydrogen atoms, C 1-20 Hydrocarbyl radical, C 1-20 Alkoxy radical or C 6-10aryloxide radicals; R and R are independently selected from hydrogen atoms, unsubstituted C 1-20 Hydrocarbyl radical, substituted C 1-20 Hydrocarbyl radical, C 1-20 Alkoxy radical or C 6-10 aryloxide radicals; and Q is independently an activatable leaving group ligand.

[0090] In this disclosure, the term "activatable" means that the ligand Q can be cleaved from the metal center M via a protonolysis reaction or abstracted from the metal center M by a suitable acidic or electrophilic catalytically active compound (also known as a "cocatalyst" compound), examples of each of which are provided below. The activatable ligand Q can also be converted into another ligand that is cleaved or abstracted from the metal center M (e.g., a halide can be converted into an alkyl group). Without wishing to be bound by a single theory, the protonolysis or abstraction reaction generates an active "cationic" metal center capable of polymerizing olefins.

[0091] In embodiments of the present disclosure, the activatable ligands Q are independently selected from the group consisting of: hydrogen atoms; halogen atoms; C 1~20 Hydrocarbyl radical, C 1~20 Alkoxy radicals, and C 6-10 an aryl or aryloxy radical, where each of the hydrocarbyl, alkoxy, aryl, or aryloxide radicals can be unsubstituted or further substituted with one or more halogens or other groups; C 1-8 Alkyl; C 1-8 Alkoxy;C 6-10 aryl or aryloxy; amido or phosphido radical, but Q is not cyclopentadienyl. Two Q ligands may also be bonded 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 halide atom, C 1~4Independently selected from the group consisting of alkyl radicals and benzyl radicals. Particularly suitable activatable ligands Q are monoanionic, such as halides (e.g., chloride) or hydrocarbyls (e.g., methyl, benzyl).

[0092] In one embodiment of the present disclosure, the single-site catalyst is diphenylmethylene(cyclopentadienyl)(2,7-di-t-butylfluorenyl)hafnium dichloride, having the following molecular formula: [(2,7-tBuFlu)PhC(Cp)HfCl].

[0093] In one embodiment of the present disclosure, the single-site catalyst is diphenylmethylene(cyclopentadienyl)(2,7-di-t-butylfluorenyl)hafnium dimethyl, having the following molecular formula: [(2,7-tBuFlu)PhC(Cp)HfMe].

[0094] In addition to the single-site catalyst molecule itself, the active single-site catalyst system may further include one or more of the following: an alkylaluminoxane cocatalyst and an ionic activator. The single-site catalyst system may also optionally include a hindered phenol.

[0095] Although the exact structure of alkylaluminoxanes is unknown, it is generally agreed among experts in the subject matter that they are oligomeric species containing repeating units of the general formula: (R)2AlO-(Al(R)-O) n -Al(R)2 (wherein the R groups can be the same or different linear, branched, or cyclic hydrocarbyl radicals containing 1 to 20 carbon atoms, and n is from 0 to about 50.) A non-limiting example of an alkylaluminoxane is methylaluminoxane (or MAO), where each R group is a methyl radical. In one embodiment of the present disclosure, R in the alkylaluminoxane is a methyl radical and m is from 10 to 40.

[0096] In one embodiment of the present disclosure, the cocatalyst is modified methylaluminoxane (MMAO). It is well known in the art that alkylaluminoxanes can play dual roles as both alkylating agents and activators. Therefore, alkylaluminoxane cocatalysts are often used in combination with activatable ligands such as halogens.

[0097] Generally, ionic surfactants are composed of a cation and a bulky anion, the latter of which is substantially non-coordinating. A non-limiting example of an ionic surfactant is a boron ionic surfactant, which is four-coordinate with four ligands attached to the boron atom. Non-limiting examples of boron ionic surfactants include those of the formula: [R 5 ] + [B(R 7 )4] - (wherein B represents a boron atom, R 5 is an aromatic hydrocarbyl (e.g., a triphenylmethyl cation), and each R 7 are independently selected from the following: a phenyl radical unsubstituted or substituted with 3 to 5 substituents selected from fluorine atoms; C unsubstituted or substituted with fluorine atoms; 1~4 alkyl or alkoxy radicals and groups of the formula -Si(R 9 ) 3 silyl radicals, where each R 9 is a hydrogen atom and C 1-4 alkyl radicals), and [(R 8 ) t ZH] + [B(R 7 )4] - (wherein 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 is C 1~8 Alkyl radicals, unsubstituted or with up to three C 1-4 a phenyl radical substituted with an alkyl radical, or one R 8may form an anilinium radical together with the nitrogen atom, and R 7 is as defined above).

[0098] In both equations, R 7A non-limiting example of is the pentafluorophenyl radical. Generally, boron ionic activators can be described as salts of tetra(perfluorophenyl)boron, and non-limiting examples include the anilinium, carbonium, oxonium, phosphonium, and sulfonium salts of tetra(perfluorophenyl)boron with anilinium and trityl (or triphenylmethylium). Additional non-limiting examples of ionic activators 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, N,N-diethyl Anilinium 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 tetrakispentafluorophenylborate, triphenylmethylium tetrakispentafluorophenylborate, benzene(diazonium)tetrakispentafluorophenylborate, tropylium tetrakis(2,3,5,6-tetrafluorophenyl)borate, triphenylmethylium tetrakis(2,3,5,6-tetrafluorophenyl)borate, benzene(diazonium)tetrakis(3,4,5-trifluorophenyl)borate, tropylium tetrakis(3,4,5-trifluorophenyl)borate, benzene(diazonium)tetrakis(3,4,5-trifluorophenyl)borate, tropylium tetrakis(1,2,2-trifluoroethenyl)borate, triphenylmethylium tetrakis(1,2,2-trifluoroethenyl)borate, benzene(diazonium)tetrakis(1,2,2-trifluoroethenyl)borate, tropylium 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. Readily available commercial ionic surfactants include N,N-dimethylanilinium tetrakispentafluorophenylborate and triphenylmethylium tetrakispentafluorophenylborate.

[0099] Non-limiting examples of hindered phenols include butylated phenol antioxidant, 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.

[0100] The amounts and molar ratios of the three or four components: single-site catalyst, alkylaluminoxane, ionic activator, and optionally, hindered phenol are optimized to produce an active single-site catalyst system.

[0101] In one embodiment, the multi-site catalyst is an in-line Ziegler-Natta catalyst system or a batch Ziegler-Natta catalyst system.

[0102] The term "inline Ziegler-Natta catalyst system" refers to the continuous synthesis of a small amount of an active Ziegler-Natta catalyst system and the immediate injection of this catalyst into at least one continuously operated reactor, where the catalyst polymerizes ethylene and one or more optional α-olefins to form ethylene polymers. The term "batch Ziegler-Natta catalyst system" or "batch Ziegler-Natta procatalyst" refers to the synthesis of a much larger amount of catalyst or procatalyst in one or more mixing vessels external to or separate from a continuously operated solution polymerization process. The prepared batch catalyst Ziegler-Natta catalyst system or batch Ziegler-Natta procatalyst is transferred to a catalyst storage tank. The term "procatalyst" refers to an inactive catalyst system (inactive with respect to ethylene polymerization), where the procatalyst is converted to an active catalyst by the addition of an alkylaluminum cocatalyst. Optionally, the procatalyst is pumped from the storage tank to at least one continuously operated reactor, where the active catalyst polymerizes ethylene and one or more optional α-olefins to form ethylene interpolymers. The procatalyst may be converted to an active catalyst in the reactor, outside the reactor, or en route to the reactor.

[0103] Non-limiting examples of active in-line (or batch) Ziegler-Natta catalyst systems for making the second ethylene interpolymer can be prepared as follows: In a first step, a solution of a magnesium compound is reacted with a solution of a chloride compound to form a magnesium chloride support suspended in the solution. Non-limiting examples of magnesium compounds include Mg(R 1 )2, wherein R 1 The groups contain 1 to 10 carbon atoms and may be the same or different, linear, branched, or cyclic hydrocarbyl radicals. Non-limiting examples of chloride compounds include R 2 Cl, wherein R 2represents a hydrogen atom or a linear, branched, or cyclic hydrocarbyl radical containing 1 to 10 carbon atoms. In the first step, the solution of magnesium compound may contain an aluminum alkyl. Non-limiting examples of aluminum alkyl include Al(R 3 )3, wherein R 3 The groups contain 1 to 10 carbon atoms and may be the same or different, linear, branched, or cyclic hydrocarbyl radicals. In a second step, a solution of the metal compound is added to a solution of magnesium chloride, and the metal compound is supported on the magnesium chloride. Non-limiting examples of suitable metal compounds include M(X) n or MO(X) n where M represents a metal selected from Groups 4-8 of the periodic table, or a mixture of metals selected from Groups 4-8, O represents oxygen, X represents chloride or bromide, and n is an integer from 3 to 6 that satisfies the oxidation state of the metal. Additional non-limiting examples of suitable metal compounds include Group 4-8 metal alkyls, metal alkoxides (which may be prepared by reacting a metal alkyl with an alcohol), and mixed-ligand metal compounds containing a mixture of halide, alkyl, and alkoxide ligands. In the third step, a solution of an alkylaluminum cocatalyst is added to the metal compound supported on magnesium chloride. A wide variety of alkylaluminum cocatalysts are suitable, as represented by the following formula: Al(R 4 ) p (OR 9 ) q (X) r (In the formula, R 4 The groups may be the same or different hydrocarbyl groups having 1 to 10 carbon atoms, OR 9 The groups may be the same or different, alkoxy or aryloxy groups, R 9is a hydrocarbyl group having 1 to 10 carbon atoms bonded to oxygen, X is chloride or bromide, and (p+q+r)=3, where p is greater than 0. Non-limiting examples of commonly used alkylaluminum cocatalysts include trimethylaluminum, triethylaluminum, tributylaluminum, dimethylaluminum methoxide, diethylaluminum ethoxide, dibutylaluminum butoxide, dimethylaluminum chloride or bromide, diethylaluminum chloride or bromide, dibutylaluminum chloride or bromide, and ethylaluminum dichloride or dibromide.

[0104] The process described in the above paragraph for synthesizing an active in-line (or batch) Ziegler-Natta catalyst system can be carried out in a variety of solvents, non-limiting examples of which include linear or branched C5-C6 alkyl esters. 12 Alkanes or mixtures thereof are included.

[0105] In solution polymerization, the monomers are dissolved / dispersed in a solvent before being fed to the reactor (or in the case of gaseous monomers, the monomers may be fed to the reactor and dissolved in the reaction mixture). Before mixing, the solvent and monomers are generally purified to remove potential catalyst poisons such as water, oxygen, and metal impurities. Feedstock purification follows standard practices in the art. For example, monomer purification uses molecular sieves, alumina beds, and oxygen removal catalysts. The solvent itself (e.g., methylpentane, cyclohexane, hexane, or toluene) is preferably treated as well.

[0106] The feedstock may be heated or cooled before being fed to the reactor.

[0107] Generally, the catalyst components may be premixed in a solvent for reaction or fed to the reactor as separate streams. In some cases, it is desirable to premix the catalyst before entering the reaction to allow time for the catalyst components to react. Such "in-line mixing" techniques are described in a number of patents in the name of DuPont Canada Inc. (e.g., U.S. Pat. No. 5,589,555, issued Dec. 31, 1996).

[0108] Solution polymerization processes for the polymerization or copolymerization of ethylene are well known in the art (see, for example, US Pat. Nos. 6,372,864 and 6,777,509).

[0109] These processes are carried out in the presence of an inert hydrocarbon solvent. In solution phase polymerization reactors, a variety of solvents can be used as process solvents, non-limiting examples of which include linear, branched or cyclic C5-C6 hydrocarbons. 12 Suitable catalyst component solvents include alkanes. Non-limiting examples of α-olefins include 1-propene, 1-butene, 1-pentene, 1-hexene, and 1-octene. Suitable catalyst component solvents include aliphatic and aromatic hydrocarbons. Non-limiting examples of aliphatic catalyst component solvents include linear, branched, or cyclic C5-C 12Aliphatic hydrocarbons include, 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), a mixture of xylene isomers, hemelitene (1,2,3-trimethylbenzene), pseudocumene (1,2,4-trimethylbenzene), mesitylene (1,3,5-trimethylbenzene), a mixture of trimethylbenzene isomers, prehenitene (1,2,3,4-tetramethylbenzene), durene (1,2,3,5-tetramethylbenzene), a mixture of tetramethylbenzene isomers, pentamethylbenzene, hexamethylbenzene, and combinations thereof.

[0110] The polymerization temperature in a conventional solution process may be about 80°C to about 300°C. In one embodiment of the present disclosure, the polymerization temperature in a solution process is about 120°C to about 250°C. The polymerization pressure in a solution process may be a "medium pressure process," meaning that the pressure in the reactor is less than about 6,000 psi (about 42,000 kilopascals or kPa). In one embodiment of the present disclosure, the polymerization pressure in a solution process may be about 10,000 to about 40,000 kPa, or about 14,000 to about 22,000 kPa (i.e., about 2,000 psi to about 3,000 psi).

[0111] Suitable monomers for copolymerization with ethylene include C 3-20 Preferred comonomers include unsubstituted or up to two C 1-6 C substituted by alkyl radicals 3-12 Alpha olefins, unsubstituted or C 1-4 C substituted with up to two substituents selected from the group consisting of alkyl radicals 8-12 Vinyl aromatic monomers, unsubstituted or C 1-4 C substituted with alkyl radicals4-12 Included are linear or cyclic diolefins. Illustrative, non-limiting examples of such alpha-olefins are one or more of propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, and 1-decene, styrene, alpha-methylstyrene, and constrained cyclic olefins, such as cyclobutene, cyclopentene, dicyclopentadiene, norbornene, alkyl-substituted norbornenes, alkenyl-substituted norbornenes, and the like (e.g., 5-methylene-2-norbornene and 5-ethylidene-2-norbornene, bicyclo-(2,2,1)-hepta-2,5-diene).

[0112] In one embodiment of the present disclosure, the ethylene interpolymer product has at least 1 mole percent of one or more α-olefins. In one embodiment of the present disclosure, the ethylene interpolymer product has at least 3 mole percent of one or more α-olefins. In one embodiment of the present disclosure, the ethylene interpolymer product has from about 1 to about 10 mole percent of one or more α-olefins. In one embodiment of the present disclosure, the ethylene interpolymer product has from about 3 to about 10 mole percent of one or more α-olefins. In one embodiment of the present disclosure, the ethylene interpolymer product has from about 3 to about 8 mole percent of one or more α-olefins.

[0113] In one embodiment of the present disclosure, the ethylene interpolymer product comprises ethylene and one or more α-olefins selected from the group comprising 1-butene, 1-hexene, 1-octene, and mixtures thereof. In one embodiment of the present disclosure, the ethylene interpolymer product comprises ethylene and one or more alpha olefins selected from the group comprising 1-hexene, 1-octene, and mixtures thereof. In one embodiment of the present disclosure, the ethylene interpolymer product comprises ethylene and 1-octene. In one embodiment of the present disclosure, the ethylene interpolymer product comprises ethylene and at least 1 mole percent 1-octene. In one embodiment of the disclosure, the ethylene interpolymer product comprises ethylene and from 1 to 10 mole percent 1-octene. In one embodiment of the present disclosure, the ethylene interpolymer product comprises ethylene and from 3 to 8 mole percent 1-octene.

[0114] In an embodiment of the disclosure, the ethylene interpolymer product has a density of about 0.900 g / cm 3 ~Approx. 0.940g / cm 3 , or about 0.905 g / cm 3 ~Approx. 0.935g / cm 3 , or about 0.908 g / cm 3 ~Approx. 0.932g / cm 3 , or about 0.910 g / cm 3 ~Approx. 0.930g / cm 3 , or about 0.912 g / cm 3 ~Approx. 0.925g / cm 3 , or about 0.913 g / cm 3 ~Approx. 0.925g / cm 3 , or about 0.913 g / cm 3 ~Approx. 0.923g / cm 3 , or about 0.913 g / cm 3 ~Approx. 0.9225g / cm 3 , or about 0.913 g / cm 3 ~Approx. 0.920g / cm 3 , or about 0.917 g / cm 3 ~Approx. 0.920g / cm 3 , or about 0.917 g / cm 3 ~Approx. 0.919g / cm 3 , or about 0.9115 g / cm 3 ~Approx. 0.9145g / cm 3 , or about 0.9130 g / cm 3 ~Approx. 0.9160g / cm 3 may be.

[0115] In embodiments of the present disclosure, the melt index I2 of the ethylene interpolymer product may be from about 0.1 dg / min to about 10.0 dg / min, or from about 0.1 dg / min to about 5.0 dg / min, or from about 0.2 dg / min to about 5.0 dg / min, or from about 0.3 dg / min to about 2.0 dg / min, or from about 0.4 dg / min to about 2.0 dg / min, or from about 0.45 dg / min to about 2.0 dg / min, or from about 0.5 dg / min to about 1.5 dg / min, or from about 0.6 dg / min to about 1.5 dg / min, or from about 0.7 dg / min to about 1.0 dg / min, or from about 0.72 dg / min to about 1.0 dg / min, or less than about 2 dg / min, or less than about 1.5 dg / min, or less than about 1.0 dg / min.

[0116] In an embodiment of the present disclosure, the ethylene interpolymer product has a high load melt index I 21 may be 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 dg / min, or about 10 dg / min to about 100 dg / min.

[0117] In an embodiment of the present disclosure, the melt flow ratio I of the ethylene interpolymer product 21 / I2 may be 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 less than about 45, or less than about 40, or less than about 38.

[0118] In an embodiment of the disclosure, the ethylene interpolymer product has a weight average molecular weight M wis about 40 kg / mol to about 300 kg / mol, or about 40 kg / mol to about 250 kg / mol, or about 50 kg / mol to about 250 kg / mol, or about 50 kg / mol to about 225 kg / mol, or about 50 kg / mol to about 200 kg / mol, or about 50 kg / mol to about 175 kg / mol, or about 50 kg / mol to about 150 kg / mol, or about 50 kg / mol to about 125 kg / mol.

[0119] In an embodiment of the disclosure, the ethylene interpolymer product has a molecular weight distribution M w / M n In an embodiment of the present disclosure, the ethylene interpolymer product has a molecular weight distribution M w / M n The upper limit is 6.0, or 5.5, or 5.0, or 4.5, or 4.0, or 3.75, or 3.5.

[0120] In an embodiment of the disclosure, the ethylene interpolymer product has a molecular weight distribution M w / M n is 2.1 to 6.0, or 2.1 to 5.5, or 2.3 to 5.0, or 2.5 to 5.0, or 2.1 to 4.0, or 2.1 to 4.0, or 2.2 to 4.0, or 2.5 to 4.0, or 2.2 to 5.0, or 2.2 to 4.5, or 2.2 to 4.0, or 2.2 to 3.5, or 2.2 to 3.0.

[0121] In an embodiment of the disclosure, the ethylene interpolymer product has a z-average molecular weight distribution M Z / M W In an embodiment of the present disclosure, the polyethylene composition has a z-average molecular weight distribution M Z / M W is 1.5 to 4.0, or 1.75 to 3.5, or 1.75 to 3.0, or 2.0 to 4.0, or 2.0 to 3.5, or 2.0 to 3.0, or 2.0 to 2.75.

[0122] In one embodiment of the present disclosure, the ethylene interpolymer product has a unimodal profile in a gel permeation chromatograph generated according to the method of ASTM D6474-99. The term "unimodal" is defined herein to mean the presence of only one clear, significant peak or maximum in the GPC curve. A unimodal profile includes broad, unimodal profiles. In contrast, the use of the term "bimodal" is meant to convey the presence of a second peak or shoulder representing a higher or lower molecular weight component in addition to a first peak (i.e., the molecular weight distribution can be said to have two maxima in the molecular weight distribution curve). Alternatively, the term "bimodal" refers to the presence of two maxima in a molecular weight distribution curve generated according to the method of ASTM D6474-99. The term "multimodal" refers to the presence of two or more, typically more than two, maxima in a molecular weight distribution curve generated according to the method of ASTM D6474-99.

[0123] In one embodiment of the present disclosure, the ethylene interpolymer product has a reverse or partially reversed comonomer distribution profile as measured using GPC-FTIR. If comonomer incorporation decreases with molecular weight as measured using GPC-FTIR, the distribution is described as "normal." If comonomer incorporation is approximately constant with molecular weight as measured using GPC-FTIR, the comonomer distribution is described as "flat" or "uniform." The terms "reverse comonomer distribution" and "partially reverse comonomer distribution" refer to the presence of one or more high molecular weight components with higher comonomer incorporation than one or more low molecular weight components in the GPC-FTIR data obtained for the copolymer. The term "reverse (d) comonomer distribution" is used herein to refer to the fact that the comonomer content of various polymer fractions across the molecular weight range of the ethylene interpolymer is not substantially uniform, with the higher molecular weight fractions having proportionally higher comonomer content (i.e., if comonomer incorporation increases with molecular weight, the distribution is described as "reverse" or "reversed"). If comonomer incorporation increases and then decreases with increasing molecular weight, the comonomer distribution is still considered "inverse," but may also be described as "partially inverse." A partially inverse comonomer distribution exhibits a peak or maximum.

[0124] In one embodiment of the present disclosure, the ethylene interpolymer product has an inverted comonomer distribution profile as measured using GPC-FTIR. In one embodiment of the present disclosure, the ethylene interpolymer product has a partially inverted comonomer distribution profile as measured using GPC-FTIR.

[0125] The ethylene interpolymer product has a non-comonomer exponential distribution (NCID). i which can be deconvoluted into a distinguishable first fraction and a distinguishable second fraction, each having a different non-comonomer index distribution NCID i1 and NCID i 2 The non-comonomer index distribution of the ethylene interpolymer products is experimentally determined using the triple detection cross-compartment chromatography (3D-CFC) technique disclosed in the "General Test Procedures" section.

[0126] In one embodiment of the disclosure, the ethylene interpolymer product has a log 10 (I6 / I2) / log 10 In a further embodiment of the disclosure, the ethylene interpolymer product has a stress index (log S.Ex.) defined as (6.48 / 2.16), wherein the stress index is less than or equal to 1.60. 10 (I6 / I2) / log 10 (6.48 / 2.16), where the stress index is less than 1.50, or less than 1.45, or less than 1.44, or less than 1.42.

[0127] In one embodiment of the present disclosure, the ethylene interpolymer product has a dimensionless long chain branching factor LCBF≧0.005. In one embodiment, the ethylene interpolymer product has an LCBF≦0.04. In one embodiment, the ethylene interpolymer product has an LCBF≧0.01. In one embodiment, the ethylene interpolymer product has an LCBF of 0.005 to 0.042, or 0.005 to 0.04, or 0.0054 to 0.04, or 0.01 to 0.0354, or 0.0114 to 0.0354, or 0.0114 to 0.0294, or 0.0174 to 0.0294. In one embodiment, the ethylene interpolymer product has an LCBF less than or equal to 0.04, or less than 0.04, or less than 0.0354, or less than 0.035, or less than 0.035, or less than 0.035, or less than 0.03, or less than 0.03, or less than 0.03, or less than 0.0294, or less than 0.0294, or less than 0.0234, or less than 0.0234. In one embodiment, the ethylene interpolymer product has an LCBF greater than or equal to 0.005, or greater than 0.0054, or greater than 0.0054, or greater than 0.01, or greater than 0.01, or greater than 0.0114, or greater than 0.0114, or greater than 0.0174, or greater than 0.0174.

[0128] In one embodiment, the ethylene interpolymer product has a total of unsaturations per 100 carbon atoms, SUM u In one embodiment, the ethylene interpolymer product has a SUM per 100 carbon atoms of 0.047 or greater. u In one embodiment, the ethylene interpolymer product has a SUM of from 0.047 per 100 carbon atoms to 0.07 per 100 carbon atoms, or from 0.047 per 100 carbon atoms to 0.0675 per 100 carbon atoms, or from 0.050 per 100 carbon atoms to 0.0675 per 100 carbon atoms, or from 0.05 per 100 carbon atoms to 0.064 per 100 carbon atoms, or from 0.05 per 100 carbon atoms to 0.06 per 100 carbon atoms. uIn one embodiment, the ethylene interpolymer product has a SUM less than or equal to 0.1 per 100 carbon atoms, or less than 0.1 per 100 carbon atoms, or less than or equal to 0.09 per 100 carbon atoms, or less than or equal to 0.07 per 100 carbon atoms, or less than 0.07 per 100 carbon atoms, or less than 0.0678 per 100 carbon atoms, or less than 0.0678 per 100 carbon atoms, or less than 0.0675 per 100 carbon atoms, or less than 0.0675 per 100 carbon atoms, or less than 0.064 per 100 carbon atoms, or less than 0.064 per 100 carbon atoms. u In one embodiment, the ethylene interpolymer product has a SUM greater than, or equal to, 0.047 per 100 carbon atoms, or greater than, or equal to, 0.047 per 100 carbon atoms, or greater than, or equal to, 0.048 per 100 carbon atoms, or greater than, or equal to, 0.048 per 100 carbon atoms, or greater than, or equal to, 0.049 ...5 per 100 carbon atoms, or greater than, or equal to, 0.05 per 100 carbon atoms, or greater than, or equal to, 0.051 per 100 carbon atoms, or greater than 0.051 per 100 carbon atoms. u It has.

[0129] <Flexible manufactured goods> The ethylene interpolymer products disclosed herein can be converted into flexible manufactured articles, such as monolayer or multilayer films.

[0130] Non-limiting examples of processes for preparing monolayer or multilayer films include blown film processes.

[0131] In the blown film extrusion process, an extruder heats, melts, mixes, and conveys a thermoplastic or thermoplastic blend. Once melted, the thermoplastic is forced through an annular die to produce a thermoplastic tube. In coextrusion, multiple extruders are used to produce multilayer thermoplastic tubes. The temperature of the extrusion process is primarily determined by the melting point or glass transition temperature of the thermoplastic or thermoplastic blend being processed, e.g., the thermoplastics, and the desired viscosity of the melt. For polyolefins, typical extrusion temperatures are 330°F to 550°F (166°C to 288°C). Upon exiting the annular die, the thermoplastic tube is inflated with air, cooled, solidified, and drawn into a pair of nip rollers. The expanding air increases the diameter of the tube, forming bubbles of the desired size. The tensile action of the nip rollers stretches the bubbles in the machine direction. Thus, the bubbles are stretched in two directions: the transverse direction (TD), where the expanding air increases the bubble diameter; and the machine direction (MD), where the nip rollers stretch the bubbles. As a result, the physical properties of blown films are typically anisotropic, i.e., the physical properties are different in the MD and TD directions; for example, the tear strength and tensile properties of a film are typically different in the MD and TD. Some prior art documents use the term "cross direction" or "CD"; these terms are equivalent to the terms "transverse direction" or "TD" used in this disclosure.

[0132] In the blown film process, air is blown around the periphery of the bubbles, cooling the thermoplastic as it exits the annular die. The final width of the film is determined by controlling the expanding air or internal bubble pressure; in other words, increasing or decreasing the diameter of the bubbles. The thickness of the film is primarily controlled by increasing or decreasing the speed of the nip rollers to control the drawdown rate. After exiting the nip rollers, the bubbles or tubes collapse and may be slit in the machine direction to create sheets. Each sheet may be wound into a roll of film. Each roll may be further slit to create a film of the desired width. Each roll of film is further processed into various consumer products, as described below.

[0133] Another example of a process for preparing a monolayer or multilayer film is the cast film process.

[0134] The cast film process is similar in that it can use single or multiple extruders, but various thermoplastic materials are metered into a flat die and extruded into a monolayer or multilayer sheet rather than a tube. In the cast film process, the extruded sheet is solidified on a chill roll.

[0135] In the cast film process, the film is extruded from a flat die onto chilled or nip rolls, optionally using a vacuum box and / or air knife. Cast films can be monolayer or coextruded multilayer films obtained by various extrusions through single or multiple dies. The resulting film can be used as is or laminated to other films or substrates, for example, by thermal lamination, adhesive lamination, or direct extrusion onto a substrate. The resulting films and laminates can be subjected to other forming processes, such as embossing, stretching, and thermoforming. Surface treatments, such as corona, can be applied, and the film can be printed.

[0136] Depending on the end use, the disclosed ethylene interpolymer products can be converted into monolayer or multilayer films spanning a wide range of thicknesses. Non-limiting examples include food packaging films ranging in thickness from about 0.5 mils to about 4 mils, and heavy duty sack applications where the film thickness ranges from about 2 mils to about 10 mils.

[0137] The ethylene interpolymer products disclosed herein may be used in monolayer films, which may include two or more ethylene interpolymer products and / or additional thermoplastics, non-limiting examples of which include polyethylene polymers and propylene polymers. The lower weight percent limit for the ethylene interpolymer product in the monolayer film may be about 3 wt%, in other cases about 10 wt%, and in still other cases about 30 wt%. The upper weight percent limit for the ethylene interpolymer product in the monolayer film may be 100 wt%, in other cases about 90 wt%, and in still other cases about 70 wt%.

[0138] The ethylene interpolymer products disclosed herein may also be used in one or more layers of multilayer film structures, non-limiting examples of which include 3, 5, 7, 9, 11, or more layers. The thickness of a particular layer (including the ethylene interpolymer product) within a multilayer film structure may be about 5%, in other cases about 15%, and in still other cases about 30% of the overall thickness of the multilayer film. In other embodiments, the thickness of a particular layer (including the ethylene interpolymer product) within a multilayer film structure may be about 95%, in other cases about 80%, and in still other cases about 65% of the overall thickness of the multilayer film structure. Individual layers of the multilayer film structure may comprise multiple ethylene interpolymer products and / or additional thermoplastics.

[0139] Additional embodiments include lamination and coating, in which monolayer or multilayer films comprising the disclosed ethylene interpolymer products are extrusion laminated, adhesive laminated, or extrusion coated. In extrusion or adhesive lamination, two or more substrates are bonded together with a thermoplastic or adhesive, respectively. In extrusion coating, a thermoplastic is applied to the surface of a substrate. These processes are well known to those skilled in the art. Adhesive or extrusion lamination is often used to bond dissimilar materials; non-limiting examples include bonding a paper web to a thermoplastic web, bonding an aluminum foil-containing web to a thermoplastic web, or bonding two chemically incompatible thermoplastic webs, such as bonding an ethylene interpolymer product-containing web to a polyester web or a polyamide web. Prior to lamination, webs comprising the disclosed ethylene interpolymer products may be monolayer or multilayer. Prior to lamination, the individual webs may be surface treated to improve bonding; non-limiting examples of surface treatments include corona treatment. A primary web or film may have a secondary web laminated to its top surface, its bottom surface, or both its top and bottom surfaces. Secondary and tertiary webs can be laminated to the primary web, where the secondary and tertiary webs differ in chemical composition. As a non-limiting example, the secondary or tertiary web can include a web that includes a barrier resin layer, such as polyamide, polyester, polypropylene, or EVOH. Such webs can include a vapor-deposited barrier layer, such as a thin silicon oxide (SiO x ) or aluminum oxide (AlO x ) layers. The multilayer web (or film) may contain 3, 5, 7, 9, 11, or more layers.

[0140] The ethylene interpolymer products disclosed herein can be used in a wide variety of articles of manufacture comprising one or more films or film layers (single or multilayer). Non-limiting examples of such articles of manufacture include: food packaging films (fresh food, frozen food, liquid food, granular food), stand-up pouches, retort packaging, and bag-in-box packaging; barrier films (oxygen, moisture, aroma, oil, etc.) and modified atmosphere packaging; lightweight and heavy-duty shrink films and wraps, collated shrink films, pallet shrink films, shrink bags, shrink ties, and shrink shrouds; lightweight and heavy-duty stretch films, hand stretch wraps, machine stretch wraps, and stretch food films; high clarity films; heavy-duty bags; household wraps, overwrap films, sandwich bags; industrial and institutional films, trash bags, can liners, magazine overwraps, newspaper bags, mailing bags, bags and envelopes, bubble wrap, carpet films, furniture bags, garment bags, coin bags, automotive panel films; gowns, dresses, and other similar products. Medical applications such as tape, surgical garments, etc.; construction films and sheets, asphalt films, insulation bags, masking films, landscaping films and bags; geomembrane liners for municipal solid waste management and mining applications; bulk seal bags; agricultural films, mulch films, greenhouse films; in-store packaging, self-service bags, boutique bags, grocery bags, carry-out bags, T-shirt bags; oriented films, machine direction and biaxially oriented films, and functional film layers (e.g., sealant and / or toughness layers) in oriented polypropylene (OPP) films. Additional articles of manufacture comprising one or more films comprising at least one ethylene interpolymer product include laminates and / or multilayer films, sealant and tie layers in multilayer films and composites, laminates with paper, aluminum foil laminates, or laminates containing vacuum-deposited aluminum, polyamide laminates, polyester laminates, extrusion-coated laminates, and hot melt adhesive formulations. The articles of manufacture summarized in this paragraph comprise at least one film (single layer or multilayer) comprising at least one embodiment of the disclosed ethylene interpolymer products.

[0141] Cast films and laminates made from the ethylene interpolymer products of the present disclosure can be used in a variety of end uses, such as, for example, food packaging (dry food, fresh food, frozen food, liquid, processed food, powder, granules), detergent, toothpaste, towels, labels, and release liner packaging. Cast films can also be used for unitized and industrial packaging, particularly stretch films. Cast films may also be suitable for hygiene and medical applications, such as breathable and non-breathable films used in diapers, adult incontinence products, feminine hygiene products, and ostomy bags. The ethylene interpolymer products of the present disclosure can also be useful in tape and artificial turf applications.

[0142] The desired physical properties of the film (single layer or multilayer) typically depend on the intended application. Non-limiting examples of desired film properties include optical properties (gloss, haze, and clarity), dart impact, Elmendorf tear, modulus (1% and 2% secant modulus), puncture-propagation tear resistance, tensile properties (yield strength, break strength, elongation at break, toughness, etc.), and heat-sealing properties (heat-seal initiation temperature and hot-tack strength). Specific hot-tack and heat-sealing properties are desired in high-speed vertical and horizontal form-fill processes, where commercial products (liquids, solids, pastes, parts, etc.) are filled and sealed into pouch-like packages.

[0143] In addition to desirable film physical properties, it is desirable that the disclosed ethylene interpolymer products be easy to process on a film line. Those skilled in the art frequently use the term "processability" to distinguish polymers with improved processability from polymers with poor processability. A commonly used measure to quantify processability is extrusion pressure; more specifically, polymers with improved processability have lower extrusion pressures (on blown film or cast film extrusion lines) compared to polymers with poor processability.

[0144] The films used in the articles of manufacture described in this section may optionally contain additives and adjuvants depending on their intended use. Non-limiting examples of additives and adjuvants include antiblocking agents, antioxidants, heat stabilizers, slip agents, processing aids, antistatic additives, colorants, dyes, filler materials, light stabilizers, light absorbers, lubricants, pigments, plasticizers, nucleating agents, and combinations thereof.

[0145] One embodiment of the present disclosure is a film layer comprising the ethylene interpolymer product described herein.

[0146] In one embodiment, the film layer is a blown film. In one embodiment, the film layer is a cast film. In one embodiment, the film layer has a thickness of 0.5 to 10 mils.

[0147] One embodiment of the present disclosure is a multilayer film structure comprising at least one film layer comprising the ethylene interpolymer product described herein.

[0148] In one embodiment, the multilayer film structure is a blown film structure. In one embodiment, the multilayer film structure has a thickness of 0.5 to 10 mils.

[0149] One embodiment of the present disclosure is a multilayer film structure comprising a core layer, the core layer comprising an ethylene interpolymer product described herein.

[0150] One embodiment of the present disclosure is a multilayer film structure comprising a sealant layer, the sealant layer comprising the ethylene interpolymer product disclosed herein.

[0151] <General Test Procedure> Prior to testing, each specimen was conditioned for at least 24 hours at 23±2°C and 50±10% relative humidity, with subsequent testing being performed at 23±2°C and 50±10% relative humidity. As used herein, the term "ASTM conditions" refers to a laboratory maintained at 23±2°C and 50±10% relative humidity, and the specimens to be tested were conditioned in this laboratory for at least 24 hours prior to testing. ASTM refers to American Society for Testing and Materials.

[0152] <density> The density of the ethylene / α-olefin copolymers in the solid state was determined using ASTM D792-13 (November 1, 2013).

[0153] <Melt index> The melt index of ethylene / α-olefin copolymers was determined using ASTM D1238 (August 1, 2013). The melt index I2 was measured at 190°C using a 2.16 kg weight.

[0154] <Melt strength> Melt strength is measured at 190°C on a Rosand RH-7 capillary rheometer (barrel diameter = 15 mm) using a flat die with a 2 mm diameter and L / D ratio of 10:1. Pressure transducer: 10,000 psi (68.95 MPa). Piston speed: 5.33 mm / min. Take-off angle: 52°. Take-off incremental speed: 50-80 m / min. 2 or 65±15m / min 2 A polymer melt sample is extruded through a capillary die at a constant rate, and then the polymer strand is withdrawn at an increasing take-up speed until it ruptures. The maximum steady-state value of force in the plateau region of the force versus time curve is defined as the melt strength of the polymer.

[0155] <Non-comonomer Index Distribution> The non-comonomer index distribution (NCID) of the ethylene interpolymer products of the present disclosure i-dimensionless) was experimentally determined using triple detection cross fractionation chromatography (3D-CFC).

[0156] For 3D-CFC experiments, a polymer sample (150–300 mg) was introduced into the sample dissolution vessel of a Polymer Char Crystal-TREF unit. The sample dissolution vessel was then filled with 35 mL of 1,2,4-trichlorobenzene (TCB) containing 250 ppm of the antioxidant 2,6-di-tert-butyl-4-methylphenol (BHT), heated to the desired dissolution temperature (e.g., 140 °C), and stirred for 2–3 h. The polymer solution (1.5 mL) was then loaded onto a TREF column packed with stainless steel beads. After equilibration at a predetermined stabilization temperature (e.g., 110 °C) for 20–45 min, the polymer solution was crystallized by decreasing the temperature from the stabilization temperature to 30 °C (0.2 °C / min). After equilibration at 30 °C for 90 min, the crystallized sample was eluted with TCB from 30 °C to 140 °C, and the eluate was divided into multiple fractions (e.g., 5–20 fractions). For each fraction, the TREF column was heated to the predetermined dissolution temperature (heating rate of 1.0 °C / min for step elution) and held at that temperature for at least 50 min, after which the fraction solution was eluted and introduced directly into the SEC system through a heated transfer line. All of the above steps (including sample dissolution, loading of the sample solution onto the TREF column, crystallization, and elution) were programmed and controlled using Polymer Char TREF software with step elution function.

[0157] The various polymer fractions were chromatographed at 140 °C on a PL220 high-temperature chromatography unit equipped with four SHODEX® columns (HT803, HT804, HT805, and HT806) or four PL Mixed ALS or BLS columns and a differential refractive index (DRI) detector as a concentration detector. Molar mass and intrinsic viscosity were measured using a double-angle light scattering detector (15° and 90°) and a differential viscometer, respectively. TCB was used as the mobile phase at a flow rate of 1.0 mL / min. BHT was added to the mobile phase at a concentration of 250 ppm to protect the SEC column from oxidative degradation. Data were acquired using CIRRUS GPC software and processed using CIRRUS® GPC software and an Excel spreadsheet to generate absolute molar mass and intrinsic viscosity [η].

[0158] Alternatively, 3D-CFC experiments can be performed using a Polymer Char CEF instrument equipped with a step elution function. A polymer sample (50–100 mg) was introduced into the sample dissolution vial of the Polymer Char Crystaf-TREF unit, and the vial was loaded into the autosampler. The sample dissolution vial was then filled with 6–7 mL of 1,2,4-trichlorobenzene (TCB) containing 250 ppm of the antioxidant 2,6-di-tert-butyl-4-methylphenol (BHT), heated to the desired dissolution temperature (e.g., 160 °C), and shaken for 2–3 h. The polymer solution (0.2 mL) was then loaded onto a TREF column packed with stainless steel beads. After equilibration at a predetermined stabilization temperature (e.g., 110 °C) for 20–45 min, the polymer solution was cooled from the stabilization temperature to 30 °C for crystallization (0.2 °C / min). After equilibration at 30 °C for 30 min, the crystallized sample was eluted with TCB from 30 °C to 140 °C, and the eluate was divided into multiple fractions (e.g., 4–10 fractions). For each fraction, the TREF column was heated to a predetermined dissolution temperature and held at that temperature for 15–30 min. The fraction's solution was then eluted and directly introduced onto a set of SEC columns installed in the upper oven. All of the above steps (including sample dissolution, loading of the sample solution onto the TREF column, crystallization, and elution) were programmed and controlled using Polymer Char CEF software with a step elution function.

[0159] The various polymer fractions were chromatographed at 140 °C using two to four PL Mixed ALS or BLS columns and a Polymer Char IR4 as a concentration detector. Intrinsic viscosity and molar mass were measured using a Polymer Char 4-bridge viscometer and a multi-angle light scattering detector (HELEOS II MALS, Wyatt Technology), respectively. TCB was used as the mobile phase at a flow rate of 0.5 or 1.0 mL / min. BHT was added to the mobile phase at a concentration of 250 ppm to protect the SEC column from oxidative degradation. Data were acquired using CIRRUS GPC software or ASTRA software and processed using CIRRUS GPC software or ASTRA software and an Excel spreadsheet to generate absolute molar mass and intrinsic viscosity [η].

[0160] The term "absolute" molar mass was used to distinguish between absolute molar mass determined by 3D-SEC and molar mass determined by conventional SEC. The viscosity-average molar mass (M v ) and intrinsic viscosity ([η]) were used for calculation, using the following formula:

number

number

number

[0161] In this disclosure, the constant A in equation (4) is defined by the slope of equation (6), specifically, A = -1000000 × (slope). Constants B and C in equation (4) were calculated from the linear correlation between the comonomer content and the weight-average elution temperature of the ethylene / α-olefin interpolymer based on the reconstructed analytical TREF profile of the ethylene / α-olefin interpolymer (see below for details). Constant B is the slope, and constant C is the intercept. For example, in this disclosure, for the α-octene comonomer, constants A, B, and C were 2.1626, -0.6737, and 63.6727, respectively.

[0162] In equation (4), the fth 3D-CFC TREF fraction T f The weight-average TREF elution temperatures were calculated based on the reconstructed analytical TREF profiles of the ethylene / α-olefin interpolymers. The reconstructed analytical TREF profiles were obtained by simply substituting the original elution temperatures in the analytical TREF analysis performed on a Polymer Char Crystaf-TREF instrument (hereafter referred to as CTREF) with the equivalent elution temperatures of the 3D-CFC. Converting the original elution temperatures to the equivalent elution temperatures of the 3D-CFC allows for correction of flow differences in the elution phase, i.e., the difference between dynamic elution (with flow) during heating on the CTREF and static elution (without flow) during heating on the 3D-CFC, as well as other differences (if any) between these instruments. To perform this conversion, a series of ethylene / α-olefin interpolymers with different comonomer contents and randomly distributed comonomer units were analyzed using both the CTREF (Polymer Char Crystaf-TREF unit) and the 3D-CFC. In this calibration procedure, the elution temperature range of each TREF fraction in the 3D-CFC analysis was very narrow (e.g., 1–2 °C, 5 °C or less, as much as possible), and the average of the lower and higher temperatures of the TREF fraction was defined as the elution temperature of the 3D-CFC TREF fraction. For example, the elution temperature of the fraction between 40 °C and 45 °C was 42.5 °C.

[0163] The weight average elution temperature of the entire ethylene / α-olefin interpolymer was calculated from the weight fraction and elution temperature of each 3D-CFC TREF fraction. From the correlation between the comonomer content of the ethylene / α-olefin interpolymer and the weight average elution temperature in 3D-CFC and CTREF, a relationship between the weight average elution temperature of 3D-CFC and CTREF could be established, and this relationship could be used to convert the original elution temperature in the CTREF analysis to the elution temperature of 3D-CFC.

[0164] In this disclosure, the weight average elution temperature and CTREF (T CTREF The relationship between the weight average dissolution temperature of CFC=0.9776×T CTREF This relationship was expressed as -0.7156. This relationship was used to reconstruct the analytical TREF profile by converting the original TREF elution temperature into the equivalent 3D-CFC elution temperature, and then calculating the weight-average TREF elution temperature of the fth 3D-CFC TREF fraction, T f was calculated and used to calculate the constants B and C in equation (4).

[0165] Without wishing to be bound by any theory, the resulting non-comonomer index distribution is believed to be a composite indicator of the presence and distribution of mid-chain branching (defined as branches that are longer than the comonomer branching length and are not rheologically active) and long-chain branching (defined as "rheologically active" branches; see next section on long-chain branching coefficient).

[0166] <Long Chain Branching Factor (LCBF)> The LCBF (dimensionless) of the ethylene interpolymer products was determined using the method described in U.S. Patent Application Publication No. 2018 / 0305531, which is incorporated herein by reference.

[0167] In the present disclosure, long chain branching is defined as the entanglement molecular weight M e It has a molecular weight of M e is a well-known concept in polymer physics (e.g., reported to be about 1 kg / mol for polyethylene; see Fetters et al., Macromolecules 1999, 32, 6847). In this disclosure, long chain branching is characterized as "rheologically active." The term "rheologically active" means that the presence of long chain branching in a sample is evident after comparing the results of rheological testing with a control sample that does not contain long chain branching. Non-limiting examples of rheological test results include flow activation energy (E a ), shear thinning or viscosity ratio, melt flow ratio (I 21 / I2, I 10 / I2, etc.), melt strength, and long chain branching factor (LCBF).

[0168] The LCBF calculation includes the polydispersity corrected zero shear viscosity (ZSV c ) and SCB corrected intrinsic viscosity (IV c ) calculation is included. Zero shear viscosity ZSV c The polydispersity correction applied to has dimensions of Poise and was performed as shown in equation (7):

number

[0169] SCB corrected intrinsic viscosity IV c The calculation of (having dimensions of dL / g) was performed as shown in equation (8):

number

[0170] Non-long chain branched ethylene interpolymer products (i.e., ethylene interpolymer products that contain no LCB or undetectable levels of LCB) are on the "baseline" defined by the following formula:

number

[0171] The calculation of LCBF is based on the horizontal shift (S h ) and vertical direction (S v ) and is given by:

number

number

[0172] In equations (10) and (11), the polydispersity-corrected zero shear viscosity ZSV c and SCB-corrected intrinsic viscosity IVc were required to have dimensions of poise and dL / g, respectively. The horizontal shift coefficient (S h ) is a constant IV c ZSV in c The physical meaning is clear except for the logarithmic function: c is the ratio of the ZSV of the sample under test c And the same IV c ZSV of the linear ethylene interpolymer product having c The horizontal shift coefficient (S h ) is dimensionless.

[0173] Vertical Shift (S v ) is a constant ZSV c IV in c Here again, the physical meaning is clear if we remove the logarithm function. c IV of the linear ethylene interpolymer product havingc and the IV of the sample under test c and two IVs c The vertical shift coefficient (S v ) is dimensionless.

[0174] Finally, in this disclosure, the dimensionless long chain branching factor (LCBF) is defined by equation (12):

number

[0175] <Comonomer content: Fourier transform infrared (FTIR) spectroscopy> The amount of comonomer in the ethylene interpolymer product was determined by FTIR and reported as short-chain branching (SCB) content, with the dimension CH3 / 1000C (number of methyl branches per 1000 carbon atoms). This test was completed using compression-molded polymer plaques and a Thermo-Nicolet 750 Magna-IR spectrophotometer in accordance with ASTM D6645-01 (2001). Polymer plaques were prepared using a compression molding apparatus (Wabash-Genesis series press) in accordance with ASTM D4703-16 (April 2016).

[0176] <Dynamic mechanical analysis (DMA)> Oscillatory shear measurements at small strain amplitudes were performed to obtain linear viscoelastic functions in the frequency range of 0.02 to 126 rad / s at 190 °C under a nitrogen atmosphere, 10% strain amplitude, and 5 points per 100 μm. Frequency sweep experiments were performed on a TA Instruments DHR3 stress-controlled rheometer using a cone-plate geometry with a 5° cone angle, 137 μm truncation, and 25 mm diameter. In this experiment, a sinusoidal strain wave was applied, and the stress response was analyzed in terms of linear viscoelastic functions. The zero shear rate viscosity (η) based on the DMA frequency sweep results was calculated as |η * |=η0[1+(τ c ω) a ] ((n-1) / a)was determined by fitting the four-parameter Carreau-Yasuda viscosity model to the curve of complex viscosity versus angular frequency defined by |η * | is the complex viscosity measured as a function of angular frequency ω, and a (or CY-a as referred to in the Examples section) is a parameter that determines the width of the transition from the Newtonian plateau to the shear thinning region, which has a slope of n-1 in a log-log plot. In this disclosure, the parameter n was set to a constant value 2 / 11, and the remaining model parameters were fitted by least squares.

[0177] Triple detection size exclusion chromatography (3D-SEC) Polymer solutions (1–3 mg / mL) were prepared by heating samples of ethylene interpolymer products in 1,2,4-trichlorobenzene (TCB) and rotating them on a wheel in an oven at 150 °C for 4 hours. To stabilize the polymer samples against oxidative degradation, the antioxidant 2,6-di-tert-butyl-4-methylphenol (BHT) was added to the mixture. The BHT concentration was 250 ppm. The sample solutions were chromatographed at 140 °C on a PL220 high-temperature chromatography unit equipped with a differential refractive index (DRI) detector, a dual-angle light scattering detector (15° and 90°), and a differential viscometer. The SEC columns used were either four SHODEX columns (HT803, HT804, HT805, and HT806) or four PL Mixed ALS or BLS columns. TCB was used as the mobile phase at a flow rate of 1.0 mL / min. To protect the SEC column from oxidative degradation, BHT was added to the mobile phase at a concentration of 250 ppm. The sample injection volume was 200 μL. The raw SEC data were processed with CIRRUS GPC software to obtain absolute molar mass, intrinsic viscosity ([η]), and viscosity-average molar mass (M v ) was generated. The term "absolute" molar mass was used to distinguish between absolute molar mass determined by 3D-SEC and molar mass determined by conventional SEC. Viscosity-average molar mass (M v ) and intrinsic viscosity ([η]) were used in the calculation to determine the long chain branching factor (LCBF).

[0178] <Conventional Size Exclusion Chromatography (SEC)> Polymer solutions (1–3 mg / mL) were prepared by heating the polymer in 1,2,4-trichlorobenzene (TCB) and rotating it on a wheel in an oven at 150 °C for 4 hours. To stabilize the polymer against oxidative degradation, the antioxidant 2,6-di-tert-butyl-4-methylphenol (BHT) was added to the mixture. The BHT concentration was 250 ppm. The polymer solution was chromatographed at 140 °C on a PL 220 high-temperature chromatography unit equipped with four SHODEX columns (HT803, HT804, HT805, and HT806) using TCB as the mobile phase at a flow rate of 1.0 mL / min and differential refractive index (DRI) as the concentration detector. To protect the GPC column from oxidative degradation, BHT was added to the mobile phase at a concentration of 250 ppm. The sample injection volume was 200 μL. The GPC column was calibrated with narrow-distribution polystyrene standards. Polystyrene molecular weights were converted to polyethylene molecular weights using the Mark-Houwink equation as described in Standard Test Method D6474-12 (December 2012). GPC raw data were processed with CIRRUS GPC software to obtain molar mass averages (M n , M w , M z ) and molar mass distribution (e.g., polydispersity, M w / M n In the polyethylene field, the commonly used term equivalent to SEC is GPC, i.e., gel permeation chromatography.

[0179] <Unsaturation> The amount of unsaturated groups (double bonds) in the ethylene interpolymer product was determined in accordance with ASTM D3124-98 (published March 2011) and ASTM D6248-98 (published July 2012). Samples of the ethylene interpolymer product were a) first extracted overnight with carbon disulfide to remove additives that may interfere with the analysis; b) the sample (pellets, films, or granules) was compressed into plaques of uniform thickness (0.5 mm); c) the plaques were analyzed by FTIR to quantify the amount of terminal unsaturation (vinyl) and internal unsaturation (trans-vinylene); and d) the sample plaques were brominated and reanalyzed by FTIR to quantify the amount of side-chain unsaturation (vinylidene). The IR resonances of these groups are at 908 cm and 910 cm, respectively. -1 , 965cm -1 , and 888 cm -1 This procedure is based on Beer's law: A = a x b x d x c, where a is the extinction coefficient of the particular unsaturation being measured, b is the thickness of the plaque, d is the density of the plaque, and c is the selected unsaturation. Experimentally, the weight and area of ​​the plaque are measured, rather than the density and thickness of the plaque. In this disclosure, the internal unsaturation (I u ), side chain unsaturation (SC u ), and terminal unsaturation (T u ) to calculate the sum of unsaturations per 100 carbon atoms (SUM u ) to SUM u =2×I u +SC u +T u was calculated according to

[0180] <gpc-ftir> Polymer solutions were prepared by heating 2–4 mg / mL samples of ethylene interpolymer products in 1,2,4-trichlorobenzene (TCB) and rotating them on a wheel in an oven at 150 °C for 4 h. An 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. The sample solution was chromatographed at 140 °C on a Waters GPC 150C chromatography unit equipped with four SHODEX columns (HT803, HT804, HT805, and HT806) using TCB as the mobile phase at a flow rate of 1.0 mL / min. An FTIR spectrometer and a heated FTIR flow-through cell were connected to the chromatography unit through a heated transfer line as the detection system. To protect the SEC column from oxidative degradation, BHT was added to the mobile phase at a concentration of 250 ppm. The sample injection volume was 300 μL. The raw FTIR spectra were processed using OPUS® FTIR software, and polymer concentration and methyl content were calculated in real time using the OPUS-associated Chemometric software (PLS technique). Polymer concentration and methyl content were then acquired and baseline corrected using CIRRUS GPC software. The SEC column was calibrated with narrow-dispersion polystyrene standards. Polystyrene molecular weights were converted to polyethylene molecular weights using the Mark-Houwink equation, as described in ASTM standard test method D6474. Comonomer content was calculated based on polymer concentration and methyl content predicted by PLS technique, as described in Paul J. DesLauriers, Polymer 43, pages 159-170 (2002); incorporated herein by reference.

[0181] The GPC-FTIR method measures the total methyl content, including the methyl groups located at the end of each polymer chain, i.e., the methyl end groups. Therefore, the raw GPC-FTIR data must be corrected by subtracting the contribution from the methyl end groups. To clarify, the raw GPC-FTIR data overestimates the amount of short-chain branches (SCBs), and this overestimation increases as the molecular weight decreases. In this disclosure, the raw GPC-FTIR data was corrected using the 2-methyl correction. For a given molecular weight (M), the following equation is used: N E = 28000 / M using the methyl end group (N E ) and calculate the number of N E (M dependent) was subtracted from the raw GPC-FTIR data to generate SCB (2-methyl corrected) GPC-FTIR data per 1000 carbon atoms.

[0182] <Composition Distribution Branching Index (CDBI)> The "Composition Distribution Branching Index" (hereinafter, CDBI) of the disclosed examples and comparative examples was measured using a CRYSTAF / TREF200+ unit equipped with an IR detector (hereinafter, CTREF). The acronym "TREF" stands for Temperature Rising Elution Fractionation. 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 is a function of elution temperature, Co / Ho ratio (copolymer / homopolymer ratio), and CDBI (Composition Distribution Breadth Index), i.e., CDBI 50 The chemical composition of a polymer sample as a function of pH was generated. A polymer sample (80–100 mg) was placed in a CTREF reaction vessel. 35 mL of 1,2,4-trichlorobenzene (TCB) was added to the reaction vessel, and the polymer was dissolved by heating the solution to 150 °C for 2 h. An aliquot (1.5 mL) of the solution was then loaded onto a CTREF column packed with stainless steel beads. The sample-loaded column was then stabilized at 110 °C for 45 min. The polymer was then crystallized from the solution in the column by lowering the temperature to 30 °C at a cooling rate of 0.09 °C / min. The column was then equilibrated at 30 °C for 30 min. The crystallized polymer was then eluted from the column while TCB was flowing through the column at 0.75 mL / min, and the column was slowly heated from 30 °C to 120 °C at a heating rate of 0.25 °C / min. Raw CTREF data were processed using the in-house developed Polymer ChAR software, an Excel spreadsheet, and the CTREF software. CDBI 50 is defined as the percentage of polymers whose composition is within 50% of the central comonomer composition; 50 was calculated from the composition distribution curve and the normalized cumulative integral of the composition distribution curve, as described in U.S. Pat. No. 5,376,439. Those skilled in the art will understand that a calibration curve is required to convert the CTREF elution temperature to comonomer content, i.e., the amount of comonomer in the ethylene / α-olefin polymer fraction eluting at a particular temperature. The creation of such a calibration curve is described in the prior art, e.g., Wild et al., J. Polym. Sci., Part B, Polym. Phys., Vol. 20(3), pp. 441-455, which is incorporated herein by reference in its entirety. At the end of each sample run, the CTREF column was cleaned for 30 minutes; specifically, the CTREF column temperature was brought to 160°C, and TCB was run through the column (0.5 mL / min) for 30 minutes.

[0183] <Film tension> The following film tensile properties were determined using ASTM D882-12 (August 1, 2012): tensile strength at break (MPa), elongation at break (%), tensile yield strength (MPa), tensile elongation at yield (%), and tensile energy to break (J). Tensile properties were measured in both the machine direction (MD) and transverse direction (TD) of blown films.

[0184] <Film secant coefficient> The secant modulus is a measure of film stiffness. It is the slope of the line drawn between two points on a stress-strain curve. The first point on the stress-strain curve is the origin, i.e., the point corresponding to the origin (the point of zero percent strain and zero stress), and the second point on the stress-strain curve is the point corresponding to 1% strain. Given these two points, the 1% secant modulus is calculated and expressed in force per unit area (MPa). The 2% secant modulus is calculated similarly. Because the stress-strain relationship of polyethylene does not follow Hooke's law, i.e., the stress-strain behavior of polyethylene is nonlinear due to its viscoelastic nature, this method is used to calculate the film modulus. The secant modulus was measured using a conventional Instron tensile tester equipped with a 200 lbf load cell. For testing, monolayer film specimens were cut to dimensions of 14 inches long, 1 inch wide, and 1 mil thick, ensuring that the edges of the specimens were free of scratches or notches. Film specimens were cut and tested in both the machine direction (MD) and transverse direction (TD). ASTM conditions were used to condition the specimens. The thickness of each film was accurately measured with a handheld micrometer and entered into the Instron software along with the specimen name. The specimens were mounted in the Instron with a 10-inch grip spacing and pulled at a rate of 1 inch / minute to generate stress-strain curves. The Instron software was used to calculate the 1% secant modulus and the 2% secant modulus.

[0185] <Film Dart Impact> Film dart impact strength was determined using ASTM D1709-09 Method A (May 1, 2009). In this disclosure, the dart impact test used a 1.5 inch (38 mm) diameter hemispherical-headed dart.

[0186] <Film Elmendorf tear resistance> Film tear performance was determined by ASTM D1922-09 (May 1, 2009); a similar term for tear is "Elmendorf tear." Film tear was measured in both the machine direction (MD) and transverse direction (TD) of blown films. [Example]

[0187] The following examples are presented for the purpose of illustrating selected embodiments of the present disclosure, and it is understood that the presented examples do not limit the scope of the presented claims.

[0188] <Ethylene interpolymer product> The ethylene interpolymer products in Examples 1-13 were each produced using a commercial "in-series" multi-reactor solution polymerization process using a mixed binary catalyst system, in which the ethylene interpolymer products were produced by forming a first ethylene interpolymer in a first reactor (R1), a second ethylene interpolymer in a second reactor (R2), and a third ethylene interpolymer in a third reactor (R3), with R1, R2, and R3 configured in series with one another. "In-series" multi-reactor, liquid-phase polymerization processes, including those using mixed binary catalysts, are described in U.S. Patent Application Publication No. 2018 / 0305531.

[0189] The pressure in R1 was approximately 14 MPa to approximately 18 MPa, and R2 was operated at a lower pressure to facilitate continuous flow from R1 to R2. Both R1 and R2 were continuously stirred reactors (CSTRs) and were agitated to ensure thorough mixing of the reactor contents. The two CSTR reactors (R1 and R2) were configured in series, followed by a third reactor (R3), which was a tubular reactor. The process was operated continuously by feeding fresh process solvent, ethylene, 1-octene, and hydrogen to the first and second reactors (R1 and R2) and removing the product. Methylpentane was used as the process solvent (a commercially available blend of methylpentane isomers). The monomer (ethylene) and comonomer (1-octene) were purified using conventional feed preparation systems (e.g., contact with various absorption media to remove impurities such as water, oxygen, and polar contaminants) before adding them to the reactors. The reactor feeds were pumped to reactors R1 and R2 at the rates shown in Tables 1A-1C. The R1 feed temperature in Examples 1-13 was controlled at 24.1, 30.0, 30.0, 23.9, 23.9, 24.0, 24.0, 24.1, 30.0, 24.2, 24.0, 24.0, and 24.0, respectively. The R2 feed temperature in Examples 1-13 was controlled at 25.0, 40.0, 40.0, 41.9, 24.9, 25.0, 25.0, 25.0, 40.0, 25.0, 25.0, and 25.0, respectively.

[0190] In operating the continuous solution polymerization process shown in Tables 1A-1C, the total amount of ethylene fed to the process was distributed or split to three reactors R1, R2, and R3. In Tables 1A, 1B, and 1C, this operating variable is referred to as the ethylene split (ES), and ES R1 , E.S. R2 , and ES R3 refers to the weight percent of ethylene injected into R1, R2, and R3, respectively, where ES R1 +ES R2 +ES R3 = 100%. 1-Octene was also added to the continuous solution polymerization process and distributed or split into R1, R2, and R3. In Tables 1A, 1B, and 1C, this manipulated variable is referred to as 1-octene split (OS), and OS R1 , OS R2 , and OS R3 represent the weight percent of 1-octene comonomer injected into R1, R2, and R3, respectively, where OS R1 +OS R2 +OS R3 =100%.

[0191] When operating the continuous solution polymerization process shown in Tables 1A-1C, the total amount of ethylene converted in each reactor is monitored. R1 The term Q represents the percentage of ethylene added to R that is converted to the first ethylene interpolymer by the catalyst formulation. R2 and Q R3 represents the percentage of ethylene added to R2 and the remaining ethylene that flows from R1 and R2 to R3 that is converted to the second ethylene interpolymer and the third ethylene interpolymer, respectively.

[0192] In Table 1A to Table 1C, Q T The term Q represents the total ethylene conversion throughout the continuous solution polymerization plant, i.e., Q T = 100 × [weight of ethylene in interpolymer product] / ([weight of ethylene in interpolymer product] + [weight of unreacted ethylene]).

[0193] In Examples 1-13, a first ethylene interpolymer was prepared in a first reactor (R1) configured in series with a second reactor (R2) and a third reactor (R3) using the following single-site catalyst components: Component A, diphenylmethylene(cyclopentadienyl)(2,7-di-t-butylfluorenyl)hafnium dimethide [(2,7-tBuFlu)PhC(Cp)HfMe]; Component M, methylaluminoxane (MMAO-07); Component B, trityl tetrakis(pentafluorophenyl)borate (tritylborate), and Component P, 2,6-di-tert-butyl-4-ethylphenol (BHEB). Methylaluminoxane (MMAO-07); and 2,6-di-tert-butyl-4-ethylphenol were premixed in-line and combined with diphenylmethylene(cyclopentadienyl)(2,7-di-t-butylfluorenyl)hafnium dimethide and trityl tetrakis(pentafluorophenyl)borate just 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 Tables 1A-1C), the molar ratios of the catalyst components (i.e., [M] / [A], [P] / [M], and [B] / [A] listed in Tables 1A-1C), and the R1 catalyst inlet temperature (not shown in Tables 1A-1C). The R1 catalyst inlet temperature was controlled between 20 and 40 °C.

[0194] In Examples 1 through 13, a second ethylene interpolymer was prepared in a second reactor (R2) using an in-line Ziegler-Natta catalyst formulation. The in-line Ziegler-Natta catalyst formulation contained the following components: butylethylmagnesium [component v]; tertiary butyl chloride [component vi]; titanium tetrachloride [component vii]; diethylaluminum ethoxide [component viii]; and triethylaluminum [component ix]. Using methylpentane as the catalyst component solvent, the in-line Ziegler-Natta catalyst formulation was prepared using the following steps and then injected into the second reactor (R2). In Step 1, a solution of triethylaluminum and butylethylmagnesium (Mg:Al=20, mol:mol) was mixed with a solution of tertiary butyl chloride and allowed to react for approximately 30 seconds to form the MgCl2 support. In Step 2, a solution of titanium tetrachloride was added to the mixture formed in Step 1 and allowed to react for approximately 14 seconds before being injected into the second reactor (R2). The in-line Ziegler-Natta catalyst was activated in the reactor by injecting a solution of diethylaluminum ethoxide into R2. The efficiency of the in-line Ziegler-Natta catalyst formulation was optimized by adjusting the amount of titanium tetrachloride added to the reactor (listed in Tables 1A-1C as R2 catalyst (ppm)), the molar ratios of the catalyst components (i.e., [vi] / [v], [viii] / [vii], and [ix] / [vii] as listed in Tables 1A-1C), and the R2 catalyst inlet temperature (not shown in Tables 1A-1C). The R2 catalyst inlet temperature was controlled between 20 and 40 °C.

[0195] In Examples 1-13, fresh ethylene, 1-octene, hydrogen, and catalyst were not pumped to the third reactor. Residual ethylene, 1-octene, and active catalyst from upstream reactors R1 and R2 entered the third reactor (R3) to form the third ethylene interpolymer in these examples.

[0196] Polymerization in the continuous solution polymerization process was terminated by adding a catalyst deactivator to the third reactor outlet stream. The ethylene interpolymer product was recovered from the process solvent using a multistage phase separation process. In this process, the third reactor outlet stream was heated and passed through two V / L separators configured in series with each other. The polymer-rich stream exiting the final V / L separator contained 94.5 to 96.5 weight percent of the ethylene interpolymer product and was fed to a twin-screw extruder for additive addition and pelletization.

[0197] Examples 1-13 were carried out under process conditions for producing multicomponent ethylene interpolymer products, which contained detectable levels of long chain branching as evidenced by a long chain branching factor (LCBF) of 0.005 or greater. The ethylene interpolymer products in Examples 1-13 further had a total unsaturation per 100 carbons SUM u is also characterized by a value of 0.047 or greater (see Table 4).

[0198] The multicomponent ethylene interpolymer products prepared in Examples 3-13 contained first and second fractions with different non-comonomer index distribution characteristics. The weight percent of the first and second fractions, the molecular weight distribution index M w / M n The experimentally measured molecular weight distribution and non-comonomer index distribution (NCID) of the ethylene interpolymer product are deconvoluted via the deconvolution scheme described in Eqs. (13) to (15). i ) was determined by deconvolution.

[0199] Example 1 shows 40 wt. % of the first fraction (1.99 M w / M n ) and 60 wt. % of the second fraction (having an M of 2.11 w / M n The second fraction in Example 1 contained an incremental molar mass M i Deconvolved NCID that decreases monotonically as increases i 2 As shown in Figures 1 and 2, the deconvoluted NCIDs of Example 1 were characterized based on i 2 The value is inequality (1b) ≦ NCID i 2 ≦(1a) changes within the range defined in NCID i 2 The first semi-logarithmic derivative of (dNCID i 2 / dlogM i ) was less than -0.0001. i 2 is defined by equation (3), and β0, β1, β2, β3, and M0 were 0.970, -0.0005, 0.0015, -0.00065, and 80000, respectively. The first fraction in Example 1 was the constant NCID i 1 The value is 0.980 and the NCID i 1 The first semi-logarithmic derivative of was zero.

[0200] Example 2 shows 38 wt. % of the first fraction (M of 3.24 w / M n ) and 62 wt. % of the second fraction (having an M of 2.16 w / M n The second fraction in Example 2 contained an incremental molar mass M i Deconvolved NCID that decreases monotonically as increases i 2 As shown in Figures 1 and 2, the deconvoluted NCIDs of Example 2 were characterized based on i 2 The value is inequality (1b) ≦ NCID i 2 ≦(1a) changes within the range defined in NCID i 2 The first semi-logarithmic derivative of (dNCID i 2 / dlogM i ) was less than -0.0001. i 2 is defined by equation (3), and β0, β1, β2, β3, and M0 are 0.985, -0.002, 0.0015, -0.0008, and 70000, respectively. The first fraction in Example 2 is the constant NCID i 1 The value is 0.980 and the NCID i 1 The first semi-logarithmic derivative of was zero.

[0201] Example 3 shows 40 wt. % of the first fraction (M of 3.90) w / M n ) and 60 wt. % of the second fraction (having an M of 2.03 w / M n The second fraction in Example 3 contained an incremental molar mass M i Deconvolved NCID that decreases monotonically as increases i 2 As shown in Figures 1 and 2, the deconvoluted NCIDs of Example 3 were characterized based on i 2 The value is inequality (1b) ≦ NCID i 2 ≦(1a) changes within the range defined in NCID i 2 The first semi-logarithmic derivative of (dNCID i 2 / dlogM i ) was less than -0.0001. i 2 is defined by equation (3), and β0, β1, β2, β3, and M0 are 0.930, -0.008, 0.001, -0.00015, and 70000, respectively. The first fraction in Example 3 is the constant NCID i 1 The value is 0.980 and the NCID i 1 The first semi-logarithmic derivative of was zero.

[0202] Example 4 shows 38 wt. % of the first fraction (M of 3.22) w / M n ) and 62 wt. % of the second fraction (having an M of 2.31 w / M n The second fraction in Example 4 contained an incremental molar mass M i Deconvolved NCID that decreases monotonically as increases i 2 As shown in Figures 1 and 2, the deconvoluted NCIDs of Example 4 were characterized based on i 2 The value is inequality (1b) ≦ NCID i 2 ≦(1a) changes within the range defined in NCID i 2 The first semi-logarithmic derivative of (dNCID i 2 / dlogM i ) was less than -0.0001. i 2 is defined by equation (3), and β0, β1, β2, β3, and M0 were 1.020, -0.002, 0.0002, -0.0001, and 58000, respectively. The first fraction in Example 4 was calculated using the constant NCID i 1 The value is 0.980 and the NCID i 1 The first semi-logarithmic derivative of was zero.

[0203] Example 5 shows 42 wt. % of the first fraction (M of 3.21 w / M n ) and 58 wt. % of the second fraction (having an M of 2.03 w / M n The second fraction in Example 5 contained an incremental molar mass M i Deconvolved NCID that decreases monotonically as increases i 2 As shown in Figures 1 and 2, the deconvoluted NCIDs of Example 5 were characterized based on i 2 The value is inequality (1b) ≦ NCID i 2 ≦(1a) changes within the range defined in NCID i 2 The first semi-logarithmic derivative of (dNCID i 2 / dlogM i ) was less than -0.0001. i 2 is defined by equation (3), and β0, β1, β2, β3, and M0 were 0.990, -0.006, -0.002, 0.00005, and 60000, respectively. The first fraction in Example 5 was calculated using the constant NCID i 1 The value is 0.965 and the NCID i 1 The first semi-logarithmic derivative of was zero.

[0204] Example 6 shows 40 wt. % of the first fraction (M of 3.26) w / M n ) and 60 wt. % of the second fraction (having an M of 2.31 w / M n The second fraction in Example 6 contained an incremental molar mass M i Deconvolved NCID that decreases monotonically as increases i 2 As shown in Figures 1 and 2, the deconvoluted NCIDs of Example 6 were characterized based on i 2 The value is inequality (1b) ≦ NCID i 2 ≦(1a) changes within the range defined in NCID i 2 The first semi-logarithmic derivative of (dNCID i 2 / dlogM i ) was less than -0.0001. i 2 is defined by equation (3), and β0, β1, β2, β3, and M0 were 1.000, -0.015, 0.0001, -0.0001, and 58000, respectively. The first fraction in Example 6 was calculated using the constant NCID i 1 The value is 0.965 and the NCID i 1 The first semi-logarithmic derivative of was zero.

[0205] Example 7 shows 38 wt. % of the first fraction (2.75 M w / M n ) and 62 wt. % of the second fraction (having an M of 2.16 w / M n The second fraction in Example 7 contained an incremental molar mass M i Deconvolved NCID that decreases monotonically as increases i 2 As shown in Figures 1 and 2, the deconvoluted NCID of Example 7 i 2 The value is inequality (1b) ≦ NCID i 2 ≦(1a) changes within the range defined in NCID i 2 The first semi-logarithmic derivative of (dNCID i 2 / dlogM i ) was less than -0.0001. i 2 is defined by equation (3), and β0, β1, β2, β3, and M0 were 1.000, -0.014, 0.0002, -0.00015, and 58000, respectively. The first fraction in Example 7 was calculated using the constant NCID i 1 The value is 0.960 and the NCID i 1 The first semi-logarithmic derivative of was zero.

[0206] Example 8 shows 40 wt. % of the first fraction (M of 2.75 w / M n ) and 60 wt. % of the second fraction (having an M of 2.38 w / M n The second fraction in Example 8 contained an incremental molar mass M i Deconvolved NCID that decreases monotonically as increases i 2 As shown in Figures 1 and 2, the deconvoluted NCID of Example 8 i 2 The value is inequality (1b) ≦ NCID i 2 ≦(1a) changes within the range defined in NCID i 2 The first semi-logarithmic derivative of (dNCID i 2 / dlogM i ) was less than -0.0001. i 2 is defined by equation (3), and β0, β1, β2, β3, and M0 were 1.000, -0.014, 0.0002, -0.00015, and 55000, respectively. The first fraction in Example 8 was calculated using the constant NCID i 1 The value is 0.960 and the NCID i 1 The first semi-logarithmic derivative of was zero.

[0207] Example 9 shows 40 wt. % of the first fraction (M of 3.93 w / M n ) and 60 wt. % of the second fraction (having an M of 2.03 w / M n The second fraction in Example 9 contained an incremental molar mass M i Deconvolved NCID that decreases monotonically as increases i 2 As shown in Figures 1 and 2, the deconvoluted NCID of Example 9 i 2 The value is inequality (1b) ≦ NCID i 2 ≦(1a) changes within the range defined in NCID i 2 The first semi-logarithmic derivative of (dNCID i 2 / dlogM i ) was less than -0.0001. i 2 is defined by equation (3), and β0, β1, β2, β3, and M0 were 0.990, -0.001, 0.0015, -0.0008, and 55000, respectively. The first fraction in Example 9 was calculated using the constant NCID i 1 The value is 0.980 and the NCID i 1 The first semi-logarithmic derivative of was zero.

[0208] Example 10 shows 40 wt. % of the first fraction (M of 3.26) w / M n ) and 60 wt. % of the second fraction (having an M of 2.31 w / M n The second fraction in Example 10 contained an incremental molar mass M i Deconvolved NCID that decreases monotonically as increases i 2 As shown in Figures 1 and 2, the deconvoluted NCID of Example 10 i 2 The value is inequality (1b) ≦ NCID i 2 ≦(1a) changes within the range defined in NCID i 2 The first semi-logarithmic derivative of (dNCID i 2 / dlogM i ) was less than -0.0001. i 2 is defined by equation (3), and β0, β1, β2, β3, and M0 were 0.985, -0.002, 0.0015, -0.0008, and 50000, respectively. The first fraction in Example 10 was calculated using the constant NCID i 1 The value is 0.980 and the NCID i 1 The first semi-logarithmic derivative of was zero.

[0209] Example 11 shows 38 wt. % of the first fraction (M of 3.26) w / M n ) and 62 wt. % of the second fraction (having an M of 2.31 w / M n The second fraction in Example 11 contained an incremental molar mass M i Deconvolved NCID that decreases monotonically as increases i 2 As shown in Figures 1 and 2, the deconvoluted NCID of Example 11 i 2 The value is inequality (1b) ≦ NCID i 2 ≦(1a) changes within the range defined in NCID i 2 The first semi-logarithmic derivative of (dNCID i 2 / dlogM i ) was less than -0.0001. i 2 is defined by equation (3), and β0, β1, β2, β3, and M0 were 0.970, -0.002, 0.0015, -0.0007, and 60000, respectively. The first fraction in Example 11 was calculated using the constant NCID i 1 The value is 0.975 and the NCID i 1 The first semi-logarithmic derivative of was zero.

[0210] Example 12 shows 40 wt. % of the first fraction (M of 3.26) w / M n ) and 60 wt. % of the second fraction (having an M of 2.31 w / M n The second fraction in Example 12 contained an incremental molar mass M i Deconvolved NCID that decreases monotonically as increases i 2 As shown in Figures 1 and 2, the deconvoluted NCID of Example 12 i 2 The value is inequality (1b) ≦ NCID i 2 ≦(1a) changes within the range defined in NCID i 2 The first semi-logarithmic derivative of (dNCID i 2 / dlogM i ) was less than -0.0001. i 2 is defined by equation (3), and β0, β1, β2, β3, and M0 were 0.986, -0.002, 0.0015, -0.0007, and 55000, respectively. The first fraction in Example 12 was calculated using the constant NCID i 1 The value is 0.980 and the NCID i 1 The first semi-logarithmic derivative of was zero.

[0211] Example 13 shows 45 wt. % of the first fraction (M of 2.75 w / M n ) and 55 wt. % of the second fraction (having an M of 2.31 w / M n The second fraction in Example 13 contained an incremental molar mass M i Deconvolved NCID that decreases monotonically as increases i 2 As shown in Figures 1 and 2, the deconvoluted NCID of Example 13 i 2 The value is inequality (1b) ≦ NCID i 2 ≦(1a) changes within the range defined in NCID i 2 The first semi-logarithmic derivative of (dNCID i 2 / dlogM i ) was less than -0.0001. i 2 is defined by equation (3), and β0, β1, β2, β3, and M0 were 1.000, -0.014, 0.0002, -0.00015, and 58000, respectively. The first fraction in Example 13 was calculated using the constant NCID i 1 The value is 0.965 and the NCID i 1 The first semi-logarithmic derivative of was zero.

[0212] The properties of the ethylene interpolymer products of the present invention (Examples 1-13) and some comparative resins (Comparative Examples 1-20) are shown in Tables 2A-2E and 3.

[0213] Comparative Example 1 was DOWLEX® 2045G, a resin commercially available from Dow Chemical Company. DOWLEX 2045G has a density of 0.920 g / cm 3 The melt index I2 was 1.0 dg / min, which was believed to be produced in a competitive solution-phase polymerization process using a comparative Ziegler-Natta catalyst. Comparative Example 1 had a non-comonomer exponential distribution (NCID). i and log(M i ) yields a flat curve (i.e., d(NCID i ) / dlogM i =0), and the average NCID i The LCBF value of Comparative Example 1 was 7.23 × 10 -6 (dimensionless) and SUM per 100 carbon atoms u was 0.052.

[0214] Comparative Example 2 was SURPASS® FPs117-C, a resin commercially available from NOVA Chemicals Corporation. SURPASS FPs117-A has a density of 0.917 g / cm 3 and a melt index I2 of 1.0 dg / min. Comparative Example 2 was produced using a phosphinimine single-site catalyst in a dual reactor solution polymerization process in which the first and second reactors were configured in series with one another. Comparative Example 2 exhibited a flat curve (i.e., d(NCID i ) / dlogM i =0) and had an average value of 0.998. Comparative Example 2 had an LCBF value of 4.00×10 -4 (dimensionless) and SUM per 100 carbon atoms u was 0.050.

[0215] Comparative Example 3 was AFFINITY® PL 1880G, a resin commercially available from Dow Chemical Company. AFFINITY PL 1880G has a density of 0.902 g / cm 3 The melt index I2 was 1.0 dg / min, and it was believed to have been produced in a single reactor solution phase polymerization process using a single-site catalyst. i is a flat curve (i.e., d(NCID i 1 ) / dlogM i =0) with an average value of 0.944. Comparative Example 3 had an LCBF value of 4.06×10 -2 (dimensionless) and SUM per 100 carbon atoms u was 0.021.

[0216] Comparative Example 4 is Example 2 of U.S. Patent Application Publication No. 2019 / 0135958, an ethylene / 1-octene interpolymer product made in a pilot-scale dual reactor solution polymerization process using the single-site catalyst component described above. Comparative Example 4 had a density of about 0.9069 g / cm. 3 The melt index I2 is about 1.10 dg / min. i is a flat curve (i.e., d(NCID i ) / dlogM i = 0), had a mean value of 0.975, and therefore could not be deconvoluted into first and second fractions with different non-comonomer index distributions. Comparative Example 4 had an LCBF value of 5.63 x 10 -2 (dimensionless) and SUM per 100 carbon atoms u was 0.046.

[0217] Comparative Example 5 was ELITE® 5100G, a resin commercially available from Dow Chemical Company. ELITE 5100G has a density of 0.920 g / cm 3 The melt index I2 was 0.85 dg / min. Comparative Example 5 contained 44 wt. % of the first fraction (4.01 M w / M n ) and 56 wt. % of the second fraction (having an M of 2.03 w / M n The non-comonomer index distributions (NCIDs) of the first and second fractions in this comparative example were i 1 and NCID i 2 ) is the first flat curve and the second flat curve (i.e., d(NCID i 1 ) / dlogM i and d(NCID i 2 ) / dlogM i =0), with average values ​​of 0.960 and 1.000, respectively. Comparative Example 5 had an LCBF value of 8.83×10 -3 (dimensionless) and SUM per 100 carbon atoms u was 0.031.

[0218] Comparative Example 6 is Example 5 of U.S. Patent Application Publication No. 2020 / 0216645. Comparative Example 6 has a density of about 0.916 g / cm 3 and a melt index I2 of about 1.00 dg / min. Comparative Example 6 is an ethylene / 1-octene interpolymer product made in a pilot-scale dual reactor solution polymerization process, with the first and second reactors configured in series with one another, using a phosphinimine single-site catalyst and the in-line Ziegler-Natta catalyst component described above. Comparative Example 6 had a first fraction of 44 wt % (M of 5.63). w / M n ) and 56 wt. % of the second fraction (having an M of 2.38 w / M n The first fraction contained the non-comonomer index distribution (NCID i 1 ) is a flat curve (i.e., d(NCID i 1 ) / dlogM i = 0), which had a constant value of 0.997. i 2 ) is logM i The NCID in this comparative example was characterized by a monotonically decreasing curve when plotted as a function of i 2 Furthermore, inequality (1a)≦NCID i 2 ≦(1b), and the inequality (dNCID i 2 / dlogM i )≦−0.0001. In Comparative Example 6, the LCBF value was 5.47×10 -4 (dimensionless) and SUM per 100 carbon atoms u was 0.071.

[0219] Comparative Example 7 is SURPASS® VPsK914-A, a resin commercially available from NOVA Chemicals Corporation. SURPASS VPsK914-A has a density of 0.913 g / cm 3 The melt index I2 is 0.85 dg / min. Comparative Example 7 is a 55 wt. % first fraction (M of 2.16 w / M n ) and 45 wt. % of the second fraction (having an M of 2.08 w / M n The non-comonomer index distribution (NCID) of the first fraction and the second fraction was i 1 and NCID i 2 ) were similar to those of Comparative Example 6. Comparative Example 7 had an LCBF value of 6.58 × 10 -5 (dimensionless) and SUM per 100 carbon atoms u was 0.048.

[0220] Comparative Example 8 is SURPASS® SPsK919-F, a resin commercially available from NOVA Chemicals Corporation. SURPASS SPsK919-F has a density of 0.919 g / cm 3 The melt index I2 is 0.85 dg / min. Comparative Example 8 is a 50 wt. % first fraction (M of 2.16 w / M n ) and 50 wt. % of the second fraction (having an M of 2.03 w / M n The non-comonomer index distribution (NCID) of the first fraction and the second fraction was i 1 and NCID i 2 ) were similar to those of Comparative Example 6. Comparative Example 8 had an LCBF value of 6.06 × 10 -5 (dimensionless) and SUM per 100 carbon atoms u was 0.041.

[0221] Comparative Example 9 was INNATE® ST50, a resin commercially available from Dow Chemical Company. INNATE ST50 has a density of 0.918 g / cm 3 The melt index I2 was 0.85 dg / min. Comparative Example 9 contained 54 wt. % of the first fraction (M of 3.98). w / M n ) and 46 wt. % of the second fraction (having an M of 2.16 w / M n The non-comonomer index distribution index (NCID) of the first fraction was i 1 is a flat curve (i.e., d(NCID i 1 ) / dlogM i = 0) and had a constant value of 0.930. The second fraction in this comparative example had a non-comonomer exponential distribution NCID i 2 which has logM i Comparative Example 9 had a constant value of 1.000 over the entire range of LCBF. -3 (dimensionless) and SUM per 100 carbon atoms u was 0.024.

[0222] Comparative Example 10 was Example 4 of U.S. Patent Application Publication No. 2018 / 305531. Comparative Example 10 had a density of 0.917 g / cm 3 The melt index I2 was 0.70 dg / min. Comparative Example 11 was Example 3 of U.S. Patent Application Publication No. 2018 / 0305531. Comparative Example 11 had a density of 0.9177 g / cm 3 The melt index I2 was 0.92 dg / min. Comparative Examples 10 and 11 were ethylene / 1-octene interpolymer products made in a pilot-scale dual reactor solution polymerization process in which the first and second reactors were configured in series with each other using the above single-site catalyst component and in-line Ziegler-Natta catalyst component.

[0223] Comparative Example 10 is a 50% by weight first fraction (M of 1.37 w / M n ) and 50 wt. % of the second fraction (having an M of 1.82 w / M n The first fraction contained the non-comonomer index distribution index NCID i 1 , which has a flat curve (i.e., d(NCID i 1 ) / dlogM i = 0), which has a constant value of 0.970. The second fraction in this comparative example has a non-comonomer exponential distribution NCID that satisfies the inequalities of Equation (1a) and Equation (1b). i 2 and d(NCID i 2 ) / dlogM i In Comparative Example 10, the LCBF was 2.91 × 10 -2 (dimensionless) and SUM per 100 carbon atoms u was 0.034.

[0224] Comparative Example 11 contains 60 wt. % of the first fraction (M of 2.71). w / M n ) and 40 wt. % of the second fraction (having an M of 2.69 w / M n The first fraction contained the non-comonomer index distribution index NCID i 1 , which has a flat curve (i.e., d(NCID i 1 ) / dlogM i = 0), which has a constant value of 0.940. The second fraction in this comparative example has a non-comonomer exponential distribution NCID (NCID 1) that satisfies the inequalities of Equation (1a) and Equation (1b). i 2 and d(NCID i 2 ) / dlogM i In Comparative Example 11, the LCBF was 2.05 × 10 -2 (dimensionless) and SUM per 100 carbon atoms u was 0.039.

[0225] Comparative Example 12 was Example 1 of U.S. Patent Application Publication No. 2018 / 305531. Comparative Example 12 had a density of 0.9178 g / cm 3 The melt index I2 was 1.07 dg / min. Comparative Example 13 was Example 2 of U.S. Patent Application Publication No. 2018 / 0305531. Comparative Example 13 had a density of 0.9170 g / cm 3 The melt index I2 was 0.99 dg / min. Comparative Examples 12 and 13 were ethylene / 1-octene interpolymer products made in a pilot-scale dual reactor solution polymerization process in which the first and second reactors were configured in series with each other using the above single-site catalyst component and in-line Ziegler-Natta catalyst component.

[0226] Comparative Example 12 contains 40 wt. % of the first fraction (M of 3.79). w / M n ) and 60 wt. % of the second fraction (having an M of 2.31 w / M n The first fraction contained the non-comonomer index distribution index NCID i 1 , which has a flat curve (i.e., d(NCID i 1 ) / dlogM i = 0) and had a constant value of 0.950. The second fraction in this comparative example had a non-comonomer exponential distribution NCID (NCID 1) that satisfied the inequalities of Equation (1a) and Equation (1b). i 2 and d(NCID i 2 ) / dlogM i In Comparative Example 12, the LCBF was 3.39 × 10 -3 (dimensionless) and SUM per 100 carbon atoms u was 0.046.

[0227] Comparative Example 13 was prepared using 40% by weight of the first fraction (M of 3.14). w / M n ) and 60 wt. % of the second fraction (having an M of 2.31 w / M n The first fraction contained the non-comonomer index distribution index NCID i 1 , which has a flat curve (i.e., d(NCID i 1 ) / dlogM i = 0), which has a constant value of 0.960. The second fraction in this comparative example has a non-comonomer exponential distribution NCID (NCID 1) that satisfies the inequalities of Equation (1a) and Equation (1b). i 2 and d(NCID i 2 ) / dlogM i In Comparative Example 13, the LCBF was 9.94 × 10 -3 (dimensionless) and SUM per 100 carbon atoms u was 0.045.

[0228] Comparative Examples 16, 17, and 19 were invention examples 3, 4, and 6 of U.S. Patent Application Publication No. 2021 / 0032450, respectively. Comparative Example 16 had a density of 0.9128 g / cm 3 The melt index I2 was 0.84 dg / min. Comparative Example 17 had a density of 0.9123 g / cm 3 The melt index I2 was 0.76 dg / min. Comparative Example 19 had a density of 0.9133 g / cm 3 The melt index I2 was 3.56 dg / min. Comparative Examples 16, 17, and 19 were ethylene / 1-octene interpolymer products made in a pilot-scale dual reactor solution polymerization process in which the first and second reactors were configured in series with each other using the above single-site catalyst component and in-line Ziegler-Natta catalyst component.

[0229] Comparative Example 16 is a 50% by weight first fraction (M of 3.20) w / M n ) and 50 wt. % of the second fraction (having an M of 2.03 w / M n The first fraction contained the non-comonomer index distribution index NCID i 1 , which has a flat curve (i.e., d(NCID i 1 ) / dlogM i = 0), which has a constant value of 0.960. The second fraction in this comparative example has a non-comonomer exponential distribution NCID (NCID 1) that satisfies the inequalities of Equation (1a) and Equation (1b). i 2 and d(NCID i 2 ) / dlogM i In Comparative Example 16, the LCBF was 1.17 × 10 -3 (dimensionless) and SUM per 100 carbon atoms u was 0.036.

[0230] Comparative Example 17 contains 50 wt. % of the first fraction (M of 3.93). w / M n ) and 50 wt. % of the second fraction (having an M of 2.03 w / M n The first fraction contained the non-comonomer index distribution index NCID i 1 , which has a flat curve (i.e., d(NCID i 1 ) / dlogM i = 0), which has a constant value of 0.960. The second fraction in this comparative example has a non-comonomer exponential distribution NCID (NCID 1) that satisfies the inequalities of Equation (1a) and Equation (1b). i 2 and d(NCID i 2 ) / dlogM i In Comparative Example 17, the LCBF was 1.43 × 10 -3 (dimensionless) and SUM per 100 carbon atoms u was 0.037.

[0231] Comparative Example 19 is a 50% by weight first fraction (M of 3.70 w / M n ) and 50 wt. % of the second fraction (having an M of 2.03 w / M n The first fraction contained the non-comonomer index distribution index NCID i 1 , which has a flat curve (i.e., d(NCID i 1 ) / dlogM i = 0) and had a constant value of 0.950. The second fraction in this comparative example had a non-comonomer exponential distribution NCID (NCID 1) that satisfied the inequalities of Equation (1a) and Equation (1b). i 2 and d(NCID i 2 ) / dlogM i In Comparative Example 19, the LCBF was 2.66 × 10 -4 (dimensionless) and SUM per 100 carbon atoms u was 0.056.

[0232] Comparative Example 20 is Example 1 of U.S. Patent Application Publication No. 2020 / 0216645. Comparative Example 20 has a density of 0.9191 g / cm 3 and a melt index I2 of 0.9 dg / min. Comparative Example 20 is an ethylene / 1-octene interpolymer product produced in a pilot-scale dual reactor solution polymerization process in which the first and second reactors are configured in series with each other using the above-described in-line Ziegler-Natta catalyst component. Comparative Example 20 has a non-comonomer exponential distribution NCID that satisfies the inequalities of Equation (1a) and Equation (1b). i and d(NCID i ) / dlogM i In Comparative Example 20, the LCBF value was 2.49 × 10 -4 (dimensionless) and SUM per 100 carbon atoms u was 0.071.

[0233] Detailed molecular weight properties of the ethylene interpolymer product components (i.e., the first and second fractions) in Examples 1-13 and the multi-component comparative examples are shown in Tables 3A-3D. The properties of the first and second fractions shown in Tables 3A-3D were determined using Equation (13):

number

number

number

[0234] [Table 1A]

[0235] [Table 1B]

[0236] [Table 1C]

[0237] [Table 2A]

[0238] [Table 2B]

[0239] [Table 2C]

[0240] [Table 2D]

[0241] [Table 2E]

[0242] [Table 3A]

[0243] [Table 3B]

[0244] [Table 3C]

[0245] [Table 3D]

[0246] [Table 4]

[0247] <Monolayer Blown Films> Referring to Tables 2A to 2E, Examples 1 to 13 exhibit enhanced elasticity-related properties (e.g., increased melt strength and zero shear viscosity) and shear thinning properties (e.g., decreased CY-a or I 21 It is understood that the resin composition contains a sufficient amount of LCB to enhance the tensile strength (increase in tensile strength / I2). These characteristics make it possible to realize a resin composition suitable for processes such as film blowing, which require low pressure rise during the extrusion step and bubble stability during the film blowing step.

[0248] Monolayer blown films were produced on a Gloucester Blown Film Line. The line was equipped with a Gloucester extruder (2.5 inch (6.45 cm) barrel diameter, 24 / 1 L / D (barrel length / barrel diameter)) equipped with a barrier screw, a 4 inch (10.16 cm) diameter low-pressure die with a 35 mil (0.089 cm) die gap, and a Western Polymer Air ring. The extruder was equipped with a screen pack (20 / 40 / 60 / 80 / 20 mesh). Blown films (2.5:1 blow-up ratio (BUR)) approximately 1.0 mil (25.4 μm) thick were produced at a constant output rate of 100 lb / hr (45.4 kg / hr) by adjusting the extruder screw speed, and the frost line height was maintained at 15-18 inches (38.1-45.72 cm) by adjusting the quench air. As can be seen in Table 5, at an output rate of 100 lb / hr, the average extrusion pressures for Examples 3-15 were advantageously lower or equivalent to those for Comparative Examples 10 and 11.

[0249] Film properties of the ethylene interpolymer products of the present disclosure (Examples 3-15) are shown in Tables 6A and 6B, along with data for films made from Comparative Examples 10 and 11. It is noted that, compared to the films prepared from the Comparative Examples, at a given LCBF value, Examples 3-15 exhibited longer strain-hardening regions in the tensile stress-strain curves in both the MD and TD directions (e.g., the tensile yield stress σ in these examples). y and tensile stress at break σ br (Compare the difference between the LCBF values ​​and the LCBF values ​​observed in Comparative Examples 10 and 11.) For example, in Examples 5 and 7, which had LCBF values ​​within ±5% of the LCBF value of Comparative Example 11, the MD σ br -σ y Similarly, Example 4, which had an LCBF value of 0.0313, had a 75.3% and 12.5% ​​improvement in σ in the MD direction compared to Comparative Example 10, which had an LCBF value of 0.0291. br -σ y was improved by 79.4%. Additionally, Examples 4, 6, and 11-14 were noted to have improved dart impact and lubrication puncture compared to Comparative Examples 10 and 11, despite having higher densities (i.e., densities >0.9180); i.e., dart impact improved by 6.6% to 117.3%, and lubrication puncture improved by 5.7% to 26.7% compared to the dart impact and lubrication puncture values ​​observed for the Comparative Examples.

[0250] [Table 5]

[0251] [Table 6A]

[0252] [Table 6B] [Industrial Applicability]

[0253] The multi-component ethylene interpolymer products disclosed herein can be useful in articles of manufacture including one or more films or film layers, such as, for example, food packaging films.

Claims

1. 1. An ethylene interpolymer product comprising: Molecular weight distribution index M of 1.8 to 4.0 ｗ / M ｎ 30 to 45 weight percent of a first fraction having Molecular weight distribution index M of 2.0 to 6.0 ｗ / M ｎ and 55 to 70 weight percent of a second fraction having Including, The second fraction has formula (1a) and formula (1b): [Equation 1] (Formula 1a) [Equation 2] (Formula 1b) a non-comonomer exponential distribution NCID having a value characterized by ｉ ２ and In the formula, M ｏ is the peak molecular weight that characterizes the molecular weight distribution of the second fraction when fitted to a log-normal distribution, and M ｉ is the incremental molar mass characterizing the molecular weight distribution, NCID ｉ ２ The first semi-logarithmic derivative d(NCID ｉ ２ ) / dlogD ｉ Formula (2): [Equation 3] (Formula 2) has a value less than or equal to −0.0001, where the coefficient β ０ , β １ , β ２ and β ３ is NCID ｉ ２ is a third-order polynomial, Equation (3): [Equation 4] (Formula 3) is generated by fitting the ethylene interpolymer product contains detectable levels of long chain branching characterized by a dimensionless long chain branching factor LCBF of 0.005 or greater; the ethylene interpolymer product has a total unsaturation per 100 carbons of greater than or equal to 0.047; The weight percent and molecular weight distribution index of the first and second fractions are obtained by deconvoluting the experimentally measured molecular weight distribution of the ethylene interpolymer product, wherein the weight percent of the first fraction or the second fraction is defined as the weight of the first fraction or the second fraction divided by the combined weight of the first fraction and the second fraction multiplied by 100; ｉ ２ is obtained by deconvoluting the experimentally measured non-comonomer index distribution of the ethylene interpolymer product. Ethylene interpolymer products.

2. The first fraction is the first semi-logarithmic derivative d(NCID ｉ １ ) / dlogM ｉ Non-comonomer exponential distribution NCID characterized by ｉ １ and M ｉ is the incremental molar mass characterizing the molecular weight distribution of the first fraction, and ｉ １ 10. The ethylene interpolymer product of claim 1, wherein X is obtained by deconvoluting an experimentally determined non-comonomer index distribution of the ethylene interpolymer product.

3. 3. The ethylene interpolymer product of claim 1 or 2, wherein the second fraction has a weight average molecular weight less than the weight average molecular weight of the first fraction.

4. The ethylene interpolymer product has a viscosity of 0.910 g / cm ３ ~0.930g / cm ３ The ethylene interpolymer product of any one of claims 1 to 3, having a density of

5. The ethylene interpolymer product has a melt index I of 0.5 dg / min to 1.5 dg / min. ２ The ethylene interpolymer product of any one of claims 1 to 4, having

6. The ethylene interpolymer product has a composition distribution breadth index (CDBI) of 50 to 75 weight percent ５０ The ethylene interpolymer product of any one of claims 1 to 5, having

7. The ethylene interpolymer product of any one of claims 1 to 6, wherein the ethylene interpolymer product has a dimensionless long chain branching factor LCBF < 0.

04.

8. The ethylene interpolymer product of any one of claims 1 to 7, wherein the ethylene interpolymer product has a dimensionless long chain branching factor LCBF > 0.

01.

9. The ethylene interpolymer product of any one of claims 1 to 8, wherein the ethylene interpolymer product has a total of less than or equal to 0.07 unsaturations per 100 carbons.

10. The ethylene interpolymer product has a molecular weight distribution index M ｗ / M ｎ The ethylene interpolymer product of any one of claims 1 to 9, having

11. The ethylene interpolymer product of any one of claims 1 to 10, wherein the ethylene interpolymer product comprises 1 to 10 mol % of one or more α-olefins.

12. The ethylene interpolymer product of any one of claims 1 to 10, wherein the ethylene interpolymer product comprises 1 to 8 mole percent of one or more α-olefins.

13. 13. The ethylene interpolymer product of claim 11 or 12, wherein the one or more α-olefins are selected from the group consisting of 1-hexene, 1-octene, and mixtures thereof.

14. A film layer comprising the ethylene interpolymer product of any one of claims 1-13.

15. The film layer of claim 14 , wherein the film layer is a blown film.

16. A multilayer film structure comprising at least one film layer comprising the ethylene interpolymer product of any one of claims 1-13.

17. 17. The multilayer film structure of claim 16, wherein the at least one film layer is a blown film.

18. 17. The multilayer film structure of claim 16, wherein the multilayer film structure has at least three layers.

19. A multilayer film structure comprising a sealant layer, the sealant layer comprising the ethylene interpolymer product of any one of claims 1-13.

Images