Polyethylene resin composition having excellent stretching processability

Abstract

The present invention relates to a polyethylene resin composition having excellent stretching process stability and enabling the production of a film having high mechanical properties when stretched, and to a stretched film having excellent mechanical properties, which is produced therefrom.

Description

Polyethylene resin composition with excellent stretchability

[0001] Cross-citation with related application(s)

[0002] This application claims the benefit of priority based on Korean Patent Application No. 10-2024-0164516 filed November 18, 2024, and all contents disclosed in said document are incorporated herein as part of this specification.

[0003] The present invention relates to a polyethylene resin composition capable of producing a film having excellent stretching stability and excellent mechanical strength during stretching, and a stretched film comprising the same.

[0004] Thin film products manufactured from linear low-density polyethylene (LLDPE) and / or high-density polyethylene (HDPE) are widely used in packaging applications such as product bags, grocery bags, food and specialty packaging, and industrial liners. In these applications, shrink films are primarily used to package products while maintaining their shape, thereby providing protection from touch during product display.

[0005] In particular, among these shrink films, biaxially oriented polymer films are widely used for packaging applications due to their excellent mechanical properties, productivity, and printability. Commercially available packaging films generally use BOPP (biaxially oriented polypropylene), BOPET (biaxially oriented polyethylene terephthalate), or BOPA (biaxially oriented polyamide) for the printing layer and LLDPE film for the sealing layer. These composite materials are not recyclable, and the demand for single-material packaging is increasing due to the spread of packaging recycling regulations. Therefore, research and development is underway to manufacture single-material packaging films by replacing the printing layer film with biaxially oriented polyethylene (BOPE) film.

[0006] Meanwhile, when developing polyethylene stretched films, a method is generally used in which polyethylene sheets are manufactured, cut, and then evaluated for stretchability on a laboratory scale. However, if the physical properties of the resin composition are not uniform, local variations in composition or properties may occur during the sheet manufacturing process. Consequently, even if excellent performance is observed during laboratory stretchability evaluations, the expected stretchability is often not achieved during the actual mass production stage. Therefore, results evaluating stretchability from only one or two specimens cannot be considered representative of the resin's overall stretchability. For a more reliable evaluation, stretchability must be assessed on at least 10 specimens; excellent stretchability must be confirmed in at least 5 of these, and ideally at least 7, in order to reliably manufacture films with excellent stretchability during the mass production stage.

[0007] As a result of diligent efforts, the inventors of the present invention have developed a polyethylene resin composition that not only has excellent stretchability but also has uniform physical properties of the resin, so that the sheet produced from the resin consistently has excellent stretchability.

[0008] One objective of the present invention is to provide a polyethylene resin composition capable of producing a film having excellent stretching stability and high mechanical properties during stretching.

[0009] Another objective of the present invention is to provide a stretched film with excellent mechanical properties comprising the polyethylene resin composition described above.

[0010] However, the technical problems that the present invention aims to solve are not limited to those mentioned above, and other unmentioned problems will be clearly understood by those skilled in the art from the description below.

[0011] According to one embodiment of the present invention, a polyethylene resin composition comprising an ethylene homopolymer or an ethylene / C4 to C10 alpha-olefin copolymer may satisfy condition 1) below and at least one of conditions 2) to 4):

[0012] 1) The stretchability index represented by Formula 1 below is 0.7 or higher;

[0013] 2) A stiffness index expressed by the following Equation 4 is 0.5 or higher;

[0014] 3) A tensile strength index expressed by the following Equation 5 is 0.5 or higher;

[0015] 4) The puncture strength index, expressed by the following Equation 6, is 0.5 or higher.

[0016] [Equation 1]

[0017]

[0018] In the above Equation 1, Z is defined by the following Equation 2:

[0019] [Equation 2]

[0020] Z = a1 + a2 × PDI + a3 × density (g / cm³) 3 ) + a4×(deformation-softening region energy) + a5×(yield region energy)

[0021] In the above Equation 2, a1 may be 133 to 136, a2 may be 0.2 to 0.4, a3 may be -137 to -135, a4 may be -9.5 to -8, and a5 may be -11 to -9.5.

[0022] [Equation 4]

[0023]

[0024] In the above Equation 4, b1 can be 7.5 to 9, b2 can be 0.4 to 0.55, b3 can be -0.2 to -0.05, and b4 can be 25 to 30.

[0025] [Equation 5]

[0026]

[0027] In the above Equation 5, c1 can be 3 to 6, c2 can be 0.3 to 0.5, and c3 can be 0.1 to 0.3.

[0028] [Equation 6]

[0029]

[0030] In the above Equation 6, d1 may be 1 to 4, d2 may be 0.4 to 0.6, d3 may be 0.1 to 0.3, and d4 may be 0.5 to 0.8.

[0031] In the above Equations 2 and 4 to 6, the MD 5x elongation point stress, MD yield point stress, yield region energy, strain-softening region energy, and MD total strain energy may be values ​​obtained from the MD direction 5x elongation stress-strain curve. Specifically, the MD 5x elongation point stress may be the y-value (MPa) at the point where the x-axis value is 5x, and the MD yield point stress may be the y-value (MPa) at the yield point of the curve. The yield region energy may be the value (MPa) obtained by integrating the region from x-axis 0 to the x-value corresponding to the yield point in the curve. Additionally, the strain-softening region energy may be the value (MPa) obtained by integrating the region from the x-value of the yield point to the x-value corresponding to the strain-softening endpoint in the curve. The total strain energy of MD can be the value (MPa) obtained by integrating the entire region from 0 to 5 on the x-axis of the MD 5x elongation stress-strain curve.

[0032] In the above Equations 4 and 5, the TD yield point stress and the TD strain-strengthening region slope are values ​​obtained from the TD direction 8-fold elongation stress-strain curve, where the TD yield point stress is the y-value (MPa) at the yield point in the curve, and the TD strain-strengthening region slope is the average slope (MPa / strain) of the starting point and ending point of the strain-strengthening region in the curve (i.e., the point where the TD strain on the x-axis is 8).

[0033] In addition, in the above Equation 6, the SCB (short chain branch) content may be the number of methyl terminal groups per 1,000 carbons in the polyethylene resin composition.

[0034] The density of the above polyethylene resin composition is 0.920 g / cm³ 3 Above 0.940 g / cm³ 3 It may be less than.

[0035] The weight-average molecular weight (Mw) of the above polyethylene resin composition may be 60,000 g / mol or more and 120,000 g / mol or less.

[0036] The PDI (Mw / Mn) of the above polyethylene resin composition may be 1.0 to 10.0.

[0037] The above polyethylene resin composition may have a short chain branch (scb) content of 10 to 15, which is the number of methyl terminal groups per 1,000 carbon atoms.

[0038] Preferably, the polyethylene resin composition may satisfy all of the conditions 1) to 4) above.

[0039] More preferably, the polyethylene resin composition may satisfy the following conditions:

[0040] 1) The stretchability index is 0.75 or higher and 1.0 or lower;

[0041] 2) Stiffness index is 0.5 or higher and 1.2 or lower;

[0042] 3) Tensile strength index is 0.5 or higher and 1.2 or lower;

[0043] 4) Puncture strength index is 0.5 or higher and 1.2 or lower;

[0044] 5) Density is 0.922 g / cm³ 3 Above 0.940 g / cm³ 3 below;

[0045] 6) The weight-average molecular weight (Mw) is 60,000 g / mol or more and 120,000 g / mol or less;

[0046] 7) PDI is 3.0 to 9.0;

[0047] 8) SCB (short chain branch) content is 10 or more and 15 or less.

[0048] According to another embodiment of the present invention, the invention relates to an unoriented sheet comprising the polyethylene resin composition described above.

[0049] The above unoriented sheet may have a thickness of 0.1 to 5 mm.

[0050] The above-mentioned unoriented sheet may be a casting sheet.

[0051] According to another embodiment of the present invention, the invention relates to a stretched film comprising the polyethylene resin composition described above.

[0052] The above-mentioned stretched film may be a uniaxially stretched film or a biaxially stretched film.

[0053] The above-mentioned stretched film may be stretched with a stretching ratio of 5 times or more in the length (MD) direction and a stretching ratio of 5 times or more in the width (TD) direction.

[0054] The above stretched film may have a tensile strength in the longitudinal (MD) direction measured according to ASTM D 882 standards of 60 MPa or more and 180 MPa or less.

[0055] The above-mentioned stretched film may have a Young's Modulus in the longitudinal (MD) direction measured according to ASTM D882-07 standards of 300 MPa or more and 1000 MPa or less.

[0056] The above stretched film may have a puncture strength of 200 N / mm or more as measured according to EN 14477.

[0057] The polyethylene resin composition of the present invention has excellent stretchability, so it can be used to stably manufacture stretched films without phenomena such as breakage or melting. Furthermore, the polyethylene resin composition of the present invention has uniform physical properties, so stretching with said resin composition has the advantage of consistently excellent stretchability. Moreover, said stretched film has excellent mechanical properties such as Young's modulus, tensile strength, and puncture strength.

[0058] Figure 1 shows a stress-strain curve measured by stretching the polyethylene resin composition prepared in Example 1 five times in the MD direction, and shows the yield point, strain-softening end point, yield region, and strain-softening region in the curve.

[0059] Figure 2 shows the density (g / cm³) of the polyethylene resin compositions prepared in the examples and comparative examples. 3 This is a point distribution showing the correlation between ) and the stretchability index.

[0060] Figure 3 shows the correlation between the weight-average molecular weight (Mw) and the stretchability index of the polyethylene resin compositions prepared in the examples and comparative examples as a point distribution.

[0061] Figure 4 shows the stress-strain curve measured by stretching the polyethylene resin composition prepared in Example 1 eight times in the TD direction, and shows the yield point, strain-hardening region, and average slope in the strain-hardening region in the curve.

[0062] Figure 5 shows the correlation between the stiffness index of the polyethylene resin composition prepared in the example and the MD Young's modulus of the film as a point distribution.

[0063] Figure 6 shows the correlation between the tensile strength index of the polyethylene resin composition prepared in the example and the MD tensile strength of the film as a point distribution.

[0064] Figure 7 shows the correlation between the puncture strength index of the polyethylene resin composition prepared in the example and the puncture strength of the film as a point distribution.

[0065] Unless otherwise defined in this specification, all technical and scientific terms are used merely to describe exemplary embodiments and are not intended to limit the invention. Singular expressions include plural expressions unless the context clearly indicates otherwise. In this specification, terms such as “comprising,” “comprising,” or “having” are intended to specify the presence of the implemented features, numbers, steps, components, or combinations thereof, and should be understood as not precluding the existence or addition of one or more other features, numbers, steps, components, or combinations thereof.

[0066] The present invention is capable of various modifications and may take various forms, and specific embodiments are illustrated and described in detail below. However, this is not intended to limit the invention to the specific disclosed forms, and it should be understood that the invention includes all modifications, equivalents, and substitutions that fall within the spirit and scope of the invention.

[0067] The technical terms used in this specification are intended merely to refer to specific embodiments and are not intended to limit the invention. Furthermore, the singular forms used herein include plural forms unless the phrases clearly indicate otherwise.

[0068] In this specification, the terms “polyethylene” or “ethylene (co)polymer” include both ethylene homopolymers and / or copolymers of ethylene and alpha-olefins.

[0069] In addition, throughout this specification, the term “polyethylene resin” refers to a resin or resin composition comprising the ethylene (co)polymer, and is a concept that includes all resin compositions to which additives, etc., generally belonging to the technical field to which the present invention belongs, may be further added to such homopolymer or copolymer.

[0070]

[0071] According to one embodiment of the present invention, the invention relates to a polyethylene resin composition having a stretchability index defined by the following formula 1 of 0.7 or higher.

[0072] [Equation 1]

[0073]

[0074] The stretchability index calculated according to Equation 1 above is a new definition by the inventor of the present invention and is an indicator representing the stability of stretching processing due to the uniform physical properties of the polyethylene resin composition. The polyethylene resin composition of the present invention may have a stretchability index of 0.7 or higher, 0.75 or higher, 0.8 or higher, 0.85 or higher, or 0.9 or higher. The upper limit is not specifically limited, but may be 1.0 or lower. Preferably, the stretchability index of the polyethylene resin composition may be 0.7 or higher and 1.0 or lower, or 0.75 or higher and 1.0 or lower, or 0.80 or higher and 1.0 or lower, or 0.85 or higher and 1.0 or lower. If the stretchability index is less than 0.7, there is a high possibility of fracture occurring when stretching the polyethylene resin composition. Here, "probability of fracture" means the ratio of the number of fractures to the number of attempts at stretching when stretching (or biaxial stretching) is performed under the same conditions with multiple specimens derived from the same polyethylene resin composition.

[0075] Meanwhile, in the above Equation 1, Z is defined by the following Equation 2.

[0076] [Equation 2]

[0077] Z = a1 + a2 × PDI + a3 × density (g / cm³) 3 ) + a4×(deformation-softening region energy) + a5×(yield region energy)

[0078] In the above formula 2, a1 is 133 to 136, preferably 134 to 135.5 or 134 to 135, and most preferably 134.9.

[0079] The above a2 is 0.2 to 0.4, preferably 0.25 to 0.4, or 0.3 to 0.4, and most preferably 0.315.

[0080] The above a3 is -137 to -135, preferably -137 to -135.5, or -137 to -136, and most preferably -136.5.

[0081] The above a4 is -9.5 to -8, preferably -9 to -8, or -9 to -8.5, and most preferably -8.7.

[0082] The above a5 is -11 to -9.5, preferably -11 to -10, or -10.5 to -10, and most preferably -10.24.

[0083] The above a1 to a5 are all real numbers.

[0084] As an example, the above Equation 2 can be expressed as Equation 2-1 below, but is not limited thereto:

[0085] [Equation 2-1]

[0086] Z = 134.9 + (0.315)×PDI + (-136.5)×density + (-8.7)×(strain-softening region energy) + (-10.24)×(yield region energy)

[0087] In the above Equation 2, PDI is the polydispersity index (PDI) of the polyethylene resin composition, and may be measured by cross-fractionation chromatography (CFC) for the polyethylene resin composition.

[0088] The above cross-fraction chromatography (CFC) analysis can be performed under the following conditions:

[0089] 1) Analysis equipment: Polymer Char CFC (Detector: Integrated Detector IR5 MCT) is used.

[0090] 2) Sample preparation: 32 mg of polyethylene resin composition is placed in a 10 mL vial and placed in an autosampler. After adding 8 mL of 1,2,4-trichlorobenzene (TCB), the mixture is dissolved at 160 °C for 90 minutes and stabilized at 140 °C for 20 minutes. After purging with nitrogen gas, the mixture is extracted and loaded onto a temperature rising elution column (TREF column).

[0091] 3) Crystallization: After setting the sample previously loaded into the TREF column to 100 ℃, cool it from 100 ℃ to 35 ℃ at a rate of 0.5 ℃ / min.

[0092] 4) Temperature Rising Elution Temperature (TREF) Analysis: The previously crystallized sample is fixed at temperatures raised from 35°C to 125°C in 3°C increments, and the fractions eluted for 25 minutes at each temperature are analyzed. Specifically, extraction and analysis were performed at 35°C for 25 minutes, followed by extraction and analysis at temperatures raised in 3°C increments, and finally, extraction and analysis were performed at 125°C for 25 minutes.

[0093] 5) GPC-IR analysis: The fractions eluted at each temperature in the previous TREF analysis are transferred to the GPC Column of the GPC (PL-GPC220) device, the molecular weight of the eluted molecules is measured, and the number of short-chain branches (sb) of the eluted molecules at each temperature is measured using PerkinElmer Spectrum 100 FT-IR connected to the GPC (PL-GPC220).

[0094] 6) High molecular weight molecule SCB index (measurement of Iscb, high M): The value of "number of scb (short chain branches) per 1,000 carbons × elution molecule fraction" of molecules satisfying a molecular weight of 100,000 g / mol or more, as confirmed by CFC analysis, is measured according to Equation 3 below. A higher value indicates a greater amount of high molecular weight / high scb content molecules.

[0095] [Equation 3]

[0096]

[0097] In Equation 3 above, CM,i represents the molar concentration (mol / L) of each component according to molecular weight, and represents the number of SCB units of each component (number / 1000C). Here, the “SCB (short chain branch)” refers to a short chain formed in a branch-like form to the main chain of polyethylene, specifically meaning a methyl group formed to the main chain of polyethylene. It is a short branched chain formed when an alpha-olefin having 4 or more carbon atoms, such as 1-butene, 1-hexene, or 1-octene, is used as a commonomer, and its content may be proportional to the content of the α-olefin monomer included in the polymer chains. Therefore, the above scb content represents the number of methyl terminal groups per 1,000 carbon atoms (unit: number / 1,000C).

[0098] The SCB content of the above polyethylene resin composition can be calculated through GPC-IR analysis, and in addition, 1 It can be calculated through H-NMR or FT-IR analysis.

[0099] The polyethylene resin composition may have an SCB content of 9 or more, 10 or more, 11 or more, or 12 or more, and may be 18 or less, 17 or less, 16 or less, or 15 or less, and preferably may be 10 or more and 15 or less.

[0100] The weight-average molecular weight (Mw) of the polyethylene resin composition may be 50,000 g / mol or more, 60,000 g / mol or more, or 65,000 g / mol or more, and 150,000 g / mol or less, 140,000 g / mol or less, 130,000 g / mol or less, 120,000 g / mol or less, or 110,000 g / mol or less. Preferably, the weight-average molecular weight (Mw) may be 50,000 g / mol or more and 150,000 g / mol or less, 60,000 g / mol or more and 120,000 g / mol or less, or 65,000 g / mol or more and 120,000 g / mol or less.

[0101] The number average molecular weight (Mn) of the polyethylene resin composition may be 8,000 g / mol or more, 9,000 g / mol or more, or 10,000 g / mol or more, and 100,000 g / mol or less, 80,000 g / mol or less, 60,000 g / mol or less, 50,000 g / mol or less, or 30,000 g / mol or less. Preferably, the weight average molecular weight (Mw) may be 8,000 g / mol or more and 100,000 g / mol or less, 9,000 g / mol or more and 60,000 g / mol or less, or 9,000 g / mol or more and 30,000 g / mol or less.

[0102] In addition, the molecular weight distribution (Mw / Mn, PDI) of the polyethylene resin composition may be 1.0 or more, 1.5 or more, 1.8 or more, 2.0 or more, 2.5 or more, 2.8 or more, 3.0 or more, or 3.4 or more, and may be 10.0 or less, 9.5 or less, 9.0 or less, 8.5 or less, or 8.3 or less. Preferably, it may be 1.0 to 10.0, or 2.0 to 9.5, or 3.0 to 9.0.

[0103] The above weight-average molecular weight (Mw) and number-average molecular weight (Mn) are converted values ​​for standard polystyrene measured using gel permeation chromatography (GPC, gel permeation chromatography, manufactured by Water).

[0104] In Equation 2 above, the density may be measured according to ASTM D1505. The density of the polyethylene resin composition is 0.920 g / cm³. 3 Above, 0.922 g / cm³ 3 Above, 0.924 g / cm³ 3 Above, or 0.926 g / cm³ 3 Above, 0.940 g / cm³ 3 Below, 0.939 g / cm³ 3 Below, 0.938 g / cm³ 3 Below, 0.937 g / cm³ 3 Less than or equal to 0.936 g / cm³ 3 It may be less than or equal to. Preferably, the density is 0.920 g / cm³. 3 Above 0.940 g / cm³ 3 Less than or equal to 0.922 g / cm³ 3 Above 0.940 g / cm³ 3 Less than or equal to 0.925 g / cm³ 3 Above 0.938 g / cm³ 3 Less than or equal to 0.926 g / cm³ 3 Above 0.936 g / cm³ 3 It may be less than.

[0105] In Equation 2 above, the "yield region energy" and "strain-softening energy" are values ​​obtained from the stress-strain curve measured for the polyethylene resin composition. The stress-strain curve is a visual representation of how a material deforms while subjected to force; the x-axis displays the magnitude of the material strain, i.e., the elongation ratio, and the y-axis displays the internal stress (unit: MPa) of the material. From the stress-strain curve, the yield point and the strain-softening end point can be obtained. Here, the yield point refers to the point in the stress-strain curve where the first derivative is zero or closest to zero. The strain-softening end point refers to the point in the stress-strain curve where the second derivative changes from negative to positive and becomes zero. The above yield region energy refers to the value obtained by integrating the region from 0 on the x-axis to the x-value corresponding to the yield point in the stress-strain curve (unit: MPa). The above strain-softening region energy refers to the value obtained by integrating the region from the x-value of the yield point to the x-value corresponding to the strain-softening end point (unit: MPa). Figure 1 is a stress-strain curve obtained by stretching the polyethylene resin composition specimen prepared in Example 1 below five times in the longitudinal direction (MD) under a neck-in controlled environment. Figure 1 shows the yield point, strain-softening end point, yield region, and strain-softening in the curve.

[0106] 1) Preparation of specimen: A specimen with dimensions of 90 mm × 90 mm and a thickness of 0.75 mm is prepared. The above specimen can be manufactured into a 0.75 mm thick casting sheet of polyethylene resin composition using a Bruckner lab extruder line (L / D ratio: 42, Screw diameter: 25 mm, Melt / T-Die temperature: 250 ℃), but is not limited thereto.

[0107] 2) Preheating: Preheat the specimen at 122°C for 60 seconds.

[0108] 3) Stretching: Stretching can be performed at 122°C using a KARO 5.0 machine (manufacturer: Brueckner Maschinenbau) equipped with five or more jigs in the longitudinal direction to control neck-in during stretching of the specimen. The specimen is mounted on a jig of the machine, and the specimen is stretched at a stretching speed of 200% / sec so that the length of the specimen in the longitudinal direction (MD) becomes five times its original length.

[0109] 4) Stress-strain curve: A stress-strain curve is obtained from the KARO 5.0 equipment used for stretching. However, Savitzky-Golay fitting may be performed to remove unnecessary noise or fluctuations included in the data while maintaining the main features of the data obtained through the above analysis. When performing Savitzky-Golay fitting, a polynomial (e.g., a second-order or third-order polynomial) is fitted within a given data window, and the data at the center of the interval can be smoothed using the polynomial.

[0110] In polymers, the strain energy absorbed during stretching (mechanical deformation) varies depending on the crystal structure, such as molecular structure, degree of crystallization, and crystal size, as well as the stretching conditions. The reason fracture occurs during the stretching process is that the polymer's molecular structure can no longer withstand deformation caused by external stress.

[0111] Meanwhile, in the stress-strain curve obtained through stretching in the MD direction, the yield point and the strain-softening region are regions where elastic deformation and the crystal structure begin to rearrange (irreversible deformation). As a result of diligent efforts, the inventors of the present invention discovered that the yield region energy and the strain-softening region energy in the above-mentioned stress-strain curve are closely related to the stretchability (including fracture characteristics) of the polyethylene resin. Additionally, the inventors of the present invention discovered that a polyethylene resin with a Stretchability Index of 0.7 or higher, which reflects the factors of the yield region energy and strain-softening region energy, exhibits excellent stretchability and stretch stability, thereby completing the present invention.

[0112] The above yield region energy may be 0.05 MPa or more, 0.1 MPa or more, 0.15 MPa or more, 0.2 MPa or more, and 0.6 MPa or less, 0.55 MPa or less, or 0.5 MPa or less. Preferably, the above yield region energy may be 0.05 to 0.6 MPa, or 0.1 to 0.6 MPa, or 0.2 to 0.6 MPa.

[0113] In addition, the strain-softening region energy may be 0.01 MPa or more, 0.05 MPa or more, 0.08 MPa or more, or 0.1 MPa or more, and 0.45 MPa or less, 0.43 MPa or less, 0.4 MPa or less, 0.38 MPa or less, or 0.37 MPa or less. Preferably, the strain-softening region energy may be 0.01 to 0.45 MPa, or 0.05 to 0.45 MPa, or 0.05 to 0.45 MPa.

[0114] The units of the above yield region energy and strain-softening region energy are MPa·strain ratio (elongation ratio), where strain ratio (elongation ratio) = (length after elongation) / (length before elongation). However, since the strain ratio is dimensionless, it can be expressed in "MPa".

[0115] In addition, the polyethylene resin composition may have a melt index (MI2.16) measured according to the method of ASTM D1238 of 0.5 g / 10 min or more and 5.0 g / 10 min or less. Preferably, the melt index (MI2.16, 190 ℃, 2.16 kg load) may be 0.5 g / 10 min or more, 0.6 g / 10 min or more, 0.7 g / 10 min or more, or 1.0 g / 10 min or more, and 4.0 g / 10 min or less, 3.5 g / 10 min or less, 3.0 g / 10 min or less, 2.7 g / 10 min or less, or 2.5 g / 10 min or less.

[0116] The above polyethylene resin composition not only possesses the excellent elongation characteristics described above, but can also improve strength characteristics during elongation.

[0117] The above polyethylene resin composition may satisfy at least one of the following conditions 1), 2), and 3):

[0118] 1) A stiffness index expressed by the following Equation 4 is 0.5 or higher;

[0119] 2) A tensile strength index expressed by the following Equation 5 is 0.5 or higher;

[0120] 3) The puncture strength index, expressed by the following Equation 6, is 0.5 or higher.

[0121] [Equation 4]

[0122]

[0123] [Equation 5]

[0124]

[0125] [Equation 6]

[0126]

[0127] The stiffness index, tensile strength index, and puncture strength index calculated according to the above equations 4, 5, and 6 are also newly defined by the inventor of the present invention, and are each indicators for predicting the Young's modulus, tensile strength, and puncture strength of a film obtained by stretching a polyethylene resin composition.

[0128] The polyethylene resin composition of the present invention may have a stiffness index of 0.5 or more, 0.6 or more, 0.7 or more, 0.8 or more, or 0.9 or more. The upper limit is not specifically limited, but may be 1.2 or less, 1.1 or less, or 1.0 or less. Preferably, the stiffness index of the polyethylene resin composition may be 0.5 or more and 1.0 or less, or 0.6 or more and 1.0 or less, or 0.7 or more and 1.0 or less, or 0.8 or more and 1.0 or less.

[0129] In addition, the polyethylene resin composition may have a tensile strength index of 0.5 or more, 0.6 or more, 0.7 or more, 0.75 or more, or 0.8 or more. The upper limit is not specifically limited, but may be 1.2 or less, 1.1 or less, or 1.0 or less. Preferably, the stiffness index of the polyethylene resin composition may be 0.5 or more and 1.2 or less, or 0.6 or more and 1.2 or less, or 0.7 or more and 1.2 or less, or 0.75 or more and 1.2 or less, or 0.8 or more and 1.2 or less.

[0130] In addition, the polyethylene resin composition may have a puncture strength index of 0.5 or higher, 0.6 or higher, 0.65 or higher, 0.7 or higher, or 0.8 or higher. The upper limit is not specifically limited, but may be 1.2 or lower, 1.1 or lower, or 1.0 or lower. Preferably, the stiffness index of the polyethylene resin composition may be 0.5 or higher and 1.2 or lower, or 0.6 or higher and 1.2 or lower, or 0.65 or higher and 1.2 or lower, or 0.7 or higher and 1.2 or lower, or 0.8 or higher and 1.2 or lower.

[0131] The polyethylene resin composition of the present invention may satisfy at least two of the conditions 1), 2), and 3) above, and more preferably may satisfy all of the conditions 1), 2), and 3).

[0132] In the above formula 4, b1 may be 7.5 to 9, preferably 8 to 9, more preferably 8 to 8.5, and most preferably 8.3.

[0133] b2 may be 0.4 to 0.55, preferably 0.4 to 0.5, more preferably 0.45 to 0.5, and most preferably 0.49.

[0134] b3 can be -0.2 to -0.05, preferably -0.15 to -0.05, more preferably -0.13 to -0.1, and most preferably -0.1033.

[0135] b4 may be 25 to 30, preferably 26 to 28, more preferably 27 to 28, and most preferably 27.7.

[0136] The above b1 to b4 are all real numbers.

[0137] As an example, the above Equation 4 can be expressed as Equation 4-1 below, but is not limited thereto:

[0138] [Equation 4-1]

[0139]

[0140] In the above formula 5, c1 may be 3 to 6, preferably 4 to 5, more preferably 4.2 to 4.7, and most preferably 4.54.

[0141] c2 may be 0.3 to 0.5, preferably 0.3 to 0.4, more preferably 0.35 to 0.4, and most preferably 0.374.

[0142] c3 is 0.1 to 0.3, preferably 0.1 to 0.25, more preferably 0.15 to 0.25, and most preferably 0.19.

[0143] The above c1 to c3 are all real numbers.

[0144] As an example, the above Equation 5 can be expressed as Equation 5-1 below, but is not limited thereto:

[0145] [Equation 5-1]

[0146]

[0147] In the above formula 6, d1 may be 1 to 4, preferably 2 to 3, more preferably 2 to 2.5, and most preferably 2.19.

[0148] d2 may be 0.4 to 0.6, preferably 0.45 to 0.6, more preferably 0.5 to 0.55, and most preferably 0.514.

[0149] d3 is 0.1 to 0.3, preferably 0.1 to 0.25, more preferably 0.15 to 0.25, and most preferably 0.1735.

[0150] d4 may be 0.5 to 0.8, preferably 0.5 to 0.7, more preferably 0.55 to 0.65, and most preferably 0.605.

[0151] The above d1 to d4 are all real numbers.

[0152] As an example, the above Equation 6 can be expressed as Equation 6-1 below, but is not limited thereto:

[0153] [Equation 6-1]

[0154]

[0155] In the above Equations 4 to 6, "MD 5x elongation stress," "TD yield point stress," "MD total strain energy," "TD strain-strengthening region slope," and "MD yield point stress" are values ​​obtained from a stress-strain curve measured for a polyethylene resin composition. The stress-strain curve can be obtained by the method described above in relation to Equation 2, but the MD 5x elongation point stress, MD yield point stress, and MD total strain energy can be obtained from a stress-strain curve obtained by elongating the specimen in the longitudinal direction (MD) so that the length of the specimen becomes 5 times. However, the TD yield point stress and the TD strain-strengthening region slope can be obtained from a stress-strain curve obtained by elongating the specimen in the width direction (TD) so that the length of the specimen becomes 8 times. Since the yield point refers to the point in the stress-strain curve where the first derivative is zero or closest to zero, the yield point stress refers to the y-value (MPa) at the yield point. Additionally, the MD 5x elongation point stress refers to the y-value (MPa) at the point where the MD strain on the x-axis is 5 in the above curve. The MD total strain energy refers to the value (MPa) obtained by integrating the entire region from 0 to 5 on the x-axis of the MD 5x elongation stress-strain curve. The TD strain-strengthening region slope refers to the average slope (MPa / elongation ratio) between the start and end points of the strain-strengthening region in the above curve (i.e., the point where the TD strain on the x-axis is 8). Here, the start point of the strain-strengthening region is the end point of the steady flow region, and the steady flow region refers to an area where the stress remains constant or the rate of change of stress becomes gradual even as the strain increases. For example, as strain increases after yielding, the rate of change in stress It is a range of < 0.5 MPa / times (ε represents strain (elongation ratio: times), σ represents stress (MPa)), and within this range, it refers to a range of strain (x-axis) where the stress is maintained within ±10% of the maximum stress.

[0156] Figure 1 shows the yield point, strain-softening end point, yield region, strain-softening region, and steady flow region in the stress-strain curve in the MD direction measured for the polyethylene resin composition prepared in Example 1 below. Figure 4 is a stress-strain curve obtained by stretching the polyethylene resin composition specimen prepared in Example 1 below eight times in the width direction (TD) under a neck-in controlled environment. Figure 4 shows the yield point, steady flow region, strain-hardening region, and the average slope in the strain-hardening region in the curve.

[0157] The above MD yield point stress may be 0.5 MPa or more, 0.6 MPa or more, 0.7 MPa or more, 0.8 MPa or more, 0.9 MPa or more, 1.0 MPa or more, 1.1 MPa or more, 1.2 MPa or more, 1.3 MPa or more, or 1.4 MPa or more, and may be 2.0 MPa or less, 1.95 MPa or less, 1.8 MPa or less, 1.7 MPa or less, 1.6 MPa or less, or 1.5 MPa or less. Preferably, the above MD yield point stress may be 0.5 MPa or more and 2.0 MPa or less, or 0.6 MPa or more and 2.0 MPa or less, or 0.7 MPa or more and 2.0 MPa or less.

[0158] The stress at the MD 5x elongation point above is 0.5 MPa or more, 0.6 MPa or more, 0.7 MPa or more, 0.8 MPa or more, 0.9 MPa or more, 1.0 MPa or more, 1.1 MPa or more, 1.2 MPa or more, 1.3 MPa or more, or 1.4 MPa or more, and may be 1.75 MPa or less, 1.7 MPa or less, 1.6 MPa or less, 1.5 MPa or less, 1.4 MPa or less, 1.3 MPa or less, or 1.2 MPa or less. Preferably, the stress at the MD 5x elongation point may be 0.6 MPa or more and 1.75 MPa or less, or 0.7 MPa or more and 1.75 MPa or less, or 1.0 MPa or more and 1.75 MPa or less, or 1.0 MPa or more and 1.6 MPa or less, or 1.1 MPa or more and 1.4 MPa or less.

[0159] The above total MD strain energy may be 1.0 MPa or more, 1.5 MPa or more, 2.0 MPa or more, 2.5 MPa or more, 3.0 MPa or more, 4.0 MPa or more, or 5.0 MPa or more, and may be 6.5 MPa or less, 6.0 MPa or less, 5.5 or less, 5.0 MPa or less, or 4.5 MPa or less. Preferably, the above total MD strain energy may be 2.0 MPa or more and 6.5 MPa or less, or 3.0 MPa or more and 6.5 MPa or less, or 4.0 MPa or more and 6.5 MPa or less, or 4.0 MPa or more and 6.0 MPa or less. Here, the unit of the total MD strain energy is MPa·strain ratio (elongation ratio), but considering that the strain ratio is dimensionless, it may be expressed as "MPa".

[0160] The above TD yield point stress is 0.05 MPa or more, 0.07 MPa or more, 0.1 MPa or more, 0.2 MPa or more, 0.3 MPa or more, 0.4 MPa or more, 0.5 MPa or more, 0.6 MPa or more, or 0.7 MPa or more, and may be 2.0 MPa or less, 1.8 MPa or less, 1.6 MPa or less, 1.4 MPa or less, 1.2 MPa or less, 1.0 MPa or less, or 0.8 MPa or less. Preferably, the TD yield point stress may be 0.1 MPa or more and 2.0 MPa or less, or 0.1 MPa or more and 1.6 MPa or less, or 0.2 MPa or more and 1.6 MPa or less, or 0.3 MPa or more and 1.6 MPa or less, or 0.3 MPa or more and 1.2 MPa or less, or 0.3 MPa or more and 1.0 MPa or less.

[0161] The slope of the TD strain-hardening region may be 0.05 or more, 0.06 or more, 0.07 or more, 0.08 or more, 0.09 or more, or 0.1 or more, and may be 0.3 or less, 0.25 or less, 0.2 or less, 0.18 or less, 0.16 or less, or 0.14 or less. Preferably, the slope of the TD strain-hardening region may be 0.05 or more and 0.3 or less, or 0.06 or more and 0.2 or less, or 0.06 or more and 0.18 or less, or 0.08 or more and 0.16 or less, or 0.1 or more and 1.6 or less. Here, the unit of the slope of the TD strain-hardening region may be expressed as MPa / strain ratio (elongation ratio).

[0162] The definitions and preferred ranges of density in Equation 4, weight-average molecular weight (Mw) in Equation 6, and SCB content are duplicated from what was previously described, so a detailed description is omitted below.

[0163] In this specification, the stretching may include both uniaxial stretching and biaxial stretching, but preferably may be biaxial stretching. Additionally, the stretching ratio conditions are not particularly limited, but for example, the stretching ratio in the length (MD) direction may be 5 times or more and the stretching ratio in the width (TD) direction may be 5 times or more, and as an example, the stretching ratio in the MD direction may be 5 times and the stretching ratio in the TD direction may be 8 times, but is not limited thereto.

[0164] Excellent elongation means that when a sheet made of a polyethylene resin composition is biaxially stretched at the corresponding stretching temperature by a stretching ratio of 5 times or more in the length (MD) direction and 5 times or more in the width (TD) direction, it undergoes biaxial stretching without breaking, shrinkage, or melt drawing.

[0165] In the polyethylene resin composition according to the present invention, the polyethylene may be an ethylene homopolymer or an ethylene / alpha olefin copolymer having 3 to 20 carbon atoms. More specifically, the copolymer may be an ethylene / alpha olefin copolymer having 4 to 10 carbon atoms, and specific examples may be an ethylene / 1-butene copolymer, an ethylene / 1-hexene copolymer, an ethylene / 1-octene copolymer, or a mixture of two or more of these, but are not limited thereto.

[0166] The above-described polyethylene resin composition can be prepared by polymerizing ethylene monomers or copolymerizing with comonomers by introducing hydrogen gas in the presence of a catalyst.

[0167] The above comonomer may be an olefin monomer, which is an olefin compound having 3 to 20 carbon atoms or 4 to 10 carbon atoms. Specific examples may include ethylene, alpha-olefin, cyclic olefin, diene olefin or triene olefin having two or more double bonds. Specific examples 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-eicocene, norbornene, norvonadiene, ethylidenenorbornene, phenylnorbornene, vinylnorbornene, dicyclopentadiene, 1,4-butadiene, 1,5-pentadiene, 1,6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene, 3-chloromethylstyrene, etc., and two or more of these monomers may also be used.

[0168] The amount of the above olefin monomer added can be determined according to the physical properties of the polyethylene copolymer to be manufactured, but, for example, it can be added in an amount of 3.0 to 10.0 weight% relative to the total weight of ethylene.

[0169] The above polymerization reaction can be carried out under hydrogen conditions. The hydrogen can be introduced in an amount of 5 to 120 ppm based on the total weight of the monomer ethylene. More specifically, based on the total weight of ethylene, the amount can be 5 ppm or more, 10 ppm or more, 15 ppm or more, 20 ppm or more, or 21 ppm or more, and 100 ppm or less, 95 or less, 90 ppm or less, 85 ppm or less, or 80 ppm or less, but is not limited thereto.

[0170] The above 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 at 110°C or lower, or 100°C or lower, or 90°C or lower. Additionally, if pressure conditions are further controlled during the polymerization reaction, it may be carried out at a pressure of 5 bar or higher, or 10 bar or higher, or 20 bar or higher, and at 50 bar or lower, or 45 bar or lower, or 40 bar or lower. When polymerization proceeds under these temperatures and pressures, the desired physical properties of the ethylene-alpha-olefin copolymer can be more easily realized.

[0171] The above polymerization reaction may be carried out in the presence of a catalyst. In this case, the catalyst may be a Ziegler-Natta catalyst, a metallocene catalyst, or a mixture thereof, but is not limited thereto. Preferably, a metallocene catalyst may be used.

[0172] The metallocene catalyst may include one or more of a metallocene compound represented by the following Chemical Formula 1 and a metallocene compound represented by the following Chemical Formula 2. Preferably, it may include one or more first metallocene compounds selected from the compounds represented by the following Chemical Formula 1 and one or more second metallocene compounds selected from the compounds represented by the following Chemical Formula 2:

[0173] [Chemical Formula 1]

[0174]

[0175] [Chemical Formula 2]

[0176]

[0177] In the above chemical formulas 1 and 2,

[0178] M1 and M2 are each independently group 4 transition metals, and

[0179] X 11 , X 12 , X 21 , X 22Each independently, substituted or unsubstituted C 1-20 It is an alkyl or halogen, and

[0180] R1 to R5 and R7 to R 12 Each independently contains hydrogen, substituted or unsubstituted C 1-20 Alkyl, substituted, or unsubstituted C 6-60 Aryl, or -(CH2) n1 -OR 13 And,

[0181] R6 is substituted or unsubstituted C 1-20 Alkyl, substituted, or unsubstituted C 6-60 Aryl, or -(CH2) n1 -OR 13 However,

[0182] R1 to R 12 At least one of them is -(CH2) n1 -OR 13 And,

[0183] R 13 C1- substituted or unsubstituted 20 It is alkyl, and

[0184] n1 is an integer from 0 to 10, and

[0185] T2 is C (carbon) or Si (silicon), and

[0186] Q 21 and Q 22 C, each independently substituted or unsubstituted 1-20 Alkyl, substituted, or unsubstituted C 6-60 Aryl, or -(CH2) n2 -OR 32 Or, Q 21 and Q 22 C that combines with each other to become substituted or non-substituted 3-20 Forming a cycloalkyl ring,

[0187] R 20 to R 31 Each independently contains hydrogen, substituted or unsubstituted C 1-20 Alkyl, substituted, or unsubstituted C 6-60 Aryl, or -(CH2)n2 -OR 32 Or, R 20 to R 31 Among them, two adjacent C's are combined to form a substituted or unsubstituted C' 3-20 Forms a cycloalkyl ring,

[0188] R 20 to R 31 , Q 21 and Q 22 At least one of them is -(CH2) n2 -OR 32 And,

[0189] R 32 is substituted or unsubstituted C 1-20 It is alkyl, and

[0190] n2 is an integer from 0 to 10.

[0191] Halogens can be fluorine (F), chlorine (Cl), bromine (Br), or iodine (I).

[0192] The above C 1-20 The alkyl group may be a straight-chain, branched-chain, or cyclic alkyl group. Specifically, the above C 1-20 The alkyl group 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, etc.

[0193] The above C 3-20 The cycloalkyl ring may be a ring composed of carbon atoms. It may be a hydrocarbon ring having 3 to 20 carbon atoms; a hydrocarbon ring having 3 to 15 carbon atoms; or a hydrocarbon ring having 3 to 10 carbon atoms. More specifically, C 3-20The cycloalkyl ring can be a cyclopropene ring, a cyclobutene ring, a cyclopentene ring, or a cyclohexene ring, etc.

[0194] The above C 2-20 The alkenyl can be a straight-chain, branched-chain, or cyclic alkenyl. Specifically, the above C 2-20 The alkenyl of 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 of may be ethenyl, propenyl, butenyl, fentenyl, or cyclohexanyl, etc.

[0195] The above C 1-20 The alkoxy group may be a straight-chain, branched-chain, or cyclic alkoxy group. Specifically, the above C 1-20 The alkoxy group 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 cyclohexoxy group, etc.

[0196] The above C 2-20 The alkoxyalkyl group may be a substituent having a structure including -Ry-O-Rz, in which one or more hydrogens of the alkyl (-Ry) are substituted with an alkoxy (-O-Rz). Specifically, the above C2 to C 20The alkoxyalkyl group may be a methoxymethyl group, a methoxyethyl group, an ethoxymethyl group, an iso-propoxymethyl group, an iso-propoxyethyl group, an iso-propoxyhexyl group, a tert-butoxymethyl group, a tert-butoxyethyl group, or a tert-butoxyhexyl group, etc.

[0197] The above C 6-60 Aryl may refer to monocyclic, bicyclic, or tricyclic aromatic hydrocarbons. Specifically, the C6 to C 60 The aryl group can be a phenyl group, a naphthyl group, or anthracenyl group, etc.

[0198] The above C 7-20 Alkylaryl may refer to a dentate group in which one or more hydrogens of the aryl are substituted by an alkyl group. Specifically, the above C 7-20 The alkylaryl of may be methylphenyl, ethylphenyl, n-propylphenyl, iso-propylphenyl, n-butylphenyl, iso-butylphenyl, tert-butylphenyl, or cyclohexylphenyl, etc.

[0199] The above C 7-20 Arylalkyl may refer to a dentate group in which one or more hydrogens of an alkyl group are substituted by an aryl group. Specifically, the above C 7-20 The arylalkyl group can be a benzyl group, phenylpropyl or phenylhexyl, etc.

[0200] In addition, the above Group 4 transition metals may include titanium, zirconium, hafnium, etc.

[0201] The above metallocene catalyst is a hybrid catalyst comprising a first metallocene compound of high molecular weight and high crystallinity and a second metallocene compound of low molecular weight and low crystallinity.

[0202] In copolymerization in a single reactor using a hybrid metallocene catalyst, it is important to control the expression of polymerization characteristics between the metallocene compounds constituting the hybrid supported metallocene catalyst under a single copolymerization condition. In particular, to obtain a polyethylene copolymer for biaxial stretching, high molecular weight, highly crystalline components and low molecular weight, low-crystalline components must be composed together. The polyethylene copolymer of the present invention can exhibit each characteristic under a single copolymerization condition by using a hybrid metallocene catalyst obtained from a combination of the first metallocene compound and the second metallocene compound.

[0203] The first metallocene compound represented by the above chemical formula 1 has the characteristic of having a lower polymerization rate of the comonomer and a higher polymerization rate of the ethylene monomer compared to the second metallocene compound due to the structure of the non-bridged ligand bonded to the central metal.

[0204] Meanwhile, the second metallocene compound represented by Chemical Formula 2 has the characteristic of having a high polymerization rate of the comonomer and a low polymerization rate of the ethylene monomer compared to the first metallocene compound due to the bridge-type ligand structure bonded to the central metal.

[0205] In the present invention, polyethylene having uniform physical properties can be produced by using a hybrid metallocene catalyst comprising a first metallocene compound and a second metallocene compound having the characteristics described above.

[0206] Preferably, the central metal (M1) of Formula 1 may be a group 4 transition metal specifically Ti, Zr, or Hf, and more specifically Hf or Zr.

[0207] Preferably, X 11 , X 12 Each can independently be methyl or chloro, and more preferably X 11 , X 12 All of them may be methyl or all of them may be chloro.

[0208] Preferably, R1 to R5 and R7 to R 12 Each independently contains hydrogen, substituted or unsubstituted C 1-20 Alkyl, substituted, or unsubstituted C 6-20 Aryl, or -(CH2) n1 -OR 13 And, R6 is substituted or unsubstituted C 1-20 Alkyl, substituted, or unsubstituted C 6-20 Aryl, or -(CH2) n1 -OR 13 However, R1 to R 12 One or two of them are -(CH 2)n1 -OR 13 It could be.

[0209] Preferably, either R7 or R8 is -(CH2) n1 -OR 13 While, the remainder and R1 to R5 and R9 to R 12 Each independently contains hydrogen, substituted or unsubstituted C 1-20 Alkyl, substituted, or unsubstituted C 6-60 Aryl, or -(CH2) n1 -OR 13 And, R6 is substituted or unsubstituted C 1-20 Alkyl, substituted, or unsubstituted C 6-60 Aryl, or -(CH2) n1 -OR 13 It could be.

[0210] Preferably, R1 to R5 are each independently hydrogen, methyl, isopropyl, n-butyl, phenyl, or -(CH2) n1 -OR 13 It may be. More preferably, R1 to R5 may each independently be hydrogen, methyl, n-butyl, phenyl, or tert-butoxyhexyl.

[0211] Preferably, R6 is unsubstituted or C 6-10 C substituted with aryl or Si(R')3 1-20 alkyl, or C 6-20It could be Aril, and here R' is C 1-20 alkyl or C 6-10 It may be an aryl. More preferably, R6 is unsubstituted or C substituted with phenyl, trimethylsilyl, or triphenylsilyl. 1-20 alkyl, or C 6-20 It may be an aryl. Most preferably, R6 may be methyl, ethyl, isopropyl, benzyl, trimethylsilylmethyl, or phenyl.

[0212] Preferably, either R7 or R8 is -(CH2) n1 -OR 13 While being, the remainder and R9 to R 12 Each may be hydrogen. More preferably, either R7 or R8 is tertbutoxyhexyl, and the remainder and R9 to R 12 Each can be hydrogen.

[0213] Preferably, R 13 It can be tertbutyl.

[0214] Preferably, n1 can be an integer from 4 to 10, more preferably, n1 can be an integer from 4 to 7, and most preferably, n1 can be 6.

[0215] Preferably, the first metallocene compound represented by the above formula 1 may be any one selected from the group consisting of the following:

[0216]

[0217] Meanwhile, the method for preparing the first metallocene compound represented by the above chemical formula 1 is not particularly limited, but, for example, it can be prepared by the method shown in the following reaction formula 1.

[0218] Although the compound represented by the above chemical formula 1 is difficult to synthesize due to the steric hindrance of the indene ligand, the compound of the above chemical formula 1 can be prepared with high yield and high purity according to a method such as the following reaction scheme 1.

[0219] Accordingly, the compound represented by the above chemical formula 1 can be prepared by a manufacturing method comprising the steps of: reacting a compound represented by chemical formula 1-1 with a compound represented by chemical formula 1-2 to prepare a ligand of chemical formula 1-3; and reacting the ligand of chemical formula 1-3 with a compound represented by chemical formula 1-4 and a halogen salt of a transition metal represented by chemical formula 1-5:

[0220] [Reaction Equation 1]

[0221]

[0222] In the above reaction scheme 1, M1, X 11 , X 12 and R1 to R 12 is as defined in Chemical Formula 1 above, and X' is independently a halogen.

[0223] Preferably, the central metal (M2) of Formula 2 may be a group 4 transition metal such as Ti, Zr, or Hf, and more specifically, Zr.

[0224] Preferably, X 21 , X 22 Each can independently be methyl or chloro, and more preferably X 21 , X 22 Each can be chloro.

[0225] Preferably, T2 can be C (carbon).

[0226] Preferably, R 20 to R 31 , Q 21 and Q 22 At least one of them is -(CH2) n2 -OR 32 It can be. More preferably, R 20 to R 25 , Q 21 and Q 22 At least one of them is -(CH2) n2 -OR 32 It can be. More preferably, R20 to R 31 , Q 21 and Q 22 One or two of them are -(CH2) n2 -OR 32 It can be. More preferably, R 20 to R 25 , Q 21 and Q 22 One or two of them are -(CH2) n2 -OR 32 It can be. Most preferably, R 20 to R 25 , Q 21 and Q 22 Either one or two of them may be tertbutoxyhexyl.

[0227] Preferably, Q 21 and Q 22 C, each independently substituted or unsubstituted 1-20 Alkyl, substituted, or unsubstituted C 6-20 Aryl, or -(CH2) n2 -OR 32 Or, Q 21 and Q 22 C that combines with each other to be substituted or unsubstituted 3-20 It can form a cycloalkyl ring. More preferably, Q 21 and Q 22 are independently methyl, ethyl, isopropyl, phenyl, or -(CH2) n2 -OR 32 Or, Q 21 and Q 22 They can combine with each other to form a cyclopentene ring or a cyclohexene ring.

[0228] Preferably, R 20 to R 23 Each independently, hydrogen, C 1-20 Alkyl, C 6-20 Aryl, or -(CH2) n2 -OR 32 It can be, and more preferably, R 20 to R23 Each can independently be hydrogen, methyl, n-butyl, phenyl, or tertbutoxyhexyl. More preferably, R 20 to R 23 One is tertbutoxyhexyl or n-butyl, and the rest are hydrogen, or R 20 to R 23 Two of them may each independently be methyl, n-butyl, or phenyl, and the remainder may be hydrogen.

[0229] Preferably, R 24 to R 31 Each independently, hydrogen, C 1-10 Alkyl, C 6-20 Aryl, or -(CH2) n2 -OR 32 Or, R 24 to R 31 Among them, two adjacent C's are combined to form a substituted or unsubstituted C' 3-10 It can form a cycloalkyl ring. More preferably, R 24 to R 31 Each is independently hydrogen, tertbutyl, or tertbutoxyhexyl, or R 24 to R 31 Two adjacent ones can combine to form a cyclohexane ring substituted with four methyl groups.

[0230] Preferably, R 32 It could be tertbutyl.

[0231] Preferably, n2 can be an integer from 4 to 10, more preferably, n2 can be an integer from 4 to 7, and most preferably, n2 can be 6.

[0232] Preferably, the metallocene compound represented by Formula 2 may be any one selected from the group consisting of the following:

[0233]

[0234] Meanwhile, the method for preparing the second metallocene compound represented by the above chemical formula 2 is not particularly limited, but, for example, it can be prepared by the method shown in reaction formula 2 below.

[0235] Although the compound represented by the above chemical formula 2 is difficult to synthesize due to the steric hindrance of the indene ligand, the compound of the above chemical formula 2 can be prepared with high yield and high purity according to a method such as the following reaction scheme 2.

[0236] Accordingly, the compound represented by Chemical Formula 2 can be prepared by a manufacturing method comprising the steps of: reacting a compound represented by Chemical Formula 2-1 with a compound represented by Chemical Formula 2-2 to prepare a compound represented by Chemical Formula 2-3; reacting a compound represented by Chemical Formula 2-3 with a compound represented by Chemical Formula 2-4 to prepare a ligand of Chemical Formula 2-5; and reacting the ligand of Chemical Formula 2-5 with a halogen salt of a transition metal represented by Chemical Formula 2-6:

[0237] [Reaction Equation 2]

[0238]

[0239] In the above reaction scheme 2,

[0240] M2, X 21 , X 22 , T2, Q 21 , Q 22 and R 20 to R 31 is as defined in the above chemical formula 2, and X" is independently a halogen.

[0241] In the hybrid supported metallocene catalyst of the present invention, the first metallocene compound and the second metallocene compound may be included in a molar ratio of 1:1 to 25:1, 2:1 to 25:1, 3:1 to 25:1, 3:1 to 23:1, or 3:1 to 20:1. If the ratio of the first metallocene compound and the second metallocene compound falls outside the above range, it may be difficult to produce polyethylene having the desired uniform biaxial stretching processability.

[0242] The metallocene catalyst of the present invention may further include a carrier that supports the above-mentioned compound. The carrier may be a carrier having hydroxyl groups on its surface, and preferably, the carrier may be a carrier having highly reactive hydroxyl groups, silanol groups, or siloxane groups on its surface, and for this purpose, a carrier that has been surface-modified by calcination or has had moisture removed from its surface by drying may be used.

[0243] For example, silica prepared by calcining silica gel, silica dried at high temperatures, silica-alumina, and silica-magnesia may be used, and these may typically contain oxide, carbonate, sulfate, and nitrate components such as Na2O, K2CO3, BaSO4, and Mg(NO3)2.

[0244] When used in the form of a supported catalyst, the particle shape and bulk density of the polymer produced are excellent, and it can be used in conventional slurry polymerization, bulk polymerization, or gas phase polymerization processes. In addition, among the various supports, since the functional groups of the transition metal compound are chemically bonded and supported on the silica support, there is almost no catalyst released from the surface of the support during the ethylene polymerization process, and as a result, fouling caused by the entanglement of polymer particles on the reactor walls or between each other can be minimized when producing polyethylene copolymers by slurry or gas phase polymerization.

[0245] The above-mentioned carrier may have an average particle size (D50) of 20 to 60 μm. When having the above-mentioned particle size, transition metal compounds can be supported with superior efficiency, and as a result, catalytic activity can be increased. More specifically, it may be 20 μm or more, or 25 μm or more, and 60 μm or less, or 50 μm or less.

[0246] Meanwhile, in the present invention, the average particle size (D50) of the carrier refers to the particle size 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 carrier to be measured 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). The particle size distribution is calculated by measuring the difference in diffraction patterns according to particle size as the particles pass through the laser beam. The particle size at the point that is 50% of the cumulative distribution of the number of particles according to particle size in the measuring device is calculated and used as the average particle size.

[0247] In addition, when supported on the carrier, the first and second metallocene compounds may be supported in a content range of, for example, 1 mmol or more, 10 mmol or more, 15 mmol or more, 20 mmol or more, 25 mmol or more, or 30 mmol or more, respectively, based on 1,000 g of the carrier, and 500 mmol or less, 400 mmol or less, 300 mmol or less, 200 mmol or less, 100 mmol or less, 80 mmol or less, 60 mmol or less, or 52.5 mmol or less. When supported within the above content range, appropriate supported catalyst activity is exhibited, which may be advantageous in terms of maintaining catalyst activity and economic efficiency.

[0248] In addition, the above hybrid metallocene catalyst may further include a co-catalyst to improve high activity and process stability.

[0249] Specifically, the above co-catalyst may include one or more of the compounds represented by the following chemical formula 3.

[0250] [Chemical Formula 3]

[0251] -[Al(R 41 )-O] a -

[0252] In the above chemical formula 3,

[0253] R 41 is a halogen; or C substituted or unsubstituted with a halogen 1-20 It is hydrocarbil;

[0254] a is an integer greater than or equal to 2.

[0255] Meanwhile, in this specification, the hydrocarbyl group is a monovalent functional group in which a hydrogen atom has been removed from a hydrocarbon, and may include alkyl groups, alkenyl groups, alkynyl groups, aryl groups, aralkyl groups, aralkenyl groups, aralkinyl groups, alkylaryl groups, alkenylaryl groups, and alkynylaryl groups, etc. Furthermore, 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.

[0256] Examples of compounds represented by the above chemical formula 3 include alkylaluminoxane compounds such as methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, or butylaluminoxane, and any one or more of these may be used.

[0257] Among the compounds mentioned above, the co-catalyst may be, more specifically, an alkylaluminoxan-based co-catalyst such as methylaluminoxan.

[0258] The above alkylaluminoxane-based co-catalyst can further enhance catalytic activity by including a metal element that stabilizes the first and second metallocene compounds and acts as a Lewis acid to form a bond through Lewis acid-base interaction with the functional group introduced into the bridge group of the first and second metallocene compounds.

[0259] In addition, the amount of the above co-catalyst used can be appropriately adjusted according to the physical properties or effects of the desired catalyst and polyethylene copolymer. For example, when silica is used as the carrier, the above co-catalyst can be supported in an amount of 100g or more, 1000g or more, or 2000g or more, and 6000g or less, or 5500g or less, or 5400g or less, based on 1000g of silica.

[0260] A hybrid metallocene catalyst according to the present invention having the above-described composition can be manufactured by a manufacturing method comprising the steps of: supporting a co-catalyst compound on a carrier; and supporting the first and second transition metal compounds on the carrier. In this case, the order of supporting the co-catalyst and the first and second transition metal compounds may be changed as needed, and the order of supporting the first and second transition metal compounds may also be changed as needed. The first and second transition metal compounds may be supported simultaneously. Considering the effect of the supported catalyst with a structure determined by the order of support, among these, sequentially supporting the first and second transition metal compounds after supporting the co-catalyst on the carrier allows the manufactured supported catalyst to achieve superior process stability along with high catalytic activity in the manufacturing process of polyethylene copolymer.

[0261] As described above, the hybrid supported metallocene catalyst can exhibit excellent catalytic activity by including first and second metallocene compounds having a specific structure. Accordingly, the hybrid supported metallocene catalyst can be suitably used for the polymerization of ethylene and olefin monomers.

[0262] The above polymerization reaction can be carried out by the method of slurry polymerization by applying conventional apparatus and contact techniques, but, for example, it can be carried out using a gas phase polymerization reactor, a continuous slurry polymerization reactor, a loop slurry reactor, etc.

[0263] The polyethylene resin composition of the present invention includes, in addition to the polyethylene described above, solvents, heat stabilizers, antioxidants, UV absorbers, light stabilizers, metal inerts, fillers, reinforcing agents, plasticizers, lubricants, emulsifiers, pigments, optical bleaching agents, flame retardants, antistatic agents, foaming agents, etc. The types of additives are not particularly limited, and general additives known in the art may be used.

[0264]

[0265] According to another embodiment of the present invention, the invention relates to an unoriented sheet comprising the polyethylene resin composition described above.

[0266] The above-mentioned unoriented sheet may be manufactured by a casting process. For example, it may be manufactured by maintaining the cylinder temperature of a T-die extrusion laminator capable of melt extrusion at 150 to 230 ℃ and the T-die temperature at 200 to 280 ℃ and extruding the molten resin, but is not limited thereto.

[0267] The thickness of the above sheet may be 0.1 to 5 mm, 0.1 to 3 mm, 0.1 to 2 mm, 0.5 to 2 mm, or 0.5 to 1 mm, but can be appropriately adjusted according to the application of the polyethylene resin composition or according to the stretching conditions to be subsequently performed on the above sheet.

[0268] The above-mentioned unoriented sheet has high thickness smoothness, and the smoothness, which is the percentage of the standard deviation of the average thickness value, may be 10% or less, 9% or less, 8% or less, 7% or less, 6% or less, or 5% or less, and may be 0.001% or more considering the actual process limitations.

[0269] The average thickness and standard deviation of the above-mentioned unoriented sheet may be calculated from thickness measurements at 4 to 6 non-overlapping points on a sheet with dimensions of 90 mm in width and 90 mm in length. The thickness measurement method may utilize a thickness gauge, but may also be measured using other methods known in the art to which the present invention belongs.

[0270] According to another embodiment of the present invention, the invention relates to a stretched film comprising the polyethylene resin composition described above.

[0271] The above-mentioned stretched film may be obtained by stretching a sheet containing the polyethylene resin composition provided in the present invention.

[0272] The above-mentioned stretched film may be a uniaxially stretched or biaxially stretched film.

[0273] The thickness of the stretched film may be a value measured at 10 to 100 μm, for example, 20 to 95 μm, or 30 to 90 μm, or 40 to 85 μm.

[0274] The above-mentioned stretched film has high thickness smoothness, and may have an average thickness of more than 14 μm and a thickness standard deviation of 5 μm or less, but is not limited thereto.

[0275] In addition, the above-mentioned stretched film with high thickness smoothness has an average thickness greater than 14 μm, and the smoothness, which is the percentage of the standard deviation of the average thickness value, may be 15% or less, 14% or less, 13% or less, 12% or less, 11% or less, 10% or less, 9% or less, 8% or less, 7% or less, 6% or less, or 5% or less, and may be 0.001% or more considering actual process limitations.

[0276] The average thickness and standard deviation of the above-described stretched film are the average and standard deviation values ​​of at least 20 thickness measurements taken at at least 20 non-overlapping points of the stretched film when the size is 210 mm in width and 297 mm in length. The thickness measurement method may be measured using other methods known in the technical field to which the present invention belongs.

[0277] The above-mentioned polyethylene stretched film may have a tensile strength in the MD direction measured according to ASTM D 882 of 60 MPa or more, 70 MPa or more, 80 MPa or more, 90 MPa or more, 95 MPa or more, 100 MPa or more, or 110 MPa or more and 150 MPa or less. Additionally, the tensile strength in the TD direction may be 150 MPa or more, 170 MPa or more, 190 MPa or more, or 210 MPa or more and 280 MPa or less.

[0278] The above-described polyethylene stretched film may have a Young's Modulus in the MD direction, measured according to ASTM D882-07, of 300 MPa or more, 400 MPa or more, 500 MPa or more, 600 MPa or more, or 700 MPa or more, and may be 1000 MPa or less, 950 MPa or less, 900 MPa or less, 800 MPa or less, or 700 MPa or less. Specifically, the Young's Modulus in the MD direction may be 300 MPa or more and 1000 MPa or less, 400 MPa or more and 1000 MPa or less, or 500 MPa or more and 1000 MPa or less, but is not limited thereto.

[0279] The above-mentioned polyethylene stretched film may have a tensile modulus in the MD direction measured according to ASTM D 882 of 300 MPa or more, 500 MPa or more, 700 MPa or more, 900 MPa or more, 1000 MPa or more, or 1100 MPa or more. However, in terms of simultaneously achieving excellent stretchability and transparency of the final film, it may be 3000 MPa or less, 2500 MPa or less, 2000 MPa or less, 1500 MPa or less, 1400 MPa or less, 1300 MPa or less, or 1200 MPa or less.

[0280] In addition, the polyethylene stretched film may have a tensile modulus in the TD direction measured according to ASTM D 882 of 300 MPa or more, 500 MPa or more, 700 MPa or more, 900 MPa or more, 1000 MPa or more, 1100 MPa or more, or 1200 MPa or more. However, in terms of simultaneously achieving excellent stretchability and transparency of the final film, it may be 3000 MPa or less, 2500 MPa or less, 2000 MPa or less, 1900 MPa or less, 1800 MPa or less, or 1700 MPa or less.

[0281] The above-mentioned polyethylene stretched film may have a tensile elongation in the MD direction of 80% to 300% or 90% to 270% as measured according to ASTM D 882, and a tensile elongation in the TD direction of 30% to 150% or 35% to 130%.

[0282] The above-mentioned polyethylene stretched film may have a tear strength in the MD direction measured according to ASTM 1922 that is greater than 0, 0.5 N / mm or more, 1 N / mm or more, 2 N / mm or more, or 3 N / mm or more, and 20 N / mm or less, 15 N / mm or less, or 14 N / mm or less. The tear strength in the TD direction may be greater than 0, 0.5 N / mm or more, 1 N / mm or more, or 1.5 N / mm or more, and 6.5 N / mm or less, 6 N / mm or less, or 5.5 N / mm or less.

[0283] In addition, the polyethylene stretched film may have a puncture strength of 200 N / mm or more as measured according to EN 14477. Preferably, it may be 210 N / mm, 220 N / mm or more, or 230 N / mm or more, and 510 N / mm or less.

[0284] The above-mentioned polyethylene stretched film may have a haze of 15% or less, 13% or less, 12% or less, 11% or less, 10% or less, 9% or less, 8% or less, 7.5% or less, 7% or less, 6.5% or less, 6% or less, 5.5% or less, or 5% or less as measured according to ASTM 1003 standards.

[0285] Here, the physical properties of the stretched film may be measured values ​​when the thickness of the film is 10 μm to 100 μm, for example, 12 μm to 85 μm, or 15 μm to 50 μm, or 18 μm to 45 μm, or 20 μm to 30 μm. Specifically, the stretched film may be stretched with a stretching ratio of 5X8 (MD×TD) and the thickness may be measured to be about 14 μm to about 30 μm.

[0286] The polyethylene stretched film produced in the present invention can be highly advantageously applied as a packaging material for various products, such as product bags, food bags, food and special packaging, and industrial liners.

[0287] The present invention will be explained in detail below through the following examples. However, the following examples are merely illustrative of the present invention, and the scope of the present invention is not limited by the following examples.

[0288] Examples

[0289] [Preparation Example 1-1] Preparation of Metallocene Compound A1

[0290]

[0291] 1. Preparation of ligands

[0292] Under an argon (Ar) atmosphere, 27.2 g (100 mmol) of 3-(6-tert-butoxyhexyl)-1H-indene and 250 mL of n-hexane were added to a dry 2 L Schlenk flask. After cooling to -78 °C, 42 mL (1.05 eq., 105 mmol) of 2.5 M n-BuLi in hexane was added dropwise. The reaction mixture was slowly heated to room temperature and stirred for 8 hours. After cooling again to -78 °C, 21.3 g (1.5 eq., 150 mmol) of iodomethane was added dropwise. After slowly raising the temperature to room temperature and stirring for 24 hours, the organic layer was separated using water and diethyl ether and dried with MgSO4 to obtain 24.1 g (84.2 mmol, 84.2% yield) of 3-(6-tert-butoxyhexyl)-1-methyl-1H-indene.

[0293] 1 H NMR (500 MHz, CDCl3): 1.12 (9H, s), 1.29 (3H, d), 1.42 (4H, m), 1.56 (2H, m), 1.70 (2H, m), 2.52 (2H, t), 3.34 (2H, t), 3.42 (1H, m), 6.25 (1H, brs), 7.21 (1H, t), 7.25-7.32 (2H, m), 7.40 (1H, d).

[0294] 2. Preparation of Metallocene Compounds

[0295] Under an Ar atmosphere, 5.73 g (20 mmol) of the ligand synthesized above and 70 mL of diethyl ether were added to a dried 250 mL Schlenk flask. After cooling to -78 °C, 8.4 mL (1.05 eq., 21 mmol) of 2.5 M n-BuLi in hexane was added dropwise. The reaction mixture was slowly heated to room temperature and stirred for 8 hours. After cooling again to -78 °C, 8.46 g (1.0 eq., 20 mmol) of (1-n-butyl-3-methylcyclopentadienyl)ZrCl3-dimethoxyethane complex was added along with 30 mL of diethyl ether. After slowly heating to room temperature and stirring for 24 hours, the reaction mixture was dried under reduced pressure and dichloromethane was added. The resulting suspension was filtered under Ar to remove LiCl, the filtrate was dried under reduced pressure, and n-hexane was added. The resulting suspension was filtered under an argon atmosphere to obtain 7.52 g (12.9 mmol, 64.5% yield) of a solid metallocene compound represented by Chemical Formula 3 above.

[0296] 1 H NMR (500 MHz, CDCl3): 0.77-0.81 (3H, m), 1.09 (9H, s), 1.16-1.28 (6H, m), 1.48-1.56 (6H, m), 1.95 (3H, d), 2.14 (1H, m), 2.42 (4H, m), 2.68 (1H, m), 2.90 (1H, m), 3.23 (2H, t), 4.97 (1H, dt), 5.11 (1H, dt), 5.76 (1H, t), 6.41 (1H, brs), 7.13-7.15 (2H, m), 7.46-7.48 (2H, m).

[0297] [Preparation Example 1-2] Preparation of Metallocene Compound A2

[0298]

[0299] 1. Synthesis of ligands

[0300] Under Ar, 54.5 g (200 mmol) of 3-(6-tert-butoxyhexyl)-1H-indene and 500 mL of n-hexane were added to a dried 2 L Schlenk flask. After cooling to -78 °C, 84 mL (1.05 eq., 210 mmol) of 2.5 M n-BuLi in hexane was added dropwise. The reaction mixture was slowly heated to room temperature and stirred for 8 hours. After cooling again to -78 °C, 46.8 g (1.5 eq., 300 mmol) of iodoethane was added dropwise. After slowly raising the temperature to room temperature and stirring for 24 hours, the organic layer was separated using water and diethyl ether and dried with MgSO4 to obtain 43.3 g (144 mmol, 72% yield) of 3-(6-tert-butoxyhexyl)-1-ethyl-1H-indene.

[0301] 1 H NMR (500 MHz, CDCl3): 0.94 (3H, t), 1.12 (9H, s), 1.29 (2H, m), 1.32-1.90 (8H, m), 2.52 (2H, t), 3.34 (2H, t), 3.45 (1H, m), 6.27 (1H, brs), 7.22 (1H, t), 7.25-7.35 (2H, m), 7.39 (1H, d).

[0302] 2. Synthesis of Metallocene Compounds

[0303] Under Ar, 6.61 g (22 mmol) of the ligand synthesized above and 80 mL of diethyl ether were added to a dried 250 mL Schlenk flask. After cooling to -78 °C, 9.3 mL (1.06 eq., 23.3 mmol) of 2.5 M n-BuLi in hexane was added dropwise. The reaction mixture was slowly heated to room temperature and stirred for 8 hours. After cooling again to -78 °C, 9.00 g (1.0 eq., 22 mmol) of the (n-butylcyclopentadienyl)ZrCl3 dimethoxyethane complex was added along with 30 mL of diethyl ether. After slowly heating to room temperature and stirring for 24 hours, the reaction mixture was dried under reduced pressure and dichloromethane was added. The resulting suspension was filtered under Ar to remove LiCl, the filtrate was dried under reduced pressure, and n-hexane was added. The resulting suspension was filtered under Ar to obtain 8.10 g (13.9 mmol, 63.2% yield) of solid metalocene compound A2.

[0304] 1 H NMR (500 MHz, CDCl3): 0.75-0.85 (3H, m), 0.87 (3H, m), 1.11 (9H, s), 1.18-1.29 (6H, m), 1.47-1.56 (6H, m), 2.16 (1H, m), 2.40-2.65 (4H, m), 2.89 (1H, m), 3.26 (2H, t), 4.96-5.94 (4H, m), 6.40 (1H, brs), 7.11-7.17 (2H, m), 7.44-7.48 (2H, m).

[0305] [Preparation Example 1-3] Preparation of Metallocene Compound A3

[0306]

[0307] 1. Synthesis of ligands

[0308] Under Ar, 27.3 g (100 mmol) of 3-(6-tert-butoxyhexyl)-1H-indene and 250 mL of n-hexane were added to a dry 2 L Schlenk flask. After cooling to -78 °C, 42 mL (1.05 eq., 105 mmol) of 2.5 M n-BuLi in hexane was added dropwise. The reaction mixture was slowly heated to room temperature and stirred for 8 hours. After cooling again to -78 °C, 13.6 g (1.1 eq., 111 mmol) of 2-bromopropane was added dropwise. After slowly raising the temperature to room temperature and stirring for 24 hours, the organic layer was separated using water and diethyl ether and dried with MgSO4 to obtain 26.4 g (84 mmol, 84% yield) of 3-(6-tert-butoxyhexyl)-1-isopropyl-1H-indene.

[0309] 1 H NMR (500 MHz, CDCl3): 0.88 (6H, d), 1.24 (9H, s), 1.34 (4H, m), 1.47 (3H, m), 1.57 (2H, m), 1.73 (2H, m), 2.55 (2H, t), 3.39 (2H, t), 3.45 (1H, m), 6.17 (1H, brs), 7.23 (1H, t), 7.31 (2H, m), 7.44 (1H, d).

[0310] 2. Synthesis of Metallocene Compounds

[0311] Under Ar, 6.29 g (20 mmol) of the ligand synthesized above and 70 mL of diethyl ether were added to a dried 250 mL Schlenk flask. After cooling to -78 °C, 8.4 mL (1.05 eq., 21 mmol) of 2.5 M n-BuLi in hexane was added dropwise. The reaction mixture was slowly heated to room temperature and stirred for 8 hours. After cooling again to -78 °C, 8.46 g (1.0 eq., 20 mmol) of the (1-n-butyl-3-methylcyclopentadienyl)ZrCl3 dimethoxyethane complex was added along with 30 mL of diethyl ether. After slowly heating to room temperature and stirring for 24 hours, the reaction mixture was dried under reduced pressure and dichloromethane was added. The resulting suspension was filtered under Ar to remove LiCl, the filtrate was dried under reduced pressure, and n-hexane was added. The resulting suspension was filtered under Ar to obtain 7.70 g (12.6 mmol, 63% yield) of solid metallocene compound A3.

[0312] 1 H NMR (500 MHz, CDCl3): 0.79-0.91 (9H, m), 1.19 (9H, s), 1.29-1.30 (6H, m), 1.52-1.54 (4H, m), 1.65-1.71 (2H, m), 2.03 (3H, s), 2.11-2.22 (2H, m), 2.51-2.55 (1H, m), 2.77-2.86 (1H, m), 2.99-3.07 (1H, m), 3.34 (2H, t), 4.53 (1H, dt), 5.22 (1H, dt), 5.82 (1H, t), 6.62 (1H, brs), 7.11-7.28 (2H, m), 7.56-7.63 (2H, m).

[0313] [Preparation Example 1-4] Preparation of Metallocene Compound A4

[0314]

[0315] 1. Synthesis of ligands

[0316] Under Ar, 120 g (440 mmol) of 3-(6-tert-butoxyhexyl)-1H-indene and 1.1 L of n-hexane were added to a dried 2 L Schlenk flask. After cooling to -78 °C, 185 mL (1.05 eq., 462.5 mmol) of 2.5 M n-BuLi in hexane was added dropwise. The reaction mixture was slowly heated to room temperature and stirred for 8 hours. After cooling again to -78 °C, 82.8 g (1.1 eq., 484 mmol) of benzyl bromide was added dropwise. After slowly raising the temperature to room temperature and stirring for 24 hours, the organic layer was separated using water and diethyl ether and dried with MgSO4 to obtain 137 g (377 mmol, 85.7% yield) of 3-(6-tert-butoxyhexyl)-1-benzyl-1H-indene.

[0317] 1 H NMR (500 MHz, CDCl3): 1.22 (9H, s), 1.32 (4H, m), 1.44 (2H, m), 1.57 (2H, m), 1.73 (2H, m), 2.59 (2H, m), 3.38 (2H, t), 3.75 (1H, m), 6.14 (1H, brs), 7.14-7.45 (9H, m).

[0318] 2. Synthesis of Metallocene Compounds

[0319] Under Ar, 9.06 g (25 mmol) of the ligand synthesized above and 90 mL of diethyl ether were added to a dried 250 mL Schlenk flask. After cooling to -78 °C, 11 mL (1.05 eq., 27.5 mmol) of 2.5 M n-BuLi in hexane was added dropwise. The reaction mixture was slowly heated to room temperature and stirred for 8 hours. After cooling again to -78 °C, 10.6 g (1.0 eq., 25 mmol) of the (1-n-butyl-3-methylcyclopentadienyl)ZrCl3 dimethoxyethane complex was added along with 30 mL of diethyl ether. After slowly heating to room temperature and stirring for 24 hours, the reaction mixture was dried under reduced pressure and dichloromethane was added. The resulting suspension was filtered under Ar to remove LiCl, the filtrate was dried under reduced pressure, and n-hexane was added. The resulting suspension was filtered under Ar to obtain 8.76 g (13.3 mmol, 53.2% yield) of solid metallocene compound A4.

[0320] 1 H NMR (500 MHz, CDCl3): 0.88-0.91 (3H, m), 1.22 (9H, s), 1.29-1.40 (8H, m), 1.52-1.76 (4H, m), 2.06 (3H, s), 2.11-2.22 (2H, m), 2.59-2.68 (2H, m), 2.99-3.07 (2H, m), 3.34 (2H, t), 4.43 (1H, dt), 5.21 (1H, dt), 5.78 (1H, t), 6.47 (1H, brs), 7.11-7.63 (9H, m).

[0321] [Preparation Example 1-5] Preparation of Metallocene Compound A5

[0322]

[0323] 1. Synthesis of ligands

[0324] Under Ar, 35.4 g (130 mmol) of 3-(6-tert-butoxyhexyl)-1H-indene and 350 mL of n-hexane were added to a dry 2 L Schlenk flask. After cooling to -78 °C, 55 mL (1.05 eq., 137 mmol) of 2.5 M n-BuLi in hexane was added dropwise. The reaction mixture was slowly heated to room temperature and stirred for 8 hours. After cooling again to -78 °C, 23.9 g (1.5 eq., 195 mmol) of (chloromethyl)trimethylsilane was added dropwise. After slowly raising the temperature to room temperature and stirring for 24 hours, the organic layer was separated using water and diethyl ether and dried with MgSO4 to obtain 27.6 g (77 mmol, 59.2% yield) of 3-(6-tert-butoxyhexyl)-1-(trimethylsilyl)methyl-1H-indene.

[0325] 1 H NMR (500 MHz, CDCl3): 0.05 (9H, s), 0.88 (2H, m), 1.24 (9H, s), 1.33 (4H, m), 1.45 (2H, m), 1.57 (2H, m), 2.57 (2H, m), 3.35 (2H, t), 3.71 (1H, m), 6.16 (1H, brs), 7.12-7.45 (4H, m).

[0326] 2. Synthesis of Metallocene Compounds

[0327] Under Ar, 9.68 g (27 mmol) of the ligand synthesized above and 100 mL of diethyl ether were added to a dried 250 mL Schlenk flask. After cooling to -78 °C, 11.4 mL (1.06 eq., 28.5 mmol) of 2.5 M n-BuLi in hexane was added dropwise. The reaction mixture was slowly heated to room temperature and stirred for 8 hours. After cooling again to -78 °C, 38.61 g (1.0 eq., 27 mmol) of (tetramethylcyclopentadienyl)ZrCl was added along with 30 mL of diethyl ether. After slowly heating to room temperature and stirring for 24 hours, the reaction mixture was dried under reduced pressure and dichloromethane was added. The resulting suspension was filtered under Ar to remove LiCl, the filtrate was dried under reduced pressure, and n-hexane was added. The resulting suspension was filtered under Ar to obtain 8.76 g (13.3 mmol, 53.2% yield) of the solid metallocene compound A5.

[0328] 1 H NMR (500 MHz, CDCl3): -0.05 (9H, s), 0.75 (2H, m), 1.24 (9H, s), 1.25-1.42 (4H, m), 1.52-1.76 (4H, m), 1.81 (12H, brs), 2.10-2.22 (2H, m), 3.33 (2H, t), 5.01 (1H, brs), 6.41 (1H, brs), 7.10-7.58 (4H, m).

[0329] [Preparation Example 1-6] Preparation of Metallocene Compound A6

[0330]

[0331] 1. Synthesis of ligands

[0332] Under Ar, 44.2 g (230 mmol) of 3-phenyl-1H-indene and 600 mL of tetrahydrofuran were added to a dried 2 L Schlenk flask. After cooling to -78 °C, 97 mL (1.06 eq., 243 mmol) of 2.5 M n-BuLi in hexane was added dropwise. The reaction mixture was slowly heated to room temperature and stirred for 8 hours. After cooling again to -78 °C, 44.4 g (1.0 eq., 230 mmol) of 6-tert-butoxyhexyl chloride was added dropwise. After slowly raising the temperature to room temperature and stirring for 24 hours, the organic layer was separated using water and diethyl ether and dried with MgSO4 to obtain 31.7 g (91.0 mmol, 39.5% yield) of 1-(6-tert-butoxyhexyl)-3-phenyl-1H-indene.

[0333] 1 H NMR (500 MHz, CDCl3): 1.18 (9H, s), 1.32 (4H, m), 1.42 (2H, m), 1.55 (2H, m), 1.97 (2H, m), 3.32 (2H, t), 3.61 (1H, m), 6.66 (1H, brs), 7.08-7.50 (9H, m).

[0334] 2. Synthesis of Metallocene Compounds

[0335] Under Ar, 11.5 g (33 mmol) of the ligand synthesized above and 120 mL of diethyl ether were added to a dried 250 mL Schlenk flask. After cooling to -78 °C, 13.9 mL (1.05 eq., 34.8 mmol) of 2.5 M n-BuLi in hexane was added dropwise. The reaction mixture was slowly heated to room temperature and stirred for 8 hours. After cooling again to -78 °C, 11.0 g (1.0 eq., 33 mmol) of (pentamethylcyclopentadienyl)ZrCl3 was added along with 30 mL of diethyl ether. After slowly heating to room temperature and stirring for 24 hours, the reaction mixture was dried under reduced pressure and dichloromethane was added. The resulting suspension was filtered under Ar to remove LiCl, the filtrate was dried under reduced pressure, and n-hexane was added. The resulting suspension was filtered under Ar to obtain 15.3 g (23.7 mmol, 71.8% yield) of solid metallocene compound A6.

[0336] 1 H NMR (500 MHz, CDCl3): 1.21 (9H, s), 1.26-1.43 (4H, m), 1.55-1.71 (4H, m), 1.74 (15H, brs), 2.24 (2H, m), 3.32 (2H, t), 6.61 (1H, brs), 7.10-7.65 (9H, m).

[0337] [Preparation Example 1-7] Preparation of Metallocene Compound A7

[0338]

[0339] Under Ar, 7.25 g (20 mmol) of the ligand synthesized in Preparation Example 1-4, 1. and 70 mL of diethyl ether were added to a dried 250 mL Schlenk flask. After cooling to -78 °C, 8.4 mL (1.05 eq., 21 mmol) of 2.5 M n-BuLi in hexane was added dropwise. The reaction mixture was slowly heated to room temperature and stirred for 8 hours. After cooling again to -78 °C, 6.66 g (1.0 eq., 20 mmol) of (pentamethylcyclopentadienyl)ZrCl3 was added along with 30 mL of diethyl ether. After slowly heating to room temperature and stirring for 24 hours, the reaction mixture was dried under reduced pressure and dichloromethane was added. The resulting suspension was filtered under Ar to remove LiCl, the filtrate was dried under reduced pressure, and n-hexane was added. The resulting suspension was filtered under Ar to obtain 7.45 g (11.3 mmol, 56.5% yield) of solid metallocene compound A7.

[0340] 1 H NMR (500 MHz, CDCl3): 1.23 (9H, s), 1.25-1.41 (4H, m), 1.54-1.75 (4H, m), 1.79 (15H, brs), 2.21 (2H, m), 2.93 (2H, m), 3.32 (2H, t), 6.45 (1H, brs), 7.05-7.64 (9H, m).

[0341] [Preparation Example 1-8] Preparation of Metallocene Compound A8

[0342]

[0343] Under Ar, 9.43 g (26 mmol) of the ligand synthesized in Preparation Example 1-4, 1. and 90 mL of diethyl ether were added to a dried 250 mL Schlenk flask. After cooling to -78 °C, 11 mL (1.06 eq., 27.5 mmol) of 2.5 M n-BuLi in hexane was added dropwise. The reaction mixture was slowly heated to room temperature and stirred for 8 hours. After cooling again to -78 °C, 11.5 g (1.0 eq., 26 mmol) of the (1-phenyl-3-methylcyclopentadienyl)ZrCl3 dimethoxyethane complex was added along with 30 mL of diethyl ether. After slowly heating to room temperature and stirring for 24 hours, the reaction mixture was dried under reduced pressure and dichloromethane was added. The resulting suspension was filtered under Ar to remove LiCl, the filtrate was dried under reduced pressure, and n-hexane was added. The resulting suspension was filtered under Ar to obtain 10.9 g (16.1 mmol, 61.9% yield) of solid metallocene compound A8.

[0344] 1 H NMR (500 MHz, CDCl3): 1.23 (9H, s), 1.25-1.41 (4H, m), 1.54-1.75 (4H, m), 2.17 (5H, m), 2.61 (2H, m), 3.32 (2H, t), 4.45 (1H, dt), 5.22 (1H, dt), 5.99 (1H, t), 6.45 (1H, brs), 7.09-7.58 (14H, m).

[0345] [Preparation Example 1-9] Preparation of Metallocene Compound A9

[0346]

[0347] 1. Synthesis of ligands

[0348] Under Ar, 54.5 g (200 mmol) of 2-(6-tert-butoxyhexyl)-1H-indene and 500 mL of tetrahydrofuran were added to a dried 2 L Schlenk flask. After cooling to -78 °C, 84 mL (1.05 eq., 210 mmol) of 2.5 M n-BuLi in hexane was added dropwise. The reaction mixture was slowly heated to room temperature and stirred for 8 hours. After cooling again to -78 °C, 46.8 g (1.5 eq., 300 mmol) of iodoethane was added dropwise. After slowly raising the temperature to room temperature and stirring for 24 hours, the organic layer was separated using water and diethyl ether and dried with MgSO4 to obtain 41.2 g (137 mmol, 68.5% yield) of 2-(6-tert-butoxyhexyl)-1-ethyl-1H-indene.

[0349] 1 H NMR (500 MHz, CDCl3): 0.96 (3H, t), 1.11 (9H, s), 1.22-1.90 (10H, m), 3.34 (3H, m), 6.46 (1H, brs), 7.12-7.55 (4H, m).

[0350] 2. Synthesis of Metallocene Compounds

[0351] Under Ar, 8.11 g (27 mmol) of the ligand synthesized above and 90 mL of diethyl ether were added to a dried 250 mL Schlenk flask. After cooling to -78 °C, 11.4 mL (1.06 eq., 28.5 mmol) of 2.5 M n-BuLi in hexane was added dropwise. The reaction mixture was slowly heated to room temperature and stirred for 8 hours. After cooling again to -78 °C, 13.7 g (1.0 eq., 27 mmol) of the (6-tert-butoxyhexyl)cyclopentadienyl)ZrCl3 dimethoxyethane complex was added along with 30 mL of diethyl ether. After slowly heating to room temperature and stirring for 24 hours, the reaction mixture was dried under reduced pressure and dichloromethane was added. The resulting suspension was filtered under Ar to remove LiCl, the filtrate was dried under reduced pressure, and n-hexane was added. The resulting suspension was filtered under Ar to obtain 11.5 g (16.8 mmol, 62.2% yield) of solid metallocene compound A9.

[0352] 1 H NMR (500 MHz, CDCl3): 0.88 (3H, m), 1.14 (18H, brs), 1.19-1.35 (8H, m), 1.51-1.70 (8H, m), 2.18 (1H, m), 2.40-2.65 (4H, m), 2.77 (1H, m), 3.25 (4H, m), 4.86-5.90 (4H, m), 6.66 (1H, brs), 7.07-7.21 (2H, m), 7.40-7.51 (2H, m).

[0353] [Preparation Example 1-10] Preparation of Metallocene Compound A10

[0354]

[0355] Under Ar, 10.9 g (30 mmol) of the ligand synthesized in Preparation Example 1-4, 1. and 110 mL of diethyl ether were added to a dried 250 mL Schlenk flask. After cooling to -78 °C, 12.6 mL (1.05 eq., 31.5 mmol) of 2.5 M n-BuLi in hexane was added dropwise. The reaction mixture was slowly heated to room temperature and stirred for 8 hours. After cooling again to -78 °C, 15.3 g (1.0 eq., 30 mmol) of ((6-tert-butoxyhexyl)cyclopentadienyl)ZrCl3 dimethoxyethane complex was added along with 30 mL of diethyl ether. After slowly heating to room temperature and stirring for 24 hours, the reaction mixture was dried under reduced pressure and dichloromethane was added. The resulting suspension was filtered under Ar to remove LiCl, the filtrate was dried under reduced pressure, and n-hexane was added. The resulting suspension was filtered under Ar to obtain 13.3 g (17.8 mmol, 59.3% yield) of the solid metallocene compound A10.

[0356] 1 H NMR (500 MHz, CDCl3): 1.13 (18H, brs), 1.17-1.35 (8H, m), 1.52-1.66 (8H, m), 2.16 (1H, m), 2.40-2.65 (2H, m), 2.74 (1H, m), 2.98 (2H, m), 3.22 (4H, m), 4.89-5.88 (4H, m), 6.36 (1H, brs), 7.05-7.54 (9H, m).

[0357] [Preparation Example 1-11] Preparation of Metallocene Compound A11

[0358]

[0359] Under Ar, 9.06 g (25 mmol) of the ligand synthesized in 1. of Preparation Example 1-4 and 90 mL of diethyl ether were added to a dried 250 mL Schlenk flask. After cooling to -78 °C, 11 mL (1.05 eq., 27.5 mmol) of 2.5 M n-BuLi in hexane was added dropwise. The reaction mixture was slowly heated to room temperature and stirred for 8 hours. After cooling again to -78 °C, 12.8 g (1.0 eq., 25 mmol) of the (1-n-butyl-3-methylcyclopentadienyl)HfCl3 dimethoxyethane complex was added along with 30 mL of diethyl ether. After slowly heating to room temperature and stirring for 24 hours, the reaction mixture was dried under reduced pressure and toluene was added. The resulting suspension was filtered under Ar to remove LiCl, and then 25 mL (3.0 eq., 75 mmol) of 3.0 M methylmagnesium bromide in diethyl ether was added dropwise to the filtrate. The reaction mixture was heated to 80 °C and stirred for 2 days. After cooling to room temperature, 1,4-dioxane was added. The resulting suspension was filtered under Ar to remove Mg salt, and then the reaction mixture was dried under reduced pressure to obtain 12.9 g (18.3 mmol, 73.2% yield) of the oil-form metallocene compound A11.

[0360] 1 H NMR (500 MHz, CDCl3): -1.19 (6H, d), 0.85-0.88 (3H, m), 1.20 (9H, s), 1.22-1.37 (8H, m), 1.50-1.66 (4H, m), 2.01 (3H, s), 2.10-2.18 (2H, m), 2.52-2.58 (2H, m), 2.95-3.03 (2H, m), 3.32 (2H, t), 4.81 (1H, dt), 5.35 (1H, dt), 5.54 (1H, t), 5.71 (1H, brs), 7.05-7.53 (9H, m).

[0361] [Preparation Example 1-12] Preparation of Metallocene Compound A12

[0362]

[0363] Under Ar, 5.73 g (20 mmol) of the ligand synthesized in Preparation Example 1-1, 1. and 70 mL of diethyl ether were added to a dried 250 mL Schlenk flask. After cooling to -78 °C, 8.4 mL (1.05 eq., 21 mmol) of 2.5 M n-BuLi in hexane was added dropwise. The reaction mixture was slowly heated to room temperature and stirred for 8 hours. After cooling again to -78 °C, 8.12 g (1.0 eq., 20 mmol) of (tetramethylcyclopentadienyl)HfCl3 was added along with 30 mL of diethyl ether. After slowly heating to room temperature and stirring for 24 hours, the reaction mixture was dried under reduced pressure and toluene was added. The resulting suspension was filtered under Ar to remove LiCl, and then 20 mL (3.0 eq., 60 mmol) of 3.0 M methylmagnesium bromide in diethyl ether was added dropwise to the filtrate. The reaction mixture was heated to 80 °C and stirred for 2 days. After cooling back to room temperature, 1,4-dioxane was added. The resulting suspension was filtered under Ar to remove Mg salt, and then the reaction mixture was dried under reduced pressure to obtain 7.80 g (12.7 mmol, 63.4% yield) of the oil-form metallocene compound A12.

[0364] 1 H NMR (500 MHz, CDCl3): -1.39 (6H, d), 1.17 (9H, s), 1.30-1.37 (4H, m), 1.45-1.70 (4H, m), 1.81-1.90 (12H, m), 2.27 (3H, s), 2.30-2.41 (1H, m), 2.72-2.80 (1H, m), 3.30 (2H, t), 4.92 (1H, brs), 5.56 (1H, brs), 7.10-7.19 (2H, m), 7.39-7.46 (2H, m).

[0365] [Preparation Example 1-13] Preparation of Metallocene Compound A13

[0366]

[0367] Under Ar, 9.06 g (25 mmol) of the ligand synthesized in 1. of Preparation Example 1-4 and 90 mL of diethyl ether were added to a dried 250 mL Schlenk flask. After cooling to -78 °C, 11 mL (1.05 eq., 27.5 mmol) of 2.5 M n-BuLi in hexane was added dropwise. The reaction mixture was slowly heated to room temperature and stirred for 8 hours. After cooling again to -78 °C, 10.5 g (1.0 eq., 25 mmol) of (pentamethylcyclopentadienyl)HfCl3 was added along with 30 mL of diethyl ether. After slowly heating to room temperature and stirring for 24 hours, the reaction mixture was dried under reduced pressure and toluene was added. The resulting suspension was filtered under Ar to remove LiCl, and then 25 mL (3.0 eq., 75 mmol) of 3.0 M methylmagnesium bromide in diethyl ether was added dropwise to the filtrate. The reaction mixture was heated to 80 °C and stirred for 2 days. After cooling to room temperature, 1,4-dioxane was added. The resulting suspension was filtered under Ar to remove Mg salt, and then the reaction mixture was dried under reduced pressure to obtain 9.45 g (13.4 mmol, 53.7% yield) of the oil-form metallocene compound A13.

[0368] 1 H NMR (500 MHz, CDCl3): -1.25 (6H, d), 1.19 (9H, s), 1.22-1.37 (4H, m), 1.50-1.66 (4H, m), 1.85-2.05 (15H, m), 2.28 (1H, m), 2.78 (1H, m), 2.92-3.01 (2H, m), 3.32 (2H, t), 5.69 (1H, brs), 7.05-7.53 (9H, m).

[0369] [Preparation Example 2-1] Preparation of Metallocene Compound B1

[0370]

[0371] 1. Synthesis of ligands

[0372] Under Ar, 7.33 g (60 mmol) of n-butylcyclopentadiene, 6.97 g (2.0 eq., 120 mmol) of acetone, and 120 mL of methanol were added to a dried 250 mL Schlenk flask. After cooling to 0 °C, 6.40 g (1.5 eq., 90 mmol) of pyrrolidine was added dropwise. The reaction mixture was slowly heated to room temperature and stirred for 24 hours. After cooling the reaction mixture to 0 °C, 120 mL of 10 vol% aq. acetic acid was added and stirred for 30 minutes. The organic layer was separated using water and diethyl ether and dried with MgSO4 to obtain 9.17 g (56.5 mmol, 94.1% yield) of 2-n-butyl-5-isopropylidene-cyclopenta-1,3-diene.

[0373] Under Ar, 12.9 g (40 mmol) of 2-(6-tert-butoxyhexyl)fluorene and 160 mL of tetrahydrofuran were added to another dry 250 mL Schlenk flask. After cooling to -78 °C, 19.2 mL (1.2 eq., 48 mmol) of 2.5 M n-BuLi in hexane was added dropwise. The reaction mixture was slowly heated to room temperature and stirred for 8 hours. After cooling to -78 °C, 6.49 g (1.0 eq., 40 mmol) of the 2-n-butyl-5-isopropylidene-cyclopenta-1,3-diene synthesized above was added along with 30 mL of tetrahydrofuran. After slowly raising the temperature to room temperature and stirring for 24 hours, the organic layer was separated using water and diethyl ether and dried with MgSO4 to obtain 17.8 g of ligand (36.7 mmol, 91.8% yield).

[0374] 1H NMR (500 MHz, CDCl3): 0.91-0.97 (9H, m), 1.12 (9H, s), 1.25-1.62 (12H, m), 2.15 (2H, m), 2.68 (2H, m), 2.92 (4H, m), 3.36 (2H, t), 3.73 (1H, brs), 6.13 (1H, m), 6.28 (1H, brs), 7.21-8.01 (7H, m).

[0375] 2. Synthesis of Metallocene Compounds

[0376] Under Ar, 14.5 g (30 mmol) of the ligand synthesized above, 30 mL of methyl t-butyl ether, and 120 mL of toluene were added to a dried 250 mL Schlenk flask. After cooling to -78 °C, 26.4 mL (2.2 eq., 66 mmol) of a 2.5 M n-BuLi solution in hexane was added dropwise. The reaction mixture was slowly heated to room temperature and stirred for 8 hours. After cooling to -78 °C, 211.3 g (1.0 eq., 30 mmol) of ZrCl4(THF) was added along with 10 mL of methyl t-butyl ether. After slowly heating to room temperature and stirring for 24 hours, the reaction mixture was dried under reduced pressure at room temperature to remove the methyl t-butyl ether. The resulting toluene suspension was filtered under Ar to remove LiCl, the filtrate was dried under reduced pressure at 50 °C, and n-hexane was added. The resulting suspension was filtered under Ar to obtain 8.25 g (12.8 mmol, 42.7% yield) of solid metallocene compound B1.

[0377] 1H NMR (500 MHz, C6D6): 0.91-1.04 (9H, m), 1.13 (9H, s), 1.25-1.38 (6H, m), 1.44-1.65 (6H, m), 2.25 (2H, m), 2.85 (2H, m), 3.37 (2H, t), 5.42-6.21 (3H, m), 7.26-7.39 (3H, m), 7.42-7.55 (2H, m), 7.78 (1H, d), 7.93 (2H, d).

[0378] [Preparation Example 2-2] Preparation of Metallocene Compound B2

[0379]

[0380] 1. Preparation of ligands

[0381] Under an Ar gas atmosphere, 100 g (450 mmol) of 2-(6-tert-butoxyhexyl)cyclopentadiene, 103 g (2.0 eq., 900 mmol) of 2,4-dimethyl-3-pentanone, and 1 L of ethanol were added to a dry 250 mL Schlenk flask. After cooling to 0 °C, 48.0 g (1.5 eq., 675 mmol) of pyrrolidine was added dropwise. The reaction mixture was slowly heated to room temperature and stirred for 24 hours. After cooling the reaction mixture to 0 °C, 1 L of 10 vol% aq. acetic acid was added and stirred for 30 minutes. The organic layer was separated using water and diethyl ether and dried with MgSO4 to obtain 44.9 g (141 mmol, 31.3% yield) of 2-(6-tert-butoxyhexyl)-5-(2,4-dimethylpentane-3-ylidene)-cyclopenta-1,3-diene.

[0382] Under an Ar gas atmosphere, 1.66 g (10 mmol) of fluorene and 40 mL of tetrahydrofuran were added to another dry 250 mL Schlenk flask. After cooling to -78 °C, 4.8 mL (1.2 eq., 12 mmol) of 2.5 M n-BuLi in hexane was added dropwise. The reaction mixture was slowly heated to room temperature and stirred for 8 hours. After cooling to -78 °C, 3.19 g (1.0 eq., 10 mmol) of the 2-(6-tert-butoxyhexyl)-5-(2,4-dimethylpentane-3-ylidene)-cyclopenta-1,3-diene synthesized above was added along with 10 mL of tetrahydrofuran. After slowly raising the temperature to room temperature and stirring for 24 hours, the organic layer was separated using water and diethyl ether and dried with MgSO4 to obtain 3.94 g of ligand (8.12 mmol, 81.2% yield).

[0383] 1 H NMR (500 MHz, CDCl3): 0.87 (12H, d), 1.12 (9H, s), 1.34 (2H, m), 1.41 (2H, m), 1.46 (2H, m), 1.55 (4H, m), 2.18 (2H, t), 2.91 (2H, d), 3.36 (2H, t), 3.73 (1H, s), 6.15 (1H, t), 6.25 (1H, brs), 7.25-7.44 (4H, m), 7.55 (2H, dd), 7.90 (2H, dd).

[0384] 2. Preparation of Metallocene Compounds

[0385] Under an Ar gas atmosphere, 3.94 g (8.12 mmol) of the ligand synthesized above, 5 mL of methyl t-butyl ether, and 20 mL of toluene were added to a dried 250 mL Schlenk flask. After cooling to -78 °C, 7.1 mL (2.2 eq., 17.8 mmol) of a 2.5 M n-BuLi solution in hexane was added dropwise. The reaction mixture was slowly heated to room temperature and stirred for 8 hours. After cooling to -78 °C, 23.06 g (1.0 eq., 8.12 mmol) of ZrCl4(THF) was added along with 5 mL of methyl t-butyl ether. After slowly heating to room temperature and stirring for 24 hours, the reaction mixture was dried under reduced pressure at room temperature to remove the methyl t-butyl ether. The resulting toluene suspension was filtered under Ar to remove LiCl, the filtrate was dried under reduced pressure at 50 °C, and n-hexane was added. The resulting suspension was filtered under Ar to obtain 2.61 g (4.04 mmol, 49.8% yield) of solid metallocene compound B2.

[0386] 1 H NMR (500 MHz, C6D6): 0.91 (12H, d), 1.13 (9H, s), 1.15-1.38 (6H, m), 1.40-1.55 (6H, m), 3.22 (2H, t), 5.32-6.12 (3H, m), 7.20-7.32 (2H, t), 7.47-7.55 (2H, dd), 7.72 (2H, d), 7.93 (2H, t).

[0387] [Preparation Example 2-3] Preparation of Metallocene Compound B3

[0388]

[0389] 1. Synthesis of ligands

[0390] Under Ar, 4.45 g (20 mmol) of 2-tert-butylfluorene and 80 mL of tetrahydrofuran were added to another dry 250 mL Schlenk flask. After cooling to -78 °C, 9.6 mL (1.2 eq., 24 mmol) of 2.5 M n-BuLi in hexane was added dropwise. The reaction mixture was slowly heated to room temperature and stirred for 8 hours. After cooling to -78 °C, 6.38 g (1.0 eq., 20 mmol) of 2-(6-tert-butoxyhexyl)-5-(2,4-dimethylpentane-3-ylidene)-cyclopenta-1,3-diene synthesized in B2 was added along with 10 mL of tetrahydrofuran. After slowly raising the temperature to room temperature and stirring for 24 hours, the organic layer was separated using water and diethyl ether and dried with MgSO4 to obtain 7.30 g of ligand (13.5 mmol, 67.5% yield).

[0391] 1 H NMR (500 MHz, CDCl3): 0.85 (12H, d), 1.14 (9H, s), 1.25 (9H, s), 1.31-1.60 (10H, m), 2.22 (2H, m), 2.92 (2H, m), 3.33 (2H, t), 3.76 (1H, brs), 6.11 (1H, m), 6.35 (1H, brs), 7.25-7.42 (3H, m), 7.50-7.62 (2H, d), 7.81-7.92 (2H, d).

[0392] 2. Synthesis of Metallocene Compounds

[0393] Under Ar, 7.30 g (13.5 mmol) of the ligand synthesized above, 10 mL of methyl t-butyl ether, and 40 mL of toluene were added to a dried 250 mL Schlenk flask. After cooling to -78 °C, 11.9 mL (2.2 eq., 29.8 mmol) of a 2.5 M n-BuLi in hexane solution was added dropwise. The reaction mixture was slowly heated to room temperature and stirred for 8 hours. After cooling to -78 °C, 25.09 g (1.0 eq., 13.5 mmol) of ZrCl4(THF) was added along with 10 mL of methyl t-butyl ether. After slowly heating to room temperature and stirring for 24 hours, the reaction mixture was dried under reduced pressure at room temperature to remove the methyl t-butyl ether. The resulting toluene suspension was filtered under Ar to remove LiCl, the filtrate was dried under reduced pressure at 50 °C, and n-hexane was added. The resulting suspension was filtered under Ar to obtain 5.31 g (7.57 mmol, 56.1% yield) of solid metallocene compound B3.

[0394] 1 H NMR (500 MHz, C6D6): 0.90 (12H, d), 1.12 (9H, s), 1.15-1.38 (15H, m), 1.44-1.55 (6H, m), 3.21 (2H, t), 5.30-6.15 (3H, m), 7.23-7.55 (5H, m), 7.73 (1H, d), 7.92 (1H, d).

[0395] [Preparation Example 2-4] Preparation of Metallocene Compound B4

[0396]

[0397] 1. Synthesis of ligands

[0398] Under Ar, 5.01 g (18 mmol) of 2,7-di-tert-butylfluorene and 80 mL of tetrahydrofuran were added to another dry 250 mL Schlenk flask. After cooling to -78 °C, 8.6 mL (1.2 eq., 21.5 mmol) of 2.5 M n-BuLi in hexane was added dropwise. The reaction mixture was slowly heated to room temperature and stirred for 8 hours. After cooling to -78 °C, 5.73 g (1.0 eq., 18 mmol) of 2-(6-tert-butoxyhexyl)-5-(2,4-dimethylpentane-3-ylidene)-cyclopenta-1,3-diene synthesized in B2 was added along with 10 mL of tetrahydrofuran. After slowly raising the temperature to room temperature and stirring for 24 hours, the organic layer was separated using water and diethyl ether and dried with MgSO4 to obtain 6.92 g of ligand (11.6 mmol, 64.4% yield).

[0399] 1 H NMR (500 MHz, CDCl3): 0.85 (12H, d), 1.14 (9H, s), 1.27 (18H, s), 1.31-1.60 (10H, m), 2.22 (2H, m), 2.92 (2H, m), 3.33 (2H, t), 3.76 (1H, brs), 6.11 (1H, m), 6.35 (1H, brs), 7.40 (2H, m), 7.49-7.62 (2H, m), 7.78-7.91 (2H, m).

[0400] 2. Synthesis of Metallocene Compounds

[0401] Under Ar, 6.92 g (11.6 mmol) of the ligand synthesized above, 10 mL of methyl t-butyl ether, and 40 mL of toluene were added to a dried 250 mL Schlenk flask. After cooling to -78 °C, 10.2 mL (2.2 eq., 25.5 mmol) of a 2.5 M n-BuLi solution in hexane was added dropwise. The reaction mixture was slowly heated to room temperature and stirred for 8 hours. After cooling to -78 °C, 24.38 g (1.0 eq., 11.6 mmol) of ZrCl4(THF) was added along with 10 mL of methyl t-butyl ether. After slowly heating to room temperature and stirring for 24 hours, the reaction mixture was dried under reduced pressure at room temperature to remove the methyl t-butyl ether. The resulting toluene suspension was filtered under Ar to remove LiCl, the filtrate was dried under reduced pressure at 50 °C, and n-hexane was added. The resulting suspension was filtered under Ar to obtain 4.12 g (5.44 mmol, 46.9% yield) of solid metallocene compound B4.

[0402] 1 H NMR (500 MHz, C6D6): 0.90 (12H, d), 1.12 (9H, s), 1.15-1.38 (24H, m), 1.44-1.55 (6H, m), 3.21 (2H, t), 5.30-6.15 (3H, m), 7.44 (2H, dd), 7.65 (2H, d), 7.91 (2H, d).

[0403] [Preparation Example 2-5] Preparation of Metallocene Compound B5

[0404]

[0405] 1. Synthesis of ligands

[0406] Under Ar, 10.2 g (45.8 mmol) of 2-(6-tert-butoxyhexyl)cyclopentadiene, 7.71 g (2.0 eq., 91.6 mmol) of cyclopentanone, and 100 mL of methanol were added to a dry 250 mL Schlenk flask. After cooling to 0 °C, 4.89 g (1.5 eq., 68.7 mmol) of pyrrolidine was added dropwise. The reaction mixture was slowly heated to room temperature and stirred for 24 hours. After cooling the reaction mixture to 0 °C, 100 mL of 10 vol% aq. acetic acid was added and stirred for 30 minutes. The organic layer was separated using water and diethyl ether and dried with MgSO4 to obtain 11.3 g (39.2 mmol, 85.6% yield) of 2-(6-tert-butoxyhexyl)-5-(cyclopentylidene)-cyclopenta-1,3-diene.

[0407] Under Ar, 7.80 g (28 mmol) of 2,7-di-tert-butylfluorene and 100 mL of tetrahydrofuran were added to another dry 250 mL Schlenk flask. After cooling to -78 °C, 13.4 mL (1.2 eq., 33.5 mmol) of 2.5 M n-BuLi in hexane was added dropwise. The reaction mixture was slowly heated to room temperature and stirred for 8 hours. After cooling to -78 °C, 8.08 g (1.0 eq., 28 mmol) of the 2-(6-tert-butoxyhexyl)-5-(cyclopentylidene)-cyclopenta-1,3-diene synthesized above was added along with 15 mL of tetrahydrofuran. After slowly raising the temperature to room temperature and stirring for 24 hours, the organic layer was separated using water and diethyl ether and dried with MgSO4 to obtain 11.8 g of ligand (20.8 mmol, 74.3% yield).

[0408] 1H NMR (500 MHz, CDCl3): 1.11 (9H, s), 1.25 (18H, s), 1.31-1.60 (14H, m), 1.64-1.88 (4H, m), 2.26 (2H, m), 2.94 (2H, m), 3.36 (2H, t), 3.74 (1H, brs), 6.12 (1H, m), 6.32 (1H, brs), 7.41 (2H, m), 7.47-7.62 (2H, m), 7.75-7.89 (2H, m).

[0409] 2. Synthesis of Metallocene Compounds

[0410] Under Ar, 11.8 g (20.8 mmol) of the ligand synthesized above, 20 mL of methyl t-butyl ether, and 80 mL of toluene were added to a dried 250 mL Schlenk flask. After cooling to -78 °C, 18.3 mL (2.2 eq., 45.8 mmol) of a 2.5 M n-BuLi solution in hexane was added dropwise. The reaction mixture was slowly heated to room temperature and stirred for 8 hours. After cooling to -78 °C, 27.85 g (1.0 eq., 20.8 mmol) of ZrCl4(THF) was added along with 15 mL of methyl t-butyl ether. After slowly heating to room temperature and stirring for 24 hours, the reaction mixture was dried under reduced pressure at room temperature to remove the methyl t-butyl ether. The resulting toluene suspension was filtered under Ar to remove LiCl, the filtrate was dried under reduced pressure at 50 °C, and n-hexane was added. The resulting suspension was filtered under Ar to obtain 10.1 g (13.9 mmol, 66.8% yield) of solid metallocene compound B5.

[0411] 1H NMR (500 MHz, C6D6): 1.12 (9H, s), 1.15-1.36 (26H, m), 1.44-1.55 (4H, m), 1.62-1.81 (4H, m), 3.31 (2H, t), 5.30-6.25 (3H, m), 7.42-7.51 (2H, dd), 7.68 (2H, d), 7.87 (2H, d).

[0412] [Preparation Example 2-6] Preparation of Metallocene Compound B6

[0413]

[0414] 1. Synthesis of ligands

[0415] Under Ar, 5.57 g (25 mmol) of 2-(6-tert-butoxyhexyl)cyclopentadiene, 4.91 g (2.0 eq., 50 mmol) of cyclohexanone, and 50 mL of methanol were added to a dry 250 mL Schlenk flask. After cooling to 0 °C, 2.67 g (1.5 eq., 37.5 mmol) of pyrrolidine was added dropwise. The reaction mixture was slowly heated to room temperature and stirred for 24 hours. After cooling the reaction mixture to 0 °C, 50 mL of 10 vol% aq. acetic acid was added and stirred for 30 minutes. The organic layer was separated using water and diethyl ether and dried with MgSO4 to obtain 5.54 g (18.3 mmol, 73.2% yield) of 2-(6-tert-butoxyhexyl)-5-(cyclohexylidene)-cyclopenta-1,3-diene.

[0416] Under Ar, 2.49 g (15 mmol) of fluorene and 50 mL of tetrahydrofuran were added to another dry 250 mL Schlenk flask. After cooling to -78 °C, 7.2 mL (1.2 eq., 18 mmol) of 2.5 M n-BuLi in hexane was added dropwise. The reaction mixture was slowly heated to room temperature and stirred for 8 hours. After cooling to -78 °C, 4.54 g (1.0 eq., 15 mmol) of the 2-(6-tert-butoxyhexyl)-5-(cyclohexylidene)-cyclopenta-1,3-diene synthesized above was added along with 10 mL of tetrahydrofuran. After slowly raising the temperature to room temperature and stirring for 24 hours, the organic layer was separated using water and diethyl ether and dried with MgSO4 to obtain 5.06 g of ligand (10.8 mmol, 72% yield).

[0417] 1 H NMR (500 MHz, CDCl3): 1.22 (9H, s), 1.29-1.71 (16H, m), 1.81-1.91 (2H, t), 2.24-2.47 (2H, m), 2.63-2.93 (2H, m), 3.37 (2H, t), 3.94 (1H, brs), 5.66-6.17 (2H, m), 7.14-7.36 (6H, m), 7.65-7.77 (2H, m).

[0418] 2. Synthesis of Metallocene Compounds

[0419] Under Ar, 5.06 g (10.8 mmol) of the ligand synthesized above, 10 mL of methyl t-butyl ether, and 40 mL of toluene were added to a dried 250 mL Schlenk flask. After cooling to -78 °C, 9.5 mL (2.2 eq., 23.8 mmol) of a 2.5 M n-BuLi solution in hexane was added dropwise. The reaction mixture was slowly heated to room temperature and stirred for 8 hours. After cooling to -78 °C, 24.07 g (1.0 eq., 10.8 mmol) of ZrCl4(THF) was added along with 10 mL of methyl t-butyl ether. After slowly heating to room temperature and stirring for 24 hours, the reaction mixture was dried under reduced pressure at room temperature to remove the methyl t-butyl ether. The resulting toluene suspension was filtered under Ar to remove LiCl, the filtrate was dried under reduced pressure at 50 °C, and n-hexane was added. The resulting suspension was filtered under Ar to obtain 4.15 g (6.60 mmol, 61.1% yield) of solid metallocene compound B6.

[0420] 1 H NMR (500 MHz, C6D6): 1.18 (9H, s), 1.20-1.64 (18H, m), 1.77-1.96 (2H, m), 3.30 (2H, t), 5.40-6.14 (3H, m), 7.25-7.61 (4H, m), 7.72 (2H, dd), 7.89 (2H, t).

[0421] [Preparation Example 2-7] Preparation of Metallocene Compound B7

[0422]

[0423] 1. Synthesis of ligands

[0424] Under Ar, 22.3 g (100 mmol) of 2-(6-tert-butoxyhexyl)cyclopentadiene, 36.4 g (2.0 eq., 200 mmol) of benzophenone, and 200 mL of ethanol were added to a dried 500 mL Schlenk flask. After cooling to 0 °C, 10.7 g (1.5 eq., 150 mmol) of pyrrolidine was added dropwise. The reaction mixture was slowly heated to room temperature and stirred for 24 hours. After cooling the reaction mixture to 0 °C, 200 mL of 10 vol% aq. acetic acid was added and stirred for 30 minutes. The organic layer was separated using water and diethyl ether and dried with MgSO4 to obtain 28.4 g (73.5 mmol, 73.5% yield) of 2-(6-tert-butoxyhexyl)-5-(diphenylmethylidene)-cyclopenta-1,3-diene.

[0425] Under Ar, 5.45 g (16.9 mmol) of 2-(6-tert-butoxyhexyl)fluorene and 50 mL of tetrahydrofuran were added to another dry 250 mL Schlenk flask. After cooling to -78 °C, 8.1 mL (1.2 eq., 20.3 mmol) of 2.5 M n-BuLi in hexane was added dropwise. The reaction mixture was slowly heated to room temperature and stirred for 8 hours. After cooling to -78 °C, 6.53 g (1.0 eq., 16.9 mmol) of the 2-(6-tert-butoxyhexyl)-5-(diphenylmethylidene)-cyclopenta-1,3-diene synthesized above was added along with 10 mL of tetrahydrofuran. After slowly raising the temperature to room temperature and stirring for 24 hours, the organic layer was separated using water and diethyl ether and dried with MgSO4 to obtain 9.71 g of ligand (13.7 mmol, 81.1% yield).

[0426] 1H NMR (500 MHz, CDCl3): 1.12 (18H, brs), 1.22-1.67 (16H, m), 2.12 (2H, t), 2.68 (2H, t), 2.93 (2H, m), 3.33 (4H, m), 4.73 (1H, brs), 6.11 (1H, m), 6.33 (1H, brs), 7.21-8.01 (17H, m).

[0427] 2. Synthesis of Metallocene Compounds

[0428] Under Ar, 9.71 g (13.7 mmol) of the ligand synthesized above, 20 mL of methyl t-butyl ether, and 80 mL of toluene were added to a dried 250 mL Schlenk flask. After cooling to -78 °C, 12 mL (2.2 eq., 30 mmol) of a 2.5 M n-BuLi solution in hexane was added dropwise. The reaction mixture was slowly heated to room temperature and stirred for 8 hours. After cooling to -78 °C, 25.17 g (1.0 eq., 13.7 mmol) of ZrCl4(THF) was added along with 15 mL of methyl t-butyl ether. After slowly heating to room temperature and stirring for 24 hours, the reaction mixture was dried under reduced pressure at room temperature to remove the methyl t-butyl ether. The resulting toluene suspension was filtered under Ar to remove LiCl, the filtrate was dried under reduced pressure at 50 °C, and n-hexane was added. The resulting suspension was filtered under Ar to obtain 6.25 g (7.19 mmol, 52.5% yield) of solid metallocene compound B7.

[0429] 1 H NMR (500 MHz, C6D6): 1.06-1.15 (18H, brs), 1.23-1.72 (16H, m), 2.21 (2H, t), 2.75 (2H, t), 3.33 (2H, t), 5.52-6.41 (3H, m), 7.16-7.69 (15H, m), 7.91 (2H, d).

[0430] [Preparation Example 2-8] Preparation of Metallocene Compound B8

[0431]

[0432] 1. Synthesis of ligands

[0433] Under Ar, 5.45 g (18.6 mmol) of 2-tert-butylfluorene and 60 mL of tetrahydrofuran were added to another dry 250 mL Schlenk flask. After cooling to -78 °C, 8.9 mL (1.2 eq., 22.3 mmol) of 2.5 M n-BuLi in hexane was added dropwise. The reaction mixture was slowly heated to room temperature and stirred for 8 hours. After cooling to -78 °C, 7.19 g (1.0 eq., 18.6 mmol) of 2-(6-tert-butoxyhexyl)-5-(diphenylmethylidene)-cyclopenta-1,3-diene synthesized in B7 was added along with 10 mL of tetrahydrofuran. After slowly raising the temperature to room temperature and stirring for 24 hours, the organic layer was separated using water and diethyl ether and dried with MgSO4 to obtain 9.68 g of ligand (15.9 mmol, 85.5% yield).

[0434] 1 H NMR (500 MHz, CDCl3): 1.10 (9H, s), 1.24 (9H, s), 1.27-1.66 (8H, m), 2.13 (2H, t), 2.91 (2H, m), 3.34 (2H, t), 4.53 (1H, brs), 6.21 (1H, m), 6.36 (1H, brs), 7.05-7.90 (17H, m).

[0435] 2. Synthesis of Metallocene Compounds

[0436] Under Ar, 9.68 g (15.9 mmol) of the ligand synthesized above, 20 mL of methyl t-butyl ether, and 80 mL of toluene were added to a dried 250 mL Schlenk flask. After cooling to -78 °C, 14 mL (2.2 eq., 35 mmol) of a 2.5 M n-BuLi solution in hexane was added dropwise. The reaction mixture was slowly heated to room temperature and stirred for 8 hours. After cooling to -78 °C, 26.00 g (1.0 eq., 15.9 mmol) of ZrCl4(THF) was added along with 15 mL of methyl t-butyl ether. After slowly heating to room temperature and stirring for 24 hours, the reaction mixture was dried under reduced pressure at room temperature to remove the methyl t-butyl ether. The resulting toluene suspension was filtered under Ar to remove LiCl, the filtrate was dried under reduced pressure at 50 °C, and n-hexane was added. The resulting suspension was filtered under Ar to obtain 6.37 g (8.28 mmol, 52.1% yield) of solid metallocene compound B8.

[0437] 1 H NMR (500 MHz, C6D6): 1.15 (9H, s), 1.21 (9H, s), 1.24-1.68 (16H, m), 2.24 (2H, t), 3.34 (2H, t), 5.62-6.44 (3H, m), 7.10-7.73 (13H, m), 7.75-7.94 (2H, m).

[0438] [Preparation Example 2-9] Preparation of Metallocene Compound B9

[0439]

[0440] 1. Synthesis of ligands

[0441] Under Ar, 4.45 g (20 mmol) of 2-(6-tert-butoxyhexyl)cyclopentadiene, 8.01 g (2.0 eq., 40 mmol) of 8-tert-butoxy-2-octanone, and 50 mL of methanol were added to a dried 250 mL Schlenk flask. After cooling to 0 °C, 2.13 g (1.5 eq., 30 mmol) of pyrrolidine was added dropwise. The reaction mixture was slowly heated to room temperature and stirred for 24 hours. After cooling the reaction mixture to 0 °C, 50 mL of 10 vol% aq. acetic acid was added and stirred for 30 minutes. The organic layer was separated using water and diethyl ether and dried with MgSO4 to obtain 6.31 g (15.6 mmol, 78% yield) of 2-(6-tert-butoxyhexyl)-5-(1-methyl-7-tert-butoxyheptylidene)-cyclopenta-1,3-diene.

[0442] Under Ar, 3.47 g (15.6 mmol) of 2-tert-butylfluorene and 50 mL of tetrahydrofuran were added to another dry 250 mL Schlenk flask. After cooling to -78 °C, 7.4 mL (1.2 eq., 18.5 mmol) of 2.5 M n-BuLi in hexane was added dropwise. The reaction mixture was slowly heated to room temperature and stirred for 8 hours. After cooling to -78 °C, 6.31 g (1.0 eq., 15.6 mmol) of the 2-(6-tert-butoxyhexyl)-5-(1-methyl-7-tert-butoxyheptylidene)-cyclopenta-1,3-diene synthesized above was added along with 10 mL of tetrahydrofuran. After slowly raising the temperature to room temperature and stirring for 24 hours, the organic layer was separated using water and diethyl ether and dried with MgSO4 to obtain 8.59 g of ligand (13.7 mmol, 87.8% yield).

[0443] 1H NMR (500 MHz, CDCl3): 0.97 (3H, brs), 1.11 (18H, brs), 1.17 (2H, m), 1.25 (9H, s), 1.27-1.65 (16H, m), 2.10 (2H, t), 2.90 (2H, m), 3.33 (2H, m), 3.83 (1H, brs), 6.13 (1H, m), 6.26 (1H, brs), 7.21-7.44 (3H, m), 7.51-7.65 (2H, m), 7.78 (1H, d), 7.91 (1H, d).

[0444] 2. Synthesis of Metallocene Compounds

[0445] Under Ar, 8.59 g (13.7 mmol) of the ligand synthesized above, 20 mL of methyl t-butyl ether, and 80 mL of toluene were added to a dried 250 mL Schlenk flask. After cooling to -78 °C, 12 mL (2.2 eq., 30 mmol) of a 2.5 M n-BuLi solution in hexane was added dropwise. The reaction mixture was slowly heated to room temperature and stirred for 8 hours. After cooling to -78 °C, 25.17 g (1.0 eq., 13.7 mmol) of ZrCl4(THF) was added along with 15 mL of methyl t-butyl ether. After slowly heating to room temperature and stirring for 24 hours, the reaction mixture was dried under reduced pressure at room temperature to remove the methyl t-butyl ether. The resulting toluene suspension was filtered under Ar to remove LiCl, the filtrate was dried under reduced pressure at 50 °C, and n-hexane was added. The resulting suspension was filtered under Ar to obtain 6.35 g (8.07 mmol, 58.9% yield) of solid metallocene compound B9.

[0446] 1H NMR (500 MHz, C6D6): 1.04 (3H, brs), 1.12 (20H, brs), 1.27 (9H, , 1.34-1.70 (16H, m), 2.27 (2H, t), 3.34 (4H, m), 5.42-6.36 (3H, m), 7.12-7.39 (3H, m), 7.48-7.61 (2H, m), 7.73-7.94 (2H, m).

[0447] [Preparation Example 2-10] Preparation of Metallocene Compound B10

[0448]

[0449] 1. Synthesis of ligands

[0450] Under Ar, 2.72 g (20 mmol) of 1-methyl-3-n-butylcyclopenta-1,3-diene, 8.01 g (2.0 eq., 40 mmol) of 8-tert-butoxy-2-octanone, and 50 mL of methanol were added to a dried 250 mL Schlenk flask. After cooling to 0 °C, 2.13 g (1.5 eq., 30 mmol) of pyrrolidine was added dropwise. The reaction mixture was slowly heated to room temperature and stirred for 24 hours. After cooling the reaction mixture to 0 °C, 50 mL of 10 vol% aq. acetic acid was added and stirred for 30 minutes. The organic layer was separated using water and diethyl ether and dried with MgSO4 to obtain 4.56 g (14.3 mmol, 78% yield) of 1-methyl-3-n-butyl-5-(1-methyl-7-tert-butoxyheptylidene)-cyclopenta-1,3-diene.

[0451] Under Ar, 3.98 g (14.3 mmol) of 2,7-di-tert-butylfluorene and 50 mL of tetrahydrofuran were added to another dry 250 mL Schlenk flask. After cooling to -78 °C, 6.8 mL (1.2 eq., 17 mmol) of 2.5 M n-BuLi in hexane was added dropwise. The reaction mixture was slowly heated to room temperature and stirred for 8 hours. After cooling to -78 °C, 4.56 g (1.0 eq., 14.3 mmol) of the 1-methyl-3-n-butyl-5-(1-methyl-7-tert-butoxyheptylidene)-cyclopenta-1,3-diene synthesized above was added along with 10 mL of tetrahydrofuran. After slowly raising the temperature to room temperature and stirring for 24 hours, the organic layer was separated using water and diethyl ether and dried with MgSO4 to obtain 6.92 g of ligand (11.6 mmol, 81.2% yield).

[0452] 1 H NMR (500 MHz, CDCl3): 0.95 (6H, m), 1.10 (9H, s), 1.16 (2H, m), 1.28 (18H, brs), 1.30-1.65 (12H, m), 1.81 (3H, m), 2.16 (2H, t), 2.91 (2H, m), 3.34 (2H, t), 3.78 (1H, brs), 6.30 (1H, brs), 7.41 (2H, dd), 7.61 (2H, d), 7.87 (2H, d).

[0453] 2. Synthesis of Metallocene Compounds

[0454] Under Ar, 6.92 g (11.6 mmol) of the ligand synthesized above, 20 mL of methyl t-butyl ether, and 80 mL of toluene were added to a dried 250 mL Schlenk flask. After cooling to -78 °C, 10.2 mL (2.2 eq., 25.5 mmol) of 2.5 M n-BuLi in hexane solution was added dropwise. The reaction mixture was slowly heated to room temperature and stirred for 8 hours. After cooling to -78 °C, 24.38 g (1.0 eq., 11.6 mmol) of ZrCl4(THF) was added along with 15 mL of methyl t-butyl ether. After slowly heating to room temperature and stirring for 24 hours, the reaction mixture was dried under reduced pressure at room temperature to remove the methyl t-butyl ether. The resulting toluene suspension was filtered under Ar to remove LiCl, the filtrate was dried under reduced pressure at 50 °C, and n-hexane was added. The resulting suspension was filtered under Ar to obtain 5.25 g (6.93 mmol, 59.7% yield) of solid metallocene compound B10.

[0455] 1 H NMR (500 MHz, C6D6): 0.88 (3H, s), 1.07 (3H, m), 1.16 (9H, s), 1.20 (2H, m), 1.31 (18H, brs), 1.34-1.69 (12H, m), 1.85 (3H, s), 2.20 (2H, t), 3.30 (2H, t), 6.02-6.36 (2H, m), 7.36 (2H, dd), 7.51 (2H, d), 7.79 (2H, d).

[0456] [Preparation Example 2-11] Preparation of Metallocene Compound B11

[0457]

[0458] 1. Synthesis of ligands

[0459] Under Ar, 3.12 g (20 mmol) of 1-methyl-3-phenylcyclopenta-1,3-diene, 8.01 g (2.0 eq., 40 mmol) of 8-tert-butoxy-2-octanone, and 50 mL of methanol were added to a dried 250 mL Schlenk flask. After cooling to 0 °C, 2.13 g (1.5 eq., 30 mmol) of pyrrolidine was added dropwise. The reaction mixture was slowly heated to room temperature and stirred for 24 hours. After cooling the reaction mixture to 0 °C, 50 mL of 10 vol% aq. acetic acid was added and stirred for 30 minutes. The organic layer was separated using water and diethyl ether and dried with MgSO4 to obtain 4.57 g (13.5 mmol, 67.5% yield) of 1-methyl-3-phenyl-5-(1-methyl-7-tert-butoxyheptylidene)-cyclopenta-1,3-diene.

[0460] Under Ar, 3.76 g (13.5 mmol) of 2,7-di-tert-butylfluorene and 50 mL of tetrahydrofuran were added to another dry 250 mL Schlenk flask. After cooling to -78 °C, 6.4 mL (1.2 eq., 16 mmol) of 2.5 M n-BuLi hexane was added dropwise. The reaction mixture was slowly heated to room temperature and stirred for 8 hours. After cooling to -78 °C, 4.57 g (1.0 eq., 13.5 mmol) of the 1-methyl-3-phenyl-5-(1-methyl-7-tert-butoxyheptylidene)-cyclopenta-1,3-diene synthesized above was added along with 10 mL of tetrahydrofuran. After slowly raising the temperature to room temperature and stirring for 24 hours, the organic layer was separated using water and diethyl ether and dried with MgSO4 to obtain 6.60 g of ligand (10.7 mmol, 79.3% yield).

[0461] 1H NMR (500 MHz, CDCl3): 0.93 (3H, m), 1.15 (9H, s), 1.19 (2H, m), 1.23 (18H, s), 1.26-1.61 (8H, m), 1.91 (3H, m), 2.95 (2H, m), 3.37 (2H, t), 3.75 (1H, brs), 6.79 (2H, m), 7.11-7.25 (3H, m), 7.44 (2H, dd), 7.61 (2H, d), 7.83 (2H, d).

[0462] 2. Synthesis of Metallocene Compounds

[0463] Under Ar, 6.60 g (10.7 mmol) of the ligand synthesized above, 20 mL of methyl t-butyl ether, and 80 mL of toluene were added to a dried 250 mL Schlenk flask. After cooling to -78 °C, 9.4 mL (2.2 eq., 23.5 mmol) of a 2.5 M n-BuLi solution in hexane was added dropwise. The reaction mixture was slowly heated to room temperature and stirred for 8 hours. After cooling to -78 °C, 24.04 g (1.0 eq., 10.7 mmol) of ZrCl4(THF) was added along with 15 mL of methyl t-butyl ether. After slowly heating to room temperature and stirring for 24 hours, the reaction mixture was dried under reduced pressure at room temperature to remove the methyl t-butyl ether. The resulting toluene suspension was filtered under Ar to remove LiCl, the filtrate was dried under reduced pressure at 50 °C, and n-hexane was added. The resulting suspension was filtered under Ar to obtain 4.47 g (5.75 mmol, 53.7% yield) of solid metallocene compound B11.

[0464] 1H NMR (500 MHz, C6D6): 1.05 (3H, m), 1.18 (9H, s), 1.22 (2H, m), 1.30 (18H, brs), 1.32-1.59 (8H, m), 1.91 (3H, s), 3.34 (2H, t), 6.12-6.76 (2H, m), 7.16 (2H, m), 7.30-7.45 (5H, m), 7.66 (2H, d), 7.99 (2H, d).

[0465] [Preparation Example 2-12] Preparation of Metallocene Compound B12

[0466]

[0467] 1. Synthesis of ligands

[0468] Under Ar, 5.57 g (25 mmol) of 2-(6-tert-butoxyhexyl)cyclopentadiene, 4.31 g (2.0 eq., 50 mmol) of 3-pentanone, and 60 mL of methanol were added to a dried 250 mL Schlenk flask. After cooling to 0 °C, 2.67 g (1.5 eq., 37.5 mmol) of pyrrolidine was added dropwise. The reaction mixture was slowly heated to room temperature and stirred for 24 hours. After cooling the reaction mixture to 0 °C, 60 mL of 10 vol% aq. acetic acid was added and stirred for 30 minutes. The organic layer was separated using water and diethyl ether and dried with MgSO4 to obtain 3.49 g (12.0 mmol, 48% yield) of 2-(6-tert-butoxyhexyl)-5-(pentane-3-ylidene)-cyclopenta-1,3-diene.

[0469] Under Ar, 4.64 g (12 mmol) of 1,1,4,4,7,7,10,10-octamethyl-2,3,4,7,8,9,10,12-octahydro-1H-dibenzo[b,h]fluorene and 50 mL of tetrahydrofuran were added to another dry 250 mL Schlenk flask. After cooling to -78 °C, 5.7 mL (1.2 eq., 14.3 mmol) of 2.5 M n-BuLi in hexane was added dropwise. The reaction mixture was slowly heated to room temperature and stirred for 8 hours. After cooling to -78 ℃, 3.49 g (1.0 eq., 12 mmol) of the 2-(6-tert-butoxyhexyl)-5-(pentane-3-ylidene)-cyclopenta-1,3-diene synthesized above was added together with 10 mL of tetrahydrofuran. The temperature was slowly raised to room temperature and stirred for 24 hours, after which the organic layer was separated using water and diethyl ether and dried with MgSO4 to obtain 4.64 g of ligand (6.85 mmol, 57.1% yield).

[0470] 1 H NMR (500 MHz, CDCl3): 0.86 (30H, m), 1.12 (9H, s), 1.19 (4H, m), 1.26-1.61 (16H, m), 2.21 (2H, t), 2.91 (2H, m), 3.32 (2H, t), 3.71 (1H, brs), 6.01-6.48 (2H, m), 7.49 (2H, s), 7.84 (2H, s).

[0471] 2. Synthesis of Metallocene Compounds

[0472] Under Ar, 4.64 g (6.85 mmol) of the ligand synthesized above, 20 mL of methyl t-butyl ether, and 80 mL of toluene were added to a dried 250 mL Schlenk flask. After cooling to -78 °C, 6 mL (2.2 eq., 15 mmol) of 2.5 M n-BuLi in hexane solution was added dropwise. The reaction mixture was slowly heated to room temperature and stirred for 8 hours. After cooling to -78 °C, 22.58 g (1.0 eq., 6.85 mmol) of ZrCl4(THF) was added along with 10 mL of methyl t-butyl ether. After slowly heating to room temperature and stirring for 24 hours, the reaction mixture was dried under reduced pressure at room temperature to remove the methyl t-butyl ether. The resulting toluene suspension was filtered under Ar to remove LiCl, the filtrate was dried under reduced pressure at 50 °C, and n-hexane was added. The resulting suspension was filtered under Ar to obtain 2.70 g (3.22 mmol, 47% yield) of solid metallocene compound B12.

[0473] 1 H NMR (500 MHz, C6D6): 0.75 (6H, t), 0.87 (24H, s), 1.15 (9H, s), 1.25 (4H, m), 1.30-1.57 (16H, m), 2.34 (2H, t), 3.37 (2H, t), 6.02-6.57 (3H, m), 7.39 (2H, s), 7.90 (2H, s).

[0474] [Preparation Example 2-13] Preparation of Metallocene Compound B13

[0475]

[0476] 1. Synthesis of ligands

[0477] Under Ar, 6.57 g (17 mmol) of 1,1,4,4,7,7,10,10-octamethyl-2,3,4,7,8,9,10,12-octahydro-1H-dibenzo[b,h]fluorene and 80 mL of tetrahydrofuran were added to another dry 250 mL Schlenk flask. After cooling to -78 °C, 8.1 mL (1.2 eq., 20.3 mmol) of 2.5 M n-BuLi in hexane was added dropwise. The reaction mixture was slowly heated to room temperature and stirred for 8 hours. After cooling to -78 ℃, 5.42 g (1.0 eq., 17 mmol) of 2-(6-tert-butoxyhexyl)-5-(2,4-dimethylpentane-3-ylidene)-cyclopenta-1,3-diene synthesized in B2 was added along with 10 mL of tetrahydrofuran. The temperature was slowly raised to room temperature and stirred for 24 hours; afterward, the organic layer was separated using water and diethyl ether and dried with MgSO4 to obtain 5.24 g of ligand (7.43 mmol, 43.7% yield).

[0478] 1 H NMR (500 MHz, CDCl3): 0.82 (12H, m), 0.92 (24H, s), 1.10 (9H, s), 1.26-1.65 (18H, m), 2.15 (2H, t), 2.91 (2H, m), 3.34 (2H, t), 3.78 (1H, brs), 6.02-6.50 (2H, m), 7.43 (2H, s), 7.82 (2H, s).

[0479] 2. Synthesis of Metallocene Compounds

[0480] Under Ar, 5.24 g (7.43 mmol) of the ligand synthesized above, 20 mL of methyl t-butyl ether, and 80 mL of toluene were added to a dried 250 mL Schlenk flask. After cooling to -78 °C, 6.5 mL (2.2 eq., 16.3 mmol) of a 2.5 M n-BuLi solution in hexane was added dropwise. The reaction mixture was slowly heated to room temperature and stirred for 8 hours. After cooling to -78 °C, 22.80 g (1.0 eq., 7.43 mmol) of ZrCl4(THF) was added along with 10 mL of methyl t-butyl ether. After slowly heating to room temperature and stirring for 24 hours, the reaction mixture was dried under reduced pressure at room temperature to remove the methyl t-butyl ether. The resulting toluene suspension was filtered under Ar to remove LiCl, the filtrate was dried under reduced pressure at 50 °C, and n-hexane was added. The resulting suspension was filtered under Ar to obtain 2.93 g (3.39 mmol, 45.6% yield) of solid metallocene compound B13.

[0481] 1 H NMR (500 MHz, C6D6): 0.71 (12H, m), 0.84 (24H, s), 1.13 (9H, s), 1.27-1.57 (20H, m), 2.24 (2H, t), 3.32 (2H, t), 5.82-6.47 (3H, m), 7.49 (2H, s), 7.77 (2H, s).

[0482]

[0483] [Preparation Example 1] Preparation of a hybrid supported catalyst

[0484] Silica (SP 952, manufactured by Grace Davision) was dehydrated and dried under vacuum at 200°C for 12 hours. 800 g of the dried silica was placed in a 20 L SUS reactor, and 6 kg of a methylaluminoxan (MAO) solution (10 wt% in toluene) was added to a toluene solution. The mixture was then reacted slowly at 70°C for 1 hour while stirring. After the reaction was complete, the unreacted aluminum compound was washed several times with a sufficient amount of toluene until it was completely removed. A solution prepared by dissolving 25.4 g of the metallocene compound A1 and 2.8 g of the metallocene compound B2 in toluene was sequentially added to the reactor and reacted at 40°C for 4 hours while stirring. After washing with a sufficient amount of toluene, the mixture was vacuum dried to obtain a hybrid supported metallocene catalyst as a solid powder.

[0485]

[0486] [Preparation Examples 2 to 25] Preparation of Hybrid Supported Catalysts

[0487] Hybrid supported metallocene catalysts 2 to 25 were prepared in the same manner as in Preparation Example 1 above, except that the type and content of the metallocene compounds were used as described in Table 1 below instead of 25.4 g of metallocene compound A1 and 2.8 g of metallocene compound B2.

[0488]

[0489] [Preparation Examples 26 and 27] Preparation of Hybrid Supported Catalysts

[0490] Hybrid supported metallocene catalysts 26 and 27 were prepared in the same manner as in Preparation Example 1, except that the type and content of the metallocene compounds were used as listed in Table 1 below instead of 25.4 g of metallocene compound A1 and 2.8 g of metallocene compound B2. The structures of metallocene compounds A14, A15, B14, and B15 used in Preparation Examples 26 and 27 are as follows.

[0491]

[0492] Preparation Example Catalyst Metallocene Compound 1 Metallocene Compound 2 Ratio Metallocene Compound 1 (g) Metallocene Compound 2 (g) Preparation Example 1 Catalyst 1 A 1 B 2 10 25.4 2.8 Preparation Example 2 Catalyst 2 A 2 B 2 7 24.5 3.9 Preparation Example 3 Catalyst 3 A 3 B 2 8 26.1 3.4 Preparation Example 4 Catalyst 4 A 4 B 2 20 30.1 1.5 Preparation Example 5 Catalyst 5 A 5 B 2 6 26.4 4.4 Preparation Example 6 Catalyst 6 A 6 B 2 15 29.0 1.9 Preparation Example 7 Catalyst 7A7B2425.36.2 Preparation Example 8 Catalyst 8A8B2324.47.7 Preparation Example 9 Catalyst 9A9B2728.73.9 Preparation Example 10 Catalyst 10A10B21733.81.7 Preparation Example 11 Catalyst 11A11B21231.32.4 Preparation Example 12 Catalyst 12A12B2322.17.7 Preparation Example 13 Catalyst 13A13B2528.25.2 Preparation Example 14 Catalyst 14A3B11126.92.8 Preparation Example 15 Catalyst 15A3B3926.43.4 Preparation Example 16 Catalyst 16A3B41227.13.0 Preparation Example 17 Catalyst 17A3B5826.13.8 Preparation Example 18 Catalyst 18A3B61627.61.8 Preparation Example 19 Catalyst 19A3B71427.41.9 Preparation Example 20 Catalyst 20A3B81 227.13.0 Preparation Example 21 Catalyst 21A3B96 25.14.0 Preparation Example 22 Catalyst 22A3B107 25.7 4.3 Preparation Example 23 Catalyst 23A3B115 24.4 5.6 Preparation Example 24 Catalyst 24A3B1213 27.2 1.8 Preparation Example 25 Catalyst 25A3B136 25.12.9 Preparation Example 26 Catalyst 26A14B143 14.6 6.1 Preparation Example 27 Catalyst 27A15B15 213.4 6.8

[0493] (The 'ratio' in Table 1 above refers to 'moles of metallocene compound 1 / moles of metallocene compound 2'.)

[0494]

[0495] [Examples 1 to 20 and Comparative Examples 1 to 9] Preparation of Polyethylene Resin

[0496] The polymerization reactor was a continuous reactor using an isobutane slurry loop process, with a reactor volume of 140 L, and operated at a reaction flow rate of approximately 7 m / s. The gases (ethylene, hydrogen) and comonomers required for polymerization were fed continuously and at constant rates, and their individual flow rates were adjusted according to the target product. The concentrations of all gases and the comonomer 1-hexene were monitored using a real-time online gas chromatograph. The supported catalyst was fed into the isobutane slurry, the reactor pressure was maintained at 40 bar, and the polymerization was carried out at a temperature of 80 ℃.

[0497] Polyethylene resin was prepared by adjusting the amount of ethylene input, the amount of solvent i-butane input, the 1-hexene / ethylene input ratio, and the hydrogen / ethylene input ratio as shown in Table 2 below.

[0498] Catalyst Ethylene (kg / hh) i-Butane (kg / h) 1-Hexene / Ethylene (Wt%) Hydrogen / Ethylene (ppmw) Example 1 3 25.228 6.735 Example 2 10 25.026 7.955 Example 3 2 25.328 6.938 Example 4 1 2 25.127 6.650 Example 5 5 25.029 8.252 Example 6 1 325.1266.755 Example 7 17 25.2266.648 Example 8 22 25.3277.951 Example 9 4 25.3267.145 Example 10 19 25.2266.470 Example 11 24 25.1296.268 Example 12 6 25.2257.956 Example 13 25 25.2278.172 Example Example 147 25.1266.648 Example 15 21 25.2286.071 Example 169 25.2296.578 Example 17 18 25.1266.175 Example 18 11 25.3266.671 Example 19 125.0267.760 Example 208 25.2267.758 Comparative Example 124 25.0296.9 38 Comparative Example 2 27 25.1 25 6.1 34 Comparative Example 3 7 25.1 25 5.4 27 Comparative Example 4 10 25.3 28 5.9 23 Comparative Example 5 12 25.2 25 5.1 21 Comparative Example 6 8 25.1 25 5.2 42 Comparative Example 7 16 25.3 26 5.9 40 Comparative Example 8 20 25.1 26 5.3 32 Comparative Example 9 3 25.0 25 5.9 32

[0499]

[0500] [Experimental Example 1] Evaluation of Stretchability Index of Polyethylene Resin Composition

[0501] To evaluate the stretchability index of the polyethylene resin compositions prepared in the above examples and comparative examples, stress-strain curves were obtained for the polyethylene resin compositions through cross-fraction chromatography (CFC) analysis and biaxial stretching.

[0502] 1. Cross-fractionation chromatography (CFC) analysis

[0503] Density and PDI were measured for the polyethylene resin compositions of the examples and comparative examples by performing cross-fraction chromatography (CFC) analysis using the method below.

[0504] 1) Analysis equipment: Polymer Char CFC (Detector: Integrated Detector IR5 MCT) was used.

[0505] 2) Sample preparation: 32 mg of polyethylene resin composition was placed in a 10 mL vial and placed in an autosampler. After adding 8 mL of 1,2,4-trichlorobenzene (TCB), the mixture was dissolved at 160 °C for 90 minutes and stabilized at 140 °C for 20 minutes. After purging with nitrogen gas, the sample was extracted and loaded onto a temperature-raising elution fractionation column (TREF column).

[0506] 3) Crystallization: The sample previously loaded into the TREF column was set to 100 ℃, and then cooled from 100 ℃ to 35 ℃ at a rate of 0.5 ℃ / min.

[0507] 4) Temperature-Increased Elution Fraction (TREF) Analysis: The previously crystallized samples were fixed at temperatures raised from 35°C to 125°C in 3°C increments, and the fractions eluted for 25 minutes at each temperature were analyzed. Specifically, extraction and analysis were performed at 35°C for 25 minutes, followed by extraction and analysis performed at 3°C ​​increments, and finally, extraction and analysis were performed at 125°C for 25 minutes.

[0508] 5) GPC-IR analysis: The fractions eluted at each temperature in the previous TREF analysis were transferred to the GPC column of the GPC (PL-GPC220) device, the molecular weight of the eluted molecules was measured, and the number of short-chain branches (sb) of the eluted molecules at each temperature was measured using PerkinElmer Spectrum 100 FT-IR connected to the GPC (PL-GPC220).

[0509] 6) High molecular weight molecule SCB index (Iscb, high M measurement): The value of "number of methyl terminal groups per 1,000 carbons × elution molecule fraction" of molecules satisfying a molecular weight of 100,000 g / mol or more, as confirmed by CFC analysis, was measured according to Equation 3 below.

[0510] [Equation 3]

[0511]

[0512] In Equation 3 above, CM,i represents the molar concentration (mol / L) of each component according to molecular weight, and represents the number of scb units of each component (number / 1000C).

[0513] Density (g / cm³) 3)Mw(g / mol)PDI(Mw / Mn)SCB Content(CH3 / 1000TC) Example 1 0.9321076488.7112.4 Example 2 0.927892814.7614.8 Example 3 0.9311009208.0612.7 Example 4 0.932897254.5512.2 Example 5 0.928874914.5814.9 Example 6 0.934831375.7111.9 Example 7 0.934887653.8211 .3 Example 80.927895225.1814.7 Example 90.931919647.1012.8 Example 100.933758336.0112.6 Example 110.936764725.8710.8 Example 120.932887415.1013.0 Example 130.933712345.9513.4 Example 140.932894104.3012.3 Example 150.9 36723595.6811.2 Example 160.934676596.7012.1 Example 170.935692425.7611.6 Example 180.933701716.5212.2 Example 190.926821227.5814.5 Example 200.927854215.7414.4 Comparative Example 10.93510344610.8812.7 Comparative Example 20.93610510 610.2911.0 Comparative Example 30.94212027512.208.7 Comparative Example 40.93814111010.1510.0 Comparative Example 50.94415183312.257.9 Comparative Example 60.942944244.468.2 Comparative Example 70.937987136.9410.6 Comparative Example 80.9431058517.618.4 Comparative Example 90.93710811610.2310.7

[0514] 2. Derivation of a stress-strain curve through stretching. The polyethylene resin compositions of the example and comparative example were biaxially stretched to obtain a stress-strain curve, and the yield region energy and strain-softening energy were calculated from it.

[0515] 1) Preparation of specimens: The polyethylene resin compositions of the examples and comparative examples were prepared into 0.75 mm thick casting sheets using a Bruckner lab extruder line (L / D ratio: 42, Screw diameter: 25 mm, Melt / T-Die temperature: 250 ℃). The sheets were cut to obtain specimens with dimensions of 90 mm × 90 mm.

[0516] 2) Preheating: The specimen was preheated at 122 ℃ for 60 seconds.

[0517] 3) Stretching: Stretching was performed at 122°C using a KARO 5.0 machine (Manufacturer: Brueckner Maschinenbau). The specimen was mounted on the jig of the machine, and the specimen was stretched at a stretching speed of 200% / sec so that the length of the specimen in the longitudinal direction (MD) was five times.

[0518] 4) Stress-strain curve: Stress-strain curves for MD 5x elongation and TD 8x elongation were obtained from the KARO 5.0 equipment used for elongation. However, Savitzky-Golay fitting can be performed to remove unnecessary noise or fluctuations included in the data while maintaining the main features of the data obtained through the above analysis. When performing Savitzky-Golay fitting, a second or third-order polynomial was fitted within a given data window, and the data at the center of the corresponding interval was smoothed using the polynomial.

[0519] 5) Calculation of yield region energy and strain-softening region energy

[0520] For each example and comparative example, the yield point, which is the point where the first derivative is zero or closest to zero, and the strain-softening end point, which is the point where the second derivative changes from negative to positive and becomes zero, were identified in the stress-strain curve obtained. Subsequently, the value obtained by integrating the region from the x-axis 0 of the curve to the x value corresponding to the yield point was calculated and represented as the yield region energy, and the value obtained by integrating the region from the x value of the yield point to the x value corresponding to the strain-softening end point was represented as the strain-softening region energy.

[0521] MD Yield Point Stress (MPa) MD Yield Zone Energy (MPa) MD Strain-Softening Zone Energy (MPa) Example 1 1.94 70.53 80.370 Example 2 0.81 50.28 40.084 Example 3 1.57 00.43 60.225 Example 4 1.27 90.36 80.255 Example 5 1.01 50.31 80.224 Example 6 1.31 00.38 90.283 Example 7 1.32 10.39 50.171 Example 80.7920.2800.172 Example 91.4800.4740.325 Example 101.2830.4160.250 Example 111.3010.4390.286 Example 121.3210.4170.250 Example 131.2000.3790.189 Example 141.4180.4800.344 Example 151 .5200.5280.258 Example 16 1.3120.4780.226 Example 17 1.439 0.4880.258 Example 18 1.293 0.5000.228 Example 19 0.772 0.214 0.156 Example 20 0.823 0.263 0.096 Comparative Example 12.275 0.623 0.562 Comparative Example 22.636 0.6900.650 Comparative Example 33.8450.8920.746 Comparative Example 42.8910.7570.835 Comparative Example 54.1171.0981.073 Comparative Example 62.3970.8230.475 Comparative Example 72.1340.7070.482 Comparative Example 82.5580.8780.599 Comparative Example 92.0800.6430.612

[0522] 3. Derivation of Stretchability Index The PDI, density, MD yield region energy, and MD strain-softening region energy obtained from the above analysis were substituted into Equation 2-1 below to obtain the Z value. Subsequently, the Z value was substituted into Equation 1 below to obtain the Stretchability Index.

[0523] [Equation 2-1]

[0524] Z = 134.9 + (0.315)×PDI + (-136.5)×density + (-8.7)×(strain-softening region energy) + (-10.24)×(yield region energy)

[0525] [Equation 1]

[0526]

[0527] The elongation indices derived for each example and comparative example are shown in Table 4 below. In addition, the distribution of density and elongation index for each example and comparative example, and the distribution of weight-average molecular weight (Mw) and elongation index are shown in Figures 2 and 3.

[0528] Stretchability Index Example 1 0.842 Example 2 0.998 Example 3 0.980 Example 4 0.957 Example 5 0.988 Example 6 0.936 Example 7 0.957 Example 8 0.996 Example 9 0.911 Example 100.951 Example 11 0.875 Example 12 0.945 Example 13 0.981 Example 14 0.758 Example 1 50.770 Example 1 60.932 Example 1 70.860 Example 1 80.920 Example 1 90.999 Example 2 00.999 Comparative Example 10.360 Comparative Example 20.090 Comparative Example 30.004 Comparative Example 40.007 Comparative Example 50.000 Comparative Example 60.007 Comparative Example 70.096 Comparative Example 80.004 Comparative Example 90.157

[0529] As shown in Table 5 above and Figures 2 and 3, the polyethylene resin composition according to the present invention has a density of approximately 0.922 g / cm³ 3 Above 0.940 g / cm³3 It was observed that the weight-average molecular weight (Mw) was between 60,000 g / mol and 120,000 g / mol, and the elongation index was 0.7 or higher. On the other hand, the polyethylene resin composition of the comparative example had a density of 0.935 g / cm³. 3 Above, the weight-average molecular weight (Mw) showed a distribution of 90,000 g / mol to 160,000 g / mol, and the elongation index was found to be 0.4 or less.

[0530] [Experimental Example 2] Evaluation of Stretch Stability

[0531] To evaluate the repeatability of the polyethylene resin compositions of the above examples and comparative examples, 10 biaxial stretches were performed using the following method. Specifically, using a Bruckner lab extruder line (L / D ratio: 42, Screw diameter: 25 mm, Melt / T-Die temperature: 250 ℃), the polyethylene resin compositions of each example and comparative example were prepared into casting sheets with a thickness of 0.75 mm. The sheets were cut to produce 10 specimens with dimensions of 90 mm × 90 mm. Subsequently, the specimens were preheated at 122 ℃ for 60 seconds, mounted on a jig of a KARO 5.0 machine (manufacturer: Brueckner Maschinenbau), and then stretched at a stretching speed of 200% / second so that the length of the specimen in the longitudinal direction (MD) was 5 times and the length of the specimen in the transverse direction (TD) was 8 times. The number of specimens that successfully underwent biaxial elongation without fracture, melting, or melt drawing among 10 specimens was measured, and the results are shown in Table 6 below.

[0532] Number of successes / Number of extensions Example 19 / 10 Example 2 10 / 10 Example 3 10 / 10 Example 4 10 / 10 Example 5 10 / 10 Example 6 10 / 10 Example 7 10 / 10 Example 8 10 / 10 Example 9 9 / 10 Example 10 9 / 10 Example 11 9 / 10 Example 12 10 / 10 Example 13 10 / 10 Example 14 7 / 10 Example 158 / 10 Example 16 10 / 10 Example 17 10 / 10 Example 18 10 / 10 Example 19 10 / 10 Example 20 10 / 10 Comparative Example 14 / 10 Comparative Example 20 / 10 Comparative Example 30 / 10 Comparative Example 40 / 10 Comparative Example 50 / 10 Comparative Example 60 / 10 Comparative Example 72 / 10 Comparative Example 80 / 10 Comparative Example 92 / 10

[0533] As shown in Table 6 above, the polyethylene resin composition according to the present invention has uniform physical properties, and it was observed that stretching was successful in at least 7 out of a total of 10 biaxial stretching attempts. In particular, in the case of the polyethylene resin compositions of Examples 1 to 13 and 16 to 20, stretching was successful in at least 9 out of 10 biaxial stretching attempts. However, the polyethylene resin compositions of Comparative Examples 2 to 6 and 8 had very poor stretchability, so biaxially stretched films could not be manufactured. For the polyethylene resin composition of Comparative Example 1, biaxial stretching was achieved in 4 out of 10 specimens, but successful biaxial stretching was not achieved in the remaining 6 specimens, and the polyethylene resin compositions of Comparative Examples 7 and 9 had even poorer stretchability than Comparative Example 1, so biaxial stretching was achieved in only 2 out of 10 specimens.

[0534] [Experimental Example 3] Evaluation of Mechanical Strength Index of Polyethylene Resin Composition

[0535] To evaluate the stiffness index, tensile strength index, and puncture strength index of the polyethylene resin composition prepared in the above example, the following experiment was performed. A stress-strain curve was obtained for the polyethylene resin composition through biaxial stretching. Basically, the experiment was performed in the same manner as Experimental Example 1, but the specimen was stretched five times in the longitudinal direction (MD) to obtain a stress-strain curve, and in a separate experiment, the specimen was stretched eight times in the transverse direction (TD) to obtain an additional stress-strain curve.

[0536] 1. Calculation of MD yield point stress, MD 5x elongation point stress, MD yield region energy, MD strain-softening energy, and MD total strain energy

[0537] In the stress-strain curve in the MD 5x elongation direction obtained for each example, the MD yield point stress, MD 5x elongation point stress, MD yield region energy, MD strain-softening energy, and MD total strain energy were calculated. In the curve, the y-value at the point where the MD strain on the x-axis is 5 was represented as the MD 5x elongation point stress. In addition, the yield point, which is the point where the first derivative is 0 or closest to 0, and the strain-softening end point, which is the point where the second derivative changes from negative to positive and becomes 0, were identified in the curve. Subsequently, the integral of the region from x-axis 0 to the x-value corresponding to the yield point was calculated and represented as the yield region energy, and the integral of the region from the x-value of the yield point to the x-value corresponding to the strain-softening endpoint was represented as the strain-softening region energy. In addition, the integral of the entire region of the curve from x-axis 0 to x-axis 5 was represented as the total strain energy.

[0538] MD Yield point stress (MPa) MD 5x elongation point stress (MPa) MD Yield zone energy (MPa) MD Deformation-softening zone energy (MPa) MD Total strain energy (MPa) Example 1 1.947 1.728 0.538 0.370 6.434 Example 2 0.815 0.74 0.28 40.08 42.735 Example 3 1.570 1.562 0.436 0.225 5.567 Example 4 1.279 1.076 0.368 0.255 4.076 Example 5 1.015 0.94 0.318 0.224 3.4 62 Example 61.3101.1530.3890.2834.377 Example 71.3211.1590.3950.1714.322 Example 80.7920.7040.2800.1722.633 Example 91.4801.2650.4740.3254.789 Example 101.2831.1120.4160.2504.08 Example 111.3011.0990.4390.2864.245 Example 121.3211.1830.4170.2504.364 Example 131.2001.0340.3790.1893.845 Example 141.4181.3230.4800.3444.863 Example 151.5201.4170.5280.2585.346 Example 161.3121.2660.4780.2264.743 Example 171.4391.3280.4880.2585.056 Example 181.2931.2460.5000.2284.541 Example 190.7720.6140.2140.1562.302 Example 200.8230.6350.2630.0962.953

[0539] 2. Calculation of yield point stress and TD strain-hardening region slope. In the stress-strain curve in the TD 8x elongation direction obtained in each example, the TD yield point stress was represented as the y-value at the yield point. The TD strain-hardening region slope was represented by calculating the average slope between the starting point of the strain-hardening region (the end point of the steady flow region) and the end point (i.e., the point where the TD strain on the x-axis is 8) in the curve.

[0540] TD Yield Point Stress (MPa) TD Strain-Hardening Zone Slope (MPa / times) Example 1 1.5 50.142 Example 2 0.13 40.067 Example 3 0.5 70.136 Example 4 0.33 60.104 Example 5 0.21 20.065 Example 6 0.30 40.072 Example 7 0.32 0.108 Example 8 0.37 0.106 Example 9 1.10 60.153 Example 10 0.62 50.161 Example 1 10.76 60.146 Example 1 20.78 10.136 Example 1 30.55 30.125 Example 1 40.49 60.156 Example 1 50.50 50.17 Example 1 60.35 0.149 Example 1 70.33 40.151 Example 1 80.28 60.153 Example 1 90.30 40.094 Example 2 00.13 40.091

[0541] 3. Derivation of Stiffness Index, Tensile Strength Index, and Puncture Strength Index The Stiffness Index was obtained by substituting the MD 5x elongation point stress, TD yield point stress, and density obtained from the above analysis into Equation 4-1 below. In addition, the Tensile Strength Index was obtained by substituting the MD total strain energy and the TD strain-strengthening region slope into Equation 5-1 below. The Puncture Strength Index was obtained by substituting the MD yield point stress, weight-average molecular weight (Mw), and scb content into Equation 6-1 below.

[0542] [Equation 4-1]

[0543]

[0544] [Equation 5-1]

[0545]

[0546] [Equation 6-1]

[0547]

[0548] The stiffness index, tensile strength index, and puncture strength index derived for each example are shown in Table 9 below.

[0549] Stiffness Index Tensile Strength Index Perforation Strength Index Example 1 0.84 0.86 0.86 Example 2 0.62 0.54 0.59 Example 3 0.87 0.81 0.77 Example 4 0.78 0.69 0.67 Example 5 0.68 0.59 0.66 Example 6 0.88 0.66 0.66 Example 7 0.86 0.71 0.64 Example 8 0.55 0.59 0.58 Example 9 0.73 0.78 0.74 Example 100.77 0.75 0.66 Example 110.820.740.61 Example 1 20.740.740.70 Example 1 30.740.700.66 Example 1 40.820.790.70 Example 1 50.980.830.66 Example 1 60.900.780.64 Example 1 70.950.800.66 Example 1 80.890.770.64 Example 1 90.510.540.56 Example 200.560.590.58

[0550] As shown in Table 9 above, the stiffness index, tensile strength index, and puncture strength index of the polyethylene resin composition according to the present invention all showed values ​​of 0.5 or higher and 1.2 or lower.

[0551] [Experimental Example 4] Evaluation of Mechanical Properties of Biaxially Stretched Film

[0552] In order to evaluate the mechanical properties of a biaxially stretched film prepared from the polyethylene resin composition of the above example, a biaxially stretched film was prepared in the same manner as in Experimental Example 2.

[0553] For the manufactured biaxially stretched films, the tensile strength in the MD direction was measured according to ASTM D 882, the Young's modulus in the MD direction was measured according to ASTM D882-07, and the puncture strength was measured according to EN 14477, and the results are shown in Table 10 below. In addition, to confirm the correlation between the stiffness index and the Young's modulus of the actual stretched film, the correlation between the tensile strength index and the MD tensile strength of the stretched film, and the correlation between the puncture strength index and the puncture strength of the stretched film for each example, point distributions were shown in Figures 5 to 7.

[0554] MD Tensile Strength (MPa) MD Young's Modulus (MPa) Piercing Strength (N / mm) Example 1 124677404 Example 2 95504317 Example 3 116783400 Example 4 116663361 Example 5 99588335 Example 6 108713332 Example 7 115644356 Example 8 92412296 Example 9 120647375 Example 1012163 5353 Example 11117710332 Example 12114588352 Example 13101556338 Example 14111756313 Example 15121894328 Example 16110792311 Example 17113803309 Example 18114806305 Example 1984412283 Example 2090475295

[0555] As shown in Table 10 above, it was observed that the biaxially stretched film produced from the polyethylene resin composition according to the present invention has excellent mechanical properties, with a tensile strength in the MD direction of 80 MPa or more, a Young's modulus in the MD direction of 400 MPa or more and 1000 MPa or less, and a puncture strength of 290 N / mm or more. In addition, as shown in Figures 5 to 7, it was observed that the stiffness index, tensile strength index, and puncture strength index of the polyethylene resin according to the present invention each have a high correlation with the Young's modulus, tensile strength, and puncture strength of the stretched film produced from this resin, and it was confirmed that all stretched films in which the indices fall within the range according to the present invention have excellent mechanical properties.

[0556] Through the above-described experiment, it was confirmed that the sheet produced from the polyethylene resin composition according to the present invention has uniform physical properties, and that stable stretching is achieved regardless of which part of the sheet is taken and biaxial stretching is performed; furthermore, it was found that the film produced by stretching in this way also has excellent mechanical properties.

[0557] Although the present invention has been described above by limited embodiments, the present invention is not limited thereto, and it is obvious that various modifications and variations are possible within the scope of the technical spirit of the present invention and the equivalent scope of the claims described below by those skilled in the art to which the present invention belongs.

Claims

A polyethylene resin composition comprising an ethylene homopolymer or an ethylene / C4 to C10 alpha olefin copolymer, A polyethylene resin composition satisfying condition 1) below and at least one of conditions 2) to 4): 1) The stretchability index represented by Formula 1 below is 0.7 or higher; 2) A stiffness index expressed by the following Equation 4 is 0.5 or higher; 3) A tensile strength index expressed by the following Equation 5 is 0.5 or higher; 4) The puncture strength index, expressed by the following Equation 6, is 0.5 or higher. [Equation 1] In the above Equation 1, Z is defined by the following Equation 2, [Equation 2] Z = a1 + a2 × PDI + a3 × density (g / cm³) 3 ) + a4×(deformation-softening region energy) + a5×(yield region energy) [Equation 4] [Equation 5] [Equation 6] In the above Equation 2, a1 is 133 to 136, a2 is 0.2 to 0.4, a3 is -137 to -135, a4 is -9.5 to -8, and a5 is -11 to -9.5, and In the above Equation 4, b1 is 7.5 to 9, b2 is 0.4 to 0.55, b3 is -0.2 to -0.05, and b4 is 25 to 30; In the above Equation 5, c1 is 3 to 6, c2 is 0.3 to 0.5, and c3 is 0.1 to 0.3; In the above Equation 6, d1 is 1 to 4, d2 is 0.4 to 0.6, d3 is 0.1 to 0.3, and d4 is 0.5 to 0.8; In the above Equations 2 and 4 to 6, the MD 5x elongation point stress is the y-value (MPa) at the point where the MD strain on the x-axis is 5 in the MD direction 5x elongation stress-strain curve, the MD yield point stress is the y-value (MPa) at the yield point of the curve, the yield region energy is the value obtained by integrating the region from x-axis 0 to the x-value corresponding to the yield point in the curve (MPa), the strain-softening region energy is the value obtained by integrating the region from the x-value of the yield point to the x-value corresponding to the strain-softening endpoint in the curve (MPa), and the MD total strain energy is the value obtained by integrating the entire region from x-axis 0 to 5 in the MD 5x elongation stress-strain curve (MPa); In the above Equations 4 and 5, the TD yield point stress is the y-value (MPa) at the yield point in the TD direction 8-fold elongation stress-strain curve, and the TD strain-strengthening region slope is the average slope at the starting point of the strain-strengthening region and the point where the TD strain on the x-axis is 8 in the curve, and In the above Equation 6, the SCB (short chain branch) content is the number of methyl terminal groups per 1,000 carbons. In paragraph 1, A polyethylene resin composition having a stretchability index of 0.75 or higher and 1.0 or lower. In paragraph 1, The density of the above polyethylene resin composition is 0.920 g / cm³ 3 Above 0.940 g / cm³ 3 Polyethylene resin composition, including the above. In paragraph 1, A polyethylene resin composition having a weight-average molecular weight (Mw) of 60,000 g / mol or more and 120,000 g / mol or less. In paragraph 1, A polyethylene resin composition having a PDI (Mw / Mn) of 1.0 to 10.

0. In paragraph 1, The above polyethylene resin composition is a polyethylene resin composition having a short chain branch (SCB) content, which is the number of methyl terminal groups per 1,000 carbon atoms, of 10 or more and 15 or less. In paragraph 1, The above polyethylene resin composition is a polyethylene resin composition that satisfies all of the conditions 1) to 4). In paragraph 1, The above polyethylene resin composition is a polyethylene resin composition that satisfies the following conditions: 1) The stretchability index is 0.75 or higher and 1.0 or lower; 2) Stiffness index is 0.5 or higher and 1.2 or lower; 3) Tensile strength index is 0.5 or higher and 1.2 or lower; 4) Puncture strength index is 0.5 or higher and 1.2 or lower; 5) Density is 0.922 g / cm³ 3 Above 0.940 g / cm³ 3 below; 6) The weight-average molecular weight (Mw) is 60,000 g / mol or more and 120,000 g / mol or less; 7) PDI is 3.0 to 9.0; 8) SCB (short chain branch) content is 10 or more and 15 or less. An unoriented sheet comprising a polyethylene resin composition according to any one of claims 1 to 8. In Paragraph 9, The above-mentioned unoriented sheet is a casting sheet having a thickness of 0.1 to 5 mm. A stretched film comprising a polyethylene resin composition according to any one of claims 1 to 8. In Paragraph 11, The above-mentioned stretched film is a uniaxially stretched film or a biaxially stretched film. In Paragraph 11, The above-mentioned stretched film is a stretched film that is stretched with a stretching ratio of 5 times or more in the length (MD) direction and a stretching ratio of 5 times or more in the width (TD) direction. In Paragraph 11, The above-mentioned stretched film is a stretched film having a tensile strength in the machine direction (MD) measured according to ASTM D 882 of 60 MPa or more and 180 MPa or less. In Paragraph 11, The above-mentioned stretched film is a stretched film having a Young's modulus measured according to ASTM D882-07 of 300 MPa or more and 1000 MPa or less. In Paragraph 11, The above stretched film is a stretched film having a puncture strength of 200 N / mm or more as measured according to EN 14477.

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