Reactor-blended ethylene polymer compositions and films produced therefrom

Abstract

The present invention provides a reactor-blended ethylene polymer composition comprising at least two identifiable components having different structural and compositional properties, namely a first ethylene polymer and a second ethylene copolymer. The ethylene polymer composition is produced by a continuous solution polymerization process, wherein the first ethylene polymer is formed by polymerizing ethylene and optionally at least one α-olefin in a first solution polymerization reactor using a first homogeneous catalyst composition, and the second ethylene copolymer is formed by polymerizing ethylene and at least one α-olefin in a second solution polymerization reactor using a second homogeneous catalyst composition. The ethylene polymer composition of the present invention can be advantageously used in applications where an easily openable single-material packaging system is required.

Description

[Technical Field]

[0001] The present invention provides reactor blend ethylene polymer compositions and films produced therefrom. The ethylene polymer composition comprises at least two identifiable ethylene polymer components having defined structural characteristics. [Background technology]

[0002] A heat-sealable film structure is a single-layer or multi-layer structure that can form a bond when brought into close contact with itself or a substrate (e.g., another film structure or a rigid / semi-rigid structure) in a partially molten state. Based on functional requirements, the variables of the heat-sealing process and the heat-sealable film structure can be designed to obtain two types of bonds: lock-up seals and peelable seals.

[0003] Lock-up seals are preferred in hermetically sealed applications, while peel-off seals are preferred in applications involving easy-open packaging systems. Known techniques for easy-open seals include cohesive peeling, adhesive peeling, and interlayer delamination. Regardless of the technique employed, heat-sealable easy-open film structures incorporate one or more non-polyethylene thermoplastic polymers, non-limiting examples of which include polypropylene resins, polybutene-1 resins, ethylene-vinyl acetate copolymers, ethylene-acrylic acid copolymers, ethylene-methyl acrylate copolymers, and ionomers. Multilayer films containing more than 10% by weight of non-polyethylene material are known to present challenges in the mechanical recycling process of polyethylene. Therefore, there is still a need for polyethylene compositions applicable in applications requiring easy-open and single-material packaging systems. [Overview of the project]

[0004] In a first embodiment, a reactor blend ethylene polymer composition is provided. The composition comprises 30% to 70% by weight of a first ethylene polymer, the first ethylene polymer comprising ethylene and optionally at least one α-olefin, having a weight-average molecular weight (Mw) of 70 kg / mol to 250 kg / mol, 0 to 6 short-chain branchings per 1000 carbon atoms, and a polydispersity (Mw / Mn) of 1.7 to 2.3; and 30% to 70% by weight of a second ethylene copolymer, the second ethylene copolymer comprising ethylene and at least one α-olefin, having a weight-average molecular weight (Mw) of 20 kg / mol to 75 The second ethylene copolymer has a molecular weight of 25-55 short-chain branches per 1000 carbon atoms, a polydispersity (Mw / Mn) of 1.7-2.3, and the weight-average molecular weight of the second ethylene copolymer is smaller than that of the first ethylene polymer; the ethylene polymer composition is produced by a continuous solution polymerization process, which includes polymerizing ethylene and optionally at least one α-olefin in a first solution polymerization reactor using a first homogeneous catalyst composition to form a first ethylene polymer; and polymerizing ethylene and at least one α-olefin in a second solution polymerization reactor using a second homogeneous catalyst composition to form a second ethylene copolymer.

[0005] In some embodiments, the ethylene polymer composition has a comonomer distribution profile in GPC-FTIR analysis, the comonomer distribution profile having a secant slope of -55 short-chain branches / 1000 carbons or more and -20 short-chain branches / 1000 carbons or less, where the secant slope is defined as the value obtained by subtracting the number of short-chain branches per 1000 carbons at a molecular weight of 30 kg / mol from the number of short-chain branches per 1000 carbons at a molecular weight of 300 kg / mol.

[0006] In some embodiments, the comonomer distribution profile is a normal comonomer distribution profile.

[0007] In some embodiments, one or both of the first homogeneous catalyst composition and the second homogeneous catalyst composition include a bridged metallocene catalyst having the following formula (I). [Chemical Formula] Where M is a Group 4 metal selected from titanium, zirconium or hafnium, G is a Group 14 element selected from carbon, silicon, germanium, tin or lead, R1 is a hydrogen atom, C , , 1-20 , , 6-10 , , 3 , 1-20 ,

[0010] , 3 , 6-10 ,

[0008] , , 1-20 , , 1-20 ,

[0011] , , 1-20 ,

[0009] , , 3 , 3 hydrocarbyl group, C 1-20 alkoxy group or C 6-10 aryloxy group, and R2 and R3 are each independently a hydrogen atom, C 1-20 hydrocarbyl group, C 1-20 alkoxy group or C 6-10 aryloxy group, and R4 and R5 are each independently a hydrogen atom, unsubstituted C 1-20 hydrocarbyl group, substituted C 1-20 hydrocarbyl group, C 1-20 alkoxy group or C 6-10 aryloxy group, and Q is each independently an activatable leaving group ligand.

[0008] In some embodiments, one or both of the first homogeneous catalyst and the second homogeneous catalyst include a phosphinimine catalyst.

[0009] In some embodiments, the first ethylene polymer is a first ethylene homopolymer.

[0010] In some embodiments, the ethylene polymer composition has a density measured according to ASTM D792-13 of 0.880 g / cm 3 ~0.920 g / cm 3 .

[0011] In some embodiments, the ethylene polymer composition has a density measured according to ASTM D792-13 of 0.900 g / cm 3 ~0.920 g / cm 3That is the case.

[0012] In some embodiments, the ethylene polymer composition has a melt index I2 of 2 dg / min to 10 dg / min, measured at 190°C with a load of 2.16 kg according to ASTM D1238-13.

[0013] In some embodiments, the ethylene polymer composition has a molecular weight distribution with a polydispersity (Mw / Mn) of 2.3 to 6.0.

[0014] In some embodiments, the ethylene polymer composition has a molecular weight distribution with a polydispersity (Mw / Mn) of 2.3 to 4.5.

[0015] In some embodiments, the ethylene polymer composition has a unimodal molecular weight distribution.

[0016] In some embodiments, the ratio of the weight-average molecular weight of the first ethylene polymer to the weight-average molecular weight of the second ethylene copolymer is 1.5 or more and 6 or less.

[0017] In some embodiments, the ratio of the weight-average molecular weight of the first ethylene polymer to the weight-average molecular weight of the second ethylene copolymer is 2 or more and 4 or less.

[0018] In some embodiments, the ethylene polymer composition contains a detectable level of long-chain branching, characterized by a long-chain branching coefficient (LCBF) of 0.001 or greater.

[0019] In some embodiments, the second ethylene copolymer is present in the ethylene polymer composition in an amount of 50% to 65% by weight.

[0020] In some embodiments, the first ethylene polymer is present in the ethylene polymer composition in an amount of 35% to 50% by weight.

[0021] In some embodiments, the ethylene polymer composition has a number-average molecular weight (Mn) of 10 kg / mol to 35 kg / mol.

[0022] In some embodiments, the ethylene polymer composition has a number-average molecular weight (Mn) of 15 kg / mol to 30 kg / mol.

[0023] In some embodiments, the ethylene polymer composition has a weight-average molecular weight (Mw) of 65 kg / mol to 100 kg / mol.

[0024] In some embodiments, the ethylene polymer composition has a weight-average molecular weight (Mw) of 70 kg / mol to 95 kg / mol.

[0025] In some embodiments, the second ethylene copolymer has a number-average molecular weight of 10 kg / mol to 38 kg / mol.

[0026] In some embodiments, the second ethylene copolymer has a number-average molecular weight of 15 kg / mol to 34 kg / mol.

[0027] In some embodiments, the second ethylene copolymer has a weight-average molecular weight of 30 kg / mol to 65 kg / mol.

[0028] In some embodiments, the second ethylene copolymer has 27 to 48 short-chain branches per 1000 carbon atoms.

[0029] In some embodiments, the first ethylene polymer has a weight-average molecular weight of 70 kg / mol to 160 kg / mol.

[0030] In some embodiments, the first ethylene polymer has a weight-average molecular weight of 100 kg / mol to 160 kg / mol.

[0031] In some embodiments, the ethylene polymer composition has a melt flow ratio of I measured at 190°C using loads of 2.16 kg and 21.6 kg according to ASTM D1238-13. 21 / I2 is between 15 and 40.

[0032] In some embodiments, the ethylene polymer composition further contains more than 0 to 20% by weight of a third ethylene copolymer comprising ethylene and at least one α-olefin, wherein the third ethylene copolymer has a polydispersity (Mw / Mn) of 1.7 to 2.3 and a weight-average molecular weight smaller than the weight-average molecular weights of the first ethylene polymer and the second ethylene copolymer.

[0033] In some embodiments, the third ethylene copolymer has a weight-average molecular weight of 20 kg / mol to 50 kg / mol and a short-chain branching number of 25 to 50 per 1000 carbon atoms.

[0034] In some embodiments, the continuous solution polymerization process further includes a step of forming a third ethylene copolymer by polymerizing ethylene and at least one α-olefin using a third homogeneous catalyst composition in a third solution polymerization reactor, wherein the first, second, and third solution phase polymerization reactors are configured in series with respect to each other.

[0035] In some embodiments, the third homogeneous catalyst composition comprises a crosslinked metallocene catalyst having the following formula (I). [ka] Here, M is a group 4 metal selected from titanium, zirconium, or hafnium, G is a group 14 element selected from carbon, silicon, germanium, tin, or lead, R1 is a hydrogen atom, C 1-20 Hydrocarbyl group, C 1-20 Alkoxy group or C 6-10 It is an aryloxy group, and R2 and R3 are independently hydrogen atoms and C 1-20Hydrocarbyl group, C 1-20 Alkoxy group or C 6-10 Selected from aryloxy groups, R4 and R5 are independently a hydrogen atom and an unsubstituted C. 1-20 Hydrocarbyl group, substituted C 1-20 Hydrocarbyl group, C 1-20 Alkoxy group or C 6-10 Selected from aryloxy groups, Q is an independently activatable leaving ligand.

[0036] In some embodiments, the third homogeneous catalyst includes a phosphinimine catalyst.

[0037] In some embodiments, at least one α-olefin is C3-C 10 Selected from the group consisting of α-olefins.

[0038] In some embodiments, at least one α-olefin is selected from the group consisting of 1-hexene, 1-octene, and a mixture of 1-hexene and 1-octene.

[0039] In some embodiments, at least one α-olefin is 1-octene.

[0040] In a second embodiment, a total polyethylene film layer comprising the ethylene polymer composition defined in the first embodiment is provided.

[0041] In some embodiments, the film layer is an inflation film.

[0042] In some embodiments, the film layer is a cast film.

[0043] In some embodiments, the film layer further has a density of 0.910 g / cm³ 3 ~0.940 g / cm 3It contains linear low-density polyethylene (LLDPE) having a melt index I2 of 0.1 dg / min to 10 dg / min.

[0044] In some embodiments, the film layer contains 10% to 40% by weight of LLDPE and 60% to 90% by weight of the ethylene polymer composition described in any of claims 1 to 32.

[0045] In a third embodiment, a total polyethylene multilayer film structure is provided, the film structure having at least one skin layer comprising the ethylene polymer composition as defined in the first embodiment.

[0046] In some embodiments, the film structure has a sublayer adjacent to the at least one skin layer, the sublayer having a density of 0.945 g / cm³ 3 The above applies, and the material includes high-density polyethylene (HDPE) with a melt index I2 of 0.1 dg / min to 10 dg / min.

[0047] In some embodiments, the HDPE is a blend of at least two ethylene homopolymer mixed components, the blend having a density of 0.950 to 0.975 g / cm³. 3 The first ethylene homopolymer mixed component is present in an amount of 30% to 95% by weight, and has a density of 0.950 to 0.975 g / cm³. 3 The mixture contains 5% to 70% by weight of a second ethylene homopolymer mixture, and the ratio of the melt index I2 of the second ethylene homopolymer mixture to the melt index I2 of the first ethylene homopolymer mixture is 10 or more.

[0048] In some embodiments, the HDPE comprises 100 to 3000 ppm of a nucleating agent or a mixture of nucleating agents.

[0049] In some embodiments, the HDPE has a polydispersity (Mw / Mn) of 7 to 18.

[0050] In some embodiments, the at least one skin layer further has a density of 0.910 g / cm³ 3 ~0.940 g / cm 3 It contains linear low-density polyethylene (LLDPE) having a melt index I2 of 0.1 dg / min to 10.0 dg / min.

[0051] In some embodiments, the at least one skin layer comprises 10% to 40% by weight of LLDPE and 60% to 90% by weight of the ethylene polymer composition as defined in the first embodiment.

[0052] In some embodiments, the film structure has at least three layers.

[0053] In some embodiments, the film structure has 3 to 9 layers.

[0054] In some embodiments, the at least one skin layer is a sealant layer.

[0055] In some embodiments, the film structure has a seal initiation temperature of 70°C to 115°C, where the seal initiation temperature is the minimum seal temperature of the film structure that has a seal strength of 3.4 N per 25.4 mm seal width.

[0056] In some embodiments, the film structure has a seal strength of 3.4 N to 15.0 N per 25.4 mm seal width at a seal temperature in the range of SIT to SIT+40°C.

[0057] In some embodiments, the film structure has a seal strength of 3.4 N to 15.0 N per 25.4 mm of seal width at a seal temperature in the range of SIT to SIT+25°C. [Brief explanation of the drawing]

[0058] [Figure 1a]Figure 1a shows a gel permeation chromatogram with Fourier transform infrared detection (GPC-FTIR gel permeation chromatogram with Fourier transform infrared detection) obtained for the ethylene polymer composition produced in Example 1 of the present invention. The comonomer content is shown on the secondary y-axis as the number of short-chain branches per 1000 carbon atoms as a function of molecular weight. [Figure 1b] Figure 1b shows the melting endothermic curve obtained during the second heating cycle for Example 1 of the present invention. The dashed line represents a virtual baseline drawn from 20°C to the end of melting. [Figure 2a] Figure 2a shows a gel permeation chromatogram with Fourier transform infrared detection (GPC-FTIR gel permeation chromatogram with Fourier transform infrared detection) obtained for the ethylene polymer composition produced in Example 2 of the present invention. The comonomer content is shown on the secondary y-axis as the number of short-chain branches per 1000 carbon atoms as a function of molecular weight. [Figure 2b] Figure 2b shows the melting endothermic curve obtained during the second heating cycle for Example 2 of the present invention. The dashed line represents a virtual baseline drawn from 20°C to the end of melting. [Figure 3a] Figure 3a shows a gel permeation chromatogram with Fourier transform infrared detection (GPC-FTIR gel permeation chromatogram with Fourier transform infrared detection) obtained for the ethylene polymer composition produced in Example 3 of the present invention. The comonomer content is shown on the secondary y-axis as the number of short-chain branches per 1000 carbon atoms as a function of molecular weight. [Figure 3b] Figure 3b shows the melting endothermic curve obtained during the second heating cycle for Example 3 of the present invention. The dashed line represents a virtual baseline drawn from 20°C to the end of melting. [Figure 4a]Figure 4a shows the seal strength of the multilayer film structures fabricated in Examples 1F-3F and 1FB-2FB of the present invention as a function of seal temperature. The dashed horizontal lines represent the upper and lower limits of the seal strength range of 3.4-15 N / 25 mm. The error bars show the ± standard deviation range of five seal strength measurements at each seal temperature. [Figure 4b] Figure 4b shows the seal strength of the multilayer film structure fabricated in Comparative Example 1F of the present invention as a function of seal temperature. The dashed horizontal line represents the upper and lower limits of the seal strength range of 3.4 to 15 N / 25 mm. The error bars show the ± standard deviation range of five seal strength measurements at each seal temperature. [Figure 4c] Figure 4c shows the seal strength of the multilayer film structures fabricated in Comparative Examples 3F to 6F of the present invention as a function of seal temperature. The dashed horizontal lines represent the upper and lower limits of the seal strength range of 3.4 to 15 N / 25 mm. The error bars show the ± standard deviation range of five seal strength measurements at each seal temperature. [Figure 5] Figure 5 shows the seal strength of the multilayer film structures fabricated in Examples 4F to 6F of the present invention as a function of seal temperature. The dashed horizontal lines represent the upper and lower limits of the seal strength range of 3.4 to 15 N / 25 mm. The error bars show the ± standard deviation range of five seal strength measurements at each seal temperature.

[0059] Definition of Terms Unless otherwise stated or illustrated, all numerical values ​​or expressions relating to the amount of ingredients, extrusion conditions, etc., used in this specification and the claims are understood to be modified by the word "approximately." Therefore, unless otherwise specified, the numerical parameters described in the following specification and the appended claims are approximations that may vary depending on the desired characteristics sought by the various embodiments. At the very least, and without attempting to limit the scope of the doctrine of equivalents, each numerical parameter should be interpreted using common rounding techniques based on the reported number of significant figures. The numerical values ​​described in the specific examples are reported as accurately as possible. However, each value inevitably contains a certain degree of error due to the standard deviation observed in the respective test measurements.

[0060] Numerical ranges described herein should be understood as being intended to include all subranges contained within that range. For example, the range "1 to 10" is intended to include the range between the stated minimum value of 1 and the stated maximum value of 10, and all subranges containing them, i.e., all ranges where the minimum value is 1 or greater and the maximum value is 10 or less. Since the disclosed numerical ranges are continuous, they include all values ​​between the minimum and maximum values. Unless otherwise explicitly stated, the various numerical ranges defined in this application are approximations.

[0061] All compositional ranges expressed herein are in practice limited to a maximum of 100% (volume % or weight %) in total, and not exceed that. Where a composition may contain multiple components, the sum of the maximum amounts of each component may exceed 100%, but as will be readily apparent to those skilled in the art, the amounts of components actually used are adjusted so that the sum is a maximum of 100%.

[0062] To better understand the disclosures of the present invention, the following terms are defined and will be used in conjunction with the accompanying drawings and descriptions of the various embodiments throughout this specification.

[0063] In this specification, the term "monomer" refers to a small molecule that can undergo chemical reactions and chemically bond with itself or other monomers to form polymers. In this specification, the term "α-olefin" or "alpha-olefin" refers to a monomer having a double bond at one end of the chain and a linear hydrocarbon chain with n=3 to 20 carbon atoms, and its chemical formula is CnH2n. A synonym is "linear α-olefin".

[0064] In this specification, the terms “polyethylene,” “polyethylene polymer,” or “ethylene polymer” refer to polymers produced from ethylene monomers and, optionally, at least one α-olefin monomer, regardless of the specific catalyst or process used to produce the ethylene polymer. The polymerized form of ethylene polymer contains more than 50% by weight of ethylene monomer units (based on the weight of the ethylene polymer). Common polyethylenes include high-density polyethylene (HDPE), medium-density polyethylene (MDPE), linear low-density polyethylene (LLDPE), very low-density polyethylene (VLDPE), extremely low-density polyethylene (ULDPE), plastomers, and elastomers. The term polyethylene also includes combinations or blends of the above polyethylenes.

[0065] In this specification, the term "ethylene homopolymer" refers to a polymer that is produced using only ethylene as the polymerizable monomer, among the polymers included in the "ethylene polymer" group.

[0066] The term "ethylene copolymer" refers to a polymer produced from ethylene and at least one α-olefin, which is included in the group of polymers called "ethylene polymers." Therefore, in this specification, the term "ethylene copolymer" includes both ethylene polymers prepared from two polymerizable monomer units (i.e., ethylene and one α-olefin) and ethylene polymers prepared from three or more polymerizable monomer units (i.e., ethylene and two or more α-olefins).

[0067] The term "heterogeneous branched ethylene copolymer" refers to a subset of ethylene copolymers produced using heterogeneous catalyst systems, including, but not limited to, the Ziegler-Natta catalyst and chromium catalyst, which are well known to those skilled in the art.

[0068] The term "homogeneous branched ethylene copolymer" refers to a subset of ethylene copolymers produced using a single active site catalyst, and non-limiting examples include metallocene catalysts, phosphinimine catalysts, and restricting structure catalysts, which are well known to those skilled in the art.

[0069] Typically, homogeneous branched ethylene copolymers have a narrow molecular weight distribution, with Mw / Mn values ​​in gel permeation chromatography (GPC) being less than approximately 2.8, and especially less than approximately 2.3, although exceptions may occur. Here, Mw and Mn refer to the weight-average molecular weight and number-average molecular weight, respectively. In contrast, the Mw / Mn of heterogeneous branched ethylene copolymers is usually greater than that of homogeneous branched ethylene copolymers. Generally, homogeneous branched ethylene copolymers also have a narrow compositional distribution, meaning that each polymer within the molecular weight distribution has a similar α-olefinic comonomer content.

[0070] A blend of two or more homogeneous branched ethylene copolymers with different weight-average molecular weights (Mw) may have an Mw / Mn ratio of 2.8 or higher. In this specification, such a blend is defined as a homogeneous blend or homogeneous composition.

[0071] The term "thermoplastic polymer" refers to polymers that become liquid when heated, flow under pressure, and solidify when cooled. Thermoplastic polymers include not only ethylene polymers but also other polymers used in the plastics industry. Non-exclusive examples of other polymers commonly used in film applications include barrier resins (e.g., EVOH), tie resins, polyethylene terephthalate (PET), polyamides, and ethylene vinyl acetate copolymers (EVA).

[0072] In this specification, the term "single-layer film" refers to a film comprising one or more layers of thermoplastic polymers.

[0073] In this specification, 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 types of thermoplastic polymers.

[0074] In this specification, the term "total polyethylene film layer" refers to a single-layer film containing 90% or more of one or more types of ethylene polymers, based on the total weight of the film layer.

[0075] In this specification, the term "all polyethylene multilayer film structure" refers to a multilayer film structure containing 90% or more of one or more types of ethylene polymers, based on the total weight of the multilayer film structure excluding the non-thermoplastic layer (if present).

[0076] In this specification, the term "tie resin" refers to a thermoplastic resin that, when formed as an intermediate layer or "tie layer" in a multilayer film structure, promotes adhesion between adjacent film layers with different chemical compositions.

[0077] In this specification, the term "sealant layer" refers to a layer of thermoplastic film that is bonded to a second substrate and can form a leak-proof seal. The "sealant layer" may be a skin layer or the innermost layer in a multilayer film structure.

[0078] In this specification, the terms “adhesive lamination” and “extrusion lamination” refer to a continuous process of combining two or more substrates or material webs to form a multilayer product or sheet, in which case the two or more webs are joined using an adhesive or a molten thermoplastic film.

[0079] In this specification, the term “extrusion coating” refers to a continuous process of combining or depositing a molten thermoplastic layer onto a moving solid web or substrate. Non-limiting examples of substrates include paper, cardboard, foil, single-layer plastic film, multi-layer plastic film, or textiles. The molten thermoplastic layer may be single-layer or multi-layer.

[0080] In this specification, the terms "hydrocarbon," "hydrocarbyl radical," or "hydrocarbyl group" refer to linear or cyclic aliphatic, olefinic, acetyleneic, and aryl (aromatic) radicals composed of hydrogen and carbon, lacking one hydrogen atom.

[0081] In this specification, “alkyl radical” includes linear, branched, and cyclic paraffinic radicals lacking one hydrogen radical, with non-limiting examples being the methyl (-CH3) radical and the ethyl (-CH2CH3) radical. The term “alkenyl radical” refers to linear, branched, and cyclic hydrocarbons having at least one carbon-carbon double bond and lacking one hydrogen radical.

[0082] In this specification, the “aryl” group includes phenyl, naphthyl, pyridyl, and other radicals having an aromatic ring structure, and non-limiting examples include naphthylene, phenanthrene, and anthracene. The “arylalkyl” group is an alkyl group having an aryl group as a side chain, and non-limiting examples include benzyl, phenethyl, and tolylmethyl. The “alkylaryl” group is an aryl group having one or more alkyl groups as side chains, and non-limiting examples include tolyl, xylyl, mesityl, and cumyl.

[0083] In this specification, the term "heteroatom" includes atoms other than carbon and hydrogen that can bond to carbon. A "heteroatom-containing group" is a hydrocarbyl radical containing a heteroatom, which may contain one or more identical or different heteroatoms. 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, oxoazolines, heterocyclic compounds, oxazolines, and thioethers. The term "heterocyclic" refers to a cyclic system having a carbon skeleton and containing 1 to 3 atoms selected from the group consisting of boron, aluminum, silicon, germanium, nitrogen, phosphorus, oxygen, and sulfur.

[0084] In this specification, "unsubstituted" means that a hydrogen radical is bonded to the following molecular group. "Substituted" means that the following group has one or more hydrogen radicals replaced by one or more substituents (non-hydrogen radicals) at any position within the group. Non-limiting examples of substituents 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-C 30 Alkyl alkyl groups, C2-C 30 Examples include alkenyl groups and combinations thereof. Non-limiting examples of substituted alkyls and substituted aryls include acyl radicals, alkylsilyl radicals, alkylamino radicals, alkoxy radicals, allyloxy radicals, alkylthio radicals, dialkylamino radicals, alkoxycarbonyl radicals, allyloxycarbonyl radicals, carbamoyl radicals, alkyl and dialkylcarbamoyl radicals, acyloxy radicals, acylamino radicals, arylamino radicals and combinations thereof. [Modes for carrying out the invention]

[0085] In the present invention, the reactor blend ethylene polymer composition comprises at least two identifiable components, namely, a first ethylene polymer having a defined weight-average molecular weight (Mw), a defined short-chain branching content, and a defined polydispersity (Mw / Mn), and a second ethylene copolymer having a defined weight-average molecular weight (Mw), a defined short-chain branching content, and a defined polydispersity (Mw / Mn). In some embodiments, the ethylene polymer composition further comprises a third ethylene copolymer.

[0086] The first ethylene polymer, the second ethylene copolymer, and any third ethylene copolymer can be identified using known fractionation techniques (e.g., thermal fractionation) and / or deconvolution by reaction simulation. The first ethylene polymer, the second ethylene copolymer, and any third ethylene copolymer, as well as the ethylene polymer compositions comprising them, will be described further below.

[0087] First ethylene polymer The first ethylene polymer comprises ethylene and optionally at least one α-olefin. In embodiments of the present invention, the at least one α-olefin polymerized with ethylene to produce the first ethylene polymer may be selected from the group consisting of 1-propene, 1-butene, 1-pentene, 1-hexene, 1-octene, and mixtures thereof.

[0088] In one embodiment of the present invention, the first ethylene polymer is a first ethylene homopolymer.

[0089] In one embodiment of the present invention, the first ethylene polymer is a first ethylene copolymer.

[0090] In one embodiment of the present invention, the first ethylene polymer is a first ethylene / 1-octene copolymer.

[0091] In one embodiment of the present invention, the first ethylene copolymer is a first homogeneous branched ethylene copolymer.

[0092] In one embodiment of the present invention, the first ethylene polymer is produced using a first homogeneous catalyst, non-limiting examples of which include phosphinimine catalysts and crosslinked metallocene catalysts well known to those skilled in the art.

[0093] In one embodiment of the present invention, a first ethylene polymer is produced using a first homogeneous catalyst having hafnium (Hf) as an active metal center (i.e., the catalyst is a hafnosene catalyst).

[0094] In one embodiment of the present invention, the first ethylene polymer is produced using a crosslinked metallocene catalyst.

[0095] In one embodiment of the present invention, the first ethylene polymer is produced using a crosslinked metallocene catalyst having the following formula (I). [ka]

[0096] 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, and R1 is a hydrogen atom, C 1-20 Hydrocarbyl radical, C 1-20 Alkyl radical or C 6-10 It is an aryloxy radical, where R2 and R3 are independently a hydrogen atom and C 1-20 Hydrocarbyl radical, C 1-20 Alkyl radical or C 6-10 Selected from aryloxy radicals, R4 and R5 are independently a hydrogen atom and an unsubstituted C atom. 1-20 Hydrocarbyl radical, substituted C 1-20 Hydrocarbyl radical, C 1-20 Alkyl radical or C 6-10 Selected from aryloxy radicals, Q is an independently activatable leaving ligand.

[0097] In one embodiment, R4 and R5 are each independently aryl groups.

[0098] In one embodiment, R4 and R5 are each independently a phenyl group or a substituted phenyl group.

[0099] In one embodiment, R4 and R5 are phenyl groups.

[0100] In one embodiment, R4 and R5 are each independently substituted phenyl groups.

[0101] In one embodiment, R4 and R5 are substituted phenyl groups, where the phenyl groups are substituted with substituted silyl groups.

[0102] In one embodiment, R4 and R5 are substituted phenyl groups, where the phenyl groups are substituted with trialkylsilyl groups.

[0103] In one embodiment, R4 and R5 are substituted phenyl groups, where the phenyl groups are substituted with a trialkylsilyl group at the para position. In one embodiment, R 1 and R 2 R is a substituted phenyl group, where the phenyl group is substituted with a trimethylsilyl group at the para position. In one embodiment, R 1 and R 2 This is a substituted phenyl group, where the phenyl group is substituted by a triethylsilyl group at the para position.

[0104] In one embodiment, R4 and R5 are each independently alkyl groups.

[0105] In one embodiment, R4 and R5 are each independently alkenyl groups.

[0106] In one embodiment, R1 is hydrogen.

[0107] In one embodiment, R1 is an alkyl group.

[0108] In one embodiment, R1 is an aryl group.

[0109] In one embodiment, R1 is an alkenyl group.

[0110] In one embodiment, R2 and R3 are each independently a hydrocarbyl group having 1 to 30 carbon atoms.

[0111] In one embodiment, R2 and R3 are each independently aryl groups.

[0112] In one embodiment, R2 and R3 are each independently alkyl groups.

[0113] In one embodiment, R2 and R3 are each independently alkyl groups having 1 to 20 carbon atoms.

[0114] In one embodiment, R2 and R3 are each independently a phenyl group or a substituted phenyl group.

[0115] In one embodiment, R2 and R3 are tert-butyl groups.

[0116] In one embodiment, R2 and R3 are hydrogen.

[0117] In one embodiment, M is hafnium (Hf).

[0118] In one embodiment of the present invention, the first ethylene polymer is produced using a crosslinked metallocene catalyst having the following formula (Ia). [ka]

[0119] In formula (Ia), G is a Group 14 element selected from carbon, silicon, germanium, tin, or lead, and R1 is a hydrogen atom, C 1-20 Hydrocarbyl radical, C 1-20Alkyl radical or C 6-10 It is an aryloxy radical, where R2 and R3 are independently a hydrogen atom and C 1-20 Hydrocarbyl radical, C 1-20 Alkyl radical or C 6-10 Selected from aryloxy radicals, R4 and R5 are independently a hydrogen atom and an unsubstituted C atom. 1-20 Hydrocarbyl radical, substituted C 1-20 Hydrocarbyl radical, C 1-20 Alkyl radical or C 6-10 Selected from aryloxy radicals, Q is an independently activatable leaving ligand.

[0120] In the present invention, "activatable" means that ligand Q can be cleaved from the metal center M by a proton decomposition reaction, or abstracted from the metal center M by a suitable acidic or electrophilic catalytic activating compound (also called a "co-catalyst"), examples of which are described below. Activatable ligand Q may also be converted to other ligands that can be cleaved or abstracted from the metal center M (for example, when a halide is converted to an alkyl group), and is not intended to be bound by a single theory, however, proton decomposition or abstraction reactions are thought to generate an active "cationic" metal center capable of polymerizing olefins.

[0121] In embodiments of the present invention, the activatable ligand Q is a hydrogen atom, a halogen atom, and C 1-20 Hydrocarbyl radical, C 1-20 Alkoxy radicals and C 6-10 Each is independently selected from the group consisting of aryl or allyloxy radicals, and each hydrocarbyl radical, alkoxy radical, aryl radical, or allyloxy radical may be unsubstituted or further substituted with one or more halogens or other groups, C 1-8 Alkyl, C 1-8 Alkoxy, C 6-10It may be an aryl or aryloxy, amidyl radical or phosphide radical, but Q is not cyclopentadienyl. Two Q ligands may 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 group or an acetamidinato group. In a preferred embodiment of the present invention, each Q is a halogen atom, C 1-4 Each is independently selected from the group consisting of alkyl radicals and benzyl radicals. Particularly preferred activatable ligand Qs are monovalent anions such as halogens (e.g., chloride) and hydrocarbons (e.g., methyl, benzyl).

[0122] In one embodiment of the present invention, the first homogeneous catalyst used for producing the first ethylene polymer is diphenylmethylene(cyclopentadienyl)(2,7-di-t-butylfluorenyl)hafnium dichloride having the molecular formula [(2,7-tBu2Flu)Ph2C(Cp)HfCl2].

[0123] In one embodiment of the present invention, the first homogeneous catalyst used for producing the first ethylene polymer is diphenylmethylene(cyclopentadienyl)(2,7-di-t-butylfluorenyl)hafnium dimethyl having the molecular formula [(2,7-tBu2Flu)Ph2C(Cp)HfMe2].

[0124] In one embodiment of the present invention, the first homogeneous catalyst is a phosphinimine catalyst represented by the following formula (II). (L A ) a M * (PI) b (Q) n (II) Here, (L A ) represents a bulky ligand, M * represents a metal atom, PI represents a phosphinimine ligand, Qs are each independently an activatable leaving group ligand, a is 0 or 1, b is 1 or 2, (a + b)=2, n is 1 or 2, and the sum of (a + b + n) is the metal M *It is equal to the valence of [the atom].

[0125] One embodiment of the present invention, L A The selected compound is from the group consisting of unsubstituted cyclopentadienyl, substituted cyclopentadienyl, unsubstituted indenyl, substituted indenyl, unsubstituted fluorenyl, and substituted fluorenyl.

[0126] In one embodiment of the present invention, M * It is a metal selected from the group consisting of titanium, hafnium, and zirconium.

[0127] In other non-limiting embodiments of the present invention, the bulky ligand L of formula (II) A This includes unsubstituted or substituted cyclopentadienyl ligands or cyclopentadienyl-type ligands, heteroatom-substituted and / or heteroatom-containing cyclopentadienyl-type ligands. In other non-limiting embodiments, the bulky ligand L of formula (II) A These include cyclopentaphenantrenyl ligands, unsubstituted or substituted indenyl ligands, benzindenyl ligands, unsubstituted or substituted fluorenyl ligands, octahydrofluorenyl ligands, cyclooctatetraendiyl ligands, cyclopentacyclododecene ligands, azenyl ligands, azulene ligands, pentalene ligands, phosphoyl ligands, phosphinimine ligands, pyrrolyl ligands, pyrazolyl ligands, carbazolyl ligands, borabenzene ligands, etc., and their hydrogenated forms, such as tetrahydroindenyl ligands, are also included. In other embodiments, L A is metal M * It may be any other ligand structure that can η-bond to it, and in these embodiments, metal M * η for 3 Combination and η 5 Both types of bonding are included. In other embodiments, L A It may contain one or more heteroatoms of nitrogen, silicon, boron, germanium, sulfur, and phosphorus, such as heterocyclopentadienyl auxiliary ligands, in order to form ring-opening, acyclic, fused ring, or cyclic systems in combination with carbon atoms. AAs other non-limiting embodiments, bulky amides, phosphides, alkoxides, aryloxides, imides, carbides, borolides, porphyrins, phthalocyanines, collins and other polyazomacrocycles are included.

[0128] In one embodiment of the present invention, the metal M * is titanium (Ti).

[0129] The phosphinimine ligand PI is defined by the following formula (III). (R p )3P = N - (III) Here, the R p groups are each independently a hydrogen atom, a halogen atom, an unsubstituted C 1-20 hydrocarbyl radical which may be substituted with one or more halogen atoms, a C 1-8 alkoxy radical, a C 6-10 aryl radical, a C 6-10 aryloxy radical, an amide radical, a silyl radical represented by the formula —Si(R s )3 (where the R s groups are each independently a hydrogen atom, a C 1-8 alkyl or alkoxy radical, a C 6-10 aryl radical, a C 6-10 aryloxy radical), or a germanyl radical represented by the formula —Ge(R G )3 (where the R G groups are synonymous with the R s defined in this paragraph).

[0130] In addition to the first homogeneous catalyst molecule itself, the active homogeneous catalyst system may further include one or more of an alkylaluminoxane cocatalyst and an ionic activator. The homogeneous catalyst system may optionally include a sterically hindered phenol.

[0131] Although the exact structure of the alkylaluminoxane is unknown, those skilled in the art generally agree that it is an oligomeric species containing repeating units of the following general formula. (R)2AlO-(Al(R)-O) n -Al(R)2 Here, the R groups may be the same or different, and are linear, branched, or cyclic hydrocarbyl radicals having 1 to 20 carbon atoms, with n ranging from 0 to about 50. A non-limiting example of alkylaluminoxane is methylaluminoxane (or MAO), where each R group is a methyl radical.

[0132] In one embodiment of the present invention, R of the alkylaluminoxane is a methyl radical, and m is in the range of 10 to 40.

[0133] In one embodiment of the present invention, the auxiliary catalyst is modified methylaluminoxane (MMAO).

[0134] As is well known to those skilled in the art, the alkylaluminoxane can play a dual role as both an alkylating agent and an activating agent. Therefore, alkylaluminoxane co-catalysts are often used in combination with activatable ligands such as halogens.

[0135] Generally, ionic activators consist of a cation and a bulky anion, the latter being substantially non-coordinating. A non-limiting example is a four-coordination boron-based ionic activator having four ligands bonded to a boron atom. An example of a non-limiting boron-based ionic activator is shown in the following formula. [R 5 ] + [B(R 7 )4] - Here, B represents a boron atom, and R 5 is an aromatic hydrocarbyl group (e.g., triphenylmethyl cation), and each R 7 C is a fluorine atom, and C can be substituted with a fluorine atom. 1-4 The R groups are independently selected from unsubstituted phenyl groups which may be substituted with 3 to 5 substituents selected from alkyl or alkoxy groups. 7 The formula is -Si(R 9)3 may also be a silyl group, where each R 9 is a hydrogen atom and C 1-4 It is independently selected from alkyl groups. Furthermore, [(R 8 ) t ZH] + [B(R 7 )4] - In this, B is a boron atom, H is a hydrogen atom, Z is a nitrogen atom or a phosphorus atom, t is 2 or 3, R 8 is C 1-8 Alkyl alkyl groups, up to 3 C 1-4 A phenyl group which may be substituted with an alkyl group, or one R 8 The nitrogen atom and R may combine to form an anilinium group. 7 As stated above.

[0136] In both equations, R 7A non-limiting example is the pentafluorophenyl group. In general, boron ionic activators can be described as salts of tetra(perfluorophenyl)boron, non-limiting examples of which include anilinium salts, carbonium salts, oxonium salts, phosphonium salts, and sulfonium salts, which are combined with anilinium and trityl (or triphenylmethylium). Other non-limiting examples of ionic activators include triethylammonium tetra(phenyl)borone, tripropylammonium tetra(phenyl)borone, tri(n-butyl)ammonium tetra(phenyl)borone, trimethylammonium tetra(p-tolyl)borone, trimethylammonium tetra(o-tolyl)borone, tributylammonium tetra(pentafluorophenyl)borone, tripropylammonium tetra(o,p-dimethylphenyl)borone, tributylammonium tetra(m,m-dimethylphenyl)borone, tributylammonium tetra(p-trifluoromethylphenyl)borone, tributylammonium tetra(pentafluorophenyl)borone, tri(n-butyl)ammonium tetra(o-tolyl)borone, N,N-dimethylanilinium tetra(phenyl)borone, N,N-diethylanilinium tetra(phenyl)borone, and N,N-diethyl Nylinium tetra(phenyl) n-butylborone, N,N-2,4,6-pentamethylanilinium tetra(phenyl)borone, di(isopropyl)ammonium tetra(pentafluorophenyl)borone, dicyclohexylammonium tetra(phenyl)borone, triphenylphosphonium tetra(phenyl)borone, tri(methylphenyl)phosphonium tetra(phenyl)borone, tri(dimethylphenyl)phosphonium tetra(phenyl)borone, tropylium tetrakis(pentafluorophenyl)borate, triphenylmethylium tetrakis(pentafluorophenyl)borate, benzene(diazonium) tetrakis(pentafluorophenyl)borate, tropylium tetrakis(2,3,5,6-tetrafluorophenyl)borate, triphenylmethylium tetrakis(2,3,5,6-tetrafluorophenyl)borate, benzene(diazonium) tetrakis(3,4,Examples include 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. Easily available commercially produced ionic activators include N,N-dimethylanilinium tetrakis(pentafluorophenyl) borate and triphenylmethylium tetrakis(pentafluorophenyl) borate.

[0137] Examples of non-limiting hindered phenols include butylated phenolic antioxidants, butylated hydroxytoluene, 2,6-di-t-butyl-4-ethylphenol, 4,4′-methylenebis(2,6-di-t-butylphenol), 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, and octadecyl-3-(3′,5′-di-t-butyl-4′-hydroxyphenyl)propionate.

[0138] To generate an active homogeneous catalytic system, the amounts and molar ratios of three or four components—a first homogeneous catalyst, an alkylaluminoxane, an ionic activator, and an optional hindered phenol—are optimized.

[0139] In one embodiment of the present invention, the first homogeneous catalyst used to produce the first ethylene polymer does not generate long-chain branching, and / or the first ethylene polymer does not contain a measurable amount of long-chain branching.

[0140] In one embodiment of the present invention, the first homogeneous catalyst used to produce the first ethylene polymer generates long-chain branches, and the first ethylene polymer contains long-chain branches (hereinafter referred to as "LCB"). LCB is a well-known structural phenomenon in ethylene polymers and is widely known to those skilled in the art.

[0141] In one embodiment of the present invention, the first ethylene polymer contains long-chain branches characterized by the LCBF disclosed herein. In an embodiment of the present invention, the upper limit of the LCBF of the first ethylene polymer may be about 0.5, about 0.4 in other embodiments, or about 0.3 (dimensionless) in still other embodiments. In an embodiment of the present invention, the lower limit of the LCBF of the first ethylene polymer may be about 0.001, about 0.0015 in other embodiments, or about 0.002 (dimensionless) in still other embodiments.

[0142] In some embodiments of the present invention, the upper limit of the molecular weight distribution (Mw / Mn) of the first ethylene polymer may be about 2.3, or about 2.2, or about 2.1, or about 2.0. In some embodiments of the present invention, the lower limit of the molecular weight distribution (Mw / Mn) of the first ethylene polymer may be about 1.7, or about 1.8, or about 1.9.

[0143] In some embodiments of the present invention, the first ethylene polymer may have a molecular weight distribution (Mw / Mn) of 2.3 or less, or less than 2.3, or 2.2 or less, or less than 2.2, or 2.1 or less, or less than 2. The first ethylene polymer may have a molecular weight distribution (Mw / Mn) of about 1.7 to about 2.3, or about 1.8 to about 2.3, or about 1.8 to about 2.2 in some embodiments of the present invention.

[0144] In one embodiment, the first ethylene polymer may have 0 to 10 short-chain branches per 1000 carbon atoms. In yet another embodiment, the first ethylene polymer may have more than 0 and up to 10 short-chain branches per 1000 carbon atoms, or 0 to 6 short-chain branches, or more than 0 and up to 6 short-chain branches, or 0 to 5 short-chain branches, or more than 0 and up to 5 short-chain branches, or 0.005 to 6 short-chain branches. In yet another embodiment, the first ethylene polymer may have 0.01 to 6 short-chain branches, or 0.1 to 6 short-chain branches, or 0.5 to 6 short-chain branches per 1000 carbon atoms.

[0145] In some embodiments, the first ethylene polymer contains zero short-chain branches per 1,000 carbon atoms.

[0146] Short-chain branching (i.e., short-chain branching per 1000 carbon atoms) is branching resulting from the presence of at least one of any choice of α-olefins in the first ethylene polymer, for example, having 2 carbon atoms in the case of butene-1, 4 carbon atoms in the case of hexene-1, or 6 carbon atoms in the case of octene-1.

[0147] In one embodiment of the present invention, the first ethylene polymer has a weight-average molecular weight (Mw) of 70 kg / mol to 250 kg / mol, or 70 kg / mol to 200 kg / mol, or 70 kg / mol to 180 kg / mol, or 70 kg / mol to 160 kg / mol, or 75 kg / mol to 160 kg / mol, or 80 kg / mol to 160 kg / mol, or 85 kg / mol to 160 kg / mol, or 90 kg / mol to 160 kg / mol, or 100 kg / mol to 160 kg / mol.

[0148] In some embodiments of the present invention, the upper limit of the weight percentage of the first ethylene polymer in the ethylene polymer composition (i.e., the weight percentage of the first ethylene polymer based on the total weight of the ethylene polymer composition) is about 70% by weight, or about 65% by weight, or about 60% by weight, or about 55% by weight, or about 52% by weight, or about 50% by weight. In some embodiments of the present invention, the lower limit of the weight percentage of the first ethylene polymer in the ethylene polymer composition is about 30% by weight, or about 35% by weight, or about 40% by weight, or about 45% by weight, or about 50% by weight. In one embodiment, the first ethylene polymer is included in the ethylene polymer composition in an amount of 30% to 70% by weight. In another embodiment, the ethylene homopolymer is included in the ethylene polymer composition in an amount of 40% to 60% by weight. In yet another embodiment, the ethylene homopolymer is included in the ethylene polymer composition in an amount of 35% to 50% by weight.

[0149] Second ethylene copolymer The second ethylene copolymer comprises ethylene and at least one α-olefin. In embodiments of the present invention, the at least one α-olefin that can be copolymerized with ethylene to produce the second ethylene copolymer is selected from propene-1, butene-1, pentene-1, hexene-1, and octene-1, and mixtures thereof.

[0150] In one embodiment of the present invention, the second ethylene copolymer is a second ethylene copolymer.

[0151] In one embodiment of the present invention, the second ethylene copolymer is a second ethylene / octene-1 copolymer.

[0152] In one embodiment of the present invention, the second ethylene copolymer is a second homogeneous branched ethylene copolymer.

[0153] In one embodiment of the present invention, the second ethylene copolymer is produced using a second homogeneous catalyst. Examples of such second homogeneous catalysts include, but are not limited to, phosphinimine catalysts and bridged metallocene catalysts, all of which are well known to those skilled in the art.

[0154] In one embodiment of the present invention, the second ethylene copolymer is produced using a second homogeneous catalyst having hafnium (Hf) as an active metal center (i.e., the catalyst is a hafnosene catalyst).

[0155] In one embodiment of the present invention, the second ethylene copolymer is produced using a crosslinked metallocene catalyst.

[0156] In one embodiment of the present invention, the second ethylene copolymer is produced using a crosslinked metallocene catalyst represented by the following formula (I). [ka]

[0157] 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, and R1 is a hydrogen atom, C 1-20 Hydrocarbyl group, C 1-20 Alkoxy group or C 6-10 It is an aryloxy group, and R2 and R3 are independently hydrogen atoms and C 1-20 Hydrocarbyl group, C 1-20 Alkoxy group or C 6-10 Selected from aryloxy groups, R4 and R5 are independently a hydrogen atom and an unsubstituted C. 1-20 Hydrocarbyl group, substituted C 1-20 Hydrocarbyl group, C 1-20 Alkoxy group or C 6-10 Selected from aryloxy groups, Q is an independently activatable leaving ligand.

[0158] In one embodiment, R4 and R5 are each independently aryl groups.

[0159] In one embodiment, R4 and R5 are each independently a phenyl group or a substituted phenyl group.

[0160] In one embodiment, R4 and R5 are phenyl groups.

[0161] In one embodiment, R4 and R5 are each independently substituted phenyl groups.

[0162] In one embodiment, R4 and R5 are substituted phenyl groups, and these phenyl groups are substituted with substituted silyl groups.

[0163] In one embodiment, R4 and R5 are substituted phenyl groups, and these phenyl groups are substituted with trialkylsilyl groups.

[0164] In one embodiment, R4 and R5 are substituted phenyl groups, and the phenyl groups are substituted with a trialkylsilyl group at the para position. In one embodiment, R 1 and R 2 R is a substituted phenyl group, and the phenyl group is substituted with a trimethylsilyl group at the para position. In one embodiment, R 1 and R 2 This is a substituted phenyl group, and the phenyl group is substituted with a triethylsilyl group at the para position.

[0165] In one embodiment, R4 and R5 are independently alkyl groups.

[0166] In one embodiment, R4 and R5 are independently alkenyl groups.

[0167] In one embodiment, R1 is hydrogen.

[0168] In one embodiment, R1 is an alkyl group.

[0169] In one embodiment, R1 is an aryl group.

[0170] In one embodiment, R1 is an alkenyl group.

[0171] In one embodiment, R2 and R3 are each independently hydrocarbyl groups having 1 to 30 carbon atoms.

[0172] In one embodiment, R2 and R3 are each independently an aryl group.

[0173] In one embodiment, R2 and R3 are each independently alkyl groups.

[0174] In one embodiment, R2 and R3 are each independently alkyl groups having 1 to 20 carbon atoms.

[0175] In one embodiment, R2 and R3 are each independently a phenyl group or a substituted phenyl group.

[0176] In one embodiment, R2 and R3 are t-butyl groups.

[0177] In one embodiment, R2 and R3 are hydrogen.

[0178] In one embodiment, M is hafnium (Hf).

[0179] In one embodiment of the present invention, the second ethylene copolymer is produced using a crosslinked metallocene catalyst represented by the following formula (Ia). [ka]

[0180] In formula (Ia), G is a Group 14 element selected from carbon, silicon, germanium, tin, or lead, and R1 is a hydrogen atom, C 1-20 Hydrocarbyl radical, C 1-20 alkoxy radicals or C6-10 It is an aryloxy radical, where R2 and R3 are independently a hydrogen atom and C 1-20 Hydrocarbyl radical, C 1-20 alkoxy radicals or C 6-10 Selected from the aryloxy radicals, R4 and R5 are independently a hydrogen atom and an unsubstituted C 1-20 Hydrocarbyl radical, substituted C 1-20 Hydrocarbyl radical, C 1-20 alkoxy radicals or C 6-10 The aryloxy radicals are selected, and each Q is an independently activatable leaving ligand.

[0181] In the present invention, "activatable" means that ligand Q can be cleaved from the metal center M by a protonolysis reaction or abstracted from the metal center M by a suitable acidic or electrophilic catalytic activating compound (also called a "co-catalyst" compound). Examples of these are described below. The activatable ligand Q may be converted to other ligands that can be cleaved or abstracted from the metal center M (for example, when converting a halide to an alkyl group). While we do not wish to be bound by any particular theory, the protonolysis or abstraction reaction generates an active "cationic" metal center capable of polymerizing olefins.

[0182] In embodiments of the present invention, the activatable ligand Q is a hydrogen atom, a halogen atom, and C 1-20 Hydrocarbyl group, C 1-20 Alkoxy group, and C 6-10 A hydrocarbyl group, alkoxy group, aryl group, or aryloxy group is independently selected from the group consisting of an aryl group or an aryloxy group, and these hydrocarbyl groups, alkoxy groups, aryl groups, or aryloxy groups may be unsubstituted or further substituted with one or more halogens or other groups. Q is C 1-8 Alkyl alkyl group, C 1-8 Alkoxy group, C 6-10The Q ligand may be an aryl group or aryloxy group, an amide group or a phosphine group, but it may not be a cyclopentadienyl group. The two Q ligands may be bonded to each other, for example, to form a substituted or unsubstituted diene ligand (e.g., 1,3-butadiene), or a delocalized heteroatom-containing group such as an acetate group or an acetamidinate group. In a preferred embodiment of the present invention, each Q may be a halogen atom, C 1-4 The ligand Q is independently selected from the group consisting of alkyl groups and benzyl groups. Particularly suitable activatable ligands Q are monoanionic, such as halides (e.g., chlorides) or hydrocarbyl groups (e.g., methyl groups, benzyl groups).

[0183] In one embodiment of the present invention, the second homogeneous catalyst used to produce the second ethylene copolymer is diphenylmethylene (cyclopentadienyl)(2,7-di-t-butylfluorenyl)hafnium dichloride having the molecular formula [(2,7-tBu2Flu)Ph2C(Cp)HfCl2].

[0184] In one embodiment of the present invention, the second homogeneous catalyst used to produce the second ethylene copolymer is diphenylmethylene(cyclopentadienyl)(2,7-di-t-butylfluorenyl)hafniumdimethyl having the molecular formula [(2,7-tBu2Flu)Ph2C(Cp)HfMe2].

[0185] In one embodiment of the present invention, the second homogeneous catalyst is a phosphinimine catalyst represented by the following formula (II). (L A ) a M * (PI) b (Q) n (II) Here, (L A ) represents a bulky ligand, M * represents a metal atom, PI represents a phosphinimine ligand, and Q represents independently activatable leaving group ligands. a is 0 or 1, b is 1 or 2, and (a+b) is 2. n is 1 or 2, and the sum of (a+b+n) is metal M* It is equal to the valence of [the atom].

[0186] One embodiment of the present invention, L A The selected compound is from the group consisting of unsubstituted cyclopentadienyl, substituted cyclopentadienyl, unsubstituted indenyl, substituted indenyl, unsubstituted fluorenyl, and substituted fluorenyl.

[0187] In one embodiment of the present invention, M * This is a metal selected from the group consisting of titanium, hafnium, and zirconium.

[0188] In other non-limiting embodiments of the present invention, the bulky ligand L in formula (II) A This includes unsubstituted or substituted cyclopentadienyl ligands or cyclopentadienyl-type ligands, heteroatom-substituted and / or heteroatom-containing cyclopentadienyl-type ligands. In more non-limiting embodiments, the bulky ligand L in formula (II) is also included. A This includes cyclopentaphenantrenyl ligands, unsubstituted or substituted indenyl ligands, benzindenyl ligands, unsubstituted or substituted fluorenyl ligands, octahydrofluorenyl ligands, cyclooctatetraendiyl ligands, cyclopentacyclododecene ligands, azenyl ligands, azulene ligands, pentalene ligands, phosphoryl ligands, phosphinimine ligands, pyrrolyl ligands, pyrazolyl ligands, carbazolyl ligands, borabenzene ligands, etc., and their hydrogenated forms, such as tetrahydroindenyl ligands. In another embodiment, L A is metal M * Other ligand structures capable of η-binding may also exist, and these embodiments include metal M * to η 3 Combination and η 5 This includes both types of bonding. In yet another embodiment, L A It may be combined with a carbon atom to contain one or more heteroatoms such as nitrogen, silicon, boron, germanium, sulfur, and phosphorus, and may form an open ring structure, an acyclic structure, or a fused ring or ring system, for example, a heterocyclopentadienyl auxiliary ligand. Other non-limiting L AEmbodiments include bulky amides, phosphides, alkoxides, alyroxides, imides, carbolides, borolides, porphyrins, phthalocyanines, choline, and other polyazomacrocycles.

[0189] In one embodiment of the present invention, metal M * It is titanium (Ti).

[0190] The phosphimine ligand PI is defined by the following equation (III). (R p )3P = N - (III) Here, R p Each group may independently be substituted with a hydrogen atom, a halogen atom, or one or more halogen atoms. 1-20 The hydrocarbyl group, C 1-8 The alkoxy group of C 6-10 The aryl group, C 6-10 an allyloxy group, an amide group, or -Si(R s )3 represents a silyl group (R s Each group consists of a hydrogen atom and a carbon atom. 1-8 an alkyl group or alkoxy group, C 6-10 The aryl group, C 6-10 Selected from (the allyloxy group of) or -Ge(R G )3 represents a germanyl group (R G The base is R in this section s (This is the same as the definition of the base.)

[0191] In addition to the second homogeneous catalyst molecule itself, the effective homogeneous catalyst system may further include one or a combination thereof of an alkylaluminoxane co-catalyst and an ionic activator. The homogeneous catalyst system may further include a sterically hindered phenol as needed.

[0192] The exact structure of alkylaluminoxane is unknown, but among those skilled in the art, the general formula is known to be... (R)2AlO-(Al(R)-O) n -Al(R)2 It is generally agreed that these are oligomeric species containing repeating units. Here, the R groups may be the same or different, and are linear, branched, or cyclic hydrocarbyl groups containing 1 to 20 carbon atoms, with n ranging from 0 to about 50. A non-limiting example of alkylaluminoxane is methylaluminoxane (MAO), in which each R group is a methyl group.

[0193] In one embodiment of the present invention, R in alkylaluminoxane is a methyl group, and m is in the range of 10 to 40.

[0194] In one embodiment of the present invention, the co-catalyst is modified methylaluminoxane (MMAO).

[0195] As is well known to those skilled in the art, alkylaluminoxanes can play a dual role as both alkylating agents and activators. Therefore, alkylaluminoxane co-catalysts are often used in combination with activatable ligands such as halogens.

[0196] Generally, ionic activators consist of a cation and a bulky anion, the latter being substantially non-coordinating. A non-limiting example is a four-coordination boron ionic activator having four ligands bonded to the boron atom. A non-limiting example of a boron ionic activator is the compound shown in the following formula. [R 5 ] + [B(R 7 )4] - Here, B represents a boron atom, and R 5 is an aromatic hydrocarbyl group (e.g., triphenylmethyl cation), and each R 7 These are independently fluorine atoms, C 1-4 A phenyl group that is unsubstituted or substituted with 3 to 5 substituents selected from alkyl or alkoxy groups (both of which may be substituted with fluorine atoms), and each R 9 A hydrogen atom or C 1-4 A silyl group selected from alkyl groups (-Si(R 9)3) will be selected. Also, [(R 8 ) t ZH] + [B(R 7 )4] - Here, B is a boron atom, H is a hydrogen atom, Z is a nitrogen atom or a phosphorus atom, t is 2 or 3, and R 8 is C 1-8 Alkyl alkyl groups, up to 3 C 1-4 A phenyl group which may be substituted with an alkyl group, or one R 8 The nitrogen atom may also form an anilinium group, R 7 This is synonymous with the above.

[0197] In both equations, R 7A non-limiting example is the pentafluorophenyl group. In general, boron ionic activators are described as salts of tetra(perfluorophenyl)boron, and non-limiting examples include anilinium, carbonium, oxonium, phosphonium, and sulfonium salts of tetra(perfluorophenyl)boron (including anilinium and trityl (or triphenylmethylium)). Examples of additional non-limiting 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, and N,N-diethylanilinium Nylinium 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 tetrakis(pentafluorophenyl)borate, triphenylmethylium tetrakis(pentafluorophenyl)borate, benzene(diazonium) tetrakis(pentafluorophenyl)borate, tropylium tetrakis(2,3,5,6-tetrafluorophenyl)borate, triphenylmethylium tetrakis(2,3,5,6-tetrafluorophenyl)borate, benzene(diazonium) tetrakis(3,4,Examples include 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. Easily available commercially produced ionic activators include N,N-dimethylanilinium tetrakis(pentafluorophenyl) borate and triphenylmethylium tetrakis(pentafluorophenyl) borate.

[0198] Examples of non-limiting hindered phenols include butylated phenolic antioxidants, butylated hydroxytoluene, 2,6-di-t-butyl-4-ethylphenol, 4,4'-methylenebis(2,6-di-t-butylphenol), 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, and octadecyl-3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate.

[0199] To produce an activated homogeneous catalyst system, the amounts and molar ratios of three or four components—a first homogeneous catalyst, an alkylaluminoxane, an ionic activator, and a hindered phenol used as needed—are optimized.

[0200] In one embodiment of the present invention, the second homogeneous catalyst used to produce the second ethylene copolymer does not generate long-chain branching, and / or the second ethylene copolymer does not contain a measurable amount of long-chain branching.

[0201] In one embodiment of the present invention, a second homogeneous catalyst used to produce a second ethylene copolymer generates long-chain branching, and the second ethylene copolymer contains long-chain branching (hereinafter referred to as "LCB"). LCB is a well-known structural phenomenon in ethylene polymers and is widely known to those skilled in the art.

[0202] In one embodiment of the present invention, the second ethylene copolymer comprises long-chain branching characterized by LCBF disclosed herein. In embodiments of the present invention, the upper limit of LCBF of the second ethylene copolymer may be about 0.5, in other cases about 0.4, and in yet other cases about 0.3 (dimensionless). In embodiments of the present invention, the lower limit of LCBF of the second ethylene copolymer may be about 0.001, in other cases about 0.0015, and in yet other cases about 0.002 (dimensionless).

[0203] In some embodiments of the present invention, the upper limit of the molecular weight distribution (Mw / Mn) of the second ethylene copolymer is about 2.3, or about 2.2, or about 2.1, or about 2.0. In some embodiments of the present invention, the lower limit of the molecular weight distribution (Mw / Mn) of the second ethylene copolymer is about 1.7, or about 1.8, or about 1.9.

[0204] In some embodiments of the present invention, the molecular weight distribution (Mw / Mn) of the second ethylene copolymer is 2.3 or less, or less than 2.3, or 2.2 or less, or less than 2.2, or 2.1 or less, or less than 2.1. In some embodiments of the present invention, the molecular weight distribution (Mw / Mn) of the second ethylene copolymer is about 1.7 to about 2.3, or about 1.8 to about 2.3, or about 1.8 to about 2.2.

[0205] In one embodiment, the second ethylene copolymer has 25 to 55 short-chain branches per 1,000 carbon atoms. In yet another embodiment, the second ethylene copolymer has 30 to 50, or 30 to 45, or 30 to 40, or 31 to 55, or 31 to 50, or 33 to 45, or 33 to 40 short-chain branches per 1,000 carbon atoms. In yet another embodiment, the second ethylene copolymer has 25 to 50, or 27 to 48, or 27 to 45 short-chain branches per 1,000 carbon atoms.

[0206] As is well known to those skilled in the art, short-chain branching (i.e., short-chain branching per 1,000 carbon atoms) is branching resulting from at least one α-olefin present in the second ethylene copolymer, for example, having 2 carbon atoms in the case of 1-butene, 4 carbon atoms in the case of 1-hexene, and 6 carbon atoms in the case of 1-octene.

[0207] In one embodiment of the present invention, the second ethylene copolymer has a weight-average molecular weight (Mw) of 20 kg / mol to 75 kg / mol, or 20 kg / mol to 70 kg / mol, or 30 kg / mol to 65 kg / mol, or 35 kg / mol to 60 kg / mol, or 40 kg / mol to 60 kg / mol, or 40 kg / mol to 55 kg / mol.

[0208] The weight-average molecular weight of the second ethylene copolymer is smaller than that of the first ethylene polymer. In some embodiments, the ratio of the weight-average molecular weight of the first ethylene polymer to that of the second ethylene copolymer is between 1.5 and 6. In some embodiments, the ratio is between 2 and 4. In some embodiments, the ratio is between 2.5 and 4.0. In some embodiments, the ratio is between 2 and 3.

[0209] In one embodiment of the present invention, the second ethylene copolymer has a number-average molecular weight (Mn) of 10 kg / mol to 40 kg / mol, or 15 kg / mol to 40 kg / mol, or 15 kg / mol to 34 kg / mol, or 15 kg / mol to 30 kg / mol.

[0210] In some embodiments of the present invention, the upper limit of the weight percentage of the second ethylene copolymer in the ethylene-based polymer composition (i.e., the weight percentage of the second ethylene copolymer based on the total weight of the ethylene-based polymer composition) is about 70% by weight, or about 65% by weight, or about 60% by weight, or about 55% by weight, or about 52% by weight, or about 50% by weight. In some embodiments of the present invention, the lower limit of the weight percentage of the second ethylene copolymer in the ethylene-based polymer composition is about 30% by weight, or about 35% by weight, or about 40% by weight, or about 45% by weight, or about 50% by weight. In one embodiment, the second ethylene copolymer is included in the ethylene-based polymer composition in an amount of 30 to 70% by weight. In another embodiment, the second ethylene copolymer is included in the ethylene-based polymer composition in an amount of 40 to 60% by weight. In yet another embodiment, the second ethylene copolymer is included in the ethylene-based polymer composition in an amount of 50 to 65% by weight.

[0211] Third ethylene copolymer In one embodiment of the present invention, the third ethylene copolymer comprises ethylene and at least one α-olefin. In this embodiment, the at least one α-olefin is copolymerized with ethylene to produce the third ethylene copolymer and may be selected from the group consisting of propene-1, butene-1, pentene-1, hexene-1, and octene-1 and mixtures thereof.

[0212] In one embodiment of the present invention, the third ethylene copolymer is a third ethylene / octene-1 copolymer.

[0213] In one embodiment of the present invention, the third ethylene copolymer is a third uniformly branched ethylene copolymer.

[0214] In one embodiment of the present invention, the third ethylene copolymer is produced using a third homogeneous catalyst, non-limiting examples of the catalyst include phosphinimine catalysts and crosslinked metallocene catalysts, which are well known to those skilled in the art.

[0215] In one embodiment of the present invention, the third ethylene copolymer is produced using a third homogeneous catalyst (i.e., a hafnocene catalyst) having hafnium (Hf) as the active metal center.

[0216] In one embodiment of the present invention, the third ethylene copolymer is produced using a crosslinked metallocene catalyst.

[0217] In one embodiment of the present invention, the third ethylene copolymer is produced using a crosslinked metallocene catalyst represented by formula (I). [ka]

[0218] 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, and R1 is a hydrogen atom, C 1-20 Hydrocarbyl radical, C 1-20 Alkyl radical or C 6-10 It is an aryloxy radical, where R2 and R3 are independently a hydrogen atom and C 1-20 Hydrocarbyl radical, C 1-20 Alkyl radical or C 6-10 Selected from aryloxy radicals, R4 and R5 are independently a hydrogen atom and an unsubstituted C. 1-20 Hydrocarbyl radical, substituted C 1-20 Hydrocarbyl radical, C 1-20 Alkyl radical or C 6-10 The aryloxy radicals are selected, and each Q is an independently activatable leaving group ligand.

[0219] In one embodiment, R4 and R5 are each independently aryl groups.

[0220] In one embodiment of the present invention, R4 and R5 are each independently a phenyl group or a substituted phenyl group.

[0221] In one embodiment of the present invention, R4 and R5 are phenyl groups.

[0222] In one embodiment of the present invention, R4 and R5 are each substituted phenyl groups.

[0223] In one embodiment of the present invention, R4 and R5 are substituted phenyl groups, and these phenyl groups are substituted with substituted silyl groups.

[0224] In one embodiment of the present invention, R4 and R5 are substituted phenyl groups, and these phenyl groups are substituted with trialkylsilyl groups.

[0225] In one embodiment of the present invention, R4 and R5 are substituted phenyl groups, and the phenyl groups are substituted with a trialkylsilyl group at the para position. In one embodiment of the present invention, R 1 and R 2 R is a substituted phenyl group, and the phenyl group is substituted with a trimethylsilyl group at the para position. In one embodiment of the present invention, R 1 and R 2 This is a substituted phenyl group, and this phenyl group is substituted with a triethylsilyl group at the para position.

[0226] In one embodiment of the present invention, R4 and R5 are each independently alkyl groups.

[0227] In one embodiment of the present invention, R4 and R5 are each independently an alkenyl group.

[0228] In one embodiment of the present invention, R1 is hydrogen.

[0229] In one embodiment of the present invention, R1 is an alkyl group.

[0230] In one embodiment of the present invention, R1 is an aryl group.

[0231] In one embodiment of the present invention, R1 is an alkenyl group.

[0232] In one embodiment of the present invention, R2 and R3 are hydrocarbyl groups having 1 to 30 carbon atoms.

[0233] In one embodiment of the present invention, R2 and R3 are each independently aryl groups.

[0234] In one embodiment of the present invention, R2 and R3 are each independently alkyl groups.

[0235] In one embodiment of the present invention, R2 and R3 are each an alkyl group having 1 to 20 carbon atoms independently.

[0236] In one embodiment of the present invention, R2 and R3 are each independently a phenyl group or a substituted phenyl group.

[0237] In one embodiment of the present invention, R2 and R3 are tertiary butyl groups.

[0238] In one embodiment of the present invention, R2 and R3 are hydrogen.

[0239] In one embodiment of the present invention, M is hafnium (Hf).

[0240] In one embodiment of the present invention, the third ethylene copolymer is produced using a crosslinked metallocene catalyst having the following formula (Ia). [ka]

[0241] In formula (Ia), G is a Group 14 element selected from carbon, silicon, germanium, tin, or lead, and R1 is a hydrogen atom, C 1-20 Hydrocarbyl group, C 1-20 Alkoxy group or C 6-10 It is an aryloxy group, and R2 and R3 are independently hydrogen atoms and C 1-20 Hydrocarbyl group, C 1-20 Alkoxy group or C 6-10 Selected from aryloxy groups, R4 and R5 are independently a hydrogen atom and an unsubstituted carbon atom. 1-20 Hydrocarbyl group, substituted C 1-20 Hydrocarbyl group, C 1-20 Alkoxy group or C 6-10 Selected from aryloxy groups, Q is an independently activatable leaving ligand.

[0242] In this disclosure, “activatable” means that ligand Q is cleaved from a metal center M by a protonolysis reaction or abstracted from a metal center M by a suitable acidic or electrophilic catalytic activating compound (also called a “co-catalyst” compound), specific examples of which are described below. The activatable ligand Q may be converted to another ligand that is cleaved or abstracted from the metal center M (for example, a halide may be converted to an alkyl group). Although not intended to be bound by any particular theory, protonolysis or abstraction reactions generate an active “cationic” metal center capable of polymerizing olefins.

[0243] In embodiments of the present invention, the activatable ligand Q is a hydrogen atom, a halogen atom, and C 1-20 Hydrocarbyl group, C 1-20 Alkoxy groups and C 6-10 Aryl group or aryloxy group (each hydrocarbyl group, alkoxy group, aryl group, or aryloxy group may be unsubstituted or substituted with one or more halogens or other groups), C 1-8 Alkyl alkyl group, C 1-8 Alkoxy group, C 6-10Q is independently selected from the group consisting of an aryl group or aryloxy group, an amide group or a phosphine group, but Q is not a cyclopentadienyl group. The two Q ligands may be bonded to each other, for example, to form a substituted or unsubstituted diene ligand (e.g., 1,3-butadiene) or a delocalized heteroatom-containing group such as an acetate base or acetamidinate group. In preferred embodiments of the present invention, each Q is a halogen atom, C 1-4 The ligand Q is independently selected from the group consisting of alkyl groups and benzyl groups. Particularly preferred activatable ligands Q are monoanionic, such as halides (e.g., chlorides) and hydrocarbyl groups (e.g., methyl groups, benzyl groups).

[0244] In embodiments of the present invention, the third homogeneous catalyst used to produce the third ethylene copolymer is a molecular formula [(2,7-tBu2Flu)Ph2C(Cp)HfCl2] This is diphenylmethylene(cyclopentadienyl)(2,7-di-t-butylfluorenyl)hafnium dichloride, which has the following properties:

[0245] In embodiments of the present invention, the third homogeneous catalyst used to produce the third ethylene copolymer is a molecular formula [(2,7-tBu2Flu)Ph2C(Cp)HfMe2] This is diphenylmethylene(cyclopentadienyl)(2,7-di-t-butylfluorenyl)hafniumdimethyl, which has the following properties:

[0246] In embodiments of the present invention, the third homogeneous catalyst is a phosphinimine catalyst represented by the following formula (II). (L A ) a M * (PI) b (Q) n (II) Here, (L A ) represents a bulky ligand, M *represents a metal atom, PI represents a phosphinimine ligand, Q is an independently activatable leaving group ligand, a is 0 or 1, b is 1 or 2, (a+b) is 2, n is 1 or 2, and the sum of (a+b+n) is metal M * It is equal to the valence of [the atom].

[0247] Embodiments of the present invention, L A This is selected from the group consisting of unsubstituted cyclopentadienyl, substituted cyclopentadienyl, unsubstituted indenyl, substituted indenyl, unsubstituted fluorenyl, and substituted fluorenyl.

[0248] Embodiments of the present invention, M * This is a metal selected from the group consisting of titanium, hafnium, and zirconium.

[0249] In more limited embodiments of the present invention, the bulky ligand L of formula (II) A This includes unsubstituted or substituted cyclopentadienyl ligands, or cyclopentadienyl-type ligands, heteroatom-substituted and / or heteroatom-containing cyclopentadienyl-type ligands. In another, less limiting embodiment, bulky ligand L of formula (II) A This includes cyclopentaphenantrenyl ligands, unsubstituted or substituted indenyl ligands, benzindenyl ligands, unsubstituted or substituted fluorenyl ligands, octahydrofluorenyl ligands, cyclooctatetraendiyl ligands, cyclopentacyclododecene ligands, azenyl ligands, azulene ligands, pentalene ligands, phosphoyl ligands, phosphinimine ligands, pyrrolyl ligands, pyrazolyl ligands, carbazolyl ligands, borabenzene ligands, etc., and their hydrogenated derivatives (e.g., tetrahydroindenyl ligands). In another embodiment, L A is metal M * It may be any other ligand structure capable of η-binding to it, and the above embodiment includes η 3 Combination and η 5 Both types of joining are included. In another embodiment, L AL contains one or more heteroatoms such as nitrogen, silicon, boron, germanium, sulfur, and phosphorus in combination with carbon atoms, and may form an open ring structure, an acyclic structure, or a fused ring or ring system (e.g., a heterocyclopentadienyl auxiliary ligand). A These include bulky amides, phosphaides, alkoxides, alyroxides, imides, carbolides, borolides, porphyrins, phthalocyanines, choline, and other polyazomacrocycles.

[0250] In one embodiment of the present invention, metal M * It is titanium (Ti).

[0251] In one embodiment of the present invention, the phosphinimine ligand PI is defined by formula (III). (R p )3P = N - (III) Here, R p The group consists of a hydrogen atom, a halogen atom, a hydrocarbyl group having 1 to 20 carbon atoms (the hydrocarbyl group may be unsubstituted or substituted with one or more halogen atoms), C 1-8 Alkoxy group, C 6-10 Aryl group, C 6-10 Aryloxy group, amide group, formula -Si(R s )3 represents a silyl group (where R s Each group is independent of the hydrogen atom and C. 1-8 Alkyl or alkoxy group, C 6-10 Aryl group, C 6-10 (Selected from aryloxy groups), or formula -Ge(R G )3 represents a germanyl group (where R G The basis is R in this paragraph s They are selected independently from (which are defined similarly to) the others.

[0252] In addition to the first homogeneous catalyst molecule itself, the activated homogeneous catalyst system may further contain one or more alkylaluminoxane co-catalysts and ionic activators. The homogeneous catalyst system may optionally contain sterically hindered phenols.

[0253] Although the precise structure of alkylaluminoxanes is uncertain, those skilled in the art generally agree that alkylaluminoxanes are oligomeric species containing repeating units of the following general formula. (R)2AlO-(Al(R)-O) n -Al(R)2 Here, the R groups are identical or different linear, branched, or cyclic hydrocarbyl groups containing 1 to 20 carbon atoms, and n is 0 to about 50. A non-limiting example of alkylaluminoxane is methylaluminoxane (or MAO), in which case each R group is a methyl group.

[0254] In one embodiment of the present invention, R in alkylaluminoxane is a methyl group, and m is 10 to 40.

[0255] In one embodiment of the present invention, the co-catalyst is a modified methylaluminoxane (MMAO).

[0256] As is well known in the art, alkylaluminoxanes can play a dual role as both alkylating agents and activators. Therefore, alkylaluminoxane co-catalysts are often used in combination with activatable ligands such as halogens.

[0257] Generally, ionic activators consist of a cation and a bulky anion, the latter being substantially non-coordinating. A non-limiting example is a four-coordination boron ionic activator, in which four ligands are bonded to a boron atom. A non-limiting example of a boron ionic activator is represented by the following formula. [R 5 ] + [B(R 7 )4] - Here, B represents a boron atom, and R5 is an aromatic hydrocarbyl group (e.g., triphenylmethyl cation), and each R 7 C is independent of fluorine atoms, or whether or not it is substituted with fluorine atoms. 1-4 A phenyl group substituted with 3 to 5 substituents selected from alkyl or alkoxy groups, or an unsubstituted phenyl group, or a group of the formula -Si(R 9 Selected from the silyl groups represented by )3, each R 9 These are independently hydrogen atoms or C 1-4 Selected from alkyl groups. [(R 8 ) t ZH] + [B(R 7 )4] - Here, B is a boron atom, H is a hydrogen atom, Z is a nitrogen atom or a phosphorus atom, t is 2 or 3, and R 8 is C 1-8 Alkyl alkyl group, C 1-4 A phenyl group that is substituted with up to three alkyl groups or is unsubstituted, or R 8 One of these is selected from those in which a nitrogen atom and R combine to form an anilinium group. 7 This is the same as the definition above.

[0258] In both equations, R 7A non-limiting example is the pentafluorophenyl group. In general, boron ionic activators can be described as salts of tetra(perfluorophenyl)boron. Non-limiting examples include anilinium salts, carbonium salts, oxonium salts, phosphonium salts, and sulfonium salts, with anilinium and trityl (or triphenylmethylium) being preferred. Other 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-diethylanilinium tetra(phenyl)n- Butylboron, N,N-2,4,6-pentamethylaniliniumtetra(phenyl)boron, di(isopropyl)ammoniumtetra(pentafluorophenyl)boron, dicyclohexylammoniumtetra(phenyl)boron, triphenylphosphoniumtetra(phenyl)boron, tri(methylphenyl)phosphoniumtetra(phenyl)boron, tri(dimethylphenyl)phosphoniumtetra(phenyl)boron, tropyliumtetrakis(pentafluorophenyl)borate, triphenylmethyliumtetrakis(pentafluorophenyl)borate, benzene(diazonium)tetrakis(pentafluorophenyl)borate, tropyliumtetrakis(2,3,5,6-tetrafluorophenyl)borate, triphenylmethyliumtetrakis(2,3,5,6-tetrafluorophenyl)borate, benzene(diazonium)tetrakis(3,Examples include 4,5-trifluorophenyl) borate, benzene(diazonium)tetrakis(3,4,5-trifluorophenyl) borate, tropyliumtetrakis(1,2,2-trifluoroethenyl) borate, triphenylmethyliumtetrakis(1,2,2-trifluoroethenyl) borate, benzene(diazonium)tetrakis(1,2,2-trifluoroethenyl) borate, tropyliumtetrakis(2,3,4,5-tetrafluorophenyl) borate, triphenylmethyliumtetrakis(2,3,4,5-tetrafluorophenyl) borate, and benzene(diazonium)tetrakis(2,3,4,5-tetrafluorophenyl) borate. Easily available commercially produced ionic activators include N,N-dimethylaniliniumtetrakis(pentafluorophenyl) borate and triphenylmethyliumtetrakis(pentafluorophenyl) borate.

[0259] Examples of non-limiting hindered phenols include butylated phenolic antioxidants, butylated hydroxytoluene, 2,6-di-tert-butyl-4-ethylphenol, 4,4'-methylenebis(2,6-di-tert-butylphenol), 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, and octadecyl-3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate.

[0260] To produce the activated homogeneous catalyst system of the present invention, the amounts and molar ratios of three or four components, including a first homogeneous catalyst, an alkylaluminoxane, an ionic activator, and an optional hindered phenol, are optimized.

[0261] In one embodiment of the present invention, the third homogeneous catalyst used to produce the third ethylene copolymer does not generate long-chain branching, and / or the third ethylene copolymer does not contain a measurable amount of long-chain branching.

[0262] In one embodiment of the present invention, the third homogeneous catalyst used to produce the third ethylene copolymer generates long-chain branching, and the third ethylene copolymer contains long-chain branching (hereinafter referred to as "LCB"). LCB is a known structural phenomenon in ethylene polymers and is widely known to those skilled in the art.

[0263] In one embodiment of the present invention, the third ethylene copolymer includes long-chain branching characterized by LCBF disclosed herein. In another embodiment, the upper limit of LCBF of the third ethylene copolymer may be about 0.5, in other cases about 0.4, and in yet another case about 0.3 (dimensionless). In yet another embodiment, the lower limit of LCBF of the third ethylene copolymer may be about 0.001, in other cases about 0.0015, and in yet another case about 0.002 (dimensionless).

[0264] In some embodiments of the present invention, the upper limit of the molecular weight distribution (Mw / Mn) of the third ethylene copolymer may be about 2.3, or about 2.2, or about 2.1, or about 2.0. In some embodiments of the present invention, the lower limit of the molecular weight distribution (Mw / Mn) of the third ethylene copolymer may be about 1.7, or about 1.8, or about 1.9.

[0265] In some embodiments of the present invention, the third ethylene copolymer may have a molecular weight distribution (Mw / Mn) of 2.3 or less, or less than 2.3, or 2.2 or less, or less than 2.2, or 2.1 or less, or less than 2.1. In some embodiments of the present invention, the third ethylene copolymer may have a molecular weight distribution (Mw / Mn) of about 1.7 to about 2.3, or about 1.8 to about 2.3, or about 1.8 to about 2.2.

[0266] In one embodiment of the present invention, the third ethylene copolymer has 25 to 50 short-chain branches per 1,000 carbon atoms. In yet another embodiment, the third ethylene copolymer may have 30 to 50, or 30 to 45, or 30 to 40, or 31 to 55, or 31 to 50, or 33 to 45, or 33 to 40 short-chain branches per 1,000 carbon atoms. In yet another embodiment, the third ethylene copolymer may have 25 to 55, or 27 to 48, or 27 to 45 short-chain branches per 1,000 carbon atoms.

[0267] As is well known to those skilled in the art, the short-chain branching (i.e., short-chain branching per 1,000 carbon atoms) is due to at least one α-olefin present in the third ethylene copolymer, for example, 2 carbon atoms in the case of 1-butene, 4 carbon atoms in the case of 1-hexene, and 6 carbon atoms in the case of 1-octene.

[0268] In an embodiment of the present invention, the number of short-chain branches per 1,000 carbon atoms of the third ethylene copolymer is greater than the number of short-chain branches of the second ethylene copolymer, that is, the number of short-chain branches per 1,000 carbon atoms of the third ethylene copolymer (SCB3) and the number of short-chain branches per 1,000 carbon atoms of the second ethylene copolymer (SCB2) satisfy the inequality SCB3 > SCB2.

[0269] In one embodiment of the present invention, the third ethylene copolymer has a weight-average molecular weight (Mw) of 20 kg / mol to 50 kg / mol, or 20 kg / mol to 48 kg / mol, or 20 kg / mol to 46 kg / mol, or 23 kg / mol to 48 kg / mol, or 24 kg / mol to 46 kg / mol, or 25 kg / mol to 45 kg / mol.

[0270] In some embodiments of the present invention, the third ethylene copolymer has a weight average molecular weight that is less than both the weight average molecular weight of the first ethylene polymer and the weight average molecular weight of the second ethylene copolymer. That is, the weight average molecular weights of the first ethylene polymer, the second ethylene copolymer, and the third ethylene copolymer (Mw1, Mw2, and Mw3, respectively) satisfy the inequalities Mw3 < Mw1 and Mw3 < Mw2.

[0271] In some embodiments of the present invention, the upper limit of the weight percentage of the third ethylene copolymer in the ethylene polymer composition (i.e., the weight percentage of the third ethylene copolymer based on the total weight of the ethylene polymer composition) is about 20 wt%, or about 15 wt%, or about 12 wt%, or about 10 wt%, or about 8 wt%, or about 5 wt%. In some further embodiments, the lower limit of the weight percentage of the third ethylene copolymer is 0 wt%, or a value greater than 0 wt%, or about 1 wt%, or about 3 wt%, or about 5 wt%. In an embodiment, the third ethylene copolymer is present in the ethylene polymer composition in an amount of 0 to 20 wt%. In another embodiment, the third ethylene copolymer is present in the ethylene polymer composition in an amount greater than 0 and up to 20 wt%. In yet another embodiment, the third ethylene copolymer is present in the ethylene polymer composition in an amount of 0 to 10 wt%. In yet another embodiment, the third ethylene copolymer is present in the ethylene polymer composition in an amount greater than 0 and up to 10 wt%.

[0272] Ethylene polymer composition The ethylene polymer compositions disclosed herein are reactor blends of a first ethylene polymer, a second ethylene copolymer, and optionally a third ethylene copolymer. The term “reactor blend” refers to a blend formed during the polymerization reaction and is hereby distinguished from a physical post-reactor blend. The term “post-reactor blend” refers to a blend formed by combining two or more blend components, each of which has already been polymerized and recovered from the polymerization process. This recovery process may include, but is not limited to, catalyst deactivation, phase separation, defoliation of unreacted monomers and / or process solvents, pelletization, etc., and is subsequently combined with other blend components.

[0273] In one embodiment of the present invention, an ethylene polymer composition is produced by obtaining a first ethylene polymer using a first homogeneous catalyst in a first reactor, and then obtaining a second ethylene copolymer using a second homogeneous catalyst in a second reactor.

[0274] In one embodiment of the present invention, an ethylene polymer composition is produced by obtaining a first ethylene polymer using a first homogeneous catalyst in a first reactor, obtaining a second ethylene copolymer using a second homogeneous catalyst in a second reactor, and further obtaining a third ethylene copolymer using a third homogeneous catalyst in a third reactor.

[0275] In one embodiment of the present invention, an ethylene polymer composition is produced by forming a first ethylene polymer by polymerizing ethylene and optionally at least one α-olefin using a first homogeneous catalyst in a first reactor, and forming a second ethylene copolymer by polymerizing ethylene and at least one α-olefin using a second homogeneous catalyst in a second reactor.

[0276] In one embodiment of the present invention, an ethylene polymer composition is produced by forming a first ethylene homopolymer by polymerizing ethylene using a first homogeneous catalyst in a first reactor, and forming a second ethylene copolymer by polymerizing ethylene and at least one α-olefin using a second homogeneous catalyst in a second reactor.

[0277] In one embodiment of the present invention, an ethylene polymer composition is produced by forming a first ethylene homopolymer by polymerizing ethylene using a first homogeneous catalyst in a first reactor, and forming a second ethylene copolymer by polymerizing ethylene and at least one α-olefin using a second homogeneous catalyst in a second reactor.

[0278] In one embodiment of the present invention, an ethylene polymer composition is produced by polymerizing ethylene and at least one α-olefin using a first homogeneous catalyst in a first reactor to form a first ethylene copolymer, and by polymerizing ethylene and at least one α-olefin using a second homogeneous catalyst in a second reactor to form a second ethylene copolymer.

[0279] In one embodiment of the present invention, an ethylene polymer composition is produced by forming a first ethylene polymer by polymerizing ethylene and optionally at least one α-olefin using a first homogeneous catalyst in a first reactor, forming a second ethylene copolymer by polymerizing ethylene and at least one α-olefin using a second homogeneous catalyst in a second reactor, and further forming a third ethylene copolymer by polymerizing ethylene and at least one α-olefin using a third homogeneous catalyst in a third reactor.

[0280] In one embodiment of the present invention, an ethylene polymer composition is produced by forming a first ethylene homopolymer by polymerizing ethylene using a first homogeneous catalyst in a first reactor, forming a second ethylene copolymer by polymerizing ethylene and at least one α-olefin using a second homogeneous catalyst in a second reactor, and further forming a third ethylene copolymer by polymerizing ethylene and at least one α-olefin using a third homogeneous catalyst in a third reactor.

[0281] In one embodiment of the present invention, an ethylene polymer composition is produced by forming a first ethylene polymer by polymerizing ethylene and optionally at least one α-olefin using a first homogeneous catalyst in a first solution-phase polymerization reactor, and forming a second ethylene copolymer by polymerizing ethylene and at least one α-olefin using a second homogeneous catalyst in a second solution-phase polymerization reactor.

[0282] In one embodiment of the present invention, an ethylene polymer composition is produced by forming a first ethylene homopolymer by polymerizing ethylene using a first homogeneous catalyst in a first solution-phase polymerization reactor, and forming a second ethylene copolymer by polymerizing ethylene and at least one α-olefin using a second homogeneous catalyst in a second solution-phase polymerization reactor.

[0283] In one embodiment of the present invention, an ethylene polymer composition is produced by forming a first ethylene polymer by polymerizing ethylene and optionally at least one α-olefin using a first homogeneous catalyst in a first solution-phase polymerization reactor; forming a second ethylene copolymer by polymerizing ethylene and at least one α-olefin using a second homogeneous catalyst in a second solution-phase polymerization reactor; and forming a third ethylene copolymer by polymerizing ethylene and at least one α-olefin using a third homogeneous catalyst in a third solution-phase polymerization reactor.

[0284] In one embodiment of the present invention, an ethylene polymer composition is produced by forming a first ethylene homopolymer by polymerizing ethylene using a first homogeneous catalyst in a first solution-phase polymerization reactor, forming a second ethylene copolymer by polymerizing ethylene and at least one α-olefin using a second homogeneous catalyst in a second solution-phase polymerization reactor, and forming a third ethylene copolymer by polymerizing ethylene and at least one α-olefin using a third homogeneous catalyst in a third solution-phase polymerization reactor.

[0285] In one embodiment of the present invention, an ethylene polymer composition is produced by forming a first ethylene polymer by polymerizing ethylene and optionally at least one α-olefin using a first homogeneous catalyst in a first solution-phase polymerization reactor, forming a second ethylene copolymer by polymerizing ethylene and at least one α-olefin using a second homogeneous catalyst in a second solution-phase polymerization reactor, and wherein the first and second solution-phase polymerization reactors are configured in series with respect to each other.

[0286] In one embodiment of the present invention, an ethylene polymer composition is produced by forming a first ethylene homopolymer by polymerizing ethylene using a first homogeneous catalyst in a first solution-phase polymerization reactor, and forming a second ethylene copolymer by polymerizing ethylene and at least one α-olefin using a second homogeneous catalyst in a second solution-phase polymerization reactor, wherein the first and second solution-phase polymerization reactors are configured in series with respect to each other.

[0287] In one embodiment of the present invention, an ethylene polymer composition is produced by forming a first ethylene polymer by polymerizing ethylene and optionally at least one α-olefin using a first homogeneous catalyst in a first solution-phase polymerization reactor, forming a second ethylene copolymer by polymerizing ethylene and at least one α-olefin using a second homogeneous catalyst in a second solution-phase polymerization reactor, and wherein the first and second solution-phase polymerization reactors are configured in parallel with each other.

[0288] In one embodiment of the present invention, an ethylene polymer composition is produced by forming a first ethylene homopolymer by polymerizing ethylene using a first homogeneous catalyst in a first solution-phase polymerization reactor, and forming a second ethylene copolymer by polymerizing ethylene and at least one α-olefin using a second homogeneous catalyst in a second solution-phase polymerization reactor, wherein the first and second solution-phase polymerization reactors are configured in parallel with each other.

[0289] In one embodiment of the present invention, an ethylene polymer composition is produced by forming a first ethylene polymer by polymerizing ethylene and optionally at least one α-olefin using a first homogeneous catalyst in a first solution-phase polymerization reactor, forming a second ethylene copolymer by polymerizing ethylene and at least one α-olefin using a second homogeneous catalyst in a second solution-phase polymerization reactor, forming a third ethylene copolymer by polymerizing ethylene and at least one α-olefin using a third homogeneous catalyst in a third solution-phase polymerization reactor, wherein the first and second solution-phase polymerization reactors are configured in series with respect to each other.

[0290] In one embodiment of the present invention, an ethylene polymer composition is produced by forming a first ethylene homopolymer by polymerizing ethylene with a first homogeneous catalyst in a first solution-phase polymerization reactor, forming a second ethylene copolymer by polymerizing ethylene and at least one α-olefin with a second homogeneous catalyst in a second solution-phase polymerization reactor, forming a third ethylene copolymer by polymerizing ethylene and at least one α-olefin with a third homogeneous catalyst in a third solution-phase polymerization reactor, wherein the first and second solution-phase polymerization reactors are configured in series with respect to each other.

[0291] In one embodiment of the present invention, an ethylene polymer composition is produced by forming a first ethylene polymer by polymerizing ethylene and optionally at least one α-olefin using a first homogeneous catalyst in a first solution-phase polymerization reactor; forming a second ethylene copolymer by polymerizing ethylene and at least one α-olefin using a second homogeneous catalyst in a second solution-phase polymerization reactor; forming a third ethylene copolymer by polymerizing ethylene and at least one α-olefin using a third homogeneous catalyst in a third solution-phase polymerization reactor, wherein at least two of the first, second, and third solution-phase polymerization reactors are configured in series with respect to each other.

[0292] In one embodiment of the present invention, an ethylene polymer composition is produced by forming a first ethylene homopolymer by polymerizing ethylene using a first homogeneous catalyst in a first solution-phase polymerization reactor, forming a second ethylene copolymer by polymerizing ethylene and at least one α-olefin using a second homogeneous catalyst in a second solution-phase polymerization reactor, forming a third ethylene copolymer by polymerizing ethylene and at least one α-olefin using a third homogeneous catalyst in a third solution-phase polymerization reactor, and wherein at least two of the first, second, and third solution-phase polymerization reactors are configured in series with respect to each other.

[0293] In one embodiment of the present invention, an ethylene polymer composition is produced by polymerizing ethylene and optionally at least one α-olefin using a first homogeneous catalyst in a first solution-phase polymerization reactor to form a first ethylene polymer, by polymerizing ethylene and at least one α-olefin using a second homogeneous catalyst in a second solution-phase polymerization reactor to form a second ethylene copolymer, and by polymerizing ethylene and at least one α-olefin using a third homogeneous catalyst in a third solution-phase polymerization reactor, wherein the first, second, and third solution-phase polymerization reactors are configured in series with respect to each other.

[0294] In one embodiment of the present invention, an ethylene polymer composition is produced by forming a first ethylene homopolymer by polymerizing ethylene using a first homogeneous catalyst in a first solution-phase polymerization reactor, forming a second ethylene copolymer by polymerizing ethylene and at least one α-olefin using a second homogeneous catalyst in a second solution-phase polymerization reactor, and forming a third ethylene copolymer by polymerizing ethylene and at least one α-olefin using a third homogeneous catalyst in a third solution-phase polymerization reactor, wherein the first, second, and third solution-phase polymerization reactors are configured in series with respect to each other.

[0295] In one embodiment of the present invention, an ethylene polymer composition is produced by polymerizing ethylene and optionally at least one α-olefin using a first homogeneous catalyst in a first solution-phase polymerization reactor to form a first ethylene polymer, by polymerizing ethylene and at least one α-olefin using a second homogeneous catalyst in a second solution-phase polymerization reactor to form a second ethylene copolymer, and by polymerizing ethylene and at least one α-olefin using a third homogeneous catalyst in a third solution-phase polymerization reactor, wherein the first, second, and third solution-phase polymerization reactors are configured in series with respect to each other.

[0296] In one embodiment of the present invention, an ethylene polymer composition is produced by polymerizing ethylene and optionally at least one α-olefin using a first homogeneous catalyst in a first solution-phase polymerization reactor to form a first ethylene polymer, by polymerizing ethylene and at least one α-olefin using a second homogeneous catalyst in a second solution-phase polymerization reactor to form a second ethylene copolymer, and by polymerizing ethylene and at least one α-olefin using a third homogeneous catalyst in a third solution-phase polymerization reactor, wherein the first, second, and third solution-phase polymerization reactors are configured in parallel with each other.

[0297] In one embodiment of the present invention, an ethylene polymer composition is produced by forming a first ethylene homopolymer by polymerizing ethylene using a first homogeneous catalyst in a first solution-phase polymerization reactor, forming a second ethylene copolymer by polymerizing ethylene and at least one α-olefin using a second homogeneous catalyst in a second solution-phase polymerization reactor, and forming a third ethylene copolymer by polymerizing ethylene and at least one α-olefin using a third homogeneous catalyst in a third solution-phase polymerization reactor, wherein the first, second, and third solution-phase polymerization reactors are configured in parallel with each other.

[0298] In one embodiment of the present invention, an ethylene polymer composition is produced by polymerizing ethylene and optionally at least one α-olefin using a first homogeneous catalyst in a first solution-phase polymerization reactor to form a first ethylene polymer; polymerizing ethylene and at least one α-olefin using a second homogeneous catalyst in a second solution-phase polymerization reactor to form a second ethylene copolymer; and polymerizing ethylene and at least one α-olefin using a third homogeneous catalyst in a third solution-phase polymerization reactor to form a third ethylene copolymer, wherein the first and second solution-phase polymerization reactors are configured in series with each other, and the third solution-phase polymerization reactor is configured in parallel with the first and second reactors.

[0299] In one embodiment of the present invention, an ethylene polymer composition is produced by forming a first ethylene homopolymer by polymerizing ethylene using a first homogeneous catalyst in a first solution-phase polymerization reactor, forming a second ethylene copolymer by polymerizing ethylene and at least one α-olefin using a second homogeneous catalyst in a second solution-phase polymerization reactor, and forming a third ethylene copolymer by polymerizing ethylene and at least one α-olefin using a third homogeneous catalyst in a third solution-phase polymerization reactor, wherein the first and second solution-phase polymerization reactors are configured in series with each other, and the third solution-phase polymerization reactor is configured in parallel with the first and second reactors.

[0300] In one embodiment of the present invention, 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.

[0301] In one embodiment of the present invention, 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 type reactor.

[0302] In one embodiment of the present invention, 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.

[0303] In one embodiment of the present invention, the first and second solution-phase reactors used as solution-phase polymerization reactors are continuous-stirred tank reactors, and the third solution-phase reactor used as a solution-phase polymerization reactor is a tubular reactor.

[0304] In one embodiment of the present invention, in solution polymerization, monomers are dissolved or dispersed in the solvent before being supplied to the reactor (or, in the case of gaseous monomers, supplied to the reactor and dissolved in the reaction mixture). Before mixing, the solvent and monomers are generally purified to remove water, oxygen, or metal impurities that may act as catalyst poisons. Purification of the raw materials is carried out according to standard methods of those skilled in the art, for example, molecular sieves, alumina layers, and oxygen removal catalysts are used for the purification of monomers. The solvent itself is also preferably treated in a similar manner (e.g., methylpentane, cyclohexane, hexane, or toluene).

[0305] In one embodiment of the present invention, the raw materials may be heated or cooled before being supplied to the reactor.

[0306] In one embodiment of the present invention, the catalyst components may be premixed in the reaction solvent or supplied to the reactor as a separate stream. In some cases, it may be desirable to premix the catalyst components to give them reaction time before they enter the reaction. Such “in-line mixing” techniques are described in numerous patents in the name of DuPont Canada Inc. (see, for example, U.S. Patent No. 5,589,555 issued December 31, 1996).

[0307] Solution polymerization processes for the polymerization or copolymerization of ethylene are known in the art (see, for example, U.S. Patents 6,372,864 and 6,777,509). These processes are carried out in the presence of an inert hydrocarbon solvent. Various solvents can be used as process solvents in solution-phase polymerization reactors, but are not limited to linear, branched, or cyclic C5-C5 polymers. 12 Alkanes are included. Examples of α-olefins (not limited to) include propene-1, butene-1, pentene-1, hexene-1, and octene-1. Suitable catalyst solvents include aliphatic hydrocarbons and aromatic hydrocarbons. Examples of aliphatic catalyst solvents (not limited to) include linear, branched, or cyclic C5-C5 12Aliphatic hydrocarbons, such as pentane, methylpentane, hexane, heptane, octane, cyclohexane, cyclopentane, methylcyclohexane, hydrolyzed naphtha, or combinations thereof, are included. Examples of aromatic catalyst solvents, not limited to these, include benzene, toluene (methylbenzene), ethylbenzene, o-xylene (1,2-dimethylbenzene), m-xylene (1,3-dimethylbenzene), p-xylene (1,4-dimethylbenzene), mixtures of xylene isomers, hemeritene (1,2,3-trimethylbenzene), pseudodocumene (1,2,4-trimethylbenzene), mesitylene (1,3,5-trimethylbenzene), mixtures of trimethylbenzene isomers, prehenytene (1,2,3,4-tetramethylbenzene), durene (1,2,3,5-tetramethylbenzene), mixtures of tetramethylbenzene isomers, pentamethylbenzene, hexamethylbenzene, and combinations thereof.

[0308] The polymerization temperature in a conventional solution process may be between approximately 80°C and approximately 300°C. In one embodiment of the present disclosure, the polymerization temperature in the solution process is between approximately 120°C and approximately 250°C. The polymerization pressure in the solution process may be a “medium-pressure process,” meaning that the pressure in the reactor is less than approximately 6,000 psi (approximately 42,000 kilopascals (kPa)). In one embodiment of the present disclosure, the polymerization pressure in the solution process may be between approximately 10,000 kPa and approximately 40,000 kPa, or between approximately 14,000 kPa and approximately 22,000 kPa (i.e., between approximately 2,000 psi and approximately 3,000 psi).

[0309] In one embodiment of the present disclosure, the ethylene polymer composition may contain at least 1 mol% of at least one α-olefin.

[0310] In one embodiment of the present disclosure, the ethylene polymer composition may contain at least 3 mol% of at least one α-olefin.

[0311] In one embodiment of the present disclosure, the ethylene polymer composition may contain at least one α-olefin in an amount from about 1 mol% to about 10 mol%.

[0312] In one embodiment of the present disclosure, the ethylene polymer composition may contain at least one α-olefin in an amount of about 3 mol% to about 10 mol%.

[0313] In one embodiment of the present disclosure, the ethylene polymer composition may contain at least one α-olefin in an amount of about 3 mol% to about 8 mol%.

[0314] In one embodiment of the present disclosure, the ethylene polymer composition may contain ethylene and at least one α-olefin selected from the group consisting of butene-1, hexene-1, octene-1, and mixtures thereof.

[0315] In one embodiment of the present disclosure, the ethylene polymer composition may contain ethylene and at least one α-olefin selected from the group consisting of hexene-1, octene-1, and mixtures thereof.

[0316] In one embodiment of the present disclosure, the ethylene polymer composition may contain ethylene and octen-1.

[0317] In one embodiment of the present disclosure, the ethylene polymer composition may contain ethylene and at least 1 mole percent of octene-1.

[0318] In one embodiment of the present disclosure, the ethylene polymer composition may contain ethylene and 1 mole percent to 10 mole percent of octen-1.

[0319] In one embodiment of the present disclosure, the ethylene polymer composition may contain ethylene and 3 mole percent to 8 mole percent of octen-1.

[0320] In some embodiments of this disclosure, the ethylene polymer composition is approximately 0.900 g / cm³ 3 From approximately 0.920 g / cm³ 3 The density is approximately 0.902 g / cm³. 3 Approximately 0.919 g / cm³ 3 It may have a density of 0.903 g / cm³. In some preferred embodiments, the ethylene polymer composition has a density of 0.903 g / cm³. 3 From 0.916 g / cm³ 3 It has a density of preferably 0.903 g / cm³. 3 From 0.914 g / cm³ 3 It has a density of 0.905 g / cm³, more preferably 0.905 g / cm³. 3 From 0.912 g / cm³ 3 It has a density of 0.905 g / cm³, and more preferably 0.905 g / cm³. 3 From 0.910 g / cm³ 3 It may have a density of [a certain value].

[0321] In some embodiments of this disclosure, the melt index (I2) of the ethylene polymer composition is approximately 0.1 dg / min to approximately 10.0 dg / min, or approximately 0.3 dg / min to approximately 10.0 dg / min, or approximately 0.5 dg / min to approximately 10.0 dg / min, or approximately 0.7 dg / min to approximately 10.0 dg / min, or approximately 1.0 dg / min to approximately 8.0 dg / min, or approximately 1.5 dg / min to approximately 6.0 dg / min, or approximately 2.0 dg / min to approximately 5.0 dg / min, or approximately 2.0 dg / min to approximately 6.0 dg / min, or approximately 2.0 dg / min to approximately 8.0 dg / min, or approximately 2.0 dg / min to approximately 10.0 dg / min, or approximately 2.5 It may be from dg / min to approximately 10.0 dg / min, or from approximately 3.0 dg / min to approximately 10.0 dg / min, or from approximately 3.0 dg / min to approximately 8.0 dg / min, or from approximately 3.0 dg / min to approximately 6.0 dg / min, or from approximately 3.0 dg / min to approximately 5.0 dg / min.

[0322] In some embodiments of this disclosure, the high load melt index (I 21The dosage may be approximately 10 dg / min to approximately 10,000 dg / min, or approximately 10 dg / min to approximately 1,000 dg / min, or approximately 10 dg / min to approximately 500 dg / min, or approximately 10 dg / min to approximately 250 dg / min, or approximately 10 dg / min to approximately 150 g / 10 min.

[0323] In some embodiments of this disclosure, the melt flow ratio (I) of the ethylene polymer composition is 21 The melt flow ratio (I2) of the ethylene polymer composition may be about 15 to about 1,000, or about 15 to about 100, or about 15 to about 75, or about 15 to about 50, or about 15 to about 40, or about 18 to about 50, or about 20 to about 75, or about 20 to about 50, or about 20 to about 45, or about 20 to about 40, or about 20 to about 38, or about 20 to about 35, or about 24 to about 48, or about 27 to about 45, or about 30 to about 42. In some embodiments of the present disclosure, the melt flow ratio (I2) of the ethylene polymer composition is 21 The melt flow ratio (I²) of the ethylene polymer composition may be 20 to 50. In some embodiments of this disclosure, the melt flow ratio (I²) of the ethylene polymer composition is used. 21 / I2) may be less than approximately 45, or less than approximately 40, or less than approximately 35.

[0324] In some embodiments of this disclosure, the weight-average molecular weight (Mw) of the ethylene polymer composition may be about 50 kg / mol to about 200 kg / mol, or about 50 kg / mol to about 180 kg / mol, or about 60 kg / mol to about 160 kg / mol, or about 65 kg / mol to about 100 kg / mol, or about 70 kg / mol to about 100 kg / mol, or about 70 kg / mol to about 95 kg / mol, or about 70 kg / mol to about 90 kg / mol.

[0325] In some of the embodiments of this disclosure, the number-average molecular weight (Mn) of the ethylene polymer composition may be about 5 kg / mol to about 35 kg / mol, or about 10 kg / mol to about 35 kg / mol, or about 10 kg / mol to about 30 kg / mol, or about 15 kg / mol to about 30 kg / mol, or about 15 kg / mol to about 25 kg / mol.

[0326] In embodiments of this disclosure, the lower limit of the molecular weight distribution (Mw / Mn) of the ethylene polymer composition may be 2.3, 2.4, 2.5, or 2.6. In embodiments of this disclosure, the upper limit of the molecular weight distribution (Mw / Mn) of the ethylene polymer composition may be 6.0, 5.5, 5.0, 4.5, 4.0, 3.75, or 3.5.

[0327] In embodiments of this disclosure, the molecular weight distribution (Mw / Mn) of the ethylene polymer composition may be 2.3 to 6.0, or 2.3 to 5.5, or 2.3 to 5.0, or 2.3 to 4.5, or 2.3 to 4.0, or 2.3 to 3.75, or 2.3 to 3.5, or 2.4 to 5.5, or 2.4 to 4.5, or 2.4 to 4.0, or 2.4 to 3.75, or 2.4 to 3.5, or 2.5 to 5.5, or 2.5 to 5.0, or 2.5 to 4.5, or 2.5 to 4.0, or 2.5 to 3.75, or 2.5 to 3.5, or 2.6 to 3.3. In some embodiments, the molecular weight distribution (Mw / Mn) of the ethylene polymer composition may be 2.3 to 5.0.

[0328] In embodiments of this disclosure, the z-average molecular weight distribution (Mz / Mw) of the ethylene polymer composition may be 4.0 or less, or less than 4.0, or 3.5 or less, or less than 3.5, or 3.0 or less, or less than 3.0, or 2.75 or less, or less than 2.75, or 2.50 or less, or less than 2.50. In embodiments of this disclosure, the z-average molecular weight distribution (Mz / Mw) of the ethylene polymer composition may be 1.5 to 4.0, or 1.5 to 3.5, or 1.75 to 3.5, or 1.75 to 3.0, or 1.75 to 2.5, or 2.0 to 4.0, or 2.0 to 3.5, or 2.0 to 3.0, or 2.0 to 2.75.

[0329] In one embodiment of this disclosure, an ethylene polymer composition has a unimodal profile in a gel permeation chromatogram prepared according to the method of ASTM D6474-99. "Unimodal" as used herein means that only one prominent peak or maximum is observed in the GPC curve. A unimodal profile also includes a broad unimodal profile. In contrast, the term "bimodal" means that in addition to the first peak, there is a second peak or shoulder indicating a higher or lower molecular weight component (i.e., there are two maximums in the molecular weight distribution curve). "Bimodal" also means that there are two maximums in the molecular weight distribution curve prepared according to the method of ASTM D6474-99. The term "multimodal" indicates that two or more, usually three or more, maximums are present in the molecular weight distribution curve prepared according to the method of ASTM D6474-99.

[0330] In one embodiment of this disclosure, the ethylene polymer composition has a typical copolymer monomer distribution profile when measured using GPC-FTIR. In this specification, "typical" means a distribution in which the amount of copolymer monomer introduced decreases monotonically with increasing molecular weight when measured using GPC-FTIR.

[0331] In one embodiment of this disclosure, the ethylene polymer composition has a partially normal copolymer monomer distribution profile when measured using GPC-FTIR. In this specification, "partially normal" means a distribution in which, when measured using GPC-FTIR, the amount of copolymer monomer introduced decreases with increasing molecular weight, and then increases with increasing molecular weight. A partially normal copolymer monomer distribution exhibits a minimum value.

[0332] In one embodiment of this disclosure, an ethylene polymer composition has a partially inverted copolymer monomer distribution profile when measured using GPC-FTIR. In this specification, "partially inverted" means a distribution in which, when measured using GPC-FTIR, the amount of copolymer monomer introduced increases with increasing molecular weight, and then decreases with increasing molecular weight. A partially inverted copolymer monomer distribution exhibits a maximum value.

[0333] In this specification, the terms “normal” and “reverse” are used in contrast to the term “flat.” When measured using GPC-FTIR, if the amount of copolymer monomer introduced is approximately constant with respect to molecular weight, the copolymer monomer distribution is described as “flat” or “homogeneous.”

[0334] In one embodiment, the ethylene polymer composition, in GPC-FTIR analysis, has a copolymer monomer distribution profile with a secant slope such that the number of short-chain branches per 1,000 carbon atoms is -55 or greater (≧) and -20 or less (≦). Here, the secant slope is defined as the value obtained by subtracting the number of short-chain branches per 1,000 carbon atoms at a molecular weight of 30,000 g / mol from the number of short-chain branches per 1,000 carbon atoms at a molecular weight of 300,000 g / mol. Furthermore, in another embodiment of the present invention, the ethylene polymer composition, in GPC-FTIR analysis, has a secant slope such that the number of short-chain branches per 1,000 carbon atoms is -50 or greater (≧) and -20 or less (≦), or -45 or greater (≧) and -20 or less (≦), or -40 or greater (≧) and -20 or less (≦), or -35 or greater (≧) and -25 or less (≦).

[0335] In one embodiment, the ethylene polymer composition has a stress index defined as log10(I6 / I2) / log10(6.48 / 2.16) and is 1.60 or less (≦). Furthermore, in another embodiment of the present invention, the ethylene polymer composition has a stress index expressed as log10(I6 / I2) / log10(6.48 / 2.16) that is less than 1.55, less than 1.50, less than 1.45, or less than 1.40.

[0336] In some embodiments, the ethylene polymer composition has a dimensionless long-chain branching coefficient (LCBF) of 0.001 or greater (≧).

[0337] In some embodiments, the ethylene polymer composition has a dimensionless long-chain branching coefficient (LCBF) of 0.001 or greater (≧) and 0.01 or less (≦).

[0338] In some other embodiments, the ethylene polymer composition has a Vicat softening temperature of over 85°C or over 88°C, as measured using ASTM 1525-17 (August 1, 2017).

[0339] Flexible molded products The ethylene polymer compositions disclosed herein can be molded into flexible articles such as single-layer or multi-layer films.

[0340] A non-limiting example of a process for manufacturing single-layer or multi-layer films is the blow molding process.

[0341] In the blown film extrusion process described herein, an extruder heats, melts, mixes, and conveys a thermoplastic resin or a blend of thermoplastic resins. After melting, the thermoplastic resin is extruded through an annular die to produce a thermoplastic resin tube. In the case of co-extrusion, multiple extruders are used to produce a multi-layer thermoplastic resin tube. The temperature of the extrusion process is determined primarily by the thermoplastic resin or blend of thermoplastic resins being processed, and is determined based on, for example, the melting point or glass transition temperature of the thermoplastic resin, as well as the desired melt viscosity. For polyolefins, a typical extrusion temperature is 330°F to 550°F (166°C to 288°C). After extrusion from the annular die, the thermoplastic resin tube is expanded with air, cooled, solidified, and taken up through a pair of nip rollers. Due to the air expansion, the diameter of the tube increases, and bubbles of the desired size are formed. Due to the traction of the nip rollers, the bubbles are stretched in the machine direction (MD). Thus, the bubbles are stretched in two directions: the transverse direction (TD), where the diameter of the bubbles increases due to the expanding air, and the machine direction (MD), where they are stretched by the nip rollers. As a result, the physical properties of blown films are usually anisotropic, meaning that their physical properties differ between the MD and TD directions. For example, the tear strength and tensile properties of a film usually differ between the MD and TD directions. Some prior art documents use the terms "cross direction" or "CD," which are synonymous with "transverse direction" or "TD" as used herein.

[0342] In the blown film process described herein, air is blown around the outer bubble to cool the thermoplastic resin extruded from the annular die. The final width of the film is determined by controlling the expanding air, i.e., the internal bubble pressure, in other words, by increasing or decreasing the bubble diameter. The film thickness is adjusted by controlling the drawdown speed, mainly by increasing or decreasing the speed of the nip roller. After passing through the nip roller, the bubble or tube is crushed and slit along the direction of the machine to form a sheet. Each sheet is wound onto a film roll. Each roll is further slit to produce films of the desired width. Each film roll is further processed into the various consumer products described below.

[0343] An example of another process for manufacturing a single-layer or multi-layer film as described herein is the cast film process.

[0344] Similarly, the cast film process can use one or more extruders, but various thermoplastic materials are metered and fed into flat dies rather than tubes and extruded into single-layer or multi-layer sheets. In the cast film process, the extruded sheets are solidified on cooling rolls.

[0345] In the cast film process, the film is extruded from a flat die onto a cooling roll or nip roll, which may be equipped with a vacuum box and / or air knife. The cast film may be a single layer or a multilayer co-extruded film obtained by various extrusions through one or more dies. The resulting film may be used as is, or it may be laminated with other films or substrates, for example, by heat lamination, adhesive lamination, or direct extrusion onto a substrate. The resulting films and laminates may be subjected to other molding processes such as embossing, stretching, and vacuum forming. Surface treatments such as corona treatment may be applied, and the film may be printed.

[0346] Examples of further single-layer or multilayer film manufacturing processes include lamination and coating processes, such as extrusion lamination, adhesive lamination, or extrusion coating, of a single-layer or multilayer film containing the ethylene polymer composition according to the present invention. In extrusion lamination and adhesive lamination, two or more substrates are joined by a thermoplastic resin or adhesive, respectively. In extrusion coating, a thermoplastic resin is applied to the surface of a substrate. These processes are known to those skilled in the art. Adhesive lamination and extrusion lamination are frequently used to join dissimilar materials, and examples, not limited to, include joining a paper web to a thermoplastic resin web, joining a web containing aluminum foil to a thermoplastic resin web, or joining two chemically incompatible thermoplastic resin webs (e.g., a web containing the ethylene copolymer product of the present invention to a polyester or polyamide web). Before lamination, the web containing the ethylene copolymer product of the present invention may be single-layer or multilayer. Before lamination, each web may be surface-treated to improve bondability, a non-limited example being corona treatment. The primary web or film may have a secondary web laminated on its top, bottom, or both top and bottom surfaces. Secondary and tertiary webs can also be laminated onto the primary web, where the secondary and tertiary webs have different chemical compositions. In non-limiting examples, the secondary or tertiary web may include a web containing a barrier resin layer such as polyamide, polyester, and polypropylene, or EVOH. Such a web may be made of, for example, silicon dioxide (SiO₂). x ) and aluminum oxide (AlO x It may also include a gas-phase vapor-deposited barrier layer such as a thin layer of ). The multilayer web (or film) may contain 3, 5, 7, 9, 11 or more layers.

[0347] The ethylene polymer composition according to the present invention can be converted into single-layer or multi-layer films of a wide range of thicknesses, depending on the end application. A non-limiting example is a film for food packaging, in which case the thickness may range from about 0.5 mils to about 10 mils.

[0348] The ethylene polymer compositions disclosed herein can be used in single-layer films, which may contain two or more ethylene polymer compositions described herein and / or additional ethylene-based or non-ethylene-based polymers. The lower limit of the weight percentage of the ethylene polymer composition in the single-layer film may be about 3% by weight, about 10% by weight in other embodiments, and about 30% by weight in yet another embodiment. The upper limit of the weight percentage of the ethylene polymer composition in the single-layer film may be 100% by weight, about 90% by weight in other embodiments, and about 70% by weight in yet another embodiment.

[0349] The ethylene polymer compositions disclosed herein can also be used in one or more layers of a multilayer film structure. Examples of non-limiting multilayer films include those having 3, 5, 7, 9, 11 or more layers. The thickness of a particular layer (including the ethylene polymer composition) within the multilayer film structure may be about 5% of the total multilayer film thickness, about 13.5% in other embodiments, about 15% in other embodiments, about 20% in other embodiments, and about 25% in yet another embodiment. In other embodiments, the thickness of a particular layer (including the ethylene polymer composition) within the multilayer film structure may be about 95% of the total multilayer film thickness, about 80% in other embodiments, and about 65% in yet another embodiment. Each layer of the multilayer film structure may contain two or more ethylene polymer compositions and / or additional polyethylene.

[0350] The ethylene polymer compositions disclosed herein can be used in a wide range of molded articles comprising one or more layers (single or multilayer) films or film layers. Non-limiting examples of such molded articles include food packaging films (for fresh and frozen foods, liquids, powders, and granular foods).

[0351] The films used in the molded articles described in this section may optionally contain additives and auxiliary agents depending on their intended use. Non-limiting examples of additives and auxiliary agents include antiblocking agents, antioxidants, heat stabilizers, lubricants, processing aids, antistatic agents, colorants, dyes, fillers, light stabilizers, light absorbers, lubricants, pigments, plasticizers, nucleating agents, and combinations thereof.

[0352] One aspect of the present invention is a total polyethylene film layer comprising the ethylene polymer composition described herein.

[0353] In one embodiment of the present invention, the entire polyethylene film layer contains 90% or more, 93%, 95%, 97%, 99%, or 100% of one or more ethylene polymers, based on the total weight of the film layer.

[0354] In one embodiment of the present invention, the entire polyethylene film layer is a blown film.

[0355] In one embodiment of the present invention, the entire polyethylene film layer is a cast film.

[0356] In one embodiment of the present invention, the total polyethylene film layer has a thickness of 0.5 mils to 10 mils.

[0357] In one embodiment of the present invention, the entire polyethylene film layer has a density of 0.910 g / cm³. 3 From 0.940 g / cm³ 3 The present invention further comprises linear low-density polyethylene (LLDPE) having a melt index I2 of 0.1 dg / min to 10 dg / min.

[0358] In one embodiment of the present invention, the total polyethylene film layer comprises 10% to 40% by weight of linear low-density polyethylene (LLDPE) and 60% to 90% by weight of the ethylene polymer composition described herein.

[0359] In one embodiment of the present invention, linear low-density polyethylene (LLDPE) is an ethylene copolymer containing at least one α-olefin.

[0360] In one embodiment of the present invention, linear low-density polyethylene (LLDPE) is at least one C3-C 20 It is an ethylene copolymer containing α-olefin.

[0361] In one embodiment of the present invention, linear low-density polyethylene is an ethylene copolymer containing at least one of butene-1, hexene-1, and octene-1.

[0362] In one embodiment of the present invention, linear low-density polyethylene is an ethylene copolymer of ethylene and octene-1.

[0363] In one embodiment of the present invention, linear low-density polyethylene is ethylene and at least one C3-C 20 It is an ethylene copolymer with an α-olefin, and contains at least 70% by weight of ethylene, or at least 80% by weight of ethylene, or at least 90% by weight of ethylene.

[0364] In one embodiment of the present invention, the linear low-density polyethylene is an ethylene copolymer of ethylene and octene-1, and contains at least 70% by weight of ethylene, or at least 80% by weight of ethylene, or at least 90% by weight of ethylene.

[0365] In one embodiment of the present invention, the linear low-density polyethylene has a density of 0.910 g / cm³. 3 ~0.940g / cm 3 , or 0.910 g / cm³ 3 ~0.939 g / cm³ 3 , or 0.910 g / cm³ 3 ~0.936 g / cm³ 3 , or 0.910 g / cm³ 3 ~0.932 g / cm³ 3 , or 0.912 g / cm³ 3 ~0.940g / cm3 , or 0.912 g / cm³ 3 ~0.939 g / cm³ 3 , or 0.912 g / cm³ 3 ~0.936 g / cm³ 3 , or 0.912 g / cm³ 3 ~0.932 g / cm³ 3 , or 0.914 g / cm³ 3 ~0.930g / cm 3 , or 0.914 g / cm³ 3 ~0.939 g / cm³ 3 , or 0.914 g / cm³ 3 ~0.936 g / cm³ 3 , or 0.914 g / cm³ 3 ~0.932 g / cm³ 3 , or 0.916 g / cm³ 3 ~0.940g / cm 3 , or 0.916 g / cm³ 3 ~0.939 g / cm³ 3 , or 0.916 g / cm³ 3 ~0.936 g / cm³ 3 , or 0.916 g / cm³ 3 ~0.932 g / cm³ 3 , or 0.910 g / cm³ 3 ~0.930g / cm 3 , or 0.910 g / cm³ 3 ~0.928 g / cm³ 3 , or 0.910 g / cm³ 3 ~0.926 g / cm³ 3 , or 0.910 g / cm³ 3 ~0.924 g / cm³ 3 , or 0.912 g / cm³ 3 ~0.930g / cm 3 , or 0.912 g / cm³ 3 ~0.928 g / cm³ 3 , or 0.912 g / cm³ 3 ~0.926 g / cm³ 3 , or 0.912 g / cm³ 3 ~0.924 g / cm³ 3 , or 0.914 g / cm³ 3 ~0.930g / cm 3 , or 0.914 g / cm³ 3~0.928 g / cm³ 3 , or 0.914 g / cm³ 3 ~0.926 g / cm³ 3 , or 0.914 g / cm³ 3 ~0.924 g / cm³ 3 That is the case.

[0366] In one embodiment of the present invention, the linear low-density polyethylene has a melt index I2 of 0.01 dg / min to 100 dg / min, or 0.1 dg / min to 50 dg / min, or 0.1 dg / min to 10 dg / min, or 0.1 dg / min to 5 dg / min, or 0.5 dg / min to 5 dg / min, or 0.1 dg / min to 3 dg / min, or 0.5 dg / min to 3 dg / min.

[0367] The linear low-density polyethylene of this disclosure may be a homogeneous ethylene copolymer or a heterogeneous ethylene copolymer.

[0368] In embodiments of this disclosure, the linear low-density polyethylene may be unimodal or multimodal.

[0369] In embodiments of this disclosure, the linear low-density polyethylene has a molecular weight distribution Mw / Mn of less than 10.0, or less than 9.0, or less than 7.0, or less than 6.0, or less than 5.5, or less than 5.0, or less than 4.5, or less than 4.0, or less than 3.8. Furthermore, in some embodiments of the present disclosure, the linear low-density polyethylene has a Mw / Mn ratio of 2.0 to 10.0, or 2.0 to 8.0, or 2.0 to 6.0, or 2.0 to 5.5, or 2.0 to 5.0, or 2.0 to 4.5, or 2.0 to 4.0, or 2.2 to 6.0, or 2.2 to 5.5, or 2.2 to 5.0, or 2.2 to 4.5, or 2.2 to 4.0, or 2.5 to 6.0, or 2.5 to 5.5, or 2.5 to 5.0, or 2.5 to 4.5, or 2.5 to 4.0. In yet another embodiment, the linear low-density polyethylene has a Mw / Mn ratio of 3.0 to 5.5, or 3.0 to 4.5, or 3.0 to 4.0, or 3.2 to 5.5, or 3.2 to 5.0.

[0370] In embodiments of this disclosure, the linear low-density polyethylene has a z-average molecular weight distribution Mz / Mw of 1.5 to 6.0. Furthermore, in embodiments of this disclosure, the linear low-density polyethylene has a Mz / Mn ratio of 1.5 to 5.5, or 1.5 to 5.0, or 1.5 to 4.0, or 1.5 to 3.5, or 1.5 to 3.0, or 1.5 to 2.5.

[0371] In embodiments of the present disclosure, linear low-density polyethylene can be produced using a gas phase, a solution phase, or a slurry polymerization process, or any combination thereof, using any type of reactor or reactor configuration known to those skilled in the art, such as a fluidized bed gas-phase reactor, a loop reactor, a stirred-tank reactor, a parallel or series batch reactor, and / or any combination thereof.

[0372] In one embodiment of this disclosure, linear low-density polyethylene is produced by a solution-phase polymerization process.

[0373] In one embodiment of the present disclosure, linear low-density polyethylene is produced using a Ziegler-Natta catalyst.

[0374] In one embodiment of the present disclosure, linear low-density polyethylene is produced by a solution-phase polymerization process using a Ziegler-Natta catalyst.

[0375] In embodiments of this disclosure, linear low-density polyethylene may contain conventional additives, namely (1) primary antioxidants (e.g., hindered phenols containing vitamin E), (2) secondary antioxidants (e.g., phosphites and phosphonites), and (3) process aids (e.g., fluoroelastomers and / or polyethylene glycol-bound process aids).

[0376] In embodiments of this disclosure, other additives that may be added to linear low-density polyethylene include nitrones, antacids, ultraviolet absorbers, metal deactivators, pigments, dyes, fillers and reinforcing agents, nanoscale organic or inorganic materials, antistatic agents, lubricants such as calcium stearate, and lubricants such as erucamide and behenamide.

[0377] One embodiment of the present disclosure is a total polyethylene multilayer film structure comprising at least one skin layer A, wherein the skin layer A comprises an ethylene polymer composition as described herein.

[0378] One embodiment of the present disclosure is a total polyethylene multilayer film structure containing 90% or more, 93% or more, 95% or more, 97% or more, 99% or more, or 100% of one or more ethylene polymers, based on the total weight of the multilayer film structure excluding the non-thermoplastic layer (if present).

[0379] One embodiment of the present disclosure is a total polyethylene multilayer film structure comprising a skin layer A and a sublayer B adjacent to it, wherein the sublayer B has a density of 0.945 g / cm³ 3 The above conditions are met, and the product contains high-density polyethylene (HDPE) with a melt index I2 of 0.1 to 10 dg / min.

[0380] In embodiments of this disclosure, the high-density polyethylene has a density of 0.940 g / cm³. 3 If it exceeds or is at least 0.941 g / cm³ 3 at least 0.945 g / cm³ 3 at least 0.949 g / cm³ 3 at least 0.950 g / cm³ 3 at least 0.955 g / cm³ 3 at least 0.960 g / cm³ 3 , or at least 0.965 g / cm³ 3 That is the case.

[0381] In embodiments of this disclosure, high-density polyethylene has a density of 0.945 to 0.975 g / cm³.3 , or 0.945~0.970 g / cm³ 3 , or 0.945~0.967 g / cm³ 3 , or 0.949~0.975 g / cm³ 3 , or 0.949~0.970 g / cm³ 3 , or 0.949~0.967 g / cm³ 3 , or 0.950~0.975 g / cm³ 3 , or 0.950~0.970 g / cm³ 3 , or 0.950~0.967 g / cm³ 3 , or 0.955~0.975 g / cm³ 3 , or 0.955~0.970 g / cm³ 3 , or 0.955~0.967 g / cm³ 3 , or 0.960~0.975 g / cm³ 3 , or 0.960~0.970 g / cm³ 3 , or 0.960~0.967 g / cm³ 3 That is the case.

[0382] In embodiments of this disclosure, the high-density polyethylene has a melt index I2 of 0.01 to 100 dg / min, or 0.1 to 50 dg / min, or 0.1 to 10 dg / min, or 0.1 to 8 dg / min, or 0.5 to 10 dg / min, or 0.8 to 8 dg / min, or 0.5 to 8 dg / min, or 0.1 to 5 dg / min, or 0.5 to 5 dg / min.

[0383] In embodiments of this disclosure, the high-density polyethylene may be unimodal or multimodal.

[0384] In one embodiment of the present disclosure, the high-density polyethylene has a molecular weight distribution (Mw / Mn) ranging from about 3.0 to about 20.0.

[0385] In one embodiment of the present disclosure, the high-density polyethylene has a molecular weight distribution (Mw / Mn) from about 7.0 to about 18.0.

[0386] In embodiments of this disclosure, high-density polyethylene can be produced using known catalysts capable of producing high-density polyethylene, such as chromium catalysts, Ziegler-Natta catalysts, and so-called "homogeneous catalysts," which are not limited to metallocene catalysts, constrained structure catalysts, phosphinimine catalysts, and the like.

[0387] In embodiments of this disclosure, high-density polyethylene can be produced using gas-phase polymerization, solution-phase polymerization, or slurry polymerization processes, or any combination thereof. These can be produced using any type of reactor or reactor configuration known to those skilled in the art, such as fluidized-bed gas-phase reactors, loop reactors, stirred-tank reactors, parallel or series batch reactors, and any combination thereof.

[0388] In one embodiment of the present disclosure, the high-density polyethylene comprises a nucleating agent or a mixture of nucleating agents in an amount ranging from more than 0% by weight to 1% by weight.

[0389] In one embodiment of the present disclosure, high-density polyethylene contains 100 ppm (parts per million) to 3,000 ppm (parts per million) of a nucleating agent or a mixture of nucleating agents.

[0390] In one embodiment of the present disclosure, high-density polyethylene (HDPE) is a blend of at least two ethylene homopolymer blend components, the blend having a density of 0.950 g / cm³. 3 From 0.975 g / cm³ 3 It contains 30% to 95% by weight of a first ethylene homopolymer blend component, and has a density of 0.950 g / cm³. 3 From 0.975 g / cm³ 3 The mixture contains 5% to 70% by weight of a second ethylene homopolymer blend component, and the ratio of the melt index (I2) of the second ethylene homopolymer blend component to the melt index (I2) of the first ethylene homopolymer blend component is at least 10.

[0391] In one embodiment of this disclosure, at least one skin layer A has a density of 0.910 g / cm³3 From 0.940 g / cm³ 3 The material further comprises linear low-density polyethylene (LLDPE) having a melt index (I2) of 0.1 dg / min to 10 dg / min.

[0392] In one embodiment of the present disclosure, at least one skin layer A comprises 10% to 40% by weight of LLDPE and 60% to 90% by weight of the ethylene polymer composition described herein.

[0393] In one embodiment of the present disclosure, the entire polyethylene multilayer film structure has a seal initiation temperature of 70°C to 115°C, and the seal initiation temperature is the minimum seal temperature at which the film structure has a seal strength of more than 3.4 N per 25.4 mm of seal width.

[0394] In some embodiments of the present invention, the film structure has a seal strength of 3.4 N to 15.0 N per 25.4 mm of seal width at a seal temperature in the range of SIT to SIT+40°C.

[0395] In some embodiments of the present invention, the film structure has a seal strength of 3.4 N to 15.0 N per 25.4 mm of seal width at a seal temperature in the range of SIT to SIT+25°C.

[0396] General Examination Procedures Prior to the tests in this invention, each test specimen was conditioned at 23±2°C and 50±10% relative humidity for at least 24 hours. The tests were then conducted at 23±2°C and 50±10% relative humidity. In this specification, the term "ASTM conditions" refers to a test chamber maintained at 23±2°C and 50±10% relative humidity, where the test specimens were conditioned for at least 24 hours prior to the tests. ASTM stands for the American Society for Testing and Materials.

[0397] density The density of the ethylene polymer composition in the solid state in this invention was measured according to ASTM D792-13 (November 1, 2013).

[0398] Melt Index The melt index of the ethylene polymer composition in this invention was measured according to ASTM D1238 (August 1, 2013). Melt index I2 was measured at 190°C using a load of 2.16 kg.

[0399] VICAT softening temperature The VICAT softening temperatures of the examples and comparative examples according to the present invention were measured in accordance with ASTM D1525-17 (August 1, 2017) under a load of 10 ± 0.2 N and a heating rate of 120 ± 10 °C / hour. The initial temperature of the heat transfer medium (DOW Corning 710) was 20-23 °C. In the present invention, unless otherwise specified, the VICAT softening temperature was measured on compression-molded test specimens that were compressed at 140 °C and cooled at a cooling rate of 15 °C per minute.

[0400] Melt strength The melt strength in this invention was measured using a Rosand RH-7 capillary rheometer (barrel diameter = 15 mm) with a 2 mm diameter flat die and an L / D ratio of 10:1 mounted at 190°C. The pressure transducer was 10,000 psi (68.95 MPa). The piston speed was 5.33 mm / min, the take-up angle was 52°, and the take-up acceleration was 50-80 m / min. 2 Or 65 ± 15 m / min 2 The polymer molten sample was extruded from the capillary die at a constant speed, and then the polymer filament was taken up while increasing the take-up speed until it fractured. The maximum stable force value in the plateau region of the force-time curve was defined as the melt strength of the polymer.

[0401] Differential scanning calorimetry The endothermic fusion in this invention was obtained using differential scanning calorimetry (DSC) by the following method. First, the apparatus was calibrated with indium. After calibration, the polymer sample was equilibrated at 0°C, and then heated to 200°C at a heating rate of 10°C / min. The molten material was held isothermally at 200°C for 5 minutes, then cooled to 0°C at a cooling rate of 10°C / min, and held at 0°C for 5 minutes. Next, it was reheated to 200°C at a heating rate of 10°C / min. The heat flow signal obtained during the second heating cycle was plotted as a function of temperature.

[0402] Micro-amplitude vibration shear rheology In this invention, the small-amplitude vibration shear rheology was performed under a nitrogen atmosphere at 190°C with a strain amplitude of 10%, a frequency range of 0.02 to 126 rad / s, and 5 points per order of magnitude, to obtain the linear viscoelastic function. The frequency sweep test was performed using a TA Instruments DHR3 stress-controlled rheometer with a cone-plate shape having a cone angle of 5°, a notch of 137 μm, and a diameter of 25 mm. In this test, a sinusoidal strain wave was applied, and the stress response was analyzed as a linear viscoelastic function. The zero-shear rate viscosity (η0) based on the small-amplitude vibration shear measurement was determined by fitting the four-variable Carreau-Yasuda (CY) viscosity model to the relationship between complex viscosity and angular frequency using the least squares method. The model equation is as follows.

number

[0403] Long-chain branching coefficient The LCBF (long-chain branching coefficient, dimensionless) of the ethylene polymer composition according to the present invention was determined using the method described in U.S. Patent Publication No. 2018 / 0305531, which is incorporated herein by reference.

[0404] In this invention, long-chain branching has a molecular weight equal to or greater than the entanglement molecular weight (Me). Me is a well-known concept in polymer physics, and for example, in the case of polyethylene, it has been reported to be about 1 kg / mol (see Fetters et al., Macromolecules 1999, 32, 6847). In this invention, long-chain branching is characterized as "rheologically active." "Rheologically active" means that the presence of long-chain branching in the sample is evident by comparing the rheological test results with a comparative sample that does not contain long-chain branching. Examples of rheological test results, though not limited to these, include flow activation energy (Ea), shear thinning or viscosity ratio, and melt flow ratio (I 21 / I2, I 10 Examples include I2, melt strength, and long-chain branching coefficient (LCBF).

[0405] In this invention, the calculation of LCBF (Long Chain Branching Coefficient) is performed using the polydispersity-corrected zero shear viscosity (ZSV). c ) and SCB-corrected intrinsic viscosity (IV c This includes the calculation of ). The polydispersity correction applied to zero shear viscosity has dimensions in Poise and was performed as shown in equation (2).

number

[0406] SCB-corrected intrinsic viscosity (IV) in the present invention c The calculation of the concentration (unit: dL / g) was performed as shown in equation (3).

number

[0407] In the present invention, ethylene polymer compositions that do not have long-chain branching (i.e., ethylene polymer compositions that do not contain LCB or whose LCB content is below the detection limit) lie on the "reference line" defined by the following formula.

number

[0408] In this invention, the calculation of LCBF is performed by taking the horizontal direction (S) from the aforementioned linear reference line. h ) and vertical (S v Based on the shift of ), the following formula was used.

number

[0409] In the present invention, in formulas (5) and (6), polydispersity-corrected zero shear viscosity (ZSV) cThe SCB-corrected intrinsic viscosity IVc is required to have dimensions of Poise and dL / g, respectively. Horizontal shift coefficient (S h ) is ZSV in a certain IVc c This is a shift of . If we remove the logarithmic function, its physical meaning becomes clear, namely two ZSVs c The ratio of the ZSV of the test sample to a linear ethylene polymer composition having the same IVc. c This is the ratio of the horizontal shift coefficient (S h ) is dimensionless.

[0410] In the present invention, vertical shift (S v ) is a constant ZSV c This is the shift of IVc in . If we remove the logarithmic function, its physical meaning becomes clear, namely the same ZSV. c This is the ratio of two IVc values ​​obtained by comparing the IVc of a linear ethylene polymer composition having the properties of the IVc of the test sample with the IVc of the IVc of the test sample. Vertical shift coefficient (S v ) is dimensionless. Finally, in this invention, the dimensionless long-chain branching coefficient (LCBF) is defined by equation (7).

number

[0411] Comonomer amount: Fourier transform infrared spectroscopy (FTIR) The amount of comonomers in the ethylene polymer composition in the present invention was measured by Fourier transform infrared spectroscopy (FTIR) and reported as the short-chain branch (SCB) content having the dimension CH3 / 1000 C (number of methyl branches per 1000 carbon atoms). This test was performed using compression-molded polymer plaques and a Thermo-Nicolet 750 Magna-IR spectrometer in accordance with ASTM D6645-01 (2001). The polymer plaques were prepared using a compression molding apparatus with a Wabash-Genesis series press in accordance with ASTM D4703-16 (April 2016).

[0412] Triple Detection Size Exclusion Chromatography (3D-SEC 3 Detection Size Exclusion Chromatography) The polymer solutions (1-3 mg polymer / mL) used in this invention were prepared by heating an ethylene polymer composition sample in 1,2,4-trichlorobenzene (TCB Trichlorobenzene) and rotating it on a wheel in an oven at 150°C for 4 hours. To stabilize the polymer sample against oxidative degradation, 2,6-di-tert-butyl-4-methylphenol (BHT), an antioxidant, was added to the mixture. The BHT concentration was 250 ppm. The sample solutions were subjected to chromatographic analysis at 140°C on a PL 220 high-temperature chromatography unit equipped with a differential refractive index (DRI) detector, two-angle light scattering detectors (15° and 90°), and a differential viscometer. The SEC columns used were 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, and BHT was added to the mobile phase at a concentration of 250 ppm to protect the SEC column from oxidative degradation. The sample injection volume was 200 μL. Raw SEC data were processed with CIRRUS® GPC software to calculate the absolute molecular weight, intrinsic viscosity ([η]), and viscosity-average molecular weight (Mv). The term "absolute" molecular weight was used to distinguish between the absolute molecular weight obtained by 3D-SEC and the molecular weight obtained by conventional SEC. The viscosity-average molecular weight (Mv) and intrinsic viscosity ([η]) measured by 3D-SEC were used to calculate the long-chain branching coefficient (LCBF).

[0413] Conventional size exclusion chromatography In this invention, 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 solutions were chromatographically analyzed 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, with a differential refractive index (DRI) used as the concentration detector. BHT was added to the mobile phase at a concentration of 250 ppm to protect the GPC columns from oxidative degradation. The sample injection volume was 200 μL. The GPC columns were calibrated with polystyrene standard samples with a narrow molecular weight distribution. The molecular weight of polystyrene was converted to the molecular weight of polyethylene using the Mark-Hawwink formula described in ASTM Standard Test Method D6474-12 (December 2012). Raw GPC data were processed with CIRRUS® GPC software to calculate the number-average molecular weight (Mn), weight-average molecular weight (Mw), Z-average molecular weight (Mz), and molecular weight distribution (e.g., polydispersity, Mw / Mn). In the polyethylene field, GPC (gel permeation chromatography) is a term commonly used synonymously with SEC (size exclusion chromatography).

[0414] GPC-FTIR In this invention, polymer solutions were prepared by heating 2-4 mg / mL of an ethylene polymer composition sample 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, 2,6-di-tert-butyl-4-methylphenol (BHT), an antioxidant, was added to the mixture. The BHT concentration was 250 ppm. The sample solution was chromatographically analyzed 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. As a detection system, an FTIR spectrometer and a heated FTIR flow-through cell were connected to the chromatography unit via a heated transfer line. BHT was added to the mobile phase at a concentration of 250 ppm to protect the SEC column from oxidative degradation. The sample injection volume was 300 μL. The raw FTIR spectral data obtained were processed with OPUS FTIR software, and polymer concentrations and methyl content were calculated in real time using the chemitometric software (PLS method) associated with OPUS. Subsequently, polymer concentrations and methyl content were acquired using CIRRUS® GPC software and baseline correction was performed. The SEC column was calibrated with polystyrene standard samples with a narrow molecular weight distribution. The molecular weight of polystyrene was converted to the molecular weight of polyethylene using the Mark-Hawwink formula described in ASTM standard test method D6474. Copolymer component content was calculated based on the polymer concentrations and methyl content predicted by the PLS method, according to the method described in Paul J. DesLauriers, Polymer 43, pp.159-170 (2002). This literature is incorporated herein by reference.

[0415] The GPC-FTIR method in this invention measures the total methyl content, including methyl groups located at the ends of each polymer chain, i.e., methyl-terminated groups. Therefore, raw GPC-FTIR data needs to be corrected to subtract the contribution from methyl-terminated groups. More precisely, raw GPC-FTIR data overestimates the amount of short-chain branching (SCB), and this overestimation increases as the molecular weight decreases. In this specification, a 2-methyl correction is used for this correction. The number of methyl-terminated groups (N) at a given molecular weight (M) is... E The following formula was used to calculate it. N E = 28000 / M N E The (M-dependent) was subtracted from the raw GPC-FTIR data to obtain GPC-FTIR data for the number of short-chain branches per 1000 carbon atoms (2-methyl corrected).

[0416] In this invention, the slope of the comonomer distribution is determined using GPC-FTIR and is defined as the value obtained by subtracting the number of short-chain branches per 1,000 carbon atoms at a molecular weight of 30,000 (g / mol) from the number of short-chain branches per 1,000 carbon atoms at a molecular weight of 300,000 (g / mol) (where "-" is a subtraction symbol). The number of short-chain branches per 1,000 carbon atoms referred to here is the 2-methyl corrected comonomer content, which is determined as the number of short-chain branches per 1,000 carbon atoms at the corresponding molecular weight (i.e., absolute molecular weight) on the GPC-FTIR chromatogram.

[0417] Film heat seal strength In this specification, the "heat seal strength test" (also known as the "cold seal test") was performed using the following method. Heat seal data was obtained using a general Instron tensile testing machine. In this test, two film samples cut from the same roll were sealed within a constant temperature range. The following conditions were used for the heat seal strength (or cold seal) test: film sample width = 1 inch (25.4 mm), film sealing time = 0.5 seconds, film sealing pressure = 40 psi (0.28 N / mm²). 2The temperature range was 212°F to 302°F (100°C to 150°C), and the temperature increment was 9°F (5°C). After aging for at least 24 hours under ASTM conditions, the seal strength was measured under the following tensile conditions: tensile (crosshead) speed = 12 inches / min (2.54 cm / min), tensile direction = 90° relative to the seal, and 5 samples were tested for each temperature increment.

[0418] Examples Solution polymerization process The reactor-mixed ethylene polymer compositions in Examples 1 to 3 of the present invention were each produced by a pilot-scale "series-type" multi-reactor solution polymerization process. Here, the ethylene polymer composition was produced by generating a first ethylene polymer in the first reactor (R1), a second ethylene copolymer in the second reactor (R2), and a third ethylene copolymer in the third reactor (R3). R1, R2, and R3 were connected in series. The "series-type" multi-reactor solution-phase polymerization process is described in U.S. Patent Publication No. 2019 / 0135958.

[0419] In the "series" reactor system, the discharge flow from the first polymerization reactor (R1) flowed directly into the second polymerization reactor (R2). The pressure in R1 was approximately 14 MPa to 18 MPa, while R2 was operated at a lower pressure to facilitate continuous flow from R1 to R2. Both R1 and R2 were continuous stirred reactors (CSTR). A third reactor, R3, was a tubular reactor and was configured in series with the second reactor R2 (i.e., the contents of the second reactor flowed into the third reactor). The process was operated continuously by supplying the first and second reactors with a new process solvent, ethylene, 1-octene, and hydrogen, and removing the products. Methylpentane (a commercially available mixture of methylpentane isomers) was used as the process solvent. The first CSTR reactor (R1) had a capacity of 3.2 gallons (12 L), and the second CSTR reactor (R2) had a capacity of 5.8 gallons (22 L). The tubular reactor (R3) had a capacity of 4.755 gallons (18 L). The monomer (ethylene) and comonomer (1-octene) were purified before being added to the reaction system using a conventional feedstock preparation system (e.g., contact with water, oxygen, and various adsorption media to remove impurities such as polar contaminants). The feedstocks to the reactors were introduced in the ratios shown in Table 1.

[0420] Table 1 shows the reactor conditions used to produce each of the ethylene polymer compositions in Examples 1 to 3. Table 1 includes process parameters such as the distribution of ethylene and 1-octene between reactors (R1, R2, and R3), reactor temperature, ethylene conversion rate, concentrations of hydrogen, ethylene, and 1-octene in the new feed to the reactor, total solution flow rate of the new feed, and stirring speed of the CSTR reactors (R1 and R2).

[0421] In Examples 1 and 2, the following non-crosslinked single-site catalyst components were used to prepare the first ethylene polymer in the first CSTR reactor (R1): Component C: Cyclopentadienyltri(tertiary butyl)phosphinimine titanium dichloride {Cp[(t-Bu)3PN]TiCl2}, Component M: Methylalmoxane (MMAO-07), Component B: Trityltetrakis(pentafluorophenyl)borate, and Component P: 2,6-di-tert-butyl-4-ethylphenol. Methylpentane was used as the solvent for components M and P, and xylene was used for components C and B. The efficiency of the non-crosslinked single-site catalyst formulation was optimized by adjusting the amount of component C added to R1 [R1 catalyst (ppm) as shown in Table 1], the molar ratio of the catalyst components, i.e., [M] / [C], [P] / [M] and [B] / [C] (shown in Table 1), and the R1 catalyst inlet temperature.

[0422] In Examples 1 and 2, the following crosslinked metallocene catalyst components were used to prepare the second ethylene copolymer in the second CSTR reactor (R2): Component A: diphenylmethylene (cyclopentadienyl)(2,7-di-t-butylfluorenyl)hafnium dimethide [(2,7-tBu2Flu)Ph2C(Cp)HfMe2], Component M: methylarmoxane (MMAO-07), Component B: trityltetrakis(pentafluorophenyl)borate (tritylborate), and Component P: 2,6-di-tert-butyl-4-ethylphenol (BHEB). Methylalmoxane (MMAO-07) and 2,6-di-tert-butyl-4-ethylphenol were pre-mixed inline and then combined with diphenylmethylene (cyclopentadienyl)(2,7-di-t-butylfluorenyl)hafnium dimethide and trityltetrakis(pentafluorophenyl)borate immediately before entering the polymerization reactor (R2). Methylpentane was used as the solvent for components M and P, and xylene was used for components A and B. The efficiency of the crosslinked metallocene catalyst formulation was optimized by adjusting the amount of component A added to R2 [R2 catalyst (ppm) listed in Table 1], the molar ratio of the catalyst components, i.e., [M] / [A], [P] / [M] and [B] / [A] (shown in Table 1), and the R2 catalyst inlet temperature.

[0423] In Example 3, the following crosslinked metallocene catalyst components were used to prepare the first ethylene polymer in the first CSTR reactor (R1) and the second ethylene copolymer in the second CSTR reactor (R2): Component A: diphenylmethylene (cyclopentadienyl)(2,7-di-t-butylfluorenyl)hafnium dimethide [(2,7-tBu2Flu)Ph2C(Cp)HfMe2], Component M: methylarmoxane (MMAO-07), Component B: trityltetrakis(pentafluorophenyl)borate (tritylborate), and Component P: 2,6-di-tert-butyl-4-ethylphenol (BHEB). Methylalmoxane (MMAO-07) and 2,6-di-tert-butyl-4-ethylphenol were pre-mixed inline and then combined with diphenylmethylene (cyclopentadienyl)(2,7-di-t-butylfluorenyl)hafnium dimethide and trityltetrakis(pentafluorophenyl)borate immediately before entering the polymerization reactors (R1 and R2). Methylpentane was used as the solvent for components M and P, and xylene was used for components A and B. The efficiency of the crosslinked metallocene catalyst formulation was optimized by adjusting the amount of component A added to R1 and R2 [R1 catalyst (ppm) and R2 catalyst (ppm) listed in Table 1], the molar ratio of the catalyst components, i.e., [M] / [A], [P] / [M] and [B] / [A] (shown in Table 1), and the R1 and R2 catalyst inlet temperatures.

[0424] In the operation of the continuous solution polymerization process shown in Table 1, the total amount of ethylene supplied to the process was distributed or divided among the first reactor R1, the second reactor R2, and the third reactor R3. In Table 1, this operating variable is called the ethylene distribution (ES), i.e., ES R1 , ES R2 and ES R3 These represent the weight percentages of ethylene injected into R1, R2, and R3, respectively, and ES R1 +ES R2 +ES R3The condition is that =100%. Similarly, 1-octene was also added to the continuous solution polymerization process and distributed or split among R1, R2, and R3. In Table 1, this operating variable is called the 1-octene distribution (OS), i.e., OS R1 OS R2 and OS R3 These represent the weight percentages of 1-octenomonomers injected into R1, R2, and R3, respectively, and OS R1 +OS R2 +OS R3 The condition is that it must be 100%.

[0425] In Examples 1-3, the novel ethylene, 1-octene, hydrogen, and catalyst were not introduced into the third reactor. For example, ES R3 and OS R3 The amount was zero. The residual ethylene, residual 1-octene, and residual active catalyst flowing from the upstream reactors R1 and R2 into the third reactor (R3) formed the third ethylene copolymer in these examples.

[0426] In the operation of the continuous solution polymerization process shown in Table 1, the total amount of ethylene converted in each reactor was monitored. R1 The term represented the proportion of ethylene added to R1 that was converted into the first ethylene polymer by the catalyst. Similarly, Q R2 and Q R3 These figures represent the proportion of ethylene added to R2 and residual ethylene flowing from R1 and R2 into R3 that was converted into the second and third ethylene copolymers, respectively.

[0427] In Table 1, Q T The term Q refers to the total or overall ethylene conversion rate in the entire continuous solution polymerization plant. T = 100 × [weight of ethylene in the ethylene polymer composition] / ([weight of ethylene in the ethylene polymer composition] + [weight of unreacted ethylene]).

[0428] Polymerization in the continuous solution polymerization process was stopped by adding a catalyst deactivator to the third discharge stream from the tubular reactor (R3). The catalyst deactivator used was octanoic acid (caprylic acid), commercially available from P&G Chemicals (Cincinnati, Ohio, USA). The catalyst deactivator was added so that the number of moles of fatty acid added was 50% of the total number of moles of catalyst metal and aluminum added to the polymerization process. That is, the number of moles of octanoic acid added = 0.5 × (number of moles of hafnium + number of moles of aluminum).

[0429] A two-stage defoliation process was employed to recover the ethylene polymer composition from the process solvent. Specifically, two gas-liquid separators were used, with a second bottom flow from the second gas-liquid separator passing through a gear pump / pelletizer combination. The gear pump was a Vacorex 45 / 45 pump with a capacity of 191 L / h and jacket heating with 270 lbs of steam. The ethylene polymer composition exiting the gear pump passed through a 4-inch diameter static mixer before entering the pelletizer, where it was pushed from top to bottom through the holes in the die plate. The die had 32 holes with a diameter of 0.125 inches, each with an aspect ratio (i.e., length to diameter ratio) of 6.3:1, and the die was 1.63 inches thick and 12 inches in diameter. Six cutter knives with an outer sweep of 8.6878 inches and an inner sweep of 6.2418 inches were positioned on the die side facing the cooling water system. The die plate had heating channels inside, and the die body and plate were heated with 600 pounds or 270 pounds of steam. The cooling water system was maintained at a temperature range of 10–80°C with a flow rate of 7500–9500 kg / hour.

[0430] DHT-4V (hydrotalcite) is supplied by Kyowa Chemical Industry Co., Ltd. (Tokyo, Japan) and can be used as a passivator or acid scavenger in continuous solution processes. The DHT-4V slurry in the process solvent can be added before the first gas-liquid separator.

[0431] Prior to pelletization, the ethylene polymer composition was stabilized by adding 500 ppm of the primary antioxidant IRGANOX® 1076 and 500 ppm of the secondary antioxidant IRGAFOS® 168, based on the weight of the ethylene polymer composition. The antioxidants were dissolved in the process solvent and added between the first and second gas-liquid separators.

[0432] The Mw, Mn, Mw / Mn, weight percentage, and SCB per 1000 carbon atoms in each component produced in R1, R2, and R3 were calculated by reactor model simulation using the input conditions used in actual pilot-scale operation and are shown in Table 2a. References for relevant reactor modeling techniques include "Copolymerization" in "Comprehensive Polymer Science and Supplements," Vol. 3, Chapter 2, p. 17 (Elsevier, 1996) by A. Hamielec, J. MacGregor, and A. Penlidis, and "Copolymerization of Olefins in a Series of Continuous Stirred-Tank Slurry-Reactors using Heterogeneous Ziegler-Natta and Metallocene Catalysts. I. General Dynamic Mathematical Model" in "Polymer Reaction Engineering," 4(2&3), p. 153 (1996) by JBP Soares and AE Hamielec.

[0433] This model takes the flow rates of multiple reactive species supplied to each reactor (e.g., catalyst, monomer (ethylene, etc.), comonomer (1-octene, etc.), hydrogen, and solvent), the temperature in each reactor, and the monomer conversion rate in each reactor as inputs, and uses a terminal kinetics model for a series-connected continuous-tank reactor (CSTR) to calculate the properties of the polymer produced in each reaction zone. The "terminal kinetics model" assumes that the reaction rate depends on the monomer units in the polymer chain where the active catalyst site is located, and is described in "Copolymerization" in "Comprehensive Polymer Science and Supplements" Vol. 3, Chapter 2, p. 17 (Elsevier, 1996) by A. Hamielec, J. MacGregor, and A. Penlidis. In this model, it is assumed that the copolymer chain has a sufficiently large molecular weight, that the statistics of monomer / comonomer unit insertions at the active catalyst center are valid, and that monomers / comonomers consumed in pathways other than the growth reaction can be ignored. This assumption is known as the "long-chain approximation."

[0434] Terminal kinetic models for polymerization include reaction rate equations for activation, initiation, growth, chain transfer, and deactivation pathways. This model solves the steady-state conservation equations (e.g., total mass balance and heat balance) for the reactive fluid containing the reactive species. The total mass balance in a typical CSTR with a predetermined number of inlets and outlets is given by the following equation:

number

number

number

number

number

number

number

number

[0435] The reported weight percentage values ​​shown in Table 2a represent the sum of the weight percentages of materials produced in R1, R2, and R3, which equal 100%.

[0436] Degree of polymerization (dp) in polymerization reactions n The rate of chain growth is given by the ratio of the chain transfer / chain termination reaction rate.

number

[0437] The number-average molecular weight (Mn) of a polymer can be determined from the degree of polymerization and the molecular weight of the monomer units. Assuming a Florey-Schultz distribution for a single-site catalyst, the molecular weight distribution of the polymer can be determined from the number-average molecular weight of the polymer in a given reactor using the following relational equation.

number

number

number

number

[0438] Assuming the Florey-Schultz model, the various moments of the molecular weight distribution can be calculated using the following:

number

number

number

number

number

number

number

number

number

number

[0439] Assuming that the addition of monomer 2(1-octene) units to chains terminated by monomer 2(1-octene) units is negligible, the number of octene units after the ethylene step will be equal to the number of ethylene units after the octene step. The branching content per 1000 carbon atoms (per 500 monomer units) of the resulting polymer is the ratio of the addition rate of monomer 1 (ethylene) to the addition rate of monomer 2(1-octene).

number

[0440] In relation to Table 2a, Example 1 contained 38.9% by weight of a first ethylene polymer with a weight-average molecular weight Mw of 114.2 kg / mol, 0 SCBs per 1000 carbon atoms, and a polydispersity index Mw / Mn of 2.00; 56.9% by weight of a second ethylene copolymer with a weight-average molecular weight Mw of 39.1 kg / mol, 42 short-chain branches per 1000 carbon atoms, and a polydispersity index Mw / Mn of 2.06; and 4.2% by weight of a third ethylene copolymer with a weight-average molecular weight Mw of 25.6 kg / mol, 47 short-chain branches per 1000 carbon atoms, and a polydispersity index Mw / Mn of 2.26.

[0441] Example 2 contained 41.5% by weight of a first ethylene polymer with a weight-average molecular weight Mw of 110.2 kg / mol, 0 SCBs per 1000 carbon atoms, and a polydispersity index Mw / Mn of 2.00; 53.7% by weight of a second ethylene copolymer with a weight-average molecular weight Mw of 58.9 kg / mol, 3 short-chain branches per 1000 carbon atoms, and a polydispersity index Mw / Mn of 2.04; and 4.8% by weight of a third ethylene copolymer with a weight-average molecular weight Mw of 43.2 kg / mol, 32 short-chain branches per 1000 carbon atoms, and a polydispersity index Mw / Mn of 2.23.

[0442] Example 3 contained 39.4% by weight of a first ethylene polymer with a weight-average molecular weight Mw of 142.9 kg / mol, 0 SCBs per 1000 carbon atoms, and a polydispersity index Mw / Mn of 2.29; 53.6% by weight of a second ethylene copolymer with a weight-average molecular weight Mw of 50.3 kg / mol, 36.3 short-chain branches per 1000 carbon atoms, and a polydispersity index Mw / Mn of 2.07; and 7.0% by weight of a third ethylene copolymer with a weight-average molecular weight Mw of 26.0 kg / mol, 46 short-chain branches per 1000 carbon atoms, and a polydispersity index Mw / Mn of 2.18.

[0443] In Examples 1 to 3, it was confirmed that the weight-average molecular weight of the second ethylene copolymer (component R2) was smaller than that of the first ethylene polymer (component R1). The ratio of the weight-average molecular weight of the first ethylene polymer to the weight-average molecular weight of the second ethylene copolymer was approximately 2.67, 2.05, and 2.64 in Examples 1, 2, and 3, respectively.

[0444] As can be seen from the data in Table 2a, the first ethylene polymer produced in the first reactor (R1) was the first ethylene homopolymer. This result is that in Examples 1-3, OS R1 This was a direct result of setting it to 0%.

[0445] Furthermore, it is noteworthy that in Examples 1 to 3, the weight-average molecular weight of the second ethylene copolymer is smaller than that of the first ethylene polymer and larger than that of the third ethylene copolymer.

[0446] Table 2b lists the R1, R2, and R3 components of the simulated examples S1, S2, and S3, and shows the 1-octene distribution ratios in the experimentally prepared R1 and R2 reactors of Examples 1, 2, and 3, as shown in the OS R1 = 5.0% and OS R2= changed to 95.0%. Other polymerization process variables were kept constant between simulated examples S1-S3 and the corresponding experimentally prepared examples 1-3. To clarify, for example, the R1, R2, and R3 components of simulated example S1 were simulated using the same polymerization process variables as example 1, with the only difference being the 1-octene distribution ratio of reactors R1 and R2. As can be seen from the data in Table 2b, in simulated examples S1-S3, the first ethylene / 1-octene copolymer was synthesized in the first reactor (R1). That is, the first ethylene polymer had a comonomer content with more than 0 SCBs and 6 SCBs or less (≦) of short-chain branching per 1000 carbon atoms.

[0447] As shown in Table 3, Examples 1 and 2 included an undetectable level of long-chain branching characterized by an LCBF of less than 0.001. On the other hand, Example 3 included a detectable level of long-chain branching characterized by an LCBF of 0.001 or greater. This latter structural feature of Example 3 is compared to Examples 1 and 2, 21 Further investigation can be conducted by comparing the observed values ​​of / I2, stress index, η0, CY-a, and G′ (at G″=500Pa).

[0448] As those skilled in the art will understand, in Examples 1 and 2, the crosslinked metallocene catalyst (abbreviated as CpF in Table 1) that produces the second ethylene copolymer in the second reactor generates long-chain branched species. However, their contribution is completely masked by the presence of a first polymer of high molecular weight that does not have long-chain branching, produced at R1 using a non-crosslinked single-site catalyst (abbreviated as PIC in Table 1), which affects the fusion rheological properties described herein. [Table 2a] [Table 2b] [Table 3]

[0449] As can be understood in relation to the GPC-FTIR profiles shown in Figures 1a, 2a, and 3a, the ethylene polymer compositions prepared in Examples 1 to 3 had a typical comonomer distribution. The low molecular weight species had a short-chain branching frequency of more than 30 per 1000 carbon atoms at molecular weights less than approximately 30 kg / mol, while the high molecular weight species had an SCB content where the short-chain branching frequency approached small (almost zero) as the molecular weight exceeded approximately 300 kg / mol. Specifically, the GPC-FTIR comonomer distribution of Example 1 had a slope of -31.9 SCB per 1000 carbon atoms, the GPC-FTIR comonomer distribution of Example 2 had a slope of -31.0 SCB per 1000 carbon atoms, and the GPC-FTIR comonomer distribution of Example 3 had a slope of -28.3 SCB per 1000 carbon atoms.

[0450] Based on the DSC second heating thermograms shown in Figures 1b, 2b, and 3b, and the low / high temperature melting peaks shown in Table 3, it can be seen that Examples 1-3 had two clearly distinguishable melting peaks: a low temperature melting peak around 75-78°C and a high temperature melting peak around 125-130°C. In all examples, the heat flow signal in the temperature range of approximately 85°C to 100°C returned almost to the virtual baseline drawn between 20°C and the end of melting. In the examples shown in Figures 1b, 2b, and 3b, the maximum distance between the second heating heat flow curve and the virtual baseline in the temperature range of approximately 85°C to 100°C was less than 0.07 W / g.

[0451] A film structure that is peelable and easily openable. Examples 1F-3F were polyethylene film structures produced from the ethylene polymer compositions disclosed in Examples 1-3 using a Brampton Engineering three-layer co-extrusion film blow molding line under the following conditions: expansion ratio of 2.5, total film thickness of 2.85 mils, frost line height of 18.0 inches, discharge rate of 100.0 lbs / hour, and die gap of 35 mils. Examples 1F-3F had an A / B / C structure with a layer thickness ratio of 20 / 40 / 40, and were produced at melting temperatures of 409-413°F, 417-418°F, and 431-432°F for layers A, B, and C, respectively. The sealant layers (skin layers identified herein as layer A) of film Examples 1F, 2F, and 3F were prepared from the ethylene polymer compositions disclosed in Examples 1, 2, and 3, respectively. The sealant layer in these film examples further contained 2.0% by weight of a fluoroelastomer-based process aid masterbatch, commercially available from Ingenia Polymers under the trade name Ingenia 1150. The Ingenia 1150 masterbatch contains 5% by weight of 3M's DYNAMAR® FX 5920A, has a melt index I2 of 1.0, and a density of 0.920 g / cm³. 3 It is dispersed in an LLDPE carrier resin. Skin layer C is composed of 98% by weight of HDPE homopolymer, commercially available from NOVA Chemicals Corporation under the trade name SCLAIR® 19A, and 2.0% by weight of Ingenia 1150. SCLAIR® 19A has a melt index I2 of 0.72 dg / min and a density of 0.962 g / cm³. 3 This is an HDPE homopolymer, commercially available from NOVA Chemicals Corporation. Core layer B was prepared from 100% by weight of HDPE homopolymer, commercially available from NOVA Chemicals Corporation under the trade name SURPASS® HPs167-AB. SURPASS® HPs167-AB has a nominal melt index I2 of 1.2 dg / min and a nominal density of 0.967 g / cm³. 3 That is the case.

[0452] The film structure of Example 1FB was an A / B / C multilayer film prepared under the same conditions as those used in Examples 1F to 3F, but differed in that sealant layer A was prepared from a blend containing 78% by weight of the ethylene polymer composition produced in Example 1, 20% by weight of SCLAIR® FP120-C, and 2% by weight of Ingenia 1150. SCLAIR® FP120-C is an ethylene / 1-octene LLDPE copolymer commercially available from NOVA Chemicals Corporation, with a nominal melt index I2 of 1.0 and a nominal density of 0.920 g / cm³. 3 That is the case.

[0453] The film structure of Example 2FB was an A / B / C multilayer film produced under the same conditions as those used in Examples 1F to 3F, but differed in that the sealant layer A was prepared from a blend containing 49% by weight of the ethylene polymer composition produced in Example 1, 49% by weight of the ethylene polymer composition produced in Example 2, and 2% by weight of Ingenia 1150.

[0454] The film structure of Comparative Example 1F was an A / B / C multilayer film prepared under the same conditions as those used in Examples 1F to 3F, but differed in that sealant layer A was prepared from a blend containing 77% by weight of ELVAX® 3165, 20% by weight of TOPPYL® PB 8640M, and 3% by weight of Ingenia 1150. ELVAX® 3165 is an ethylene-vinyl acetate (EVA) copolymer commercially available from Dow Chemical Company, containing 18% by weight of vinyl acetate comonomer, with a nominal melt index I2 of 0.7 dg / min and a nominal density of 0.94 g / cm³. 3 TOPPYL® PB 8640M is a low-ethylene-content 1-butene random copolymer commercially available from LyondellBasell Industries, with a nominal melt index I2 of 1.0 dg / min and a nominal density of 0.906 g / cm³.3 That is the case.

[0455] Comparative Example 3F was an A / B / C multilayer film prepared under the same conditions as those used in Examples 1F to 3F, but differed in that sealant layer A was prepared from a blend containing 70% by weight of NOVAPOL® HB-L354-A, 28% by weight of QUEO® 8230, and 2% by weight of Ingenia 1150. NOVAPOL® HB-L354-A is a high-density polyethylene (HDPE) commercially available from NOVA Chemicals Corporation, an ethylene / 1-hexene copolymer with a nominal melt index I2 of 0.3 dg / min and a nominal density of 0.955 g / cm³. 3 QUEO® 8230 is an ethylene-based 1-octene plastomer produced by a solution process using a metallocene catalyst, with a nominal melt index I2 of 30 dg / min and a nominal density of 0.883 g / cm³. 3 The film blow molding conditions for Comparative Example 3F differed further from those of Examples 1F to 3F, with a total film thickness of 2.79 mils and melting temperatures of layers A, B, and C being 406°F, 417°F, and 433°F, respectively.

[0456] Comparative Example 4F was an A / B / C multilayer film produced under the same conditions as those used in Examples 1F to 3F, except that sealant layer A was prepared from a blend containing 70% by weight of QUEO® 8230, 28% by weight of NOVAPOL® HB-L354-A, and 2% by weight of Ingenia 1150. The film blow molding conditions for Comparative Example 4F also differed from those of Examples 1F to 3F, with a total film thickness of 2.79 mils and melting temperatures of 415°F, 416°F, and 432°F for layers A, B, and C, respectively.

[0457] Comparative Example 5F was an A / B / C multilayer film prepared under the same conditions as those used in Examples 1F to 3F, but differed in that sealant layer A was prepared from a blend containing 70% by weight of NOVAPOL® HB-W952-A, 28% by weight of QUEO® 8230, and 2% by weight of Ingenia 1150. NOVAPOL® HB-W952-A is a high-density polyethylene (HDPE) commercially available from NOVA Chemicals Corporation, an ethylene / 1-hexene copolymer with a nominal melt index I2 of 0.08 dg / min and a nominal density of 0.952 g / cm³. 3 The film blow molding conditions for Comparative Example 5F differed further from those of Examples 1F to 3F, with a total film thickness of 2.70 mils and melting temperatures of layers A, B, and C being 421°F, 417°F, and 432°F, respectively.

[0458] Comparative Example 6F was an A / B / C multilayer film produced under the same conditions as those used in Examples 1F to 3F, but differed in that sealant layer A was prepared from a blend containing 70% by weight of QUEO® 8230, 28% by weight of NOVAPOL® HB-W952-A, and 2% by weight of Ingenia 1150. The film blow molding conditions for Comparative Example 6F also differed from those of Examples 1F to 3F, with a total film thickness of 2.77 mils and melting temperatures of 407°F, 419°F, and 432°F for layers A, B, and C, respectively.

[0459] Figures 4a to 4c show the seal strength profiles for the film structures produced in Examples 1F to 3F and 1FB to 2FB, and Comparative Examples 1F and 3F to 6F, showing the seal strength as a function of the sealing temperature. Those skilled in the art will understand, from a performance design perspective, that all polyethylene film structures produced in Examples 1F to 3F and 2FB provide peelable seals that exhibit a constant (or nearly constant) seal strength over a wide sealing temperature range within a seal strength range desirable for easy opening applications (e.g., a seal strength of approximately 3.4 N / 25 mm to approximately 15 N / 25 mm). Specifically, Example 1F had a SIT of 101.8°C and exhibited a seal strength of approximately 3.4 N / 25 mm to approximately 15 N / 25 mm in the temperature range from SIT to SIT + 29.8°C. Example 2F had a SIT of 70.2°C and exhibited a seal strength of approximately 3.4 N / 25 mm to approximately 15 N / 25 mm in the temperature range from SIT to SIT + 26.9°C. Example 3F had a SIT of 92.9°C and exhibited a seal strength of approximately 3.4 N / 25 mm to approximately 15 N / 25 mm in the temperature range from SIT to SIT + 32.7°C. Example 2FB had a SIT of approximately 75°C and exhibited a seal strength of approximately 3.4 N / 25 mm to approximately 15 N / 25 mm in the temperature range from SIT to approximately SIT + 35.0°C. Example 1FB showed that the addition of 20% by weight of LLDPE component did not significantly affect the observed seal strength-seal temperature behavior. Comparative Example 1F had a SIT of 81.8°C and exhibited a seal strength of approximately 3.4 N / 25 mm to approximately 15 N / 25 mm in the temperature range from SIT to SIT + 29.2°C. In the above sealing temperature range, the sealing temperatures corresponding to seal strengths of 3.4 N and / or 15 N were estimated by linear interpolation if they were not included in the experimentally obtained data points.

[0460] Importantly, in Examples 1F-3F and 2FB, the sealing temperature range corresponding to a seal strength of approximately 3.4 N / 25 mm to approximately 15 N / 25 mm (shown by the dashed lines in Figures 4a-4c) was equivalent to or wider than that of Comparative Example 1F, which included a non-polyethylene material. This latter finding is particularly important in applications where an easily detachable monomaterial packaging system is required.

[0461] In relation to Figure 4c, it is noteworthy that the advantageous properties described above cannot be achieved when the film structure prepared in Comparative Examples 3F to 6F, i.e., when the sealant layer contains a post-physical reactor mixture of a blend component with high molecular weight and low comonomer content (i.e., a low melt index high-density blend component) and a blend component with low molecular weight and high comonomer content (i.e., a high melt index plastomer-based blend component).

[0462] VICAT improved reactor blend ethylene polymer composition The reactor-blended ethylene polymer compositions of Examples 4 to 6 were each produced by the same pilot-scale series multi-reactor solution polymerization process as used in Examples 1 to 3. However, the process conditions were adjusted to obtain reactor-blended ethylene polymer compositions with higher target densities than those of Examples 1 to 3. Table 4 shows the reactor conditions used to produce each of the ethylene polymer compositions of Examples 4 to 6. [Table 4]

[0463] In Examples 4 to 6, the following crosslinked metallocene catalyst components were used to prepare the first ethylene polymer in the first CSTR reactor (R1) and the second ethylene copolymer in the second CSTR reactor (R2): Component A: diphenylmethylene (cyclopentadienyl)(2,7-di-t-butylfluorenyl)hafnium dimethide [(2,7-tBu2Flu)Ph2C(Cp)HfMe2], Component M: methylarmoxane (MMAO-07), Component B: trityltetrakis(pentafluorophenyl)borate (tritylborate), and Component P: 2,6-di-tert-butyl-4-ethylphenol (BHEB). Methylalmoxane (MMAO-07) and 2,6-di-tert-butyl-4-ethylphenol were pre-mixed inline and then combined with diphenylmethylene (cyclopentadienyl)(2,7-di-t-butylfluorenyl)hafnium dimethide and trityltetrakis(pentafluorophenyl)borate immediately before entering the polymerization reactors (R1 and R2). Methylpentane was used as the solvent for components M and P, and xylene was used for components A and B. The efficiency of the crosslinked metallocene catalyst formulation was optimized by adjusting the amount of component A added to R1 and R2 [R1 catalyst (ppm) and R2 catalyst (ppm) listed in Table 4], the molar ratio of the catalyst components, i.e., [M] / [A], [P] / [M] and [B] / [A] (shown in Table 4), and the R1 and R2 catalyst inlet temperatures.

[0464] Based on the reactor model simulation method described herein, and using the input conditions used in actual pilot-scale operation, Examples 4-6 contained 30-70% by weight of the first ethylene polymer produced in the first reactor R1 and 30-70% by weight of the second ethylene copolymer produced in the second reactor R2. In Examples 4-6, the first ethylene polymer had zero short-chain branches per 1000 carbon atoms, i.e., the first ethylene polymer was an ethylene homopolymer. The first ethylene polymer in Examples 4-6 had a weight-average molecular weight (Mw) of approximately 100 kg / mol and a polydispersity index (Mw / Mn) of approximately 2.0. In Examples 4-6, the second ethylene copolymer contained 26-30 short-chain branches per 1000 carbon atoms. The second ethylene copolymer in Examples 4-6 had a weight-average molecular weight (Mw) of approximately 50 kg / mol and a polydispersity index (Mw / Mn) of approximately 2.1.

[0465] As shown in Table 5, Examples 4-6 contained detectable levels of long-chain branching characterized by an LCBF of 0.001 or higher. [Table 5]

[0466] In relation to Tables 3 and 5, Examples 4-6 showed advantageously higher VICAT softening temperatures compared to Examples 1-3. Those skilled in the art will understand that a manufacturing process for ethylene polymer compositions with an improved VICAT softening temperature results in a lower tendency for pellet aggregation in the finishing stages of the polymerization plant and during storage and transport.

[0467] In relation to Tables 3 and 5, the GPC-FTIR comonomer distributions of Examples 4, 5, and 6 had slopes greater than -22 SCB per 1000 carbon atoms, specifically -16.2, -15.1, and -15.4 SCB, respectively.

[0468] Figure 5 shows the seal strength profiles for the total polyethylene film structures 4F to 6F, which were prepared from the reactor blend ethylene polymer compositions disclosed in Examples 4 to 6, with the seal strength expressed as a function of the seal temperature.

[0469] The films produced in Examples 4F–6F were manufactured using a Brampton Engineering 3-layer co-extruded film blow molding line under the following conditions: expansion ratio of 3.0, total film thickness of 1.54 mils, frost line height of 20.0 inches, extrusion speed of 100.0 lbs / hour, and die gap of 35 mils. Examples 4F–6F have an A / B / C structure with a layer thickness ratio of 13.5 / 65 / 21.5, and layers A, B, and C were manufactured at melting temperatures of 404–407°F, 424–425°F, and 415–417°F, respectively. The sealant layers (surface layers identified herein as layer A) of films Examples 4F, 5F, and 6F were prepared from the ethylene polymer compositions disclosed in Examples 4, 5, and 6, respectively. The sealant layer of these film examples also contained 2.0% by weight of a fluoroelastomer process-aid masterbatch, commercially available from Ingenia Polymers under the trade name Ingenia 1150. The Ingenia 1150 masterbatch contains 5% by weight of 3M's DYNAMAR FX 5920A in an LLDPE carrier resin, which has a melt index I2 of 1.0 and a density of 0.920 g / cm³. Layer C (skin layer) contained 98% by weight of HDPE homopolymer, commercially available from NOVA Chemicals Corporation under the trade name SCLAIR 19A, and 2.0% by weight of Ingenia 1150. SCLAIR 19A has a melt index I2 of 0.72 dg / min and a density of 0.962 g / cm³. 3 It is an HDPE homopolymer.

[0470] In Examples 4 and 5, intermediate layer B was prepared by blending 78% by weight of HDPE homopolymer, commercially available from NOVA Chemicals under the trade name SURPASS® HPs167-AB, with 22% by weight of SCLAIR 19A. SURPASS HPs167-AB has a nominal melt index I2 of 1.2 dg / min and a nominal density of 0.967 g / cm³. 3 In Example 6, the intermediate layer B was prepared from 100% by weight of SURPASS HPs167-AB.

[0471] As shown in Figure 5, compared to the film structures of Examples 1F-3F and 2FB, the film structures prepared in Examples 4F-6F had a narrower sealing temperature range corresponding to a sealing strength of approximately 3.4 to approximately 15 N / 25 mm. While we do not wish to be limited to any particular theory, this latter observation can be interpreted as a result of the reduced intensity of the gradient of the GPC-FTIR comonomer distribution observed in Examples 4-6 compared to Examples 1-3. [Industrial applicability]

[0472] The reactor-blended ethylene polymer compositions disclosed herein are industrially applicable to a wide range of flexible molded articles, including, but not limited to, single-layer or multi-layer films.

[0473]

Claims

1. A reactor blend ethylene polymer composition, A first ethylene polymer in a weight-average molecular weight (Mw) of 30 to 70 kg percent, comprising ethylene and optionally at least one α-olefin, having a weight-average molecular weight (Mw) of 70 kg / mol to 250 kg / mol, a short-chain branching number of 0 to 6 per 1000 carbon atoms, and a dispersion index (Mw / Mn) of 1.7 to 2.3, A second ethylene copolymer comprising ethylene and at least one α-olefin, having a weight-average molecular weight Mw of 20 kg / mol to 75 kg / mol, a short-chain branching number of 25 to 55 per 1000 carbon atoms, and a dispersion index Mw / Mn of 1.7 to 2.3, in a weight-percentage of 30 to 70 weight percent, Includes, The weight-average molecular weight of the second ethylene copolymer is smaller than the weight-average molecular weight of the first ethylene polymer, The ethylene polymer composition is produced by a continuous solution polymerization process, and the continuous solution polymerization process is The first ethylene polymer is formed by polymerizing ethylene and, optionally, at least one α-olefin in a first solution polymerization reactor using a first homogeneous catalyst composition, and The second ethylene copolymer is formed by polymerizing ethylene and at least one α-olefin in a second solution polymerization reactor using a second homogeneous catalyst composition. A reactor blend ethylene polymer composition containing the following:

2. The ethylene polymer composition according to claim 1, wherein the ethylene polymer composition has a comonomer distribution profile in GPC-FTIR analysis, the comonomer distribution profile has a secant slope of -55 or more and -20 or less short-chain branchings per 1000 carbon atoms, and the secant slope is defined as the value obtained by subtracting the number of short-chain branchings per 1000 carbon atoms at a molecular weight of 30 kg / mol from the number of short-chain branchings per 1000 carbon atoms at a molecular weight of 300 kg / mol.

3. The ethylene polymer composition according to claim 2, wherein the comonomer distribution profile is a normal comonomer distribution profile.

4. The first homogeneous catalyst composition and the second homogeneous catalyst composition, or both thereof, contain a crosslinked metallocene catalyst having the following formula (I), [Chemistry I] In the formula, 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 １ is a hydrogen atom, a hydrocarbyl radical of C １～２０ , an alkoxy radical of C １～２０ , or an aryloxy radical of C ６～１０ ; R ２ and R ３ are each independently a hydrogen atom, a hydrocarbyl radical of C １～２０ , an alkoxy radical of C １～２０ , or an aryloxy radical of C ６～１０ ; R ４ and R ５ are each independently a hydrogen atom, an unsubstituted hydrocarbyl radical of C １～２０ , a substituted hydrocarbyl radical of C １～２０ , an alkoxy radical of C １～２０ , or an aryloxy radical of C ６～１０ ; and Q is each independently an activatable leaving group ligand. The ethylene polymer composition according to any one of claims 1 to 3.

5. The ethylene polymer composition according to any one of claims 1 to 4, wherein one or both of the first homogeneous catalyst and the second homogeneous catalyst include a phosphinimine catalyst.

6. The ethylene polymer composition according to any one of claims 1 to 5, wherein the first ethylene polymer is a first ethylene homopolymer.

7. Densities measured according to ASTM D792-13 are 0.880–0.920 g / cm³ ３ The ethylene polymer composition according to any one of claims 1 to 6.

8. Density measured according to ASTM D792-13 is 0.900–0.920 g / cm³ ３ The ethylene polymer composition according to any one of claims 1 to 6.

9. Melt Index I is measured according to ASTM D1238-13 using a load of 2.16 kg at 190°C. ２ The ethylene polymer composition according to any one of claims 1 to 8, wherein the concentration is 2 to 10 dg / min.

10. An ethylene polymer composition according to any one of claims 1 to 9, having a molecular weight distribution with a dispersion index Mw / Mn of 2.3 to 6.

0.

11. An ethylene polymer composition according to any one of claims 1 to 10, having a molecular weight distribution with a dispersion index Mw / Mn of 2.3 to 4.

5.

12. The ethylene polymer composition according to claim 10 or claim 11, having a unimodal molecular weight distribution.

13. The ethylene polymer composition according to any one of claims 1 to 12, wherein the ratio of the weight-average molecular weight of the first ethylene polymer to the weight-average molecular weight of the second ethylene copolymer is 1.5 or more and 6 or less.

14. The ethylene polymer composition according to any one of claims 1 to 12, wherein the ratio of the weight-average molecular weight of the first ethylene polymer to the weight-average molecular weight of the second ethylene copolymer is 2 or more and 4 or less.

15. The ethylene polymer composition according to any one of claims 1 to 14, comprising a detectable level of long-chain branching characterized by a long-chain branching factor (LCBF) of 0.001 or more.

16. The ethylene polymer composition according to any one of claims 1 to 15, wherein the second ethylene copolymer is contained in the ethylene polymer composition in a weight of 50 to 65 percent.

17. The ethylene polymer composition according to any one of claims 1 to 16, wherein the first ethylene polymer is contained in the ethylene polymer composition in a weight of 35 to 50 percent.

18. An ethylene polymer composition according to any one of claims 1 to 17, wherein the number average molecular weight Mn is 10 to 35 kg / mol.

19. An ethylene polymer composition according to any one of claims 1 to 18, wherein the number average molecular weight Mn is 15 to 30 kg / mol.

20. An ethylene polymer composition according to any one of claims 1 to 19, wherein the weight-average molecular weight Mw is 65 to 100 kg / mol.

21. An ethylene polymer composition according to any one of claims 1 to 19, wherein the weight-average molecular weight Mw is 70 to 95 kg / mol.

22. The ethylene polymer composition according to any one of claims 1 to 21, wherein the second ethylene copolymer has a number average molecular weight of 10 to 38 kg / mol.

23. The ethylene polymer composition according to any one of claims 1 to 21, wherein the second ethylene copolymer has a number average molecular weight of 15 to 34 kg / mol.

24. The ethylene polymer composition according to any one of claims 1 to 23, wherein the second ethylene copolymer has a weight-average molecular weight of 30 to 65 kg / mol.

25. The ethylene polymer composition according to any one of claims 1 to 24, wherein the second ethylene copolymer has 27 to 48 short-chain branches per 1,000 carbon atoms.

26. The ethylene polymer composition according to any one of claims 1 to 25, wherein the first ethylene polymer has a weight-average molecular weight of 70 to 160 kg / mol.

27. The ethylene polymer composition according to any one of claims 1 to 25, wherein the first ethylene polymer has a weight-average molecular weight of 100 to 160 kg / mol.

28. The melt flow ratio I is measured according to ASTM D1238-13 using loads of 2.16 kg and 21.6 kg at 190°C. ２１ / I ２ An ethylene polymer composition according to any one of claims 1 to 27, wherein the ratio is 15 to 40.

29. The ethylene polymer composition according to any one of claims 1 to 28, further comprising a third ethylene copolymer greater than 0 and less than or equal to 20 weight percent, wherein the third ethylene copolymer comprises ethylene and at least one α-olefin, has a dispersion index Mw / Mn of 1.7 to 2.3, and has a weight-average molecular weight smaller than the weight-average molecular weight of the first ethylene polymer and the second ethylene copolymer.

30. The ethylene polymer composition according to claim 29, wherein the third ethylene copolymer has a weight-average molecular weight of 20 to 50 kg / mol and a short-chain branching number of 25 to 50 per 1000 carbon atoms.

31. The ethylene polymer composition according to any one of claims 29 to 31, wherein the continuous solution polymerization process further comprises the step of polymerizing ethylene and at least one α-olefin in a third solution polymerization reactor using a third homogeneous catalyst composition to form the third ethylene copolymer, and the first, second and third solution phase polymerization reactors are arranged in series with respect to each other.

32. The third homogeneous catalyst composition comprises a crosslinked metallocene catalyst having the following formula (I), [Chemistry I] In the formula, M is a group 4 metal selected from titanium, zirconium, or hafnium, G is a group 14 element selected from carbon, silicon, germanium, tin, or lead, and R １ C is a hydrogen atom. １－２０ Hydrocarbyl radical, C １－２０ alkoxy radicals or C ６－１０ It is an aryloxy radical, R ２ and R ３ Each of them is independently a hydrogen atom, C １－２０ Hydrocarbyl radical, C １－２０ alkoxy radicals or C ６－１０ Selected from the aryloxy radicals, R ４ and R ５ R ５ Each of these is independently a hydrogen atom and an unsubstituted carbon atom. １－２０ Hydrocarbyl radical, substituted C １－２０ Hydrocarbyl radical, C １－２０ alkoxy radicals or C ６－１０ The ethylene polymer composition according to claim 31, wherein Q is selected from aryloxy radicals, and each is an independently activatable leaving group ligand.

33. The ethylene polymer composition according to claim 31, wherein the third homogeneous catalyst comprises a phosphinimine catalyst.

34. The above-mentioned at least one α-olefin is C ３ ~C １０ An ethylene polymer composition according to any one of claims 1 to 33, selected from the group consisting of α-olefins.

35. The ethylene polymer composition according to any one of claims 1 to 33, wherein the at least one α-olefin is selected from the group consisting of hexene-1, octene-1, and a mixture of hexene-1 and octene-1.

36. The ethylene polymer composition according to any one of claims 1 to 33, wherein the at least one α-olefin is octene-1.

37. A total polyethylene film layer comprising the ethylene polymer composition according to any one of claims 1 to 36.

38. The film layer according to claim 37, wherein the film layer is an inflation film.

39. The film layer according to claim 37, wherein the film layer is a cast film.

40. The aforementioned film layer has a density of 0.910 to 0.940 g / cm³. ３ and Melt Index I ２ The film layer according to any one of claims 37 to 39, further comprising linear low-density polyethylene (LLDPE) having a concentration of 0.1 to 10 dg / min.

41. The film layer according to claim 40, wherein the film layer comprises 10 to 40 weight percent of the LLDPE and 60 to 90 weight percent of the ethylene polymer composition according to any one of claims 1 to 32.

42. A total polyethylene multilayer film structure having at least one skin layer comprising the ethylene polymer composition described in any one of claims 1 to 36.

43. The film structure has a lower layer adjacent to the at least one skin layer, and the lower layer has a density of 0.945 g / cm³ ３ The above and Melt Index I ２ The film structure according to claim 42, comprising high-density polyethylene (HDPE) having a concentration of 0.1 to 10 dg / min.

44. The HDPE is a blend consisting of at least two ethylene homopolymer blend components, and the blend is 0.950~0.975g / cm ３ A first ethylene homopolymer blend component having a density of 30 to 95 percent by weight, 0.950~0.975g / cm ３ It contains 5 to 70 percent by weight of a second ethylene homopolymer blend component having a density of, Furthermore, the melt index I of the second ethylene homopolymer blend component ２ The melt index I of the first ethylene homopolymer blend component ２ The film structure according to claim 43, wherein the ratio to is at least 10.

45. The film structure according to claim 43 or claim 44, wherein the HDPE contains 100 to 3000 ppm (parts per million) of a nucleating agent or a mixture of nucleating agents.

46. The film structure according to any one of claims 43 to 45, wherein the HDPE has a dispersion index Mw / Mn of 7 to 18.

47. The aforementioned at least one skin layer has a density of 0.910 to 0.940 g / cm³. ３ and Melt Index I ２ The film structure according to any one of claims 42 to 46, further comprising linear low-density polyethylene (LLDPE) having 0.1 to 10.0 dg / min.

48. The film structure according to claim 47, wherein the at least one skin layer comprises 10 to 40 weight percent of the LLDPE and 60 to 90 weight percent of the ethylene polymer composition according to any one of claims 1 to 36.

49. The film structure according to any one of claims 42 to 48, wherein the film structure has at least three layers.

50. The film structure according to any one of claims 42 to 48, wherein the film structure has layers between three and nine layers.

51. The film structure according to any one of claims 42 to 50, wherein the at least one skin layer is a sealant layer.

52. The film structure according to claim 51, wherein the film structure has a seal initiation temperature (SIT) of 70°C or more and 115°C or less, and the seal initiation temperature is the minimum seal temperature at which the film structure has a seal strength of more than 3.4 N per 25.4 mm of seal width.

53. The film structure according to claim 52, wherein the film structure has a sealing strength of 3.4 N to 15.0 N per 25.4 mm of sealing width at sealing temperatures in the range of SIT to SIT + 40°C.

54. The film structure according to claim 52, wherein the film structure is a film having a sealing strength of 3.4 N to 15.0 N per 25.4 mm of sealing width at sealing temperatures in the range of SIT to SIT + 25°C.

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