Polyethylene and film comprising same

Abstract

The present invention provides polyethylene having excellent low-temperature sealing properties and stiffness, and film comprising same.

Description

Polyethylene and films containing the same

[0001] Cross-citation with related applications

[0002] This application claims the benefit of priority to Korean Patent Application No. 10-2024-0073747, filed June 5, 2024, and Korean Patent Application No. 10-2025-0073543, filed June 5, 2025, the entire contents of which are incorporated herein by reference.

[0003] The present invention relates to polyethylene having excellent low-temperature sealing properties and stiffness and to a film comprising the same.

[0004]

[0005] Linear low density polyethylene (LLDPE) is a resin manufactured by copolymerizing ethylene and alpha-olefin at low pressure using a polymerization catalyst. It has a narrow molecular weight distribution, short-chain branches of a certain length, and no long-chain branches.

[0006] Linear low-density polyethylene film has the characteristics of general polyethylene, as well as high breaking strength and elongation, excellent film processability and transparency, and superior tear strength and drop impact strength, so its use is increasing in industrial films such as food packaging and industrial laminated films, heavy-duty films, and stretch wrap films, where conventional low-density polyethylene or high-density polyethylene is difficult to apply.

[0007] Linear low-density polyethylene (LPE) is generally known to exhibit increased drop impact strength as density decreases. However, the use of large amounts of comonomers to manufacture LPE can lead to increased fouling during the slurry polymerization process, and the resulting film can become sticky, necessitating increased use of anti-blocking agents. Furthermore, production processes can become unstable, and the resulting polyethylene morphology can deteriorate, resulting in a decrease in bulk density.

[0008] Due to recent market trends in sustainability and D4R (Design For Recyclability), the demand for down-gauging (D / G) is increasing, and accordingly, the demand for linear low-density polyethylene with excellent molding processability and drop impact strength is also increasing.

[0009] Before COVID-19, D / G focused on reducing the thickness of the polyethylene layer in multilayer films from a cost perspective. However, after COVID-19, with the increased interest in environmental issues, the demand for downgauging from a recycling perspective and energy consumption issues for carbon reduction have emerged.

[0010] In addition, the D4R design from the recycling perspective is attracting attention to promote and activate the transition to a resource circular economy, and the demand for improved sealing properties of the sealant layer during co-extrusion or bonding in the manufacturing process of BOPE (Biaxially Oriented Polyethylene) film and MDO (Machine Direction Orientation) film applied to single-material All-PE film is increasing.

[0011]

[0012] In order to solve the problems of the above prior art, the present invention aims to provide polyethylene having excellent low-temperature sealing properties and stiffness.

[0013] In addition, the present invention seeks to provide a film comprising the polyethylene.

[0014]

[0015] According to the present invention, polyethylene is provided that satisfies the following mathematical formula 1:

[0016] [Mathematical Formula 1]

[0017] a * x - b ≤ y ≤a * x - b'

[0018] In the above mathematical formula 1,

[0019] y is the sealing initiation temperature (SIT) (unit: ℃) measured according to ASTM F 1921,

[0020] x is the density (unit: g / cm) measured according to ASTM D 1505 3 ) and,

[0021] a is 2924, b is between 2606 and 2620, and b' is between 2600 and 2604.

[0022] In addition, according to the present invention, a film including the polyethylene is provided.

[0023]

[0024] The polyethylene according to the present invention exhibits excellent low-temperature sealing and hot-tack properties. Furthermore, the polyethylene exhibits excellent drop impact strength and rigidity, along with improved moldability. Accordingly, downgauging is possible during film production using the polyethylene, making it advantageous for D4R applications.

[0025] The above polyethylene can be usefully used in multipurpose films such as food, agricultural, general industrial films, or stretch films, and can be applied to a sealant layer during coextrusion or bonding in the manufacturing process of BOPE (Biaxially Oriented Polyethylene) film and MDO (Machine Direction Orientation) film applied to a single-material All-PE film.

[0026] Additionally, it is advantageous in responding to PPWR as it does not contain PFAS (Per- and Polyfluoroalkyl Substances), which are subject to the Packaging and Packaging Waste Regulation (PPWR) implemented by the European Union (EU).

[0027]

[0028] In the present invention, terms such as first, second, etc. are used to describe various components, and the terms are used only for the purpose of distinguishing one component from another.

[0029] Furthermore, the terminology used herein is merely for the purpose of describing exemplary embodiments and is not intended to limit the present invention. The singular expression includes the plural expression unless the context clearly indicates otherwise. In this specification, it should be understood that the terms "comprise," "include," or "have" indicate the presence of a feature, number, step, component, or combination thereof, but do not preclude the possibility of the presence or addition of one or more other features, numbers, steps, components, or combinations thereof.

[0030] Additionally, the term “to” used in describing a numerical range in this specification includes both the upper and lower limits. For example, “1 to 3” means 1 or more and 3 or less.

[0031] The present invention is susceptible to various modifications and takes various forms. Specific embodiments are illustrated and described in detail below. However, this is not intended to limit the present invention to specific disclosed forms, but rather to encompass all modifications, equivalents, and alternatives falling within the spirit and technical scope of the present invention.

[0032] Hereinafter, the polyethylene of the present invention and the film containing the same will be described in detail.

[0033]

[0034] Polyethylene according to one embodiment of the present invention satisfies the following mathematical formula 1:

[0035] [Mathematical Formula 1]

[0036] a * x - b ≤ y ≤a * x - b'

[0037] In the above mathematical formula 1,

[0038] y is the sealing initiation temperature (SIT) (unit: ℃) measured according to ASTM F 1921,

[0039] x is the density (unit: g / cm) measured according to ASTM D 1505 3 ) and,

[0040] a is 2924, b is between 2606 and 2620, and b' is between 2600 and 2604.

[0041] More specifically, in the above mathematical expression 1, b may be 2506 or more, or 2507 or more, or 2508 or more, or 2509 or more, or 2510 or more, or 2511 or more, or 2512 or more, or 2513 or more, or 2514 or more, or 2515 or more, and 2620 or less, or 2619 or less, or 2618 or less, or 2617 or less, or 2616 or less, or 2615 or less, or 2614 or less, or 2613 or less, or 2612 or less, or 2611 or less, or 2610 or less. In addition, b' may be 2600 or more, or 2601 or more, or 2602 or more, and 2604 or less, or 2603 or less.

[0042]

[0043] The above y is the temperature at which the heat seal strength reaches 2 N / 25.4 mm when the composition containing polyethylene is molded into a single-layer film having a thickness of 45 to 55 μm, or 48 to 52 μm, more specifically 50 μm, using a blown film extruder (die diameter 120 mm, die gap 2.0 mm, BUR 2.5, Dual air-ring system) at 95 wt% or more, or 96 wt% or more, or 97 wt% or more, or 98 wt% or more, or 99 wt% or more, based on the total composition, and the sealing strength is measured according to ASTM F 1921 (sealing time 0.5 sec, sealing pressure 0.3 MPa, delay time 30.0 sec, tensile speed 200 mm / sec, Sealing machine J&B 5000 Model).

[0044]

[0045] The condition of the above mathematical expression 1 means that the polyethylene according to one embodiment of the present invention has a significantly lower sealing initiation temperature than conventional polyethylene having a similar density. As such, the polyethylene according to one embodiment of the present invention can exhibit excellent low-temperature sealing characteristics and improved stiffness, and when a low-density product is used to improve the existing low-temperature sealing characteristics as a product with a balanced sealing characteristic and stiffness, the waste of resources that are not used and discarded due to blocking problems that occur during actual application for packaging in roll form after lamination can be prevented, and additives such as anti-blocking agents used to lower the coefficient of friction can be reduced.

[0046]

[0047] In addition, polyethylene according to one embodiment of the present invention has a density of 0.900 to 0.925 g / cm as measured according to ASTM D 1505 standard. 3 am.

[0048] If the density of polyethylene is too low, it is difficult to ensure stability in the slurry polymerization process. In addition, there is a trade-off relationship between density and drop impact strength, and density and low-temperature sealing properties. If the density of polyethylene is too high, it is difficult to down-gauge during film production due to the decrease in drop impact strength and low-temperature sealing properties. More specifically, the polyethylene according to the present invention has a density of 0.900 g / cm. 3 or 0.901 g / cm 3 or 0.902 g / cm 3 or 0.903 g / cm 3 or 0.904 g / cm 3 or 0.905 g / cm 3 or 0.906 g / cm 3 or 0.907 g / cm 3 or 0.908 g / cm 3or 0.909 g / cm 3 or 0.910 g / cm 3 or 0.911 g / cm 3 or 0.912 g / cm 3 or 0.913 g / cm 3 or 0.914 g / cm 3 or 0.915 g / cm 3 Ideally, 0.925 g / cm 3 or less, or 0.924 g / cm 3 or less, or 0.923 g / cm 3 or less, or 0.922 g / cm 3 or less, or 0.921 g / cm 3 or less, or 0.920 g / cm 3 or less, or 0.919 g / cm 3 or less, or 0.918 g / cm 3 It could be as follows:

[0049]

[0050] In addition, polyethylene according to one embodiment of the present invention may exhibit a specific distribution of fraction content according to the elution temperature range during temperature rising elution fractionation (TREF) of cross-fractionation chromatography (CFC).

[0051]

[0052] For example, in the case of polyethylene according to one embodiment of the present invention, when subjected to temperature-increasing elution fractionation analysis of cross-fraction chromatography, the content of a polymer fraction eluted at an elution temperature of 30°C or higher and less than 60°C (30°C≤Te<60°C) based on the total weight of polyethylene satisfies 18.0 to 38.0 wt%. More specifically, the content of the polymer fraction eluted at the elution temperature of 30°C or more and less than 60°C may be 18.0 wt% or more, or 19.0 wt% or more, or 20.0 wt% or more, or 21.0 wt% or more, or 22.0 wt% or more, or 23.0 wt% or more, or 24.0 wt% or more, or 25.0 wt% or more, and 38.0 wt% or less, or 37.0 wt% or less, or 36.0 wt% or less, or 35.0 wt% or less, or 34.0 wt% or less, or 33.0 wt% or less.

[0053] The polymer fraction eluted at a temperature of 30°C or higher and less than 60°C delays secondary crystallization between the die and the frost line during blown film production, thereby reducing the size of the crystal lamellae, thereby improving the low-temperature sealing characteristics and hot-tack characteristics. However, if the content of the fraction is less than 18.0 wt%, the low-temperature sealing characteristics and hot-tack characteristics may deteriorate due to an increase in lamellae resulting from an increase in the crystallization rate. On the other hand, if the content of the fraction exceeds 38.0 wt%, the low-crystal content affecting the mechanical strength characteristics relatively increases, thereby causing a decrease in stiffness during film production.

[0054]

[0055] In addition, the polyethylene according to one embodiment of the present invention satisfies the content of a polymer fraction eluted at an elution temperature of 35°C or lower (Te≤35°C) based on the total weight of polyethylene in the temperature rising elution fractionation analysis of cross-fraction chromatography, which is 5.0 to 30.0 wt%. More specifically, the content of the polymer fraction eluted at the elution temperature of 35°C or lower is 5.0 wt% or more, or 6.0 wt% or more, or 7.0 wt% or more, or 8.0 wt% or more, or 9.0 wt% or more, or 10.0 wt% or more, or 11.0 wt% or more, or 12.0 wt% or more, and 30.0 wt% or less, or 29.0 wt% or less, or 28.0 wt% or less, or 27.0 wt% or less, or 26.0 wt% or less, or 25.0 wt% or less, or 24.0 wt% or less, or 23.0 wt% or less, or 22.0 wt% or less, or 21.0 wt% or less, or 20.0 wt% or less, or 19.0 wt% or less, or 18.0 wt% or less, or 17.0 wt% or less, or 16.0 % by weight or less, or 15.0% by weight or less.

[0056] The polymer fraction eluted at the above elution temperature of 35°C or lower means a molecular structure having a high amorphous ratio due to a high SCB content in the polymer or a low crystallinity with a high SCB content in the polymer, and the polyethylene according to the present invention can exhibit excellent low-temperature sealing properties and hot-tack properties due to this molecular structure.

[0057]

[0058] In addition, in the polyethylene according to one embodiment of the present invention, when subjected to temperature rising elution fractionation analysis of cross-fractionation chromatography, the content of the polymer fraction eluted at an elution temperature of 60°C or higher and lower than 80°C (60°C≤Te<80°C) satisfies 20.0 to 50.0 wt% based on the total weight of the polyethylene. More specifically, the content of the polymer fraction eluted at an elution temperature of 60°C or higher and lower than 80°C may be 20.0 wt% or more, or 21.0 wt% or more, or 22.0 wt% or more, or 23.0 wt% or more, or 24.0 wt% or more, and 30.0 wt% or less, or 29.0 wt% or less, or 28.0 wt% or less, or 27.0 wt% or less, or 26.0 wt% or less.

[0059] The above-mentioned range of elution temperature is 60°C or higher and less than 80°C, which is a key range that determines the density and MI of polyethylene. Typically, linear low-density polyethylene (LLDPE) has a high crystal distribution in the above-mentioned elution temperature range. In this regard, the polyethylene according to the present invention can exhibit excellent low-temperature sealing properties and hot-tack properties by including a fraction within the above-mentioned content range while having a low density.

[0060]

[0061] In addition, the polyethylene according to one embodiment of the present invention satisfies the content of a polymer fraction eluted at a temperature of 80°C or higher (Te≥80°C) of 30.0 to 60.0 wt% during temperature rising elution fractionation analysis of cross-fraction chromatography. More specifically, the content of the polymer fraction eluted at the elution temperature of 80° C. or higher may be 30.0 wt% or more, or 31.0 wt% or more, or 32.0 wt% or more, or 33.0 wt% or more, or 34.0 wt% or more, or 35.0 wt% or more, or 36.0 wt% or more, or 37.0 wt% or more, or 38.0 wt% or more, or 39.0 wt% or more, or 40.0 wt% or more, and 60.0 wt% or less, or 59.0 wt% or less, or 58.0 wt% or less, or 57.0 wt% or less, or 56.0 wt% or less, or 55.0 wt% or less, or 54.0 wt% or less, or 53.0 wt% or less, or 52.0 wt% or less, or 51.0 wt% or less, or 50.0 wt% or less.

[0062] The polymer fraction eluted at the elution temperature of 80°C or higher affects the stiffness of a film made of polyethylene, and the lower the fraction content, the lower the stiffness. On the other hand, if the fraction content is excessively high, the low-temperature sealing properties of the polyethylene may actually deteriorate. The polyethylene according to the present invention can exhibit excellent stiffness by including the polymer fraction eluted at the elution temperature of 80°C or higher within the above content range.

[0063]

[0064] In addition, the polyethylene according to the present invention can exhibit even better drop impact strength properties and low-temperature sealing properties by having controlled molecular weight distribution properties in addition to the crystal distribution properties described above.

[0065]

[0066] Meanwhile, in the present invention, temperature rising elution fractionation (TREF) analysis of cross-fraction chromatography (CFC) can be performed by dissolving and stabilizing polyethylene in a trichlorobenzene solvent, cooling the temperature to crystallize it, and heating the crystallized polyethylene sample to the fraction temperature at a constant heating rate while measuring the content of the eluted polymer. A more detailed measurement method is described in the examples described below.

[0067]

[0068] In addition, the polyethylene according to one embodiment of the present invention has a molecular weight distribution (MWD, Mw / Mn) of 2.0 to 5.0.

[0069] If the molecular weight distribution is narrow, less than 2.0, the mechanical properties such as toughness are excellent, but there is a risk that the molding processability may deteriorate. If the molecular weight distribution exceeds 5.0, the molding processability is excellent, but there is a risk that the mechanical properties may deteriorate. More specifically, the polyethylene has a molecular weight distribution (MWD) of 2.0 or more, or 2.1 or more, or 2.2 or more, or 2.3 or more, or 2.4 or more, or 2.5 or more, or 2.6 or more, or 2.7 or more, or 2.8 or more, or 2.9 or more, or 3.0 or more, or 3.1 or more, or 3.2 or more, or 3.3 or more, or 3.4 or more, or 3.5 or more, or 3.6 or more, or 3.65 or more, or 3.7 or more, or 3.8 or more, and 5.0 or less, or 4.9 or less, or 4.8 or less, or 4.7 or less, or 4.6 or less, or 4.5 or less, or 4.4 or less, or 4.3 or less, or 4.25 or less, or 4.2 or less, or 4.15 or less, or 4.1 or less, or It may be 4.0 or less, or 3.9 or less. The polyethylene according to the present invention can exhibit well-balanced improved molding processability and mechanical properties by satisfying the above-mentioned molecular weight distribution conditions.

[0070]

[0071] Meanwhile, in the present invention, the weight average molecular weight (Mw) and number average molecular weight (Mn) of polyethylene were measured using gel permeation chromatography (GPC), and then the molecular weight distribution was calculated as the ratio of the weight average molecular weight to the number average molecular weight (Mw / Mn). Here, the weight average molecular weight (Mw) and number average molecular weight (Mn) are polystyrene-converted molecular weights analyzed by GPC.

[0072] Specifically, a sample of polyethylene was analyzed using a Polymer Char GPC-IR using a Polymer Laboratories PLgel MIX-B 300 mm length column. ® The evaluation was performed using a device. The evaluation temperature was 160℃, 1,2,4-trichlorobenzene was used as a solvent, and the flow rate was measured at a rate of 1 mL / min. The polyethylene sample was prepared at a concentration of 16 mg / 8 mL and then supplied in an amount of 200 μL. The values ​​of Mw and Mn were measured using a calibration curve formed using polystyrene standards. The molecular weights of the polystyrene standards were 9 types: 2,000 / 10,000 / 30,000 / 70,000 / 200,000 / 700,000 / 2,000,000 / 4,000,000 / 10,000,000.

[0073]

[0074] In addition, the polyethylene according to one embodiment of the present invention has a melt index (MI) measured under a temperature of 190°C and a load of 2.16 kg according to ASTM D1238 standard. 2.16) is 0.5 to 5.0 g / 10 min. More specifically, 0.5 g / 10 min or more, or 0.6 g / 10 min or more, or 0.7 g / 10 min or more, or 0.8 g / 10 min or more, or 0.9 g / 10 min or more, or 1.0 g / min or more, or 1.1 g / 10 min or more, or 1.2 g / min or more, or 1.3 g / min or more, or 1.4 g / min or more, or 1.5 g / min or more, and 5.0 g / 10 min or less, or 4.9 g / 10 min or less, or 4.8 g / 10 min or less, or 4.7 g / 10 min or less, or 4.6 g / 10 min or less, or 4.5 g / 10 min or less, or 4.4 g / 10 min or less, or 4.3 g / 10 min or less, or 4.2 g / 10 min or less, or 4.1 g / 10 min or less, or 4.0 g / 10min or less, or 3.9 g / 10min or less, or 3.8 g / 10min or less, or 3.7 g / 10min or less, or 3.6 g / 10min or less, or 3.5 g / 10min or less, or 3.4 g / 10min or less, or 3.3 g / 10min or less, or 3.2 g / 10min or less, or 3.1 g / 10min or less, or 3.0 g / 10min or less, or 2.9 g / 10min or less, or 2.8 g / 10min or less, or 2.7 g / 10min or less, or 2.6 g / 10min or less, or 2.5 g / 10min or less, or 2.4 g / 10min or less, or 2.3 g / 10min or less, or 2.2 g / 10min or less, or 2.1 g / 10min or less, or It may be 2.0 g / 10 min or less, or 1.9 g / 10 min or less, or 1.8 g / 10 min or less, or 1.7 g / 10 min or less, or 1.6 g / 10 min or less.

[0075]

[0076] In addition to the aforementioned crystal distribution characteristics and molecular weight distribution characteristics, the polyethylene according to the present invention can exhibit improved molding processability and mechanical properties as well as excellent sealing properties and drop impact strength characteristics by satisfying the conditions of low density and optimal range molecular weight distribution and melting index.

[0077]

[0078] In addition, the polyethylene according to one embodiment of the present invention may be a copolymer of ethylene and alpha-olefin, specifically including an alpha-olefin repeating unit derived from an alpha-olefin monomer together with an ethylene repeating unit.

[0079] The above alpha-olefin monomer may specifically be an alpha-olefin monomer having 3 to 20 carbon atoms. Specific examples thereof include propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-eicosene, etc., and more preferably, it may be 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, or 1-octene. Preferably, the polyethylene according to one embodiment of the present invention may be a type of copolymer of ethylene and 1-hexene, rather than a mixture with another polyethylene.

[0080] Polyethylene having the above properties can be produced by a production method including, for example, a step of polymerizing an ethylene monomer and an alpha-olefin monomer in the presence of a hybrid supported metallocene catalyst comprising a first transition metal compound represented by the following chemical formula 1; and a second transition metal compound represented by the following chemical formula 2. The above production method is merely an example for implementing the polyethylene according to the present invention, and the polyethylene of the present invention is not limited to the above production method.

[0081] [Chemical Formula 1]

[0082]

[0083] In the above chemical formula 1,

[0084] M1 is a group 4 transition metal,

[0085] X 11 and X 12 are each independently, C 1-20 Alkyl or halogen,

[0086] A1 is carbon, silicon, or germanium,

[0087] Q 11 and Q 12 are each independently hydrogen, halogen, C 1-20 Alkyl, or C 2-20 It is an alkoxyalkyl,

[0088] R 11 Inland R 15 are each independently hydrogen or C 1-20 It is alkyl,

[0089] [Chemical Formula 2]

[0090]

[0091] In the above chemical formula 2,

[0092] M2 is a group 4 transition metal,

[0093] X 21 and X 22 are each independently, C 1-20 Alkyl or halogen,

[0094] R 21 Inland R 25 are each independently, C 1-20 It is alkyl,

[0095] R 26 is hydrogen or C 1-20 It is alkyl,

[0096] R 27 Silver hydrogen, C 1-20 Alkyl, C 2-20 Alkoxy, or C 2-20 It is an alkoxyalkyl.

[0097]

[0098] In the present invention, the substituents of the chemical formula are described more specifically as follows.

[0099] The halogen can be fluorine (F), chlorine (Cl), bromine (Br), or iodine (I).

[0100] C 1-20 The alkyl of may be straight-chain, branched-chain or cyclic alkyl. Specifically, the C 1-20 The alkyl may be a straight chain alkyl having 1 to 20 carbon atoms; a straight chain alkyl having 1 to 10 carbon atoms; a straight chain alkyl having 1 to 5 carbon atoms; a branched chain or cyclic alkyl having 3 to 20 carbon atoms; a branched chain or cyclic alkyl having 3 to 15 carbon atoms; or a branched chain or cyclic alkyl having 3 to 10 carbon atoms. More specifically, the alkyl having 1 to 20 carbon atoms may be a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group, a tert-butyl group, an n-pentyl group, an iso-pentyl group, or a cyclohexyl group.

[0101] C 2-20 The alkenyl of may be a straight-chain, branched-chain or cyclic alkenyl. Specifically, the C 2-20 The alkenyl may be a straight chain alkenyl having 2 to 20 carbon atoms, a straight chain alkenyl having 2 to 10 carbon atoms, a straight chain alkenyl having 2 to 5 carbon atoms, a branched chain alkenyl having 3 to 20 carbon atoms, a branched chain alkenyl having 3 to 15 carbon atoms, a branched chain alkenyl having 3 to 10 carbon atoms, a cyclic alkenyl having 5 to 20 carbon atoms or a cyclic alkenyl having 5 to 10 carbon atoms. More specifically, C 2-20 The alkenyl may be ethenyl, propenyl, butenyl, pentenyl or cyclohexenyl.

[0102] C 1-20 The alkoxy of may be a straight-chain, branched-chain or cyclic alkoxy group. Specifically, the C 1-20The alkoxy may be a straight chain alkoxy group having 1 to 20 carbon atoms; a straight chain alkoxy group having 1 to 10 carbon atoms; a straight chain alkoxy group having 1 to 5 carbon atoms; a branched chain or cyclic alkoxy group having 3 to 20 carbon atoms; a branched chain or cyclic alkoxy group having 3 to 15 carbon atoms; or a branched chain or cyclic alkoxy group having 3 to 10 carbon atoms. More specifically, the alkoxy group having 1 to 20 carbon atoms may be a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, an iso-butoxy group, a tert-butoxy group, an n-pentoxy group, an iso-pentoxy group, a neo-pentoxy group, or a cyclohexene group.

[0103] C 2-20 Alkoxyalkyl of -R y -OR z Alkyl (-R) with a structure containing y ) is one or more hydrogens of alkoxy (-OR z ) may be a substituent substituted with. Specifically, the alkoxyalkyl having C2 to C20 carbon atoms may be a methoxymethyl group, a methoxyethyl group, an ethoxymethyl group, an iso-propoxymethyl group, an iso-propoxyethyl group, an iso-propoxyhectyl group, a tert-butoxymethyl group, a tert-butoxyethyl group, or a tert-butoxyhexyl group.

[0104] Also, group 4 transition metals can include titanium, zirconium, and hafnium.

[0105]

[0106] The hybrid supported metallocene catalyst used in the production of polyethylene according to the present invention is a hybrid catalyst comprising a first transition metal compound with high molecular weight and high polymerizability, and a second transition metal compound with low molecular weight and low polymerizability.

[0107] Specifically, the first transition metal compound represented by the above chemical formula 1 contributes to producing a high molecular weight copolymer having a high SCB content, and the second transition metal compound represented by the above chemical formula 2 contributes to producing a low molecular weight copolymer having a low SCB content. Accordingly, the hybrid supported metallocene catalyst can exhibit high copolymerizability in the high molecular weight region of polyethylene due to the first transition metal compound, while exhibiting low copolymerizability in the low molecular weight region of polyethylene due to the action of the second transition metal compound. As a result, the polyethylene produced using the hybrid supported metallocene catalyst can easily produce polyethylene that satisfies the above-described physical property requirements through tie-molecule formation due to strong low crystallinity expression in the high molecular weight region.

[0108] Specifically, in the hybrid supported metallocene catalyst, the first transition metal compound represented by the chemical formula 1 contributes to the production of a high molecular weight copolymer and exhibits a relatively high comonomer incorporation rate compared to the second transition metal compound.

[0109] Specifically, in the above chemical formula 1, M1 may be zirconium (Zr) or titanium (Ti).

[0110] Also, X 11 and X 12 are each independently halogen, and more specifically, may be chloro.

[0111] Also, in the above chemical formula 1, A1 is silicon, and Q 11 and Q 12 are each independently hydrogen, halogen, C 1-20 Alkyl, or C 2-20 Alkoxyalkyl, Q 11 and Q 12 Either one of C 2-20 It may be a tether group of an alkoxyalkyl. More specifically, Q 11 and Q 12 One of them is C2-20 One is alkoxyalkyl, and the other is C 1-20 It could be an alkyl.

[0112] As a bridging group connecting two ligands, Q 11 and Q 12 Either one of C 2-20 When the tether group of the alkoxyalkyl is included, the atomic size becomes larger and the available angle increases compared to the carbon bridge in the conventional metallocene compound, so that the monomer can easily approach during the polymerization reaction, thereby exhibiting excellent catalytic activity. In addition, the leaching of the catalyst precursor is prevented during the polymerization reaction, and as a result, fouling due to the reaction of the leached catalyst precursor and the cocatalyst can be prevented. Such an effect is described in the above Q 11 and Q 12 Either of them is -(CH2)nR b (Above R b is C 1-6 Alkoxy group, more specifically C 1-6 Straight chain alkoxy group or C 3-6 C, such as a branched alkoxy group, more specifically a tert-butoxy group 3-6 Branched alkoxy, n is an integer from 2 to 10, or from 3 to 9, and the remainder is C 1-4 It can be further increased in the case of alkyl. More specifically, Q 11 and Q 12 One of them may be tert-butoxyhexyl and the other may be methyl.

[0113] Also, in the above chemical formula 1, R 11 Inland R 14 are each independently, C 1-10 Alkyl, more specifically C 1-4 Alkyl, more specifically methyl. In this way, the cyclopentadienyl ligand in formula 1 is R 11 Inland R 14By being substituted, it can exhibit better catalytic activity due to the inductive effect that can supply sufficient electrons.

[0114] Also, in the above chemical formula 1, R 15 is C 1-6 It can be alkyl, more specifically C 1-4 Straight chain alkyl or C 3-6 It may be a branched alkyl, more specifically tert-butyl.

[0115] Specific examples of the first transition metal compound represented by the above chemical formula 1 include compounds having the following structures, but the present invention is not limited thereto.

[0116]

[0117]

[0118] The first transition metal compound represented by the above chemical formula 1 can be synthesized by applying known reactions, and a more detailed synthesis method can be found in the examples.

[0119] Meanwhile, in the hybrid supported metallocene catalyst, the second transition metal compound represented by the chemical formula 2 has a non-crosslinked structure of a hydrogenated indene ligand, specifically, a 4,5,6,7-tetrahydro-1-indene ligand and a cyclopentadiene ligand. Accordingly, the electronic / steric environment around the transition metal can be easily controlled, and as a result, the chemical structure, molecular weight distribution, and mechanical properties of the synthesized polyethylene can be easily controlled.

[0120] Specifically, in the above chemical formula 2, M2 may be zirconium (Zr). When the second transition metal compound includes Zr as a central metal, it has more orbitals capable of accepting electrons compared to when it includes other Group 14 elements such as Hf, and thus can easily bind to the monomer with higher affinity, resulting in a superior catalytic activity improvement effect.

[0121] Also, X 21 and X 22 can each independently be a halogen, and more specifically, a chloro.

[0122] Also, in the above chemical formula 2, R 21 Inland R 25 are each independently, C 1-10 Alkyl, more specifically C 1-4 Alkyl, more specifically methyl. Thus, the cyclopentadienyl ligand in formula 2 is R 21 Inland R 25 By being substituted, it can exhibit better catalytic activity due to the inductive effect that can supply sufficient electrons. In addition, by being used in combination with the first transition metal compound represented by the above chemical formula 1, the distribution of the comonomer in the polyethylene produced is appropriately controlled, so that polyethylene satisfying the above-described physical property requirements can be easily produced.

[0123] In addition, the second transition metal compound includes a hydrogenated indene ligand, i.e., a 4,5,6,7-tetrahydro-1-indene ligand, thereby exhibiting superior hydrogen reactivity compared to a case in which an indene group is included in the prior art. Accordingly, the amount of hydrogen input and the amount of wax generated during the polymerization reaction can be reduced, and as a result, process stability can be improved. In addition, by being used in combination with the first transition metal compound represented by the above chemical formula 1, the distribution of comonomers in the final polyethylene produced is concentrated toward a high molecular weight, and as a result, the impact strength properties of the polyethylene can be significantly improved.

[0124] In addition, the 1st and 3rd positions of the above 4,5,6,7-tetrahydro-1-indene ligand are unsubstituted, or R 26 and R 27 Each of which can be replaced by R 26 is specifically hydrogen or C 1-20 Alkyl, R 27 Silver hydrogen, C 1-20 Alkyl, C 2-20 Alkoxy, or C 2-20 It may be an alkoxyalkyl. More specifically, the R 26 is hydrogen or C 1-6 Alkyl, R 27 Silver hydrogen, C 1-6 Alkyl, or -(CH2) n -R b (Above R b is C 1-6 Alkoxy group, more specifically C 1-6 Straight chain alkoxy group or C 3-6 It may be an alkoxyalkyl group having a branched alkoxy group, and n is an integer from 2 to 10. In addition, the above -(CH2) n -R b In R b is C 3-6 C, such as a branched alkoxy group, more specifically a tert-butoxy group 3-6 Branched alkoxy, and n may be an integer from 3 to 9. More specifically, the R 26is hydrogen, or methyl, and R 27 may be hydrogen, methyl, ethyl, or tert-butoxyhexyl.

[0125] Specific examples of the second transition metal compound represented by the above chemical formula 2 include compounds having the following structures, but the present invention is not limited thereto.

[0126] .

[0127] The second transition metal compound represented by the above chemical formula 2 can be synthesized by applying known reactions, and a more detailed synthesis method can be found in the examples.

[0128] In addition, the hybrid supported metallocene catalyst can increase catalytic activity and more easily implement the properties of the polymer produced by controlling the molar ratio of the first and second transition metal compounds.

[0129] For example, the hybrid supported metallocene catalyst may include the first and second transition metal compounds in a molar ratio of 1:1 to 10:1. When the above-described mixing ratio conditions are satisfied, the catalytic activity is excellently maintained, while the high and low copolymerizabilities of the polyethylene produced from the hybrid supported catalyst are optimized, thereby further improving the sealing properties, drop impact strength properties, rigidity, and molding processability. More specifically, the molar ratio of the first and second transition metal compounds may be 2:1 to 8:1, or 2:1 to 5:1.

[0130] Additionally, the hybrid supported metallocene catalyst may include a cocatalyst.

[0131] Hybrid supported metallocene catalysts exhibit improved process stability along with high catalytic activity when they include a cocatalyst.

[0132] Specifically, the cocatalyst may include at least one compound represented by the following chemical formula 3.

[0133] [Chemical Formula 3]

[0134] -[Al(R 41 )-O]a-

[0135] In the above chemical formula 3,

[0136] R 41 is a halogen; or C substituted or unsubstituted with a halogen 1-20 It is hydrocarbyl;

[0137] a is an integer greater than or equal to 2.

[0138] Meanwhile, in the present specification, a hydrocarbyl group is a monovalent functional group in the form of removing a hydrogen atom from a hydrocarbon, and may include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an aralkyl group, an aralkenyl group, an aralkynyl group, an alkylaryl group, an alkenylaryl group, and an alkynylaryl group. In addition, the hydrocarbyl group having 1 to 20 carbon atoms may be a hydrocarbyl group having 1 to 15 carbon atoms or 1 to 10 carbon atoms. Specifically, the hydrocarbyl group having 1 to 20 carbon atoms is a straight-chain, branched-chain, or cyclic alkyl group such as a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group, a tert-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, or a cyclohexyl group; Or it may be an aryl group such as a phenyl group, a naphthyl group, or anthracenyl group.

[0139] Examples of compounds represented by the above chemical formula 3 include alkylaluminoxane compounds such as methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, or butylaluminoxane, and any one of these or a mixture of two or more thereof may be used. Among the above compounds, the cocatalyst may be more specifically methylaluminoxane.

[0140] The above alkylaluminoxane cocatalyst can further enhance catalytic activity by including a metal element that stabilizes the first and second transition metal compounds and acts as a Lewis acid to form a bond through a Lewis acid-base interaction with a functional group introduced to a bridge group of the first transition metal compound.

[0141] In addition, the amount of the cocatalyst used can be appropriately adjusted depending on the properties or effects of the desired catalyst and polyethylene. For example, when silica is used as the carrier described below, the cocatalyst can be supported in an amount of 100 g or more, 1000 g or more, or 2000 g or more, and 6000 g or less, or 5500 g or less, or 5400 g or less, based on the weight of the carrier, for example, 1,000 g of silica.

[0142] In addition, the hybrid supported metallocene catalyst may include a carrier. When the hybrid supported metallocene catalyst includes a carrier, the first and second transition metal compounds are used in the form of a supported catalyst supported on the carrier.

[0143] As the carrier, a carrier having a highly reactive hydroxyl group, silanol group, or siloxane group on the surface can be used. For this purpose, a carrier whose surface has been modified by calcination or whose surface has had moisture removed by drying can be used. For example, silica such as silica manufactured by calcining silica gel, or silica dried at high temperature, silica-alumina, and silica-magnesia can be used, and these can typically contain oxides, carbonates, sulfates, and nitrate components such as Na2O, K2CO3, BaSO4, and Mg(NO3)2.

[0144] When used in a supported catalyst state, the particle shape and bulk density of the polymer produced are excellent, and it can be suitably used in conventional slurry polymerization, bulk polymerization, and gas phase polymerization processes. In addition, among various supports, the silica support is supported by chemical bonding of the functional group of the transition metal compound, so that almost no catalyst is liberated from the surface of the support during the ethylene polymerization process, and as a result, fouling caused by adhesion of the reactor wall or polymer particles to each other can be minimized when producing polyethylene by slurry or gas phase polymerization.

[0145] The above-mentioned carrier may have an average particle diameter (D50) of 20 to 40 μm. When the above-mentioned particle size is present, the transition metal compound can be supported with superior efficiency, and as a result, the catalytic activity can be enhanced. More specifically, the carrier may have an average particle diameter of 20 μm or more, or 25 μm or more, and 40 μm or less, or 30 μm or less.

[0146] Meanwhile, in the present invention, the average particle diameter (D50) of the carrier refers to the particle diameter at the 50% point of the cumulative distribution of the number of particles according to particle size (particle diameter). The D50 can be measured using a laser diffraction method. Specifically, the target carrier is dispersed in a dispersion medium such as deionized water, and then introduced into a commercially available laser diffraction particle size measuring device (e.g., Microtrac S3500), and when the particles pass through the laser beam, the difference in the diffraction pattern according to the particle size is measured to calculate the particle size distribution. The particle size at the point where it becomes 50% of the cumulative distribution of the number of particles according to the particle diameter in the measuring device is calculated, and this is taken as the average particle size.

[0147] In addition, when supported on the carrier, the first and second transition metal compounds may be supported in an amount of, for example, 1 mmol or more, 1.5 mmol or more, or 2 mmol or more, and 100 mmol or less, or 50 mmol or less, or 30 mmol or less, or 10 mmol or less, or 5 mmol or less, based on 1,000 g of the silica carrier. When supported in the above content range, it may exhibit appropriate supported catalytic activity, which may be advantageous in terms of maintaining the activity of the catalyst and economic efficiency.

[0148] The hybrid supported metallocene catalyst having the above-described configuration can be produced by a production method including a step of supporting a promoter compound on a support, and a step of supporting the first and second transition metal compounds on the support. In this case, the supporting order of the promoter and the first and second transition metal compounds can be changed as needed, and the supporting order of the first and second transition metal compounds can also be changed as needed. The first and second transition metal compounds can be supported simultaneously. Considering the effect of the supported catalyst having a structure determined according to the supporting order, among these, supporting the promoter on the support and then sequentially supporting the first and second transition metal compounds can enable the produced supported catalyst to realize high catalytic activity and better process stability in the process of producing polyethylene.

[0149] Meanwhile, in the polymerization reaction, specific examples of alpha-olefin monomers include, as described above, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-eicosene, etc., and two or more of these may be used. More specifically, the alpha-olefin monomer may be 1-hexene.

[0150] The amount of the alpha-olefin monomer added may be determined depending on the properties of the polyethylene to be manufactured. For example, considering the properties of the polyethylene to be implemented in the present invention, the alpha-olefin monomer may be added in an amount of 4 to 30 wt%, more specifically, 4 wt% or more, or 8 wt% or more, or 10 wt% or more, or 12 wt% or more, and 30 wt% or less, or 25 wt% or less, or 20 wt% or less, based on the total weight of monomers including ethylene and the alpha-olefin monomer.

[0151] In addition, the above polymerization reaction is performed under the condition of hydrogen input.

[0152] Specifically, hydrogen may be introduced in an amount of 10 to 50 ppm, more specifically 10 ppm or more, or 15 ppm or more, or 20 ppm or more, or 25 ppm or more, and 50 ppm or less, or 45 ppm or less, or 40 ppm or less, or 38 ppm or less, or 35 ppm or less, based on the total weight of monomers including ethylene monomers and alpha-olefin monomers. When introduced in the above range, it is easier to implement the physical properties of the polyethylene described above. When the polymerization reaction is performed under conditions without introducing hydrogen, the melt index (MI) of the polyethylene produced may be significantly lowered.

[0153] Additionally, the above polymerization reaction can be carried out as a slurry polymerization reaction.

[0154] In the case of solution polymerization, since the catalyst is activated by a high temperature and high pressure reaction, catalyst decomposition and chain transfer are promoted, and the resulting resin composition has a narrow molecular weight distribution (MWD) and a low high molecular weight tail content. Accordingly, the resin composition manufactured by solution polymerization exhibits deteriorated moldability when manufacturing a film. However, in the case of the slurry polymerization process of the present invention, since polymerization is performed at a relatively low temperature, it is possible to secure a molecular structure containing a wide MWD and a large amount of high molecular weight tail, which is required for a polyethylene resin composition for manufacturing a transparent film. As a result, excellent moldability can be exhibited.

[0155] In the above slurry polymerization reaction, it can be performed using a single continuous slurry polymerization reactor or a loop slurry reactor.

[0156] In addition, during the above slurry polymerization reaction, the hybrid supported catalyst can be dissolved or diluted and injected in an aliphatic hydrocarbon solvent having 4 to 12 carbon atoms, such as isobutane, pentane, hexane, heptane, nonane, decane, and isomers thereof, an aromatic hydrocarbon solvent such as toluene and benzene, a hydrocarbon solvent substituted with a chlorine atom such as dichloromethane and chlorobenzene, etc. It is preferable to use the solvent used here after removing a small amount of water or air, etc. that act as catalyst poisons, by treating it with a small amount of alkyl aluminum, and it is also possible to carry out the reaction using an additional cocatalyst.

[0157] In addition, the polymerization reaction may be carried out at a temperature of 40°C or higher, or 60°C or higher, or 80°C or higher, and 110°C or lower, or 100°C or lower, or 90°C or lower. In addition, when the pressure conditions during the polymerization reaction are further controlled, the polymerization reaction may be carried out under a pressure of 5 bar or higher, or 10 bar or higher, or 20 bar or higher, or 30 bar or higher, and 50 bar or lower, or 45 bar or lower, or 40 bar or lower. When polymerization is carried out under such temperature and pressure, the desired physical properties of polyethylene can be more easily realized.

[0158] The polyethylene produced by the above-described production method has the crystal distribution characteristics, molecular weight distribution characteristics, rheological characteristics, and processing characteristics described above. Accordingly, the polyethylene can exhibit excellent low-temperature sealing characteristics and hot-tack characteristics, and can also exhibit well-balanced improved molding processability along with excellent drop impact strength characteristics and rigidity. As a result, downgauging is possible when producing a film using the polyethylene, and the polyethylene is advantageous for D4R applications. In addition, the polyethylene can be usefully used in multi-purpose films such as food, agricultural, and general industrial films, or stretch films, and can be particularly used in the sealant layer of All-PE.

[0159] Accordingly, the present invention provides a resin composition comprising the polyethylene, specifically a composition for forming a film.

[0160] In addition, the present invention provides a film manufactured using the polyethylene or the resin composition.

[0161] The above film can be manufactured according to a conventional film manufacturing method, except that the above-mentioned polyethylene is used. For example, the film can be manufactured according to an inflation method in which a film-forming composition is manufactured by mixing only the above-mentioned polyethylene or optionally by mixing additives such as antioxidants and processing aids, and then extruding the film into a film using an extruder.

[0162] More specifically, the resin composition containing the polyethylene may be applied for a sealant layer, and co-extruded with a composition for forming another film layer, or extruded with a blown film extruder or a cast film extruder, or a film may be separately manufactured with the resin composition containing the polyethylene using extrusion coating on a substrate such as paper, and then the manufactured film may be laminated with another film. However, the present invention is not limited thereto, and any known manufacturing method may be applied to manufacture various films.

[0163]

[0164] The above film exhibits excellent low-temperature sealing properties and stiffness by including the above polyethylene.

[0165]

[0166] Specifically, when the film is a single-layer film having a film thickness of 45 to 55 μm, or 48 to 52 μm, more specifically 50 μm, the sealing initiation temperature (SIT) measured according to ASTM F 1921 is 80.0°C or less. The sealing initiation temperature is 80.0°C or less, or 79.5°C or less, or 79.0°C or less, or 78.5°C or less, or 78.0°C or less, or 77.5°C or less, or 77.0°C or less, or 76.5°C or less, or 76.0°C or less, or 75.5°C or less, or 75.0°C or less, or 74.5°C or less, or 74.0°C or less. The lower the sealing initiation temperature, the better the low-temperature sealing property and sealing strength, so there is no particular limitation on the lower limit, but for example, it may be 60.0°C or higher, or 61.0°C or higher, or 62.0°C or higher, or 63.0°C or higher, or 64.0°C or higher, or 65.0°C or higher, or 66.0°C or higher, or 67.0°C or higher, or 68.0°C or higher, or 69.0°C or higher, or 70.0°C or higher, or 71.0°C or higher, or 72.0°C or higher, or 73.0°C or higher.

[0167] For reference, the above sealing initiation temperature is the temperature at which the heat seal strength reaches 2 N / 25.4 mm when the sealing strength is measured according to ASTM F 1921 (conditions of sealing time 0.5 sec, sealing pressure 0.3 MPa, delay time 30.0 sec, tensile speed 200 mm / sec, J&B 5000) when the film thickness is 45 to 55 µm, or 48 to 52 µm, more specifically, 50 µm, in a single-layer film.

[0168]

[0169] In addition, the polyethylene film can exhibit improved drop impact strength properties in addition to the sealing properties.

[0170] Specifically, when the film is a single-layer film having a film thickness of 45 to 55 μm, or 48 to 52 μm, more specifically 50 μm, the drop impact strength measured according to ASTM D 1709 [Method A] is 1,200 gf or more, or 1,250 gf or more, or 1,300 gf or more, or 1,350 gf or more. The drop impact strength is not particularly limited in its upper limit as it is better the higher it is, but for example, it may be 3,000 gf or less, or 2,900 gf or less, or 2,800 gf or less, or 2,700 gf or less, or 2,600 gf or less, or 2,500 gf or less, or 2,400 gf or less, or 2,300 gf or less, or 2,200 gf or less, or 2,100 gf or less, or 2,000 gf or less, or 1,900 gf or less, or 1,800 gf or less, or 1,700 gf or less.

[0171]

[0172] In addition, when the film is a single-layer film having a film thickness of 45 to 55 ㎛, or 48 to 52 ㎛, more specifically 50 ㎛, the 1% secant modulus in the MD direction of the film, measured according to ASTM D882 using a Universal Testing Machine (UTM), is 1,500 kg / cm. 2 or more than 1,600 kg / cm 2 or more than 1,700 kg / cm 2 or more than 1,800 kg / cm 2 And the 1% secant modulus in the TD direction is 1,800 kg / cm 2 or more than 1,900 kg / cm 2 or more than 2,000 kg / cm 2 or more than 2,100 kg / cm 2 That's all.

[0173] The secant modulus is defined in ASTM D882 and represents the stiffness of a film. The secant modulus is related to density, and the higher the density, the higher the secant modulus and stiffness. In addition, the higher the secant modulus, the better the openability, visibility, and coefficient of friction (COF). Accordingly, the upper limit of the secant modulus is not particularly limited, but as an example, the 1% secant modulus in the MD and TD directions of the film is 3,000 kg / cm each. 2 or less, or 2,900 kg / cm 2 or less, or 2,800 kg / cm 2 or less, or 2,700 kg / cm 2 or less, or 2,600 kg / cm 2 or less, or 2,500 kg / cm 2 or less, or 2,400 kg / cm 2 It could be as follows:

[0174]

[0175] For reference, the above sealing initiation temperature, drop impact strength, and secant modulus were measured for a film formed into a single-layer film having a thickness of 45 to 55 μm, or 48 to 52 μm, more specifically 50 μm, using a blown film extruder (die diameter 120 mm, die gap 2.0 mm, BUR 2.5, Dual air-ring system) from a composition containing 95 wt% or more, or 96 wt% or more, or 97 wt% or more, or 98 wt% or more, or 99 wt% or more, of the polyethylene of the present invention based on the total composition.

[0176]

[0177] Hereinafter, preferred examples are presented to aid understanding of the present invention. However, the following examples are provided solely to facilitate understanding of the present invention and are not intended to limit the scope of the present invention.

[0178] Meanwhile, in this specification, room temperature means 23±2℃.

[0179]

[0180] <Preparation of Transition Metal Compounds>

[0181] Synthesis Example 1

[0182]

[0183] Preparation of ligands

[0184] Tetramethylcyclopentadiene (TMCP, 1 equiv) was dissolved in THF (0.3 M), and n-BuLi (1.05 eq) was slowly added dropwise at -25°C, followed by stirring at room temperature for 3 hours. t-BuOHexSiMeCl2 (1.00 eq) was added to the resulting reaction mixture at -10°C, followed by stirring at room temperature overnight. The solvent was completely vacuum-dried, and tBuNH2 (10 eq) was added and stirred at room temperature overnight. Afterwards, the mixture was worked up with water and dried to obtain the ligand.

[0185]

[0186] Preparation of transition metal compounds

[0187] The above-mentioned ligand was dissolved in toluene (0.3 M), n-BuLi (2.05 eq) was added at -25°C, and stirred at room temperature for 3 hours. In a glove box, TiCl4(THF)2 (titanium tetrachloride tetrahydrofuran adduct, 1 eq) was prepared in another flask, added to the ligand-Li flask using a cannula at -25°C, and washed and added using toluene (1.0 M).

[0188] Upon completion of the reaction, the solvent was vacuum-dried, DCM was re-introduced, LiCl was removed through a filter, and the filtrate was vacuum-dried to obtain a liquid transition metal compound (Cat 1).

[0189] 1 H NMR (500 MHz, CDCl3) δ 3.34 (t, 2H), 2.24 (d, J = 1.7 Hz, 6H), 2.13 (d, J = 3.2 Hz, 6H), 1.57 - 1.45 (m, 6H), 1.42 (s, 9H), 1.32 - 1.22 (m, 4H), 1.18 (s, 9H), 0.67 (s, 3H).

[0190]

[0191] Synthesis Example 2-1

[0192] (Cat 2-1)

[0193] Indene (1 eq) was dissolved in THF (0.3 M), and n-BuLi (1.05 eq) was slowly added dropwise at -25°C, and the mixture was stirred at room temperature for 3 hours. Then, CH3-I (1.05 eq) was added at -10°C, and the mixture was stirred overnight at room temperature, worked up with water, and dried to obtain 3-MethylIndene. 3-MethylIndene (1 eq) thus synthesized was dissolved in THF (0.3 M), and n-BuLi (1.05 eq) was slowly added dropwise at -25°C, and the mixture was stirred at room temperature for 3 hours. Then, CH3-I (1.05 eq) was added at -10°C, and the mixture was stirred overnight at room temperature, worked up with water, and dried to obtain 1,3-dimethyl-Indene.

[0194]

[0195] Preparation of transition metal compounds

[0196] The above-mentioned ligand was dissolved in Ether (0.3 M), n-BuLi (1.05 eq) was added at -25°C, and stirred at room temperature for 3 hours. In a glove box, PMCpZrCl3 (Pentamethylcyclopentadienylzirconium trichloride) (1 eq) was prepared in another flask, added to the ligand-Li flask using a cannula at -25°C, and washed and added using Ether (1.0 M).

[0197] Upon completion of the reaction, the solvent was vacuum-dried, DCM was reintroduced, LiCl was removed through a filter, the filtrate was vacuum-dried, and slurry was formed using hexane. The resulting solid was then filtered and vacuum-dried to obtain a solid metallocene compound intermediate.

[0198]

[0199] In a glove box, the above metallocene compound intermediate was placed in a mini parr, and 5 mol% of Pd / C (10 wt%) was added. A magnetic bar was inserted here and moved outside the glove box using a closing system. DCM (0.5 M) was added to the parr, and H2 gas (10 barg) was added. After repeating the vent-charge cycle three times, the mixture was placed in a 40°C oil bath and stirred. When the pressure of the parr decreased below 5 barg, the previous charging process was repeated, and the reaction was continued until there was no more consumption of H2 gas. Upon completion of the reaction, the remaining H2 gas was vented and replaced with Ar gas. After cooling to room temperature, the mixture was filtered using a cannula, and the filtrate was vacuum-dried. The dried filtrate was slurried using hexane, and this was filtered to obtain a solid transition metal compound (Cat 2-1).

[0200] 1H NMR (500 MHz, CDCl3) δ 5.60 (s, 1H), 2.90 (dt, J = 16.4, 6.3 Hz, 2H), 2.32 (dt, J = 16.3, 6.0 Hz, 2H), 2.04 (s, 15H), 1.79 - 1.66 (m, 2H), 1.67 (s, 6H), 1.64 - 1.54 (m, 2H).

[0201]

[0202] Synthesis Example 2-2

[0203] (Cat 2-2)

[0204] Preparation of ligands

[0205] Indene (1 eq) was dissolved in THF (0.3 M), n-BuLi (1.05 eq) was slowly added dropwise at -25°C, and the mixture was stirred at room temperature for 3 hours. Then, CH3-CH2-I (1.05 eq) was added at -10°C, stirred overnight at room temperature, worked up with water, and dried to obtain 3-Ethyl-Indene.

[0206]

[0207] Preparation of transition metal compounds

[0208] The above-mentioned ligand was dissolved in Ether (0.3 M), n-BuLi (1.05 eq) was added at -25°C, and stirred at room temperature for 3 hours. In a glove box, PMCpZrCl3 (Pentamethylcyclopentadienylzirconium trichloride) (1 eq) was prepared in another flask, added to the ligand-Li flask using a cannula at -25°C, and washed and added using Ether (1.0 M).

[0209] Upon completion of the reaction, the solvent was vacuum-dried, DCM was reintroduced, LiCl was removed through a filter, the filtrate was vacuum-dried, and slurry was formed using hexane. The resulting solid was then filtered and vacuum-dried to obtain a solid metallocene compound intermediate.

[0210] In a glove box, the above metallocene compound intermediate was placed in a mini parr, and 5 mol% of Pd / C (10 wt%) was added. A magnetic bar was inserted here and moved outside the glove box using a closing system. DCM (0.5 M) was added to this parr, and H2 gas (10 barg) was added. After repeating the vent-charge cycle three times, the mixture was placed in a 40°C oil bath and stirred. When the pressure of the parr decreased below 5 barg, the previous charging process was repeated, and the reaction was continued until there was no more consumption of H2 gas. When the reaction was complete, the remaining H2 gas was vented and replaced with Ar gas. After cooling to room temperature, the mixture was filtered using a cannula, and the filtrate was vacuum-dried. The dried filtrate was slurried using hexane, and this was filtered to obtain a solid transition metal compound (Cat 2-2).

[0211] 1 H NMR (500 MHz, CDCl3) δ 5.60 (d, J = 2.7 Hz, 2H), 5.20 (d, J = 2.7 Hz, 2H), 2.83 - 2.71 (m, 2H), 2.49 - 2.36 (m, 3H), 2.21 (dd, J = 15.1, 7.6 Hz, 1H), 2.01 (s, 15H), 1.98 - 1.80 (m, 2H), 1.66 - 1.51 (m, 2H), 1.03 (t, J = 7.6 Hz, 3H).

[0212]

[0213] <Catalyst Manufacturing>

[0214] Manufacturing Example 1

[0215] 2.0 kg of toluene and 1000 g of silica (SP2410, Grace Davision) were charged into a 20L SUS high-pressure reactor, and the reactor temperature was raised to 40°C while stirring. 5.4 kg of methylaluminoxane (10 wt% in toluene, Albemarle) was charged into the reactor, the temperature was raised to 70°C, and the reactor was stirred at about 200 rpm for about 12 hours. Thereafter, the temperature of the reactor was lowered to 40°C, and stirring was stopped. The reaction product was allowed to stand for about 10 minutes and then decantated. 2.0 kg of toluene was again charged into the reaction product, stirred for about 10 minutes, stopped, and the reactor was allowed to stand for about 30 minutes before decantation.

[0216] 2.0 kg of toluene was charged into the reactor, and then the compound (Cat 1) (15 mmol) prepared in Synthesis Example 1 as the first transition metal compound, the compound (Cat 2-1) (10 mmol) prepared in Synthesis Example 2-1 as the second transition metal compound, and 1000 mL of toluene were charged. The temperature of the reactor was raised to 85°C, and stirring was performed for approximately 90 minutes.

[0217] Afterwards, the temperature of the reactor was lowered to room temperature, stirring was stopped, the reaction product was allowed to stand for about 30 minutes, and the reaction product was decantated. Next, 3 kg of hexane was added to the reactor, and the hexane slurry solution was transferred to a 20 L filter dryer, the solution was filtered, and dried under reduced pressure at 50 °C for about 4 hours to obtain 1.5 kg of a hybrid metallocene catalyst.

[0218]

[0219] (Cat 1) (Cat 2-1)

[0220]

[0221] Manufacturing Examples 2 to 4

[0222] As described in Table 1 below, a hybrid supported metallocene catalyst was prepared in the same manner as in Preparation Example 1, except that the types of the first and second transition metal compounds were changed.

[0223]

[0224] Catalyst 1 Transition metal compound 2 Transition metal compound Mixing molar ratio Preparation example 1 Cat 1, 15 mmol Cat 2-1, 10 mmol 1.5:1 Preparation example 2 Cat 1, 20 mmol Cat 2-2, 10 mmol 2:1 Preparation example 3 Cat 1, 55 mmol Cat 2-1, 10 mmol 5.5:1 Preparation example 4 Cat 1, 30 mmol Cat 2-1, 10 mmol 3:1

[0225] <Manufacturing of polyethylene>

[0226] Examples 1-1 to 4-1

[0227] A 140 L continuous polymerizer capable of performing an isobutene slurry loop process with a polymerization reactor and operating at a reaction velocity of approximately 7 m / s was prepared. The reactants required for polyethylene polymerization were continuously fed into the reactor as described in Table 2. The catalysts used in each polymerization reaction were those prepared in the manufacturing examples described in Table 1, and the catalysts were mixed with the isobutene slurry and fed. Furthermore, the polymerization reaction was performed at a pressure of approximately 40 bar and a temperature of approximately 85°C, and other key conditions for the polymerization reaction are shown in Table 2 below.

[0228]

[0229] Comparative Example 1-1

[0230] HP1018, a copolymer of ethylene and 1-hexene manufactured by LG Chem, was used.

[0231]

[0232] Comparative Example 2-1

[0233] LF100A, a copolymer of ethylene and 1-octene manufactured by LG Chem, was used.

[0234]

[0235] Comparative Example 3-1

[0236] XM3137, a copolymer of ethylene and 1-hexene manufactured by LG Chem, was used.

[0237]

[0238] Catalytic ethylene input (kg / hr)1-hexene input 1 (wt%) hydrogen input 2 (ppm)Activity (kgPE / kgSiO2·hr)Example 1-1 Manufacturing Example 126.515306.5Example 2-1 Manufacturing Example 226.520406.0Example 3-1 Manufacturing Example 327.517387.0Example 4-1 Manufacturing Example 426.58405.5

[0239] In Table 2 above, the activity (Activity, kgPE / kgSiO2·hr) was calculated as the ratio of the polymer weight (kgPE) produced per the catalyst weight (kg) used per unit time (hr).

[0240] Also, the 1-hexene input amount (wt%) is calculated as a percentage of the 1-hexene input amount based on the total weight of monomers containing ethylene and 1-hexene, and the hydrogen input amount (ppm) is calculated as a percentage of the total weight of monomers containing ethylene and 1-hexene.

[0241]

[0242] Film Manufacturing

[0243] A film was manufactured using the polyethylene manufactured in the examples and comparative examples using the following method.

[0244]

[0245] Examples 1-2 to 4-2, Comparative Examples 1-2 to 3-2

[0246] Based on the total weight of the polyethylene manufactured in the above examples or comparative examples, 1200 ppm of an antioxidant (Songnox 1076 (Songwon): Songnox 1680 (Songwon) = 1:2 in weight ratio) was added and mixed, and a twin screw extruder (Twin screw extruder; TEK 30 MHS, manufactured by SMPLATECH CO., diameter 32 pi, L / D = 40) was used to extrude at an extrusion temperature of 190°C at an extrusion rate of 35 kg / hr, thereby manufacturing a composition for forming a pellet-shaped film weighing about 18 kg.

[0247] A film was manufactured by inflation molding the film-forming composition manufactured above under the following film extrusion conditions.

[0248]

[0249] <Film forming conditions>

[0250] Single Screw Extruder (Eugene Engineering Single Screw Extruder, Blown Film M / C, 50 pi, L / D=32)

[0251] Melting temperature (or extrusion temperature): 185℃

[0252] Die Gap: 2.0mm

[0253] Die diameter: 120mm

[0254] Blown-Up Ratio: 2.5

[0255] Maintain Frost Line Height at 200~250mm

[0256] Sample extrusion rate: 300~500g / min

[0257] Cooling: Uses dual air-ring

[0258] Film thickness: 50㎛

[0259]

[0260] Experimental Example 1

[0261] The physical properties of the polyethylene manufactured in the above examples and comparative examples were measured as follows, and the results are shown in Tables 3 and 5 below.

[0262]

[0263] (1) Melt Index (MI) 2.16 ): Measured according to ASTM D1238 (Condition E, 190 ℃, 2.16 kg load).

[0264]

[0265] (2) Density: Measured according to ASTM D1505 standard.

[0266]

[0267] (3) Molecular weight distribution (MWD)

[0268] For the polyethylene according to the above examples and comparative examples, the weight average molecular weight (Mw, g / mol) and number average molecular weight (Mn, g / mol) were measured through gel permeation chromatography (GPC) analysis, and the molecular weight distribution (MWD, Mw / Mn) was obtained by dividing the weight average molecular weight measured above by the number average molecular weight.

[0269] Specifically, the gel permeation chromatography (GPC) device is Polymer Char GPC-IR. ® The device was used, and a Polymer Laboratories PLgel MIX-B 300 mm long column was used. The measurement temperature was 160°C, 1,2,4-trichlorobenzene was used as a solvent, and the flow rate was 1 mL / min. Each sample of polyethylene manufactured in the examples and comparative examples was analyzed by GPC analysis equipment (Polymer Char GPC-IR). ®) was dissolved in 1,2,4-trichlorobenzene containing 0.03% BHT at 160℃ for 2 hours, pretreated, and then prepared at a concentration of 16 mg / 8 mL and supplied in an amount of 200 μL. The values ​​of Mw and Mn were calculated using a calibration curve formed using polystyrene standard specimens. The weight-average molecular weights of the polystyrene standard specimens were 9 types: 2000 g / mol, 10000 g / mol, 30000 g / mol, 70000 g / mol, 200000 g / mol, 700000 g / mol, 2000000 g / mol, 4000000 g / mol, and 10000000 g / mol.

[0270]

[0271] (4) Analysis of crystal distribution and molecular weight distribution

[0272] Cross fraction chromatography (CFC) analysis was performed on the polyethylene manufactured in the above examples and comparative examples using the following method.

[0273]

[0274] [Cross-fractionation chromatography measurement conditions (including TREF and GPC analysis)]

[0275] - Analysis equipment: Polymer Char CFC - 7890B (G3440D)

[0276] (Detector: Integrated Detector IR5 MCT)

[0277] - Sample preparation and loading: 32 mg of polyethylene manufactured in the above examples or comparative examples was placed in a 10 mL vial and placed in an autosampler, 8 mL of 1,2,4-trichlorobenzene (TCB) was added, dissolved at 160°C for 90 minutes, and stabilized at 140°C for 20 minutes. After nitrogen purge, extraction was performed and loaded onto a temperature rising elution fractionation column (TREF column).

[0278] - Crystallization: The temperature of the sample previously loaded onto the TREF column was adjusted to 140℃, then cooled from 140℃ to 35℃ at a rate of 0.5℃ / min and maintained for 15 minutes.

[0279] The detailed conditions for the above stabilization and crystallization are as follows:

[0280]

[0281]

[0282] - Temperature Rising Elution Fractionation (TREF) Analysis: The previously crystallized sample was heated from 30°C to 120°C at a rate of 1°C / min to the fraction temperature shown below, then fixed. The concentrations of the fractions eluted at that temperature for 5 minutes were measured. A TREF analysis graph was derived from the concentration measurement results.

[0283] From the TREF graph, the content ratio of the polymer fraction eluted in the region of the elution temperature 35°C or lower (Te ≤ 35°C), the content ratio of the polymer fraction eluted in the region of the elution temperature 30°C or higher and lower than 60°C (30°C≤Te<60°C), the content ratio of the polymer fraction eluted in the region of the elution temperature 60°C or higher and lower than 80°C (60°C≤Te<80°C), and the content ratio of the polymer fraction eluted in the region of the elution temperature 80°C or higher (80°C≤Te) were calculated (weight %), respectively.

[0284] <fraction temperature>

[0285] 30℃ / 35℃ / 40℃ / 43℃ / 46℃ / 49℃ / 52℃ / 55℃ / 58℃ / 61℃ / 64℃ / 67℃ / 70℃ / 73℃ / 76℃ / 79℃ / 82℃ / 85℃ / 88℃ / 91℃ / 94℃ / 97℃ / 100℃ / 105℃ / 120℃

[0286]

[0287] <Measurement conditions>

[0288]

[0289]

[0290] - GPC analysis: The fractions eluted for each temperature range in the previous TREF analysis were analyzed by GPC equipment (Polymer Char GPC-IR) ® ) After moving to the GPC column provided, GPC analysis was performed according to the following conditions.

[0291]

[0292] <Sample Preparation>

[0293] The polyethylene fraction is pretreated by dissolving it in 1,2,4-trichlorobenzene at 160°C for 10 hours, and then prepared at a concentration of 10 mg / 10 mL, and supplied in an amount of 200 μL.

[0294] <GPC 분석 조건>

[0295] GPC Device: Polymer Char GPC-IR®

[0296] GPC Column: Polymer Laboratories PLgel MIX-B 300 mm long column

[0297] Measurement temperature: 160℃

[0298] Solvent: 1,2,4-Trichlorobenzene

[0299] Flow rate: 1 mL / min

[0300] Standard specimen: Polystyrene standard specimen

[0301] (Weight average molecular weight of polystyrene standard specimens: 9 types: 2000 g / mol, 10000 g / mol, 30000 g / mol, 70000 g / mol, 200000 g / mol, 700000 g / mol, 2000000 g / mol, 4000000 g / mol, 10000000 g / mol)

[0302]

[0303] <Measurement conditions>

[0304]

[0305]

[0306] Experimental Example 2

[0307] The physical properties of the films manufactured in the examples and comparative examples were measured as follows, and the results are shown in Tables 4 and 6 below.

[0308]

[0309] (1) Dart drop impact strength

[0310] For the films of the examples and comparative examples manufactured above, the drop impact strength was measured according to the ASTM D1709 [Method A] standard, and the average value was taken by measuring at least 5 sets (20 times / 1 set) per film sample.

[0311]

[0312] (2) Sealing initiation temperature (SIT)

[0313] According to ASTM F 1921, when the seal strength was measured at each temperature at 5℃ intervals between 60℃ and 130℃ using a J&B Hot tack tester (Hot tacker 5000) under the conditions of a sealing time of 0.5 seconds, a sealing pressure of 0.3 MPa, a delay time of 30.0 seconds, and a tensile speed of 200 mm / sec, the temperature at which the heat seal strength reached 2 N / 25.4 mm was defined as the seal initiation temperature (SIT).

[0314] In the unit N / 25.4mm, “25.4mm” refers to the width of the film sample for which sealing is measured.

[0315]

[0316] (3) Secant modulus

[0317] For the films of the above examples and comparative examples, the 1% secant modulus in the machine direction (MD) and transverse direction (TD) of the films was measured according to ASTM D882 using an Instron UTM (Universal Testing Machine).

[0318]

[0319] Example 1-1 Example 2-1 Example 3-1 Example 4-1 MI (g / 10 min) 1.037 1.6 1.34 1.1 Density (g / cm3) 0.9178 0.9163 0.9171 0.915 3 Comonomer 1-hexene 1-hexene 1-hexene 1-hexene MWD 3.84 4.164.16 3.65 Crystal distribution characteristics 30 ≤ Te < 60℃, (wt%) 30.36 36.59 32.86 25.49 60 ≤ Te < 80℃, (wt%) 26.96 28.97 29.05 24.34 Te ≥ 80℃ (wt%) 42.69 34.45 38.08 5 0.18 Te ≤ 35℃(wt%)12.416.415.812.4

[0320] Example 1-2 Example 2-2 Example 3-2 Example 4-2 SIT (℃) 79747671.5 When a=2924, b=2606~2620, the value of “a*density-b” 63.65~77.65 59.26~73.26 61.60~75.60 56.34~70.34 When a=2924, b'=2600~2604, the value of “a*density-b'” 79.65~83.65 75.26~79.26 77.60~81.60 72.34~76.34 Drop impact strength (gf) 1,350 1,700 1,400 1,300 1% Secant, MD (kg / cm 2 )1,7461,8751,7701,6311% Secant, TD (kg / cm 2 )2,1192,0511,9482,134

[0321] Comparative Example 1-1 Comparative Example 2-1 Comparative Example 3-1 MI (g / 10 min) 11.2 1.26 Density (g / cm3) 0.9 18 0.9 0 2 0.9 27 Comonomer 1-hexene 1-octene 1-hexene MWD 2.4 3 2.4 1 2.8 9 Crystal distribution characteristics 30 ≤ Te < 60℃, (wt%) 5.3 40 40 60 ≤ Te < 80℃, (wt%) 50.6 59.7 59.7 Te ≥ 80℃ (wt%) 44.1 0.3 0.3 Te ≤ 35℃ (wt%) 0.7 4.9 4.9

[0322] Comparative Example 1-2 Comparative Example 2-2 Comparative Example 3-2 SIT (℃) 10 2 6 9 1 1 2 When a = 2924, b = 2606~2620, the value of “a*density-b” 64.23~78.23 17.45~31.45 90.55~104.55 When a = 2924, b' = 2600~2604, the value of “a*density-b'” 80.23~84.23 33.45~37.45 106.55~110.55 Drop impact strength (gf) 1,200 1,900 300 1% Secant, MD (kg / cm 2 )2,0006392,9421% Secant, TD (kg / cm 2 )2,3006873,266

[0323] Referring to Tables 3 to 6 above, the examples of the present invention in which the sealing initiation temperature (SIT) satisfies the range of the given mathematical expression 1 exhibited significantly lower sealing initiation temperatures at similar densities compared to the comparative examples that did not satisfy the SIT, confirming excellent low-temperature sealing properties. In addition, it was confirmed that the drop impact strength and secant modulus were also expressed at high levels, achieving a remarkable effect in which both the density-low-temperature sealing properties and the density-drop impact strength, which are in a trade-off relationship in general polyethylene, were improved.

Claims

1. Polyethylene satisfying the following mathematical formula 1: [Mathematical Formula 1] a * x - b ≤ y ≤a * x - b' In the above mathematical formula 1, y is the sealing initiation temperature (SIT) (unit: ℃) measured according to ASTM F 1921, x is the density (unit: g / cm) measured according to ASTM D 1505 3 ) and, a is 2924, b is between 2606 and 2620, and b' is between 2600 and 2604.

2. In paragraph 1, In the temperature rising elution fractionation analysis of cross-fraction chromatography, the content of the polymer fraction eluted at an elution temperature of 30°C or more and less than 60°C based on the total weight of polyethylene satisfies 18.0 to 38.0 wt%, Polyethylene.

3. In paragraph 1, In the temperature rising elution fractionation analysis of cross-fraction chromatography, the content of the polymer fraction eluted at an elution temperature of 35°C or lower based on the total weight of polyethylene satisfies 5.0 to 30.0 wt%. Polyethylene.

4. In paragraph 1, In the temperature rising elution fractionation analysis of cross-fraction chromatography, the content of the polymer fraction eluted at an elution temperature of 60°C or more and less than 80°C based on the total weight of polyethylene satisfies 20.0 to 50.0 wt%, Polyethylene.

5. In paragraph 1, In the temperature rising elution fractionation analysis of cross-fraction chromatography, the content of the polymer fraction eluted at a temperature of 80°C or higher based on the total weight of polyethylene satisfies 30.0 to 60.0 wt%, Polyethylene.

6. In paragraph 1, A density of 0.900 to 0.925 g / cm as measured according to ASTM D1505. 3 person, Polyethylene.

7. In paragraph 1, Polyethylene having a molecular weight distribution (MWD) of 2.0 to 5.

0.

8. In paragraph 1, The above polyethylene is a polyethylene having a melting index of 0.5 to 5.0 g / 10 min, measured at a temperature of 190°C and a load of 2.16 kg according to ASTM D1238.

9. In paragraph 1, The above polyethylene is a type of copolymer of ethylene and alpha olefin.

10. In paragraph 9, The above alpha olefin is 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, or 1-octene, Polyethylene.

11. A film containing polyethylene according to paragraph 1.

12. In paragraph 11, When the film thickness is 45 to 55 ㎛, the sealing initiation temperature (SIT) measured according to ASTM F 1921 is 80℃ or less. film.

13. In paragraph 11, When the film thickness is 45 to 55 ㎛, the drop impact strength measured according to ASTM D 1709 is 1,200 gf or more. film.

14. In paragraph 11, When the film thickness is 45 to 55 ㎛, the 1% secant modulus in the MD direction measured according to ASTM D882 is 1,500 kg / cm 2 And the 1% secant modulus in the TD direction is 1,800 kg / cm 2 Lee Sang-in, film.

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