Polyethylene and preparation method thereof

Abstract

The present disclosure provides a polyethylene having excellent compatibility with regenerated polyethylene and capable of exhibiting improved mechanical properties, and a method for preparing the same.

Description

Technical Field

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims the benefit of Korean Patent Application No. 10-2022-0103613 filed on August 18, 2022, and Korean Patent Application No. 10-2023-0108100 filed on August 18, 2023, in the Korean Intellectual Property Office, the disclosures of which are incorporated herein by reference in their entirety.

[0003] The present disclosure relates to polyethylene having excellent compatibility with recycled polyethylene and improved mechanical properties and a preparation method thereof. Background Art

[0004] Polyethylene resins are in increasing demand and are used in a variety of applications. With the demand for high-performance polyethylene as a relatively new plastic, polymerization processes have been developed to support the production of new polymer materials.

[0005] Olefin polymerization catalyst systems can generally be divided into Ziegler-Natta catalysts and metallocene catalysts, and these highly active catalyst systems are developed according to their characteristics. Since the development of Ziegler-Natta catalysts in the 1950s, they have been widely used in commercial processes. However, since Ziegler-Natta catalysts are multi-active site catalysts mixed with multiple active sites, they have the characteristics of having a wide molecular weight distribution of the resulting polymer. Moreover, due to the uneven distribution of the composition of the comonomer, there is a problem of being difficult to obtain the desired physical properties.

[0006] Meanwhile, metallocene catalysts include a main catalyst having a transition metal compound as a main component and an organic metal compound cocatalyst having aluminum as a main component. This catalyst is a single-site catalyst as a homogeneous complex catalyst, and provides a polymer having a narrow molecular weight distribution and a uniform composition distribution of comonomers due to the single-site characteristics. The stereoregularity, copolymerization characteristics, molecular weight, crystallinity, etc. of the resulting polymer can be controlled by changing the ligand structure of the catalyst and the polymerization conditions.

[0007] US Patent No. 5,914,289 discloses a method for controlling the molecular weight and molecular weight distribution of a polymer using metallocene catalysts respectively supported on supports. However, the preparation of supported catalysts requires a large amount of solvent and a long time, and the process of supporting the metallocene catalyst on each support is cumbersome.

[0008] Korean Patent Application No. 2003-12308 discloses a method for controlling the molecular weight distribution of a polymer, wherein polymerization is performed while changing the combination of catalysts in a reactor by loading a binuclear metallocene catalyst and a mononuclear metallocene catalyst on a carrier together with an activator. However, this method has limitations in achieving the characteristics of each catalyst at the same time. In addition, there is a disadvantage that the metallocene catalyst is released from the supported component of the obtained catalyst, resulting in fouling in the reactor.

[0009] Meanwhile, as concerns about environmental issues increase, regulations to curb CO2 emissions are being strengthened. In particular, as environmental pollution due to the increased use of plastics has become a serious problem, regulations at the manufacturing stage are being strengthened, such as mandating the use of recycled resins, especially in the United States.

[0010] However, since the recycled resin is a processed resin, its properties have been changed by the high temperature processing process. Therefore, compared with the existing original resin, it has the problem of significantly reduced impact strength, tensile strength, chemical resistance and thermal stability. In order to solve this problem, a method of adding a predetermined amount of original resin to a composition containing recycled resin has been tried. However, in order to minimize the deterioration of mechanical properties by the above method, an excessive amount of original resin is required, and the problem of deterioration of major physical properties such as environmental stress cracking resistance (ESCR) remains unsolved. In addition, as the number of processing times increases, this problem becomes more serious. Summary of the invention

[0011] Technical issues

[0012] In the present disclosure, there is provided a polyethylene having improved mechanical properties while having excellent compatibility with recycled polyethylene.

[0013] The present disclosure also provides a method for preparing the above polyethylene.

[0014] In the present disclosure, a polyethylene composition is also provided, which comprises the above polyethylene and a recycled polyethylene resin (PCR).

[0015] Technical Solution

[0016] In the present disclosure, a polyethylene is provided that satisfies the following conditions: the integral value in the region where logMw is 5.0 or above in a GPC curve diagram where the x-axis is logMw and the y-axis is dw / dlogMw is 60% or more of the total integral value, the molecular weight distribution (Mw / Mn) is 7 or above, and the weight average molecular weight is 300,000 g / mol or above.

[0017] The present disclosure also provides a method for preparing the above polyethylene.

[0018] In the present disclosure, a polyethylene composition is also provided, which comprises the above polyethylene and a recycled polyethylene resin (PCR).

[0019] Beneficial Effects

[0020] According to the present disclosure, polyethylene having improved mechanical properties while being excellent in compatibility with recycled polyethylene can be provided by enhancing a high molecular area ratio and maintaining a low molecular area ratio in a molecular structure to simultaneously optimize molecular weight distribution and weight average molecular weight. DETAILED DESCRIPTION

[0021] In the present disclosure, the terms “first” and “second” and the like are used to describe various components, and these terms are only used to distinguish a certain component from other components.

[0022] The terms used herein are only for the purpose of describing specific embodiments and are not intended to limit the present invention. The singular form is also intended to include the plural form, unless the context clearly indicates otherwise. It will be further understood that when used in this specification, the terms "comprise", "have" or "include" specify the presence of the features, quantities, steps, components or combinations thereof, but do not exclude the presence or addition of one or more other features, quantities, steps, components or combinations thereof.

[0023] The term “about” or “substantially” is intended to have the meaning of approximating a specified numerical value or range with an allowed error, and is intended to prevent the exact or absolute numerical values ​​disclosed for understanding the present invention from being illegally or unfairly used by any unconscionable third party.

[0024] For reference, "parts by weight" used herein refers to a relative concept of the ratio of the weight of the remaining materials to the weight of a specific material. For example, in a mixture containing 50 g of material A, 20 g of material B, and 30 g of material C, based on 100 parts by weight of material A, the amounts of material B and C are 40 parts by weight and 60 parts by weight, respectively.

[0025] In addition, "wt% (weight %)" refers to an absolute concept that expresses the weight of a specific material as a percentage based on the total weight. In the above mixture, based on 100% of the total weight of the mixture, the contents of materials A, B and C are 50 weight%, 20 weight% and 30 weight%, respectively. At this time, the sum of the contents of each component does not exceed 100 weight%.

[0026] Since the present invention can be variously modified and has various forms, its specific embodiments are shown by way of example and will be described in detail. However, this does not mean that the present invention is limited to the disclosed specific form, and it should be understood that the present invention includes all modifications, equivalents and substitutions within the thought and technical scope of the present invention.

[0027] Hereinafter, the present disclosure will be described in detail.

[0028] According to one embodiment of the present disclosure, a polyethylene is provided, in which the molecular weight distribution and the weight average molecular weight are optimized while the high molecular area ratio is enhanced and the low molecular area ratio is maintained in the molecular structure, so as to improve mechanical properties such as environmental stress crack resistance (ESCR) while having excellent compatibility with recycled polyethylene.

[0029] Specifically, the polyethylene disclosed herein has an integrated value in the region where log Mw is 5.0 or more in a GPC curve with log Mw on the x-axis and dw / dlogMw on the y-axis of 60% or more of the total integrated value, a molecular weight distribution (Mw / Mn) of 7 or more, and a weight average molecular weight of 300,000 g / mol or more.

[0030] Specifically, polyethylene can be effectively improved in mechanical properties such as environmental stress crack resistance (ESCR) by using a catalyst containing three or more specific metallocene compounds to enhance the high molecular area ratio in the molecular structure and maintain the low molecular area ratio while optimizing the molecular weight distribution and weight average molecular weight, while having excellent compatibility with recycled polyethylene.

[0031] Hereinafter, the polyethylene of the present disclosure will be described in more detail.

[0032] The polyethylene of the present disclosure may be an ethylene homopolymer or an ethylene / α-olefin copolymer.

[0033] The α-olefin may be at least one selected from the group consisting of 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, and mixtures thereof.

[0034] For example, the polyethylene of the present disclosure may not contain the above-mentioned α-olefin or may contain 10% by weight or less of α-olefin. That is, the content of α-olefin may be 0 to 10% by weight. Specifically, the content of α-olefin may be 8% by weight or less, 6.5% by weight or less, 5% by weight or less, 4.5% by weight or less, 4% by weight or less, 3.5% by weight or less, 3% by weight or less, 2.5% by weight or less, 2.2% by weight or less, 2% by weight or less, 1.8% by weight or less, or 1.5% by weight or less, but is not limited thereto. In addition, when the polyethylene is an ethylene / α-olefin copolymer, the content of α-olefin may be 0.1% by weight or more, 0.3% by weight or more, 0.5% by weight or more, 0.7% by weight or more, 0.85% by weight or more, 0.9% by weight or more, 1.0% by weight or more, or 1.2% by weight or more, but is not limited thereto.

[0035] For example, when the polyethylene of the present disclosure is a copolymer, 1-hexene or 1-butene may be used as the α-olefin copolymerized with ethylene, and more specifically, 1-hexene may be used.

[0036] Meanwhile, the polyethylene of the present disclosure has an integrated value in the region where logMw is 5.0 or more in a GPC graph with logMw on the x-axis and dw / dlogMw on the y-axis of 60% or more of the total integrated value, or 60% or more and less than 90%.

[0037] Specifically, the integral value in the region where Log Mw is 5.0 or more may be 60% or more, 62% or more, 63% or more, 64% or more, 65% or more, 66% or more, 68% or more, 70% or more, 72% or more, or 74% or more to ensure excellent mechanical properties when polyethylene is mixed with recycled polyethylene. However, in consideration of compatibility with recycled polyethylene, the integral value in the region where Log Mw is 5.0 or more may be less than 90%, 89% or less, 88% or less, 85% or less, 82% or less, 80% or less, 79% or less, 78% or less, 77% or less, 76% or less, or 75% or less.

[0038] When the above integral value is present in the region where LogMw is 5.0 or more, mechanical properties such as environmental stress cracking resistance (ESCR) can be improved while enhancing the high molecular weight region ratio in the polyethylene molecular structure, and compatibility with recycled polyethylene is excellent. In particular, by enhancing the high molecular weight region ratio in the polyethylene molecular structure, when mixed with recycled polyethylene, the deterioration of main physical properties such as ESCR can be minimized without using an excessive amount of virgin polyethylene resin.

[0039] In addition, in the GPC curve chart with logMw on the x-axis and dw / dlogMw on the y-axis, the integral value of polyethylene in the region where LogMw is 4.0 or less may be 20% or less and 10% or more of the total integral value. When the above integral value is satisfied in the region where LogMw is 4.0 or less (which corresponds to the low molecular weight region in the molecular structure of polyethylene), compatibility with recycled polyethylene may be improved.

[0040] Specifically, the integral value in the region where LogMw is 4.0 or less may be 10% or more, 10.5% or more, 11% or more, 11.5% or more, 12% or more, 13% or more, 14% or more, 15% or more, or 15.5% or more to ensure excellent compatibility when polyethylene is mixed with recycled polyethylene. However, the integral value in the region where LogMw is 4.0 or less may be 20% or less, 19.5% or less, 19% or less, 18.5% or less, 18% or less, 17.5% or less, 17% or less, 16.5% or less, or 16% or less to improve the mechanical properties of the recycled polyethylene.

[0041] When the above integrated value is present in the region where LogMw is 4.0 or less, the low molecular weight region in the polyethylene molecular structure is optimized, and thus mechanical properties such as environmental stress crack resistance (ESCR) can be improved while maintaining excellent compatibility with recycled polyethylene.

[0042] In the polyethylene disclosed herein, the sum of the integral values ​​in the region where logMw is 5.0 or more and the integral values ​​in the region where logMw is 4.0 or less in the GPC curve graph where the x-axis is logMw and the y-axis is dw / dlogMw is less than 100%. Specifically, the sum of the integral values ​​in the region where LogMw is 5.0 or more and the integral values ​​in the region where LogMw is 4.0 or less may be 98% or less, 96% or less, 94% or less, 93% or less, 92% or less, 91% or less, 90% or less, 89% or less, 88% or less, or 87% or less.

[0043] As described above, the polyethylene of the present disclosure may have an optimized molecular weight distribution (MWD, Mw / Mn) while enhancing the high molecular area ratio and maintaining the low molecular area ratio in the molecular structure.

[0044] Specifically, the molecular weight distribution (Mw / Mn) of the polyethylene may be 7 or more or 7 to 13. Preferably, the molecular weight distribution (Mw / Mn) of the polyethylene may be 7.5 or more, 8 or more, 8.5 or more, 8.8 or more, 9 or more, 9.2 or more, 9.3 or more, 9.5 or more, or 9.8 or more, or 10 or more, and 12.8 or less, 12.5 or less, 12.3 or less, 12 or less, 11.8 or less, 11.5 or less, 11.4 or less, or 11.2 or less.

[0045] When having the above molecular weight distribution (Mw / Mn), polyethylene can improve mechanical properties such as environmental stress cracking resistance (ESCR) while enhancing the high molecular weight region ratio and maintaining the low molecular weight region ratio in the molecular structure, and has excellent compatibility with recycled polyethylene. In particular, the molecular weight distribution (Mw / Mn) of polyethylene should be 7 or more to improve compatibility with recycled polyethylene.

[0046] For example, the ratio of the region where LogMW in the GPC graph is 5.0 or more or 4.0 or less and the molecular weight distribution (Mw / Mn, polydispersity index) can be measured using gel permeation chromatography (GPC, manufactured by Water). Specifically, they can be measured using gel permeation chromatography (GPC, manufactured by Water) using a polystyrene calibration method.

[0047] Here, the molecular weight distribution (Mw / Mn, PDI, polydispersity index) can be determined by measuring the weight average molecular weight (Mw) and the number average molecular weight (Mn) of polyethylene, and then dividing the weight average molecular weight by the number average molecular weight.

[0048] Specifically, a PL-GPC220 manufactured by Waters can be used as a gel permeation chromatography (GPC) instrument, and a Polymer Laboratories PLgelMIX-B 300 mm long column can be used. The evaluation temperature can be 160 ° C, and the solvent can use 1,2,4-trichlorobenzene at a flow rate of 1 mL / min. Each polyethylene sample can be pretreated by dissolving in 1,2,4-trichlorobenzene containing 0.0125% butylated hydroxytoluene (BHT) at 160 ° C for 10 hours using a GPC analyzer (PL-GP220), and a sample with a concentration of 10 mg / 10 mL can be supplied in an amount of 200 μL. Mw and Mn can be obtained using a calibration curve formed using a polystyrene standard. Nine polystyrene standards were used with molecular weights of 2000 g / mol, 10000 g / mol, 30000 g / mol, 70000 g / mol, 200000 g / mol, 700000 g / mol, 2000000 g / mol, 4000000 g / mol and 10000000 g / mol.

[0049] In addition, the weight average molecular weight of the polyethylene may be 300,000 g / mol or more, or 300,000 g / mol to 100,000 g / mol. Preferably, the weight average molecular weight of polyethylene can be 320000 g / mol or more, 330000 g / mol or more, 340000 g / mol or more, 345000 g / mol or more, 348000 g / mol or more, 350000 g / mol or more, 354000 g / mol or more, 400000 g / mol or more, 450000 g / mol or more, 480000 g / mol or more, 500000 g / mol or more, 550000 g / mol or more, 600000 g / mol or more, 650000 g / mol or more, 700000 g / mol or more, 750000 g / mol or more, 800000 g / mol or more, 850000 g / mol or more, 900000 g / mol or more, or 1000000 g / mol or more. However, considering the compatibility with recycled polyethylene, the weight average molecular weight may be 1,000,000 g / mol or less, 950,000 g / mol or less, 900,000 g / mol or less, 880,000 g / mol or less, 850,000 g / mol or less, 800,000 g / mol or less, 780,000 g / mol or less, 750,000 g / mol or less, 700,000 g / mol or less, 680,000 g / mol or less, 650,000 g / mol or less, 600,000 g / mol or less, 580,000 g / mol or less, 550,000 g / mol or less, 520,000 g / mol or less, or 500,000 g / mol or less.

[0050] When the weight average molecular weight (Mw) is as described above, the molecular weight distribution of the polyethylene can be optimized, and mechanical properties such as environmental stress crack resistance (ESCR) can be improved, while compatibility with recycled polyethylene is excellent.

[0051] Meanwhile, as described above, the polyethylene of the present disclosure may have an optimized melt index while optimizing the high molecular region ratio and the molecular weight distribution in the molecular structure.

[0052] The melt index (MI) of polyethylene 2.16 , ASTM D 1238, 190°C, 2.16 kg) can be 0.1 g / 10 min to 0.7 g / 10 min. Preferably, the melt index (MI) of the polyethylene 2.16, ASTM D 1238, 190°C, 2.16 kg) may be 0.65 g / 10 min or less, 0.63 g / 10 min or less, 0.6 g / 10 min or less, 0.58 g / 10 min or less, 0.56 g / 10 min or less, 0.55 g / 10 min or less, 0.52 g / 10 min or less, or 0.5 g / 10 min or less, and 0.15 g / 10 min or more, 0.2 g / 10 min or more, 0.25 g / 10 min or more, 0.3 g / 10 min or more, 0.32 g / 10 min or more, 0.35 g / 10 min or more, 0.38 g / 10 min or more, 0.4 g / 10 min or more, 0.42 g / 10 min or more, or 0.45 g / 10 min or more. When having the above melt index (MI 2.16 ), the molecular weight distribution of polyethylene can be optimized, and mechanical properties such as environmental stress crack resistance (ESCR) can be improved, while excellent compatibility with recycled polyethylene.

[0053] When the melt index is as described above, the molecular weight of the polyethylene can be optimized, and mechanical properties such as environmental stress crack resistance (ESCR) can be improved, while compatibility with recycled polyethylene is excellent. In particular, in view of compatibility with recycled polyethylene, it is preferred that the melt index (MI) of the polyethylene is 2.16 , ASTM D 1238, 190°C, 2.16kg) is above 0.1g / 10min.

[0054] Meanwhile, as described above, the polyethylene of the present disclosure may have an optimized melt flow rate ratio or density while optimizing the high molecular region ratio, molecular weight distribution, and weight average molecular weight or melt index in the molecular structure.

[0055] The melt flow rate ratio (MFRR, MI 21.6 / MI 2.16 ) may preferably be 40 to 80, preferably 42 or more, 43 or more, 45 or more, 48 or more, 50 or more, 52 or more, 55 or more, 58 or more, 60 or more, or 62 or more, and 78 or less, 75 or less, 73 or less, 70 or less, 68 or less, or 65 or less.

[0056] MFRR is the melt index (MI) measured according to ASTM D 1238 at 190°C and a load of 21.6 kg. 21.6 ) divided by the melt index (MI) measured at 190°C and a load of 2.16 kg 2.16 ) and obtain the value.

[0057] When having the above melt flow rate ratio, the molecular weight distribution of polyethylene can be optimized, and mechanical properties such as environmental stress crack resistance (ESCR) can be improved, while compatibility with recycled polyethylene is excellent.

[0058] In addition, the polyethylene may satisfy a density (ASTM D1505, 23°C) of 0.940 g / cm 3 Up to 0.957g / cm 3 of high-density polyethylene (HDPE).

[0059] More specifically, the density of polyethylene can be 0.942 g / cm 3 Above, 0.944g / cm 3 Above, or 0.945g / cm 3 More than 0.956g / cm 3 Below, or 0.955g / cm 3 the following.

[0060] When the density of polyethylene satisfies the above range, compatibility with recycled polyethylene can be improved, and when mixed with recycled polyethylene, deterioration of main physical properties such as ESCR can be minimized without excessive use of virgin polyethylene resin.

[0061] At the same time, the polyethylene of one embodiment of the present invention can ensure excellent mechanical properties (such as environmental stress crack resistance (ESCR) or notched constant toughness stress (NCLS)) by using a catalyst containing three or more specific metallocene compounds to enhance the high molecular weight region ratio in the molecular structure and maintain the low molecular weight region ratio while optimizing the molecular weight distribution and weight average molecular weight, while having excellent compatibility with recycled polyethylene.

[0062] Specifically, the polyethylene may have an environmental stress crack resistance (ESCR) measured according to ASTM D 1693 of 120 hours or more, or 120 hours to 310 hours.

[0063] More specifically, the ESCR of the polyethylene can be 125 hours or more, 130 hours or more, 135 hours or more, 140 hours or more, 143 hours or more, 145 hours or more, 148 hours or more, 150 hours or more, 155 hours or more, 160 hours or more, 165 hours or more, 170 hours or more, 175 hours or more, or 180 hours or more, and 300 hours or less, 288 hours or less, 260 hours or less, 240 hours or less, 225 hours or less, 210 hours or less, 200 hours or less, 195 hours or less, 190 hours or less, or 185 hours or less.

[0064] In addition, the polyethylene according to one embodiment of the present disclosure may have a notched constant toughness stress (NCLS) measured according to ASTM F 2136 of 11.5 hours or more, or 11.5 hours to 20 hours.

[0065] More specifically, the NCLS of the polyethylene can be greater than 11.8 hours, greater than 12 hours, greater than 12.3 hours, greater than 12.5 hours, greater than 13 hours, greater than 13.5 hours, greater than 14 hours, greater than 14.5 hours, or greater than 15 hours, and less than 19.5 hours, less than 19 hours, less than 18.5 hours, less than 18 hours, less than 17.5 hours, less than 17 hours, less than 16.5 hours, or less than 16 hours.

[0066] Meanwhile, according to another embodiment of the present disclosure, a method for preparing the above-mentioned polyethylene is provided.

[0067] The method for preparing polyethylene disclosed herein comprises the step of polymerizing ethylene in the presence of a catalyst, wherein the catalyst contains at least one first metallocene compound represented by the following chemical formula 1; at least one second metallocene compound represented by the following chemical formula 2; and at least one third metallocene compound represented by the following chemical formula 3:

[0068] [Chemical formula 1]

[0069]

[0070] In Chemical Formula 1,

[0071] At least one of R1 to R8 is -(CH2) n -OR, where R is C 1-6 A linear or branched alkyl group, wherein n is an integer from 2 to 6,

[0072] The other R1 to R8 are the same or different from each other and are each independently selected from hydrogen, halogen, C 1-20 Alkyl, C 2-20 Alkenyl, C 6-20 Aryl, C 7-40 Alkyl aryl and C 7-40 The functional group in the group consisting of arylalkyl, or two or more substituents adjacent to each other are connected to each other to form a group having no substituent or substituted with C 1-10 Hydrocarbon C 6-20 aliphatic or aromatic ring,

[0073] Q1 and Q2 are the same or different from each other and are each independently hydrogen, halogen, C 1-20 Alkyl, C 2-20 Alkenyl, C 2-20 Alkoxyalkyl, C 6-20 Aryl, C7-40 Alkyl aryl or C 7-40 Arylalkyl;

[0074] A1 is carbon (C), silicon (Si) or germanium (Ge);

[0075] M1 is a Group IV transition metal;

[0076] X1 and X2 are the same or different from each other and are each independently halogen, C 1-20 Alkyl, C 2-20 Alkenyl, C 6-20 Aryl, nitro, acylamino, C 1-20 Alkylsilyl, C 1-20 Alkoxy or C 1-20 a sulfonate group; and

[0077] m is 0 or 1,

[0078] [Chemical formula 2]

[0079]

[0080] In chemical formula 2,

[0081] Q3 and Q4 are the same or different from each other and are each independently hydrogen, halogen, C 1-20 Alkyl, C 2-20 Alkenyl, C 2-20 Alkoxyalkyl, C 6-20 Aryl, C 7-40 Alkyl aryl or C 7-40 Arylalkyl;

[0082] A2 is carbon (C), silicon (Si) or germanium (Ge);

[0083] M2 is a Group IV transition metal;

[0084] X3 and X4 are the same or different from each other and are each independently halogen, C 1-20 Alkyl, C 2-20 Alkenyl, C 6-20 Aryl, nitro, acylamino, C 1-20 Alkylsilyl, C 1-20 Alkoxy or C 1-20 a sulfonate group; and

[0085] Either one of C1 and C2 is represented by the following chemical formula 2a or 2b, and the other of C1 and C2 is represented by the following chemical formula 2c, 2d or 2e,

[0086] [Chemical formula 2a]

[0087]

[0088] [Chemical formula 2b]

[0089]

[0090] [Chemical formula 2c]

[0091]

[0092] [Chemical formula 2d]

[0093]

[0094] [Chemical formula 2e]

[0095]

[0096] In Formulae 2a, 2b, 2c, 2d and 2e, R9 to R 39 and R9' to R 21 ' are the same or different from each other and are each independently hydrogen, halogen, C 1-20 Alkyl, C 1-20 Haloalkyl, C 2-20 Alkenyl, C 1-20 Alkylsilyl, C 1-20 Alkylsilylalkylene, C 1-20 Alkoxysilyl, C 1-20 Alkoxy, C 6-20 Aryl, C 7-40 Alkyl aryl or C 7-40 Arylalkyl, provided that R 17 To R 21 and R 17 'To R 21 At least one of them is C 1-20 Haloalkyl,

[0097] R 22 To R 39 Two or more substituents adjacent to each other in the formula may be linked to each other to form a group having no substituent or substituted with C 1-10 Hydrocarbon C 6-20 an aliphatic or aromatic ring; and

[0098] * indicates the sites that bind to A2 and M2.

[0099] [Chemical formula 3]

[0100]

[0101] In chemical formula 3,

[0102] Q5 and Q6 are the same or different from each other and are each independently hydrogen, halogen, C 1-20Alkyl, C 2-20 Alkenyl, C 2-20 Alkoxyalkyl, C 6-20 Aryl, C 7-40 Alkyl aryl or C 7-40 Arylalkyl;

[0103] A3 is carbon (C), silicon (Si) or germanium (Ge);

[0104] M3 is a Group IV transition metal;

[0105] X5 and X6 are the same or different from each other and are each independently halogen, C 1-20 Alkyl, C 2-20 Alkenyl, C 6-20 Aryl, nitro, acylamino, C 1-20 Alkylsilyl, C 1-20 Alkoxy or C 1-20 a sulfonate group; and

[0106] Any one of C3 and C4 is represented by Chemical Formula 3a, 3b or 3c, provided that at least one of C3 and C4 is not represented by Chemical Formula 3c,

[0107] [Chemical formula 3a]

[0108]

[0109] [Chemical formula 3b]

[0110]

[0111] [Chemical formula 3c]

[0112]

[0113] In Formulae 3a and 3b, R 40 To R 47 and R 40 'To R 47 ' are the same or different from each other and are each independently hydrogen, halogen, C 1-20 Alkyl, C 1-20 Haloalkyl, C 2-20 Alkenyl, C 1-20 Alkylsilyl, C 1-20 Alkylsilylalkylene, C 1-20 Alkoxysilyl, C 1-20 Alkoxy, C 6-20 Aryl, C 7-40 Alkyl aryl or C 7-40 arylalkyl, and

[0114] R 48 and R48 ' are the same or different from each other and are each independently C 1-20 Alkyl, C 1-20 Alkylsilyl, C 1-20 Alkylsilylalkylene, C 1-20 Alkoxysilyl or C 1-20 Alkoxy;

[0115] In Formula 3c, R 49 To R 56 are the same or different from each other and are each independently hydrogen, halogen, C 1-20 Alkyl, C 1-20 Haloalkyl, C 2-20 Alkenyl, C 1-20 Alkylsilyl, C 1-20 Alkylsilylalkylene, C 1-20 Alkoxysilyl, C 1-20 Alkoxy, C 6-20 Aryl, C 7-40 Alkyl aryl or C 7-40 Arylalkyl, or R 49 To R 56 Two or more substituents adjacent to each other in the ring may be connected to each other to form an aliphatic ring which may be substituted or not substituted, or an aromatic ring which may be substituted or not substituted; and

[0116] * indicates the sites binding to A3 and M3.

[0117] Unless otherwise specified herein, the following terms may be defined as follows.

[0118] The halogen may be fluorine (F), chlorine (Cl), bromine (Br) or iodine (I).

[0119] The hydrocarbyl group is a monovalent functional group formed by removing hydrogen from a hydrocarbon, and may include alkyl, alkenyl, alkynyl, aryl, aralkyl, aralkenyl, aralkynyl, alkylaryl, alkenylaryl, alkynylaryl, and the like. 1-30 The hydrocarbon group may be C 1-20 or C 1-10 For example, the hydrocarbon group may be a straight chain, branched chain or cyclic alkyl group. More specifically, C 1-30 The hydrocarbon group may be a straight chain, branched chain or cyclic alkyl group, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl and cyclohexyl; or an aryl group, such as phenyl, biphenyl, naphthyl, anthracenyl, phenanthrenyl or fluorenyl. In addition, it may be an alkylaryl group such as methylphenyl, ethylphenyl, methylbiphenyl and methylnaphthyl, or an arylalkyl group such as phenylmethyl, phenylethyl, biphenylmethyl and naphthylmethyl. It may also be an alkenyl group, such as allyl, vinyl, propenyl, butenyl and pentenyl.

[0120] C 1-20 The alkyl group may be a linear, branched or cyclic alkyl group. 1-20 The alkyl group can be C 1-20 Straight chain alkyl; C 1-15 Straight chain alkyl; C 1-5 Straight chain alkyl; C 3-20 Branched or cyclic alkyl; C 3-15 Branched or cyclic alkyl; or C 3-10 More specifically, C 1-20 The alkyl group may be methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl, etc., but is not limited thereto.

[0121] C 2-20 The alkenyl group may be a straight chain or branched chain alkenyl group, and specifically, may be an allyl group, a vinyl group, a propenyl group, a butenyl group, a pentenyl group, etc., but is not limited thereto.

[0122] C 1-20 The alkoxy group may be methoxy, ethoxy, isopropoxy, n-butoxy, tert-butoxy, cyclohexyloxy, or the like, but is not limited thereto.

[0123] C 2-20 The alkoxyalkyl group is a functional group in which at least one hydrogen of the above alkyl group is substituted by an alkoxy group, and it may be an alkoxyalkyl group such as methoxymethyl, methoxyethyl, ethoxymethyl, isopropoxymethyl, isopropoxyethyl, isopropoxypropyl, isopropoxyhexyl, tert-butoxymethyl, tert-butoxyethyl, tert-butoxypropyl and tert-butoxyhexyl, but is not limited thereto.

[0124] C 6-40 The aryloxy group may be a phenoxy group, a biphenyloxy group, a naphthoxy group, or the like, but is not limited thereto.

[0125] C 7-40 The aryloxyalkyl group is a functional group in which one or more hydrogens of the above-mentioned alkyl group are substituted with an aryloxy group, and it may be a phenoxymethyl group, a phenoxyethyl group, a phenoxyhexyl group, or the like, but is not limited thereto.

[0126] C 1-20 Alkylsilyl or C 1-20The alkoxysilyl group is a functional group in which 1 to 3 hydrogens of -SiH3 are replaced by 1 to 3 of the above-mentioned alkyl or alkoxy groups, and it may be an alkylsilyl group such as methylsilyl, dimethylsilyl, trimethylsilyl, dimethylethylsilyl, diethylmethylsilyl or dimethylpropylsilyl; an alkoxysilyl group such as methoxysilyl, dimethoxysilyl, trimethoxysilyl or dimethoxyethoxysilyl; or an alkoxyalkylsilyl group such as methoxydimethylsilyl, diethoxymethylsilyl or dimethoxypropylsilyl; and the like, but are not limited thereto.

[0127] C 1-20 The silylalkyl group is a functional group in which at least one hydrogen of the above alkyl group is substituted with a silyl group, and it may be -CH2-SiH3, methylsilylmethyl, dimethylethoxysilylpropyl, or the like, but is not limited thereto.

[0128] In addition, C 1-20 The alkylene group is the same as the above-mentioned alkyl group, except that it is a divalent substituent, and it can be a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a cycloheptylene group or a cyclooctylene group, etc., but is not limited thereto.

[0129] C 6-20 Aryl can be a monocyclic, bicyclic or tricyclic aromatic hydrocarbon. 6-20 The aryl group may be phenyl, biphenyl, naphthyl, anthracenyl, phenanthrenyl, fluorenyl or the like, but is not limited thereto.

[0130] C 7-20 The alkylaryl group may refer to a substituent in which at least one hydrogen of the aromatic ring is replaced by the above-mentioned alkyl group. 7-20 The alkylaryl group may be methylphenyl, ethylphenyl, methylbiphenyl or methylnaphthyl, etc., but is not limited thereto.

[0131] C 7-20 Arylalkyl may refer to a substituent in which at least one hydrogen of an alkyl group is replaced by the above-mentioned aryl group. 7-20 The arylalkyl group may be phenylmethyl, phenylethyl, biphenylmethyl, naphthylmethyl or the like, but is not limited thereto.

[0132] In addition, C 6-20 The arylene group is the same as the above-mentioned aryl group except that it is a divalent substituent, and it may be a phenylene group, a biphenylene group, a naphthylene group, an anthrylene group, a phenanthrenyl group, a fluorenylene group, or the like, but is not limited thereto.

[0133] The fourth group transition metal may be titanium (Ti), zirconium (Zr), hafnium (Hf) or □ (Rf), and may be specifically titanium (Ti), zirconium (Zr) or hafnium (Hf). More specifically, it may be zirconium (Zr) or hafnium (Hf), but the present disclosure is not limited thereto.

[0134] In addition, the Group 13 element may be boron (B), aluminum (Al), gallium (Ga), indium (In), or thallium (Tl), and may be specifically boron (B) or aluminum (Al), but the present disclosure is not limited thereto.

[0135] Meanwhile, the first metallocene compound may be represented by any one of the following Chemical Formulae 1-1 to 1-4.

[0136] [Chemical formula 1-1]

[0137]

[0138] [Chemical formula 1-2]

[0139]

[0140] [Chemical formula 1-3]

[0141]

[0142] [Chemical formula 1-4]

[0143]

[0144] In Chemical Formulae 1-1 to 1-4, Q1, Q2, A1, M1, X1, X2 and R1 to R8 are as defined in Chemical Formula 1. R' and R" are the same as or different from each other and are each independently hydrogen or C 1-10 Hydrocarbon.

[0145] Preferably, the first metallocene compound has a structure including a biscyclopentadienyl ligand, and more preferably, the cyclopentadienyl ligand may be symmetrically constructed around the transition metal. More preferably, the first metallocene compound may be represented by Chemical Formula 1-1.

[0146] In Chemical Formula 1 and Chemical Formulas 1-1 to 1-4, at least one of R1 to R8 is -(CH2) n -OR, where R is C 1-6 A linear or branched alkyl group, and n is an integer from 2 to 6. Specifically, R is C 1-4 A linear or branched alkyl group, and n is an integer from 4 to 6. For example, at least one of R1 to R8 may be C 1-6 Alkoxy substituted C 2-6 Alkyl, or C 1-4 Alkoxy substituted C4-6 alkyl.

[0147] In Chemical Formula 1 and Chemical Formulas 1-1 to 1-4, the other members of R1 to R8 are the same as or different from each other and are each independently selected from hydrogen, halogen, C 1-20 Alkyl, C 2-20 Alkenyl, C 6-20 Aryl, C 7-40 Alkyl aryl and C 7-40 The functional groups in the group consisting of arylalkyl or two or more substituents adjacent to each other may be linked to each other to form a group having no substituent or substituted with C 1-10 Hydrocarbon C 6-20 Aliphatic or aromatic ring.

[0148] Specifically, the other R1 to R8 are the same or different from each other and can each independently be hydrogen, C 1-20 Alkyl, C 1-10 Alkyl, C 1-6 Alkyl, C 1-6 Alkoxy substituted C 2-6 Alkyl, or C 1-4 Alkoxy substituted C 4-6 Alternatively, two or more substituents adjacent to each other in R1 to R8 may be connected to each other to form a substituent substituted with C 1-3 Hydrocarbon C 6-20 Aliphatic or aromatic ring.

[0149] Preferably, in Chemical Formula 1 and Chemical Formulas 1-1 to 1-4, R3 and R6 are each C 1-6 Alkyl, or C 1-6 Alkoxy substituted C 2-6 Alkyl, provided that at least one of R3 and R6 is C 1-6 Alkoxy substituted C 2-6 Alternatively, R3 and R6 are each C 4-6 Alkyl, or C 1-4 Alkoxy substituted C 4-6 Alkyl, provided that at least one of R3 and R6 is C 1-4 Alkoxy substituted C 4-6 Alkyl. For example, R3 and R6 can each be n-butyl, n-pentyl, n-hexyl, tert-butoxybutyl or tert-butoxyhexyl, provided that at least one of R3 and R6 is tert-butoxybutyl or tert-butoxyhexyl. Preferably, R3 and R6 are the same as each other and can be tert-butoxybutyl or tert-butoxyhexyl.

[0150] In addition, in Chemical Formula 1 and Chemical Formulas 1-1 to 1-4, R1, R2, R4, R5, R7, and R8 may be hydrogen.

[0151] In Chemical Formulas 1, 1-2 and 1-4, Q1 and Q2 are the same as or different from each other and are each independently hydrogen, halogen, C 1-20 Alkyl, C 2-20 Alkenyl, C 2-20 Alkoxyalkyl, C 6-20 Aryl, C 7-40 Alkyl aryl or C 7-40 Arylalkyl.

[0152] Specifically, Q1 and Q2 can each be C 1-12 Alkyl, C 1-6 Alkyl or C 1-3 Preferably, Q1 and Q2 are the same as each other and can be C 1-3 More preferably, Q1 and Q2 can be methyl.

[0153] In Chemical Formula 1 and Chemical Formulas 1-1 to 1-4, A1 is carbon (C), silicon (Si), or germanium (Ge). Specifically, A1 may be silicon (Si).

[0154] In Chemical Formula 1 and Chemical Formulas 1-1 to 1-4, M1 is a transition metal of Group 4. Specifically, M1 may be zirconium (Zr) or hafnium (Hf), preferably zirconium (Zr).

[0155] In Chemical Formula 1 and Chemical Formulas 1-1 to 1-4, X1 and X2 are the same as or different from each other and are each independently halogen, C 1-20 Alkyl, C 2-20 Alkenyl, C 6-20 Aryl, nitro, acylamino, C 1-20 Alkylsilyl, C 1-20 Alkoxy or C 1-20 Sulfonate group. Specifically, X1 and X2 may each be a halogen, and each may be chlorine, iodine or bromine. Preferably, X1 and X2 may be chlorine.

[0156] In Chemical Formula 1, m is 0 or 1, preferably 0.

[0157] The compound represented by Chemical Formula 1 may be, for example, a compound represented by one of the following structural formulas, but is not limited thereto.

[0158]

[0159]

[0160]

[0161] Preferably, the first metallocene compound may be a compound represented by one of the following structural formulas.

[0162]

[0163] More preferably, the first metallocene compound may be a compound represented by one of the following structural formulas.

[0164]

[0165] The first metallocene compound represented by the above structural formula can be synthesized by applying known reactions, and a more detailed synthesis method can be understood with reference to the Examples.

[0166] Since the preparation method of the present invention uses one or more first metallocene compounds represented by Chemical Formula 1 or one of Chemical Formulas 1-1, 1-2, 1-3 and 1-4 and one or more second metallocene compounds and one or more third metallocene compounds described later, the molecular weight distribution and weight average molecular weight are optimized while the high molecular area ratio is enhanced and the low molecular area ratio is maintained in the molecular structure, so that mechanical properties such as environmental stress crack resistance (ESCR) can be effectively improved, and at the same time, the compatibility with recycled polyethylene is excellent.

[0167] Meanwhile, the second metallocene compound may be represented by the following Chemical Formula 2-1.

[0168] [Chemical formula 2-1]

[0169]

[0170] In chemical formula 2-1, Q3, Q4, A2, M2, X3, X4, R 11 , R 17 To R 21 and R 22 To R 29 As defined in Formula 2.

[0171] In Chemical Formulae 2 and 2-1, Q3 and Q4 are the same as or different from each other and are each independently hydrogen, halogen, C 1-20 Alkyl, C 2-20 Alkenyl, C 2-20 Alkoxyalkyl, C 6-20 Aryl, C 7-40 Alkyl aryl or C 7-40 Specifically, Q3 and Q4 can each be C 1-12 Alkyl, C 1-8 Alkyl, C 1-3 Alkyl, C 2-18 Alkoxyalkyl, C 2-14 Alkoxyalkyl or C 2-12 More specifically, Q3 and Q4 can each be C 1-3 Alkyl or C 2-12Preferably, Q3 and Q4 are different from each other, and one of Q3 and Q4 may be C 1-3 Alkyl, the other can be C 2-12 More preferably, one of Q3 and Q4 may be a methyl group and the other may be a tert-butoxyhexyl group.

[0172] In Chemical Formula 2 and Chemical Formula 2-1, A2 is carbon (C), silicon (Si), or germanium (Ge). Specifically, A2 may be silicon (Si).

[0173] In Chemical Formula 2 and Chemical Formula 2-1, M2 is a transition metal of Group 4. Specifically, M2 may be zirconium (Zr) or hafnium (Hf), preferably zirconium (Zr).

[0174] In Chemical Formula 2 and Chemical Formula 2-1, X3 and X4 are the same as or different from each other and are each independently halogen, C 1-20 Alkyl, C 2-20 Alkenyl, C 6-20 Aryl, nitro, acylamino, C 1-20 Alkylsilyl, C 1-20 Alkoxy or C 1-20 Specifically, X3 and X4 can each be a halogen, and can each be chlorine, iodine or bromine. Preferably, X3 and X4 can be chlorine.

[0175] In Chemical Formula 2, one of C1 and C2 is represented by Chemical Formula 2a or 2b, and the other of C1 and C2 is represented by Chemical Formula 2c, 2d or 2e, preferably 2c.

[0176] In Chemical Formulae 2 and 2-1, R9 to R 21 and R 9' To R 21' are the same or different from each other and are each independently hydrogen, halogen, C 1-20 Alkyl, C 1-20 Haloalkyl, C 2-20 Alkenyl, C 1-20 Alkylsilyl, C 1-20 Alkylsilylalkylene, C 1-20 Alkoxysilyl, C 1-20 Alkoxy, C 6-20 Aryl, C 7-40 Alkyl aryl or C 7-40 Arylalkyl, provided that R 17 To R 21 and R 17 'To R 21 At least one of them is C 1-20 Halogenated alkyl.

[0177] Specifically, in Chemical Formula 2, R9 to R 10 , R 12 To R 16、 R 9’ To R 10’ and R 12’ To R 16 It may be hydrogen.

[0178] Specifically, in Chemical Formulas 2 and 2-1, R 11 and R 11' Each can be C 1-6 Straight or branched chain alkyl, or C 1-3 A straight chain or branched chain alkyl group. Preferably, each of them can be a methyl group.

[0179] Specifically, in Chemical Formulas 2 and 2-1, R 17 To R 21 and R 17' To R 21' Each can be hydrogen or C 1-6 haloalkyl, provided that R 17 To R 21 and R 17' To R 21' At least one of them is C 1-6 Alternatively, R 17 To R 21 and R 17' To R 21' Each can be hydrogen or C 1-3 haloalkyl, provided that R 17 To R 21 and R 17' To R 21' At least one of them is C 1-3 For example, R 17 To R 20 and R 17' To R 20' is hydrogen, and R 21 or R 21' It is a trihalomethyl group, preferably a trifluoromethyl group.

[0180] In Chemical Formulas 2 and 2-1, R 22 To R 39 are the same or different from each other and may each independently be hydrogen, halogen, C 1-20 Alkyl, C 1-20 Haloalkyl, C 2-20 Alkenyl, C 1-20 Alkylsilyl, C 1-20 Alkylsilylalkylene, C 1-20 Alkoxysilyl, C 1-20 Alkoxy, C 6-20Aryl, C 7-40 Alkyl aryl or C 7-40 Arylalkyl, or R 22 To R 39 Two or more substituents adjacent to each other in the formula may be linked to each other to form a group having no substituent or substituted with C 1-10 Hydrocarbon C 6-20 Aliphatic or aromatic ring.

[0181] Specifically, R 22 To R 29 Each can be hydrogen, C 1-20 Alkyl, C 1-10 Alkyl, C 1-6 Alkyl or C 1-3 As an alternative, R 22 To R 29 Two or more substituents adjacent to each other in the formula (C) may be linked to each other to form a substituent having C 1-3 Hydrocarbon C 6-20 Preferably, R 22 To R 29 It may be hydrogen.

[0182] In Chemical Formulas 2 and 2-1, R 30 To R 35 Each can be hydrogen, C 1-20 Alkyl, C 1-10 Alkyl, C 1-6 Alkyl or C 1-3 alkyl.

[0183] In Chemical Formulas 2 and 2-1, R 26 To R 29 Each can be hydrogen, C 1-20 Alkyl, C 1-10 Alkyl, C 1-6 Alkyl or C 1-3 alkyl.

[0184] The compound represented by Chemical Formula 2 may be, for example, a compound represented by the following structural formula, but is not limited thereto.

[0185]

[0186] The second metallocene compound represented by the above structural formula can be synthesized by applying known reactions, and a more detailed synthesis method can be understood with reference to Examples.

[0187] Since the preparation method of the present invention uses one or more first metallocene compounds represented by Chemical Formula 1 or one of Chemical Formulas 1-1, 1-2, 1-3 and 1-4 and one or more second metallocene compounds represented by Chemical Formula 2 or one of Chemical Formula 2-1 and one or more third metallocene compounds described later, the molecular weight distribution and weight average molecular weight are optimized while the high molecular area ratio is enhanced and the low molecular area ratio is maintained in the molecular structure, so that mechanical properties such as environmental stress crack resistance (ESCR) can be effectively improved, and at the same time, the compatibility with recycled polyethylene is excellent.

[0188] Meanwhile, the third metallocene compound may be represented by the following Chemical Formula 3-1.

[0189] [Chemical formula 3-1]

[0190]

[0191] In chemical formula 3-1, Q5, Q6, A3, M3, X5, X6, R 45 , R 48 and R 49 To R 56 As defined in Formula 3.

[0192] In Chemical Formulae 3 and 3-1, Q5 and Q6 are the same as or different from each other and are each independently hydrogen, halogen, C 1-20 Alkyl, C 2-20 Alkenyl, C 2-20 Alkoxyalkyl, C 6-20 Aryl, C 7-40 Alkyl aryl or C 7-40 Specifically, Q5 and Q6 can each be C 1-12 Alkyl, C 1-8 Alkyl, C 1-3 Alkyl, C 2-18 Alkoxyalkyl, C 2-14 Alkoxyalkyl or C 2-12 More specifically, Q5 and Q6 can each be C 1-3 Alkyl or C 2-12 Preferably, Q5 and Q6 are different from each other, and one of Q5 and Q6 can be C 1-3 Alkyl, the other can be C 2-12 More preferably, one of Q5 and Q6 may be a methyl group and the other may be a tert-butoxyhexyl group.

[0193] In Chemical Formulas 3 and 3-1, A3 is carbon (C), silicon (Si), or germanium (Ge). Specifically, A3 may be silicon (Si).

[0194] In Chemical Formulae 3 and 3-1, M3 is a transition metal of Group 4. Specifically, M3 may be zirconium (Zr) or hafnium (Hf), preferably zirconium (Zr).

[0195] In Chemical Formulae 3 and 3-1, X5 and X6 are the same as or different from each other and are each independently halogen, C 1-20 Alkyl, C 2-20 Alkenyl, C 6-20 Aryl, nitro, acylamino, C 1-20 Alkylsilyl, C 1-20 Alkoxy or C 1-20 Specifically, X5 and X6 may each be a halogen, and each may be chlorine, iodine or bromine. Preferably, X5 and X6 may be chlorine.

[0196] In Chemical Formula 3, one of C1 and C2 is represented by Chemical Formula 3a or 3b, and the other of C1 and C2 may be represented by Chemical Formula 3c.

[0197] In Chemical Formulas 3 and 3-1, R 40 To R 47 and R 40 'To R 47 ' are the same or different from each other and are each independently hydrogen, halogen, C 1-20 Alkyl, C 1-20 Haloalkyl, C 2-20 Alkenyl, C 1-20 Alkylsilyl, C 1-20 Alkylsilylalkylene, C 1-20 Alkoxysilyl, C 1-20 Alkoxy, C 6-20 Aryl, C 7-40 Alkyl aryl or C 7-40 Arylalkyl.

[0198] In addition, R 48 and R 48 ' are the same or different from each other and are each independently C 1-20 Alkyl, C 1-20 Alkylsilyl, C 1-20 Alkylsilylalkylene, C 1-20 Alkoxysilyl or C 1-20 Alkoxy.

[0199] Specifically, in Chemical Formula 3, R 40 To R 44 , R 46 To R 47 , R 40’ To R 44’ and R 46’ To R 47’It may be hydrogen.

[0200] Specifically, in Chemical Formulas 3 and 3-1, R 45 and R 45’ Each can be hydrogen, halogen, C 1-6 Alkyl or C 1-6 alkoxy, or each may be hydrogen, halogen, C 1-3 Alkyl or C 1-3 Alkoxy. For example, R 45 and R 45’ Each may be hydrogen, bromine, methyl or methoxy, preferably methyl.

[0201] In addition, in Chemical Formulas 3 and 3-1, R 48 and R 48’ Each can be C 1-6 Alkyl, C 1-6 Alkylsilyl, C 1-6 Alkylsilylalkylene or C 6-12 More specifically, each can be C 1-6 Straight or branched alkyl, C 1-6 Straight-chain or branched alkylsilyl, C 1-6 Straight chain or branched chain alkylsilylalkylene or C 6-12 Aryl. For example, R 48 and R 48’ Each may be methyl, trimethylsilyl, trimethylsilylmethylene or phenyl, preferably methyl.

[0202] In Chemical Formulas 3 and 3-1, R 49 To R 56 are the same or different from each other and are each independently hydrogen, halogen, C 1-20 Alkyl, C 1-20 Haloalkyl, C 2-20 Alkenyl, C 1-20 Alkylsilyl, C 1-20 Alkylsilylalkylene, C 1-20 Alkoxysilyl, C 1-20 Alkoxy, C 6-20 Aryl, C 7-40 Alkyl aryl or C 7-40 Arylalkyl, or R 49 To R 56 Two or more substituents adjacent to each other in the formula may be linked to each other to form a group having no substituent or substituted with C 1-10 Hydrocarbon C 6-20 Aliphatic or aromatic ring.

[0203] Specifically, R 49 To R 56 Each can be hydrogen, C1-20 Alkyl, C 1-10 Alkyl, C 1-6 Alkyl or C 1-3 As an alternative, R 49 To R 56 Two or more substituents adjacent to each other in the formula (C) may be linked to each other to form a substituent having C 1-3 Hydrocarbon C 6-20 aliphatic or aromatic ring. For example, R 49 To R 56 It can be hydrogen, tert-butyl or n-hexyl, or R 49 To R 56 Two or more substituents adjacent to each other in the formula (R) may be connected to each other to form a 1,1',4,4'-methyl-substituted cyclohexyl ring. 49 To R 56 It may be hydrogen.

[0204] In Chemical Formulas 3 and 3-1, R 49 , R 52 , R 53 and R 56 It can all be hydrogen.

[0205] Specifically, according to one embodiment of the present disclosure, specific examples of the compound represented by Chemical Formula 3a include compounds represented by one of the following structural formulas, but the present invention is not limited thereto.

[0206]

[0207] According to one embodiment of the present disclosure, specific examples of the compound represented by Chemical Formula 3b include compounds represented by one of the following structural formulas, but the present invention is not limited thereto.

[0208]

[0209] According to one embodiment of the present disclosure, specific examples of the compound represented by Chemical Formula 3c include compounds represented by one of the following structural formulas, but the present invention is not limited thereto.

[0210]

[0211] According to one embodiment of the present disclosure, specific examples of the third metallocene compound represented by Chemical Formulae 3 and 3-1 include compounds represented by one of the following structural formulae, but the present invention is not limited thereto.

[0212]

[0213]

[0214]

[0215] Preferably, the compound represented by Chemical Formula 3 may be, for example, a compound represented by the following structural formula, but is not limited thereto.

[0216]

[0217] The third metallocene compound represented by the above structural formula can be synthesized by applying known reactions, and a more detailed synthesis method can be understood with reference to Examples.

[0218] In addition, the preparation method of the above metallocene compound is specifically described in Examples to be described later.

[0219] The metallocene catalyst used in the present disclosure may be supported on a carrier together with a co-catalyst compound.

[0220] The metallocene catalyst used in the present disclosure may be supported on a carrier together with a co-catalyst compound.

[0221] In the supported metallocene catalyst of the present disclosure, the cocatalyst supported on the carrier to activate the metallocene compound is an organic metal compound containing a metal of Group 13. The cocatalyst is not particularly limited as long as it can be used when polymerizing olefins in the presence of a general metallocene catalyst.

[0222] The co-catalyst is an organic metal compound containing a Group 13 metal, and is not particularly limited as long as it can be used when polymerizing ethylene in the presence of a general metallocene catalyst.

[0223] Specifically, the co-catalyst may be one or more selected from the group consisting of compounds represented by the following Chemical Formulae 4 to 6.

[0224] [Chemical formula 4]

[0225] -[Al(R 60 )-O] c -

[0226] In chemical formula 4,

[0227] R 60 are each independently halogen; or C having no substituent or substituted with halogen 1-20 hydrocarbon group, and

[0228] C is an integer greater than or equal to 2,

[0229] [Chemical formula 5]

[0230] D(R 61 )3

[0231] In Chemical Formula 5,

[0232] D is aluminum or boron, and

[0233] R 61 are independently hydrogen, halogen; or C having no substituent or substituted with halogen 1-20 Hydrocarbon,

[0234] [Chemical formula 6]

[0235] [LH] + [Q(E)4] - or [L] + [Q(E)4] -

[0236] In Chemical Formula 6,

[0237] L is a neutral or cationic Lewis base,

[0238] H is a hydrogen atom,

[0239] Q is a Group 13 element, and

[0240] E is independently C 6-20 Aryl or C 1-20 Alkyl, where C 6-20 Aryl or C 1-20 The alkyl group may be unsubstituted or substituted with at least one selected from halogen, C 1-20 Alkyl, C 1-20 Alkoxy and C 6-20 A substituent in the group consisting of an aryloxy group.

[0241] Specifically, in Chemical Formula 6, [LH] + It is a Bronsted acid.

[0242] In addition, in Chemical Formula 6, Q may be B 3+ or Al 3 .

[0243] The compound represented by Chemical Formula 4 may be used as an alkylating agent and an activating agent, the compound represented by Chemical Formula 5 may be used as an alkylating agent, and the compound represented by Chemical Formula 6 may be used as an activating agent.

[0244] The compound represented by Chemical Formula 4 is not particularly limited as long as it is an alkylaluminoxane, but may be, for example, methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, butylaluminoxane, etc. Preferably, it may be methylaluminoxane.

[0245] The compound represented by Chemical Formula 5 is not particularly limited as long as it is an alkyl metal compound, but may be, for example, trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, dimethylaluminum chloride, triisopropylaluminum, tri-sec-butylaluminum, tricyclopentylaluminum, tripentylaluminum, triisopentylaluminum, trihexylaluminum, trioctylaluminum, ethyldimethylaluminum, methyldiethylaluminum, triphenylaluminum, tri-p-tolylaluminum, dimethylmethoxyaluminum, dimethylethoxyaluminum, trimethylboron, triethylboron, triisobutylboron, tripropylboron, tributylboron, etc. Preferably, it may be selected from trimethylaluminum, triethylaluminum and triisobutylaluminum.

[0246] Examples of the compound represented by Chemical Formula 6 may include triethylammonium tetraphenylboron, tributylammonium tetraphenylboron, trimethylammonium tetraphenylboron, tripropylammonium tetraphenylboron, trimethylammonium tetra(p-tolyl)boron, tripropylammonium tetra(p-tolyl)boron, triethylammonium tetra(o,p-dimethylphenyl)boron, trimethylammonium tetra(o,p-dimethylphenyl)boron, tributylammonium tetra(p-trifluoromethylphenyl)boron, trimethylammonium tetra(p-trifluoromethylphenyl)boron, tributylammonium tetra(pentafluorophenyl)boron, N,N-dimethylaniline tetraphenylboron, N,N-diethylaniline tetraphenylboron, N,N-diethylaniline tetra(pentafluorophenyl)boron, diethylammonium tetra(pentafluorophenyl)boron, triphenylphosphonium tetraphenylboron, trimethylphosphonium tetraphenylboron, triethylammonium tetraphenyl Aluminum, tributylammonium tetraphenylaluminum, trimethylammonium tetraphenylaluminum, tripropylammonium tetraphenylaluminum, trimethylammonium tetra(p-tolyl)aluminum, tripropylammonium tetra(p-tolyl)aluminum, triethylammonium tetra(o,p-dimethylphenyl)aluminum, tributylammonium tetra(p-trifluoromethylphenyl)aluminum, trimethylammonium tetra(p-trifluoromethylphenyl)aluminum, tributylammonium tetra(pentafluorophenyl)aluminum, N,N-dimethylaniline tetraphenylaluminum, N,N-diethylaniline tetraphenylaluminum, N,N-diethylaniline tetra(pentafluorophenyl)aluminum, diethylammonium tetra(pentafluorophenyl)aluminum, triphenylphosphonium tetraphenylaluminum, trimethylphosphonium tetraphenylaluminum, triphenylcarbonium tetraphenylboron, triphenylcarbonium tetraphenylaluminum, triphenylcarbonium tetra(p-trifluoromethylphenyl)boron and triphenylcarbonium tetra(pentafluorophenyl)boron, etc.

[0247] Meanwhile, in the metallocene catalyst of the present disclosure, the molar ratio of the co-catalyst to the sum of the metallocene compounds of Chemical Formulas 1 to 3 may be from about 1:1 to about 1:10000. The molar ratio may preferably be from about 1:1 to about 1:1000, and may more preferably be from about 1:10 to about 1:100. When the molar ratio is less than about 1, the metal content of the co-catalyst is too small, and thus the catalytically active material may not be well prepared, resulting in low activity. When the molar ratio exceeds about 10000, the metal of the co-catalyst may act as a catalyst poison.

[0248] The loading amount of the co-catalyst may be about 3 mmol to 25 mmol, or about 5 mmol to 20 mmol, based on 1 g of the support.

[0249] In the supported metallocene catalyst of the present disclosure, a support containing hydroxyl groups on its surface may be used. Preferably, a support containing highly reactive hydroxyl groups and siloxane groups that has been dried to remove moisture on the surface may be used.

[0250] For example, silica, silica-alumina and silica-magnesia dried at high temperature can be used as supports, and they generally contain oxides, carbonates, sulfates and nitrates, such as Na2O, K2CO3, BaSO4 and Mg(NO3)2, etc.

[0251] The drying temperature of the carrier may preferably be about 200 to 800° C., more preferably about 300 to 600° C., and most preferably about 300 to 400° C. When the drying temperature of the carrier is lower than 200° C., surface moisture may react with the co-catalyst due to excessive moisture. When it is higher than 800° C., pores on the surface of the carrier may be combined to reduce the surface area, and a large number of hydroxyl groups on the surface may be lost, and only siloxane groups may remain, thereby reducing the reaction sites with the co-catalyst, which is not preferred.

[0252] The amount of hydroxyl groups on the surface of the carrier may preferably be about 0.1 to 10 mmol / g, more preferably about 0.5 to 5 mmol / g. The amount of hydroxyl groups on the surface of the carrier may be controlled by the preparation method and conditions of the carrier or the drying conditions (e.g., temperature, time, vacuum or spray drying, etc.).

[0253] When the amount of hydroxyl groups is less than about 0.1 mmol / g, the reaction sites with the co-catalyst may be small, and when it is greater than about 10 mmol / g, it may be derived from moisture in addition to hydroxyl groups on the surface of the carrier particles, which is not preferred.

[0254] In the supported metallocene catalyst of the present disclosure, the mass ratio of the total transition metal contained in the metallocene catalyst to the carrier can be about 1:10 to about 1:1000. When the carrier and the metallocene compound are included in the above mass ratio, the optimal shape can be achieved. In addition, the mass ratio of the co-catalyst compound to the carrier can be about 1:1 to about 1:100.

[0255] For example, the metallocene catalyst of the present disclosure can be prepared by a method comprising the steps of: loading a co-catalyst on a carrier; loading first to third metallocene compounds on the carrier loaded with the co-catalyst; and preparing a metallocene catalyst comprising the carrier loaded with the co-catalyst and the metallocene compound.

[0256] In the above method, the loading conditions are not particularly limited, and the loading step can be carried out within the range known to those skilled in the art. For example, the loading step can be appropriately carried out at high and low temperatures. For example, the loading temperature can be in the range of about -30°C to about 150°C, preferably in the range of about 50°C to about 98°C, or in the range of about 55°C to about 95°C. The loading time can be appropriately controlled according to the amount of the first to third metallocene compounds to be loaded. The reacted supported catalyst can be used without further treatment after removing the reaction solvent by filtration or reduced pressure distillation, or, if necessary, Soxhlet filtration using aromatic hydrocarbons such as toluene.

[0257] The preparation of supported catalyst can be carried out in the presence of solvent or in the absence of solvent. When using solvent, it can include aliphatic hydrocarbon solvents such as hexane or pentane, aromatic hydrocarbon solvents such as toluene or benzene, chlorinated hydrocarbon solvents such as methylene chloride, ether solvents such as diethyl ether or tetrahydrofuran (THF), and common organic solvents such as acetone or ethyl acetate. Preferably, hexane, heptane, toluene or methylene chloride are used.

[0258] Meanwhile, the polyethylene according to one embodiment of the present disclosure may be prepared by a method for preparing polyethylene, which includes the step of polymerizing ethylene in the presence of a catalyst containing first to third metallocene compounds.

[0259] For example, the ethylene polymerization reaction can be carried out using a continuous slurry polymerization reactor, a loop slurry reactor, a gas phase reactor or a solution reactor. For example, the ethylene polymerization reaction can be a slurry polymerization reaction using a continuous slurry polymerization reactor or a loop slurry reactor.

[0260] In particular, the polyethylene of the present disclosure can be prepared by homopolymerizing ethylene or copolymerizing ethylene and an α-olefin in the presence of at least one first metallocene compound represented by the above Chemical Formula 1; at least one second metallocene compound selected from the compounds represented by the above Chemical Formula 2; and at least one third metallocene compound selected from the compounds represented by the above Chemical Formula 3.

[0261] The α-olefin may be at least one selected from the group consisting of 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, and mixtures thereof.

[0262] As an example, the preparation method of the polyethylene of the present disclosure can be carried out by homopolymerizing ethylene without including the above-mentioned α-olefin, or by copolymerizing ethylene with the above-mentioned α-olefin of less than 10 weight %. That is, the content of α-olefin can be 0 to less than 10 weight %. Specifically, the content of α-olefin can be less than 8 weight %, less than 6.5 weight %, less than 5 weight %, less than 4.5 weight %, less than 4 weight %, less than 3.5 weight %, less than 3 weight %, less than 2.5 weight %, less than 2.2 weight %, less than 2 weight %, less than 1.8 weight % or less than 1.5 weight %, but not limited to this. In addition, when the polyethylene is an ethylene / α-olefin copolymer, a copolymerization step can be performed so that 0.1 weight %, more than 0.3 weight %, more than 0.5 weight %, more than 0.7 weight %, more than 0.85 weight %, more than 0.9 weight %, more than 1.0 weight % or more than 1.2 weight % of α-olefin reacts with ethylene, but not limited to this.

[0263] For example, in the process for preparing a polyethylene copolymer, when a copolymerization step is performed with ethylene, as the α-olefin, 1-hexene or 1-butene can be used, more specifically, 1-hexene can be used. For example, in slurry polymerization, a polyethylene copolymer can be prepared by polymerizing ethylene and 1-hexene.

[0264] At the same time, in the preparation method of polyethylene disclosed in the present invention, the molar ratio of the first metallocene compound, the second metallocene compound and the third metallocene compound can be adjusted within the following range, which can improve mechanical properties such as environmental stress crack resistance (ESCR) by optimizing the molecular weight distribution and the weight average molecular weight while enhancing the high molecular area ratio and maintaining the low molecular area ratio in the molecular structure, while having excellent compatibility with recycled polyethylene.

[0265] Specifically, the molar ratio of the second metallocene compound based on the molar number of the first metallocene compound may be 1:1 to 1:3, and the molar ratio of the third metallocene compound based on the molar number of the first metallocene compound may be 1:2 to 1:8. More specifically, the molar ratio of the second metallocene compound based on the molar number of the first metallocene compound may be 1:1.2 to 1:2.5, 1:1.3 to 1:2.4, 1:1.4 to 1:2.2, or 1:1.5 to 1:2. In addition, the molar ratio of the third metallocene compound based on the molar number of the first metallocene compound may be 1:2.2 to 1:7.8, 1:2.3 to 1:7.5, 1:2.4 to 1:7.3, or 1:2.5 to 1:7.

[0266] For example, the molar ratio of the first metallocene compound, the second metallocene compound and the third metallocene compound can be 1:1:2 to 1:3:8, 1:1.2:2.2 to 1:2.5:7.8, 1:1.3:2.3 to 1:2.4:7.5, 1:1.4:2.4 to 1:2.2:7.4, or 1:1.5:2.5 to 1:2:7. Preferably, the molar ratio can be 1:1.5:2.5 to 1:2:7.

[0267] The molar ratio of the catalyst precursor may be the above molar ratio in terms of improving mechanical properties such as environmental stress crack resistance (ESCR) by achieving a high middle-high molecular weight region in the molecular structure while being excellent in compatibility with recycled polyethylene.

[0268] In addition, the polymerization may be carried out at a temperature of about 25° C. to about 500° C., about 25° C. to about 300° C., about 30° C. to about 200° C., about 50° C. to about 150° C., or about 60° C. to about 120° C. In addition, the polymerization may be carried out at a temperature of about 1 kgf / cm 2 To about 100kgf / cm 2 , about 1kgf / cm 2 To about 50kgf / cm 2 , about 5kgf / cm 2 To about 45kgf / cm 2 , about 10kgf / cm 2 To about 40kgf / cm 2 , or about 15kgf / cm 2 To about 35kgf / cm 2 under pressure.

[0269] In addition, the catalyst including the first to third metallocene compounds of the present disclosure can be dissolved or diluted in a C5 to C12 aliphatic hydrocarbon solvent (e.g., pentane, hexane, heptane, nonane, decane and isomers thereof), an aromatic hydrocarbon solvent (e.g., toluene and benzene), or a chlorine-substituted hydrocarbon solvent (e.g., dichloromethane and chlorobenzene), and injected. The solvent used herein is preferably used after removing a small amount of water or air that acts as a catalyst poison by treating with a small amount of alkyl aluminum. A cocatalyst may also be further used.

[0270] In the preparation process of the metallocene compound or supported catalyst or the ethylene polymerization reaction of the present disclosure, equivalent (eq) refers to molar equivalent (eq / mol).

[0271] In addition, in the present disclosure, polyethylene can be prepared by introducing hydrogen in the presence of the above-mentioned metallocene catalyst. At this time, hydrogen can be used within the following range, which can optimize the molecular weight distribution and weight average molecular weight while enhancing the high molecular area ratio and maintaining the low molecular area ratio in the molecular structure of the polyethylene obtained after polymerization.

[0272] For example, the polymerization step can be carried out by introducing 70ppm to 120ppm of hydrogen based on ethylene content. The ethylene content corresponds to the weight of the ethylene introduced into the polymerization reactor. More specifically, hydrogen can be introduced with about 72ppm or more, about 74ppm or more, about 76ppm or more, about 78ppm or more, or about 80ppm or more and about 118ppm or less, about 116ppm or less, about 114ppm or less, about 112ppm or less, or about 110ppm or less. In improving mechanical properties such as environmental stress cracking resistance (ESCR) by realizing high medium-polymer regions in the molecular structure of the polyethylene obtained after polymerization, and excellent compatibility with recycled polyethylene, the hydrogen input amount can be maintained within the above range.

[0273] In addition, the method for preparing polyethylene includes the step of introducing hydrogen while homopolymerizing ethylene or copolymerizing ethylene with an α-olefin in the presence of a catalyst containing at least one first metallocene compound represented by Chemical Formula 1; at least one second metallocene compound represented by Chemical Formula 2; and at least one third metallocene compound represented by Chemical Formula 3. At this time, when the ethylene input amount is 10 tons / hr, the hydrogen input amount may be 700 g / hr or more and 1200 g / hr or less.

[0274] Since the method for preparing polyethylene is carried out by slurry polymerization in the presence of the above catalyst, polyethylene having excellent mechanical properties can be provided.

[0275] In particular, when ethylene is polymerized in the presence of a catalyst containing at least one metallocene compound of Chemical Formula 2 and at least one metallocene compound of Chemical Formula 3 as well as the metallocene compound of Chemical Formula 1 of the present disclosure, the molecular weight distribution and the weight average molecular weight can be optimized while enhancing the high molecular area ratio and maintaining the low molecular area ratio in the molecular structure.

[0276] The polyethylene prepared by the method of one embodiment has an optimized molecular weight distribution and weight average molecular weight while maintaining the high molecular weight region ratio and the low molecular weight region ratio, thereby improving mechanical properties such as environmental stress cracking resistance (ESCR), and having excellent compatibility with recycled polyethylene. Therefore, it can increase the recycled polyethylene content while ensuring excellent impact strength, tensile strength, chemical resistance and thermal stability close to the original resin.

[0277] According to another embodiment of the present disclosure, a polyethylene composition is provided, which includes a recycled polyethylene resin (PCR) prepared by the method of one embodiment.

[0278] In particular, when polyethylene prepared by the above-mentioned method of the present disclosure is used, a molded product having excellent processability and high mechanical properties can be manufactured even if an excessive amount of recycled polyethylene resin is used, compared with the existing method.

[0279] As an example, the polyethylene composition may include 10% to 90% by weight of recycled polyethylene resin (PCR). In particular, in terms of improving the carbon dioxide emission inhibition effect of the polyethylene composition and reducing costs, the content of the recycled polyethylene resin (PCR) may be more than 20% by weight, more than 30% by weight, more than 35% by weight, more than 40% by weight, more than 45% by weight, more than 50% by weight, or more than 55% by weight. In addition, in terms of improving the mechanical properties of the polyethylene composition such as impact strength, tensile strength, chemical resistance and thermal stability and minimizing the original resin content, the content of the recycled polyethylene resin (PCR) may be less than 85% by weight, less than 80% by weight, less than 75% by weight, less than 70% by weight, less than 65% by weight, or less than 60% by weight. For example, the content of the recycled polyethylene resin (PCR) may be 50% to 70% by weight.

[0280] Recycled polyethylene resin (PCR) may be characterized as having a viscosity of 0.940 g / cm 3 Up to 0.960g / cm 3 More specifically, the density of polyethylene can be 0.943 g / cm 3 Above, 0.945g / cm 3 Above, 0.948g / cm 3 Above, or 0.950g / cm 3 More than 0.958g / cm 3 Below, 0.956g / cm 3 Below, 0.955g / cm 3 Below, or 0.953g / cm 3 the following.

[0281] In addition, the melt index (MI) of recycled polyethylene resin (PCR) 2.16 , 190°C, measured under a load of 2.16 kg) can be 0.4 g / 10 min to 0.7 g / 10 min.

[0282] In addition, the recycled polyethylene resin (PCR) may have environmental stress crack resistance (ESCR) measured according to ASTM D 1693 of 40 to 50 hours.

[0283] According to the present disclosure, the polyethylene composition includes recycled polyethylene resin (PCR) and polyethylene as a virgin resin, wherein the polyethylene as the virgin resin has an optimized molecular weight distribution and weight average molecular weight while enhancing the high molecular area ratio and maintaining the low molecular area ratio in the molecular structure, so as to improve mechanical properties such as environmental stress crack resistance (ESCR), and at the same time has excellent compatibility with the recycled polyethylene.

[0284] As an example, the polyethylene composition can include 90% by weight to 10% by weight of polyethylene as virgin resin and recycled polyethylene resin (PCR). Particularly, in terms of improving the carbon dioxide emission inhibition effect of the polyethylene composition and reducing costs, the content of the polyethylene as the virgin resin can be minimized to less than 80% by weight, less than 70% by weight, less than 65% by weight, less than 60% by weight, less than 55% by weight, less than 50% by weight, or less than 45% by weight. In addition, in terms of maximizing the compatibility with recycled polyethylene and improving the mechanical properties of the polyethylene composition such as impact strength, tensile strength, chemical resistance and thermal stability, the content of the polyethylene as the virgin resin can be more than 15% by weight, more than 20% by weight, more than 25% by weight, more than 30% by weight, more than 35% by weight, or more than 40% by weight. For example, the content of the polyethylene as the virgin resin can be 50% by weight to 30% by weight.

[0285] The polyethylene composition of the present disclosure can increase the recycled polyethylene content while ensuring excellent impact strength, tensile strength, chemical resistance, and thermal stability close to those of virgin resin.

[0286] Specifically, the polyethylene composition may have a notched constant toughness stress (NCLS) measured according to ASTM F 2136 of 7 hours or more or 7 hours to 20 hours.

[0287] More specifically, the NCLS of the polyethylene composition can be 7.2 hours or more, 7.5 hours or more, 7.8 hours or more, 7.9 hours or more, 8 hours or more, 8.2 hours or more, 8.5 hours or more, 8.8 hours or more, 9 hours or more, 9.2 hours or more, 9.5 hours or more, 9.8 hours or more, 10 hours or more, 10.2 hours or more, 10.5 hours or more, 10.8 hours or more, 11 hours or more, or 11.5 hours or more, and 19 hours or less, 18 hours or less, 17.5 hours or less, 17 hours or less, 16.5 hours or less, 16 hours or less, 15.5 hours or less, 15 hours or less, 14.5 hours or less, 13 hours or less, 13.5 hours or less, 13 hours or less, 12.5 hours or less, or 12 hours or less.

[0288] Hereinafter, preferred embodiments are provided to help understand the present invention. However, these embodiments are only for illustrative purposes, and the present invention is not intended to be limited by these embodiments.

[0289] <Example>

[0290] <Preparation of Catalyst Precursor>

[0291] Synthesis Example 1: Preparation of the First Metallocene Compound

[0292]

[0293] Tert-butyl-O-(CH2)6-Cl was prepared using 6-chlorohexanol by the method shown in Tetrahedron Lett. 2951 (1988) and reacted with cyclopentadienyl sodium (NaCp) to obtain tert-butyl-O-(CH2)6-C5H5 (yield 60%, boiling point 80°C / 0.1 mmHg).

[0294] In addition, tert-butyl-O-(CH2)6-C5H5 is dissolved in tetrahydrofuran (THF) at -78°C, and n-butyl lithium (n-BuLi) is slowly added thereto. Thereafter, it is heated to room temperature and reacted for 8 hours. The above-synthesized lithium salt solution is slowly added to a suspension of ZrCl4(THF)2(170g, 4.50mmol) / THF(30mL) at -78°C, and further reacted at room temperature for about 6 hours. All volatiles are dried under vacuum, and the resulting oily liquid material is filtered by adding hexane solvent. The filtered solution is dried under vacuum, and hexane is added to obtain a precipitate at low temperature (-20°C). The obtained precipitate is filtered at low temperature to obtain [t-Bu-O-(CH2)6-C5H4]2ZrCl2 compound (yield 92%) in the form of a white solid.

[0295] 1 H-NMR (300MHz, CDCl3): 6.28 (t, J = 2.6 Hz, 2H), 6.19 (t, J = 2.6 Hz, 2H), 3.31 (t, 6.6 Hz, 2H), 2.62 (t, J = 8 Hz), 1.7–1.3 (m, 8H), 1.17 (s, 9H).

[0296] 13 C-NMR(CDCl3):135.09,116.66,112.28,72.42,61.52,30.66,30.31,30.14,29.18,27.58,26.00.

[0297] Synthesis Example 2: Preparation of the Second Metallocene Compound

[0298]

[0299] 2-1 Preparation of ligand compounds

[0300] 2.9 g (7.4 mmol) of 8-methyl-5-(2-(trifluoromethyl)benzyl)-5,10-dihydroindeno[1,2-b]indole was dissolved in 100 mL of hexane and 2 mL (16.8 mmol) of MTBE (methyl tert-butyl ether), and 3.2 mL (8.1 mmol) of 2.5 M n-BuLi hexane solution was added dropwise in a dry ice / acetone bath and stirred overnight at room temperature. In another 250 mL Schlenk flask, 2 g (7.4 mmol) of (6-tert-butoxyhexyl)dichloro(methyl)silane was dissolved in 50 mL of hexane and added dropwise in a dry ice / acetone bath. Then, the lithiated slurry of 8-methyl-5-(2-(trifluoromethyl)benzyl)-5,10-dihydroindeno[1,2-b]indole was added dropwise via cannula. After injection, the mixture was slowly heated to room temperature and then stirred overnight at room temperature. Meanwhile, 1.2 g (7.4 mmol) of fluorene was also dissolved in 100 mL of tetrahydrofuran (THF), and 3.2 mL (8.1 mmol) of 2.5 M n-BuLi hexane solution was added dropwise in a dry ice / acetone bath, followed by stirring at room temperature overnight.

[0301] The reaction solution (Si solution) of 8-methyl-5-(2-(trifluoromethyl)benzyl)-5,10-dihydroindeno[1,2-b]indole and (6-(tert-butoxy)hexyl)dichloro(methyl)silane was confirmed by NMR sampling.

[0302] 1 H NMR(500MHz, CDCl3):7.74-6.49(11H,m),5.87(2H,s),4.05(1H,d),3.32(2H ,m),3.49(3H,s),1.50-1.25(8H,m),1.15(9H,s),0.50(2H,m),0.17(3H,d).

[0303] After confirming the synthesis, the lithiated solution of fluorene was slowly added dropwise to the Si solution in a dry ice / acetone bath and stirred at room temperature overnight. After the reaction, it was extracted with ether / water, and the residual moisture of the organic layer was removed with MgSO4. Then, the solvent was removed under vacuum to obtain 5.5 g (7.4 mmol) of an oily ligand compound, which was obtained by 1 H-NMR confirmed.

[0304] 1H NMR(500MHz, CDCl3):7.89-6.53(19H,m),5.82(2H,s),4.26(1H,d),4.14-4.10(1H,m),3 .19(3H,s),2.40(3H,m),1.35-1.21(6H,m),1.14(9H,s),0.97-0.9(4H,m),-0.34(3H,t).

[0305] 2-2 Preparation of Metallocene Compounds

[0306] 5.4 g (Mw 742.00 g / mol, 7.4 mmol) of the ligand compound synthesized in 2-1 was dissolved in 80 mL of toluene and 3 mL (25.2 mmol) of MTBE, and 7.1 mL (17.8 mmol) of 2.5 Mn-BuLi hexane solution was added dropwise in a dry ice / acetone bath, and then stirred at room temperature overnight. 3.0 g (8.0 mmol) of ZrCl4(THF)2 was added to 80 mL of toluene to prepare a slurry. 80 mL of the toluene slurry of ZrCl4(THF)2 was transferred to the ligand-Li solution in a dry ice / acetone bath and stirred at room temperature overnight.

[0307] After filtering the reaction mixture to remove LiCl, toluene in the filtrate was removed by vacuum drying, and then 100 mL of hexane was added thereto, followed by ultrasonic treatment for 1 hour. It was filtered to obtain 3.5 g (yield 52 mol%) of a purple metallocene compound as a filtered solid.

[0308] 1 H NMR (500MHz, CDCl3): 7.90-6.69(9H,m),5.67(2H,s),3.37(2H,m),2.56(3H,s),2.13-1.51(11H,m),1.17(9H,s).

[0309] Synthesis example 3

[0310]

[0311] 3-1 Preparation of ligand compounds

[0312] 2g of fluorene was dissolved in 5mL MTBE and 100mL hexane, and 5.5mL 2.5M n-BuLi hexane solution was added dropwise in a dry ice / acetone bath, and then stirred at room temperature overnight. 3.6g (6-(tert-butoxy) hexyl) dichloro (methyl) silane was dissolved in 50mL hexane, and the fluorene-Li slurry was transferred in a dry ice / acetone bath for 30 minutes, and then stirred at room temperature overnight. At the same time, 5,8-dimethyl-5,10-dihydroindeno [1,2-b] indole (12mmol, 2.8g) was dissolved in 60mL THF, and 5.5mL 2.5M n-BuLi hexane solution was added dropwise in a dry ice / acetone bath, and then stirred at room temperature overnight. After confirming the completion of the reaction by NMR sampling of the reaction solution of fluorene and (6-(tert-butoxy)hexyl)dichloro(methyl)silane, the 5,8-dimethyl-5,10-dihydroindeno[1,2-b]indole-Li solution was transferred in a dry ice / acetone bath. Then, it was stirred at room temperature overnight. After the reaction, it was extracted with ether / water, and the residual moisture of the organic layer was removed with MgSO4 to obtain a ligand compound (Mw 597.90, 12 mmol). Thereafter, by 1 H-NMR confirmed the production of two isomers.

[0313] 1 H NMR (500MHz, d6-benzene): -0.30--0.18(3H,d),0.40(2H,m),0.65-1.45(8H,m),1.12(9H,d),2.36-2.40 (3H,d),3.17(2H,m),3.41-3.43(3H,d),4.17-4.21(1H,d),4.34-4.38(1H,d),6.90-7.80(15H,m).

[0314] 3-2 Preparation of Metallocene Compounds

[0315] 7.2 g (12 mmol) of the ligand compound synthesized in 3-1 was dissolved in 50 mL of diethyl ether, and 11.5 mL of 2.5 M n-BuLi hexane solution was added dropwise in a dry ice / acetone bath, and then stirred at room temperature overnight. It was vacuum dried to obtain a brown viscous oil. It was dissolved in toluene to obtain a slurry. ZrCl4(THF)2 was prepared, and 50 mL of toluene was added thereto to prepare a slurry. 50 mL of toluene slurry of ZrCl4(THF)2 was transferred in a dry ice / acetone bath. As the slurry was stirred at room temperature overnight, the color turned purple. The reaction solution was filtered to remove LiCl. Toluene in the filtrate was removed by vacuum drying, and hexane was then added thereto, followed by ultrasonic treatment for 1 hour. The slurry was filtered to obtain 6 g (Mw 758.02, 7.92 mmol, yield 66 mol%) of a dark purple metallocene compound as a filtered solid.1 Two isomers were observed by H-NMR.

[0316] 1 H NMR(500MHz, CDCl3):1.19(9H,d),1.71(3H,d),1.50-1.70(4H,m),1.79(2H,m) ,1.98-2.19(4H,m),2.58(3H,s),3.38(2H,m),3.91(3H,d),6.66-7.88(15H,m).

[0317] Comparative Synthesis Example 1

[0318]

[0319] To a 10 L reactor, 50 g of Mg was added at room temperature, followed by 300 mL of THF. 0.5 g of I2 was added, and the reactor temperature was maintained at 50°C. After the reactor temperature stabilized, 250 g of 6-tert-butoxyhexyl chloride was added to the reactor at a rate of 5 mL / min using a feed pump. It was observed that with the addition of 6-tert-butoxyhexyl chloride, the reactor temperature increased by 4°C to 5°C. Stir for 12 hours while continuing to add 6-tert-butoxyhexyl chloride to obtain a black reaction solution. Take 2 mL of the black solution and add water thereto to obtain an organic layer. By 1 H-NMR confirmed that the organic layer was 6-tert-butoxyhexane. This confirmed that the Grignard reaction was proceeding well. Therefore, 6-tert-butoxyhexylmagnesium chloride was synthesized.

[0320] 500g of MeSiCl3 and 1L of THF were introduced into the reactor, and then the reactor temperature was cooled to -20°C. 560g of the above-synthesized 6-tert-butoxyhexyl magnesium chloride was added to the reactor at a rate of 5mL / min using a feed pump. After the Grignard reagent feeding was completed, the mixture was stirred for 12 hours while the reactor temperature was slowly raised to room temperature. Then, it was confirmed that a white MgCl2 salt was produced. 4L of hexane was added thereto, and the salt was removed by labdori to obtain a filtered solution. After the filtered solution was added to the reactor, the hexane was removed at 70°C to obtain a light yellow liquid. By 1 H-NMR confirmed that the obtained liquid was methyl(6-tert-butoxyhexyl)dichlorosilane.

[0321] 1 H-NMR (CDCl3): 3.3(t,2H),1.5(m,3H),1.3(m,5H),1.2(s,9H),1.1(m,2H),0.7(s,3H).

[0322] 1.2mol (150g) of tetramethylcyclopentadiene and 2.4L of THF were added to the reactor, and the reactor temperature was then cooled to -20°C. 480mL of n-BuLi was added to the reactor at a rate of 5ml / min using a feed pump. After adding n-BuLi, the mixture was stirred for 12 hours while the reactor temperature was slowly raised to room temperature. Then, an equivalent of methyl (6-tert-butoxyhexyl) dichlorosilane (326g, 350mL) was quickly added to the reactor. The mixture was stirred for 12 hours while the reactor temperature was slowly raised to room temperature. Then, the reactor temperature was cooled to 0°C again, and 2 equivalents of t-BuNH2 were added. The mixture was stirred for 12 hours while the reactor temperature was slowly raised to room temperature. Then, THF was removed. Thereafter, 4L of hexane was added and the salt was removed by labdori to obtain a filtered solution. The filtered solution was added to the reactor again, and the hexane was removed at 70°C to obtain a yellow solution. By 1 H-NMR confirmed that the yellow solution obtained above was methyl(6-tert-butoxyhexyl)(tetramethyl CpH)tert-butylaminosilane.

[0323] TiCl3(THF)3 (10 mmol) was quickly added to the dilithium salt of the ligand at -78°C, which was synthesized from the ligand of n-BuLi and dimethyl(tetramethyl CpH)tert-butylaminosilane in THF solution. The reaction solution was stirred for 12 hours while slowly heating from -78°C to room temperature. Then, an equivalent amount of PbCl2 (10 mmol) was added to the reaction solution at room temperature, which was then stirred for 12 hours to obtain a dark black solution with a blue color. After removing THF from the resulting reaction solution, hexane was added to filter the product. Hexane was removed from the filtered solution, and then the product was filtered by 1 H-NMR confirmed that the product was tBu-O-(CH2)6](CH3)Si(C5(CH3)4)(tBu-N)TiCl2.

[0324] 1 H-NMR(CDCl3):3.3(s,4H),2.2(s,6H),2.1(s,6H),1.8-0.8(m),1.4(s,9H),1.2(s,9H),0.7(s,3H).

[0325] [Mixed supported catalyst]

[0326] Preparation Example 1: Preparation of supported catalyst

[0327] 6.0 kg of the toluene solution was added to a 20 L stainless steel (sus) high pressure reactor, and the reactor temperature was maintained at 40° C. 1000 g of silica (manufactured by Grace Davison, SYLOPOL 948) dehydrated at a temperature of 600° C. under vacuum for 12 hours was added to the reactor and fully dispersed, and then 60 g of the first metallocene compound of Synthesis Example 1 dissolved in toluene was added, followed by stirring at 200 rpm for 2 hours at 40° C. Thereafter, stirring was stopped, sedimentation was performed for 30 minutes, and the reaction solution was decanted.

[0328] 2.5 kg of toluene was added to the reactor, and 9.4 kg of 10 wt% methylaluminoxane (MAO) / toluene solution was added thereto, followed by stirring at 200 rpm for 12 hours at 40°C. Thereafter, stirring was stopped, followed by settling for 30 minutes, and then the reaction solution was decanted. After adding 3.0 kg of toluene and stirring for 10 minutes, stirring was stopped, followed by settling for 30 minutes, and then the toluene solution was decanted.

[0329] After 3.0 kg of toluene was added to the reactor, 102 g of the second metallocene compound of Synthesis Example 2 was dissolved in 1 L of toluene solution and added thereto, followed by stirring at 40° C. and 200 rpm for 2 hours.

[0330] A solution was prepared by adding 383 g of the third metallocene compound of Synthesis Example 3 and 1 L of toluene in a flask, and subjected to ultrasonic treatment for 30 minutes. The metallocene compound / toluene solution of Synthesis Example 3 prepared in this manner was added to a reactor and stirred at 200 rpm for 2 hours at 40 ° C for reaction. After the reactor temperature was lowered to room temperature, stirring was stopped, sedimentation was performed for 30 minutes, and the reaction solution was decanted. At this time, the first metallocene compound of Synthesis Example 1, the second metallocene compound of Synthesis Example 2, and the third metallocene compound of Synthesis Example 3 were used in a molar ratio of 1: 2: 7.

[0331] 2.0 kg of toluene was added to the reactor and stirred for 10 minutes. Then the stirring was stopped, and then settled for 30 minutes, and then the reaction solution was decanted.

[0332] 3.0 kg of hexane was added to the reactor, and the hexane slurry was transferred to a filter dryer to filter the hexane solution. 1 kg of the SiO2 mixed supported catalyst was prepared by drying under reduced pressure at 40°C for 4 hours.

[0333] Preparation Example 2: Preparation of supported catalyst

[0334] 6.0 kg of the toluene solution was added to a 20 L stainless steel (sus) high pressure reactor, and the reactor temperature was maintained at 40° C. 1000 g of silica (manufactured by Grace Davison, SYLOPOL948) dehydrated at a temperature of 600° C. under vacuum for 12 hours was added to the reactor and fully dispersed, and then 121 g of the first metallocene compound of Synthesis Example 1 dissolved in toluene was added, followed by stirring at 200 rpm for 2 hours at 40° C. Thereafter, stirring was stopped, sedimentation was performed for 30 minutes, and the reaction solution was decanted.

[0335] 2.5 kg of toluene was added to the reactor, and 9.4 kg of 10 wt% methylaluminoxane (MAO) / toluene solution was added thereto, followed by stirring at 200 rpm for 12 hours at 40°C. Thereafter, stirring was stopped, followed by settling for 30 minutes, and then the reaction solution was decanted. After adding 3.0 kg of toluene and stirring for 10 minutes, stirring was stopped, followed by settling for 30 minutes, and then the toluene solution was decanted.

[0336] After 3.0 kg of toluene was added to the reactor, 154 g of the second metallocene compound of Synthesis Example 2 was dissolved in 1 L of toluene solution and added thereto, followed by stirring at 40° C. and 200 rpm for 2 hours.

[0337] A solution was prepared by adding 274 g of the third metallocene compound of Synthesis Example 3 and 1 L of toluene in a flask, and subjected to ultrasonic treatment for 30 minutes. The metallocene compound / toluene solution of Synthesis Example 3 prepared in this manner was added to a reactor and stirred at 200 rpm for 2 hours at 40 ° C for reaction. After the reactor temperature was lowered to room temperature, stirring was stopped, sedimentation was performed for 30 minutes, and the reaction solution was decanted. At this time, the first metallocene compound of Synthesis Example 1, the second metallocene compound of Synthesis Example 2, and the third metallocene compound of Synthesis Example 3 were used in a molar ratio of 2: 3: 5.

[0338] 2.0 kg of toluene was added to the reactor and stirred for 10 minutes. Then the stirring was stopped, and then settled for 30 minutes, and then the reaction solution was decanted.

[0339] 3.0 kg of hexane was added to the reactor, and the hexane slurry was transferred to a filter dryer to filter the hexane solution. 1 kg of the SiO2 mixed supported catalyst was prepared by drying under reduced pressure at 40°C for 4 hours.

[0340] Comparative Preparation Example 1: Preparation of Supported Catalyst

[0341] 5.0 kg of the toluene solution was added to a 20 L stainless steel (sus) high pressure reactor, and the reactor temperature was maintained at 40° C. 1000 g of silica (manufactured by Grace Davison, SYLOPOL948) dehydrated at a temperature of 600° C. under vacuum for 12 hours was added to the reactor and fully dispersed, and then 84 g of the metallocene compound of Synthesis Example 1 dissolved in toluene was added, followed by stirring at 200 rpm for 2 hours at 40° C. Thereafter, stirring was stopped, sedimentation was performed for 30 minutes, and the reaction solution was decanted.

[0342] 2.5 kg of toluene was added to the reactor, and 9.4 kg of 10 wt% methylaluminoxane (MAO) / toluene solution was added thereto, followed by stirring at 200 rpm for 12 hours at 40°C. Thereafter, stirring was stopped, followed by settling for 30 minutes, and then the reaction solution was decanted. After adding 3.0 kg of toluene and stirring for 10 minutes, stirring was stopped, followed by settling for 30 minutes, and then the toluene solution was decanted.

[0343] After adding 3.0 kg of toluene to the reactor, 116 g of the metallocene compound of Synthesis Example 2 was dissolved in 1 L of toluene solution and added thereto, and then stirred at 200 rpm for 2 hours at 40 ° C. After the reactor temperature was lowered to room temperature, stirring was stopped, sedimentation was performed for 30 minutes, and the reaction solution was decanted. At this time, the first metallocene compound of Synthesis Example 1 and the second metallocene compound of Synthesis Example 2 were used in a molar ratio of about 1.5:2.35.

[0344] 2.0 kg of toluene was added to the reactor and stirred for 10 minutes. Then the stirring was stopped, and then settled for 30 minutes, and then the reaction solution was decanted.

[0345] 3.0 kg of hexane was added to the reactor, and the hexane slurry was transferred to a filter dryer to filter the hexane solution. 1 kg of the SiO2 mixed supported catalyst was prepared by drying under reduced pressure at 40°C for 4 hours.

[0346] Comparative Preparation Example 2: Preparation of Supported Catalyst

[0347] 5.0 kg of the toluene solution was added to a 20 L stainless steel (sus) high pressure reactor, and the reactor temperature was maintained at 40° C. 1000 g of silica (manufactured by Grace Davison, SYLOPOL948) dehydrated at a temperature of 600° C. under vacuum for 12 hours was added to the reactor and fully dispersed, and then 121 g of the metallocene compound of Synthesis Example 1 dissolved in toluene was added, followed by stirring at 200 rpm for 2 hours at 40° C. Thereafter, stirring was stopped, sedimentation was performed for 30 minutes, and the reaction solution was decanted.

[0348] 2.5 kg of toluene was added to the reactor, and 9.4 kg of 10 wt% methylaluminoxane (MAO) / toluene solution was added thereto, followed by stirring at 200 rpm for 12 hours at 40°C. Thereafter, stirring was stopped, followed by settling for 30 minutes, and then the reaction solution was decanted. After adding 3.0 kg of toluene and stirring for 10 minutes, stirring was stopped, followed by settling for 30 minutes, and then the toluene solution was decanted.

[0349] After adding 3.0 kg of toluene to the reactor, 274 g of the metallocene compound of Synthesis Example 3 was dissolved in 1 L of toluene solution and added thereto, and then stirred at 200 rpm for 2 hours at 40 ° C. After the reactor temperature was lowered to room temperature, stirring was stopped, sedimentation was performed for 30 minutes, and the reaction solution was decanted. At this time, the first metallocene compound of Synthesis Example 1 and the third metallocene compound of Synthesis Example 3 were used in a molar ratio of about 2:5.

[0350] 2.0 kg of toluene was added to the reactor and stirred for 10 minutes. Then the stirring was stopped, and then settled for 30 minutes, and then the reaction solution was decanted.

[0351] 3.0 kg of hexane was added to the reactor, and the hexane slurry was transferred to a filter dryer to filter the hexane solution. 1 kg of the SiO2 mixed supported catalyst was prepared by drying under reduced pressure at 40°C for 4 hours.

[0352] Comparative Preparation Example 3: Preparation of Supported Catalyst

[0353] 3.0kg toluene solution is added to 20L stainless steel (sus) high pressure reactor, and reactor temperature is maintained at 40 ℃.500g silica (SP2212, manufactured by Grace Davison) dehydrated for 12 hours under vacuum at a temperature of 600 ℃ is added to reactor and fully dispersed, then 2.78kg 10 wt % methylaluminoxane (MAO) / toluene solution is added thereto, then stirred at 80 ℃ for more than 15 hours with 200rpm.After reactor temperature is reduced to 40 ℃, 300g7.5 wt % synthesis example 1 / toluene solution is added to reactor and stirred at 200rpm for 1 hour.Then, 250g8.8 wt % synthesis example 3 / toluene solution is added to reactor and stirred at 200rpm for 1 hour.Comparative synthesis example 1 (20g) is dissolved in toluene, then added to reactor, then stirred at 200rpm for 2 hours. 70g of co-catalyst (aniline tetrakis (pentafluorophenyl) borate) was diluted in toluene, then added to the reactor, and then stirred at 200rpm for more than 15 hours. After the reactor temperature was lowered to room temperature, stirring was stopped, and then sedimentation for 30 minutes and the reaction solution was decanted. The toluene slurry was transferred to a filter dryer and filtered. After adding 3.0kg toluene and stirring for 10 minutes, stirring was stopped and filtered. After adding 3.0kg hexane to the reactor and stirring for 10 minutes, stirring was stopped and filtered. It was dried under reduced pressure at 50°C for 4 hours to prepare a 500g-SiO2 mixed supported catalyst.

[0354] [Preparation of polyethylene]

[0355] Example 1-1

[0356] The supported catalyst prepared in Preparation Example 1 was added to a single slurry polymerization process to prepare high density polyethylene.

[0357] First, go 100m 3 The reactor was charged with 25 ton / hr of hexane, 10 ton / hr of ethylene and 10 kg / hr of triethylaluminum (TEAL), and the supported mixed metallocene catalyst of Preparation Example 1 was injected into the reactor at 0.5 kg / hr. The polymerization process was carried out while introducing 800 g / hr of hydrogen, and the hydrogen input amount was 80 ppm based on the ethylene content. Thereafter, ethylene was added at a reactor temperature of 82°C and a pressure of 7.0 kg / cm 2 Up to 7.5kg / cm 2 The reaction was continued in a hexane slurry state under a pressure of . Then, the solvent was removed and dried to prepare a high-density polyethylene of Example 1-1 in a powder form.

[0358] Example 1-2

[0359] The high density polyethylene of Example 1-2 was prepared in the same manner as Example 1-1, except that the supported catalyst prepared in Preparation Example 2 was added to the single slurry polymerization process instead of the supported catalyst prepared in Preparation Example 1.

[0360] Example 3

[0361] High density polyethylene was prepared by adding the supported catalyst prepared in Preparation Example 1 to a single slurry polymerization process.

[0362] First, go 100m 3 The reactor was charged with 25 tons / hr of hexane, 10 tons / hr of ethylene and 10 kg / hr of triethylaluminum (TEAL), and the supported mixed metallocene catalyst of Preparation Example 1 was injected into the reactor at 0.5 kg / hr. The polymerization process was carried out while introducing 800 g / hr of hydrogen, and the hydrogen input was 80 ppm based on the ethylene content. The polymerization process was carried out while adding 1-hexene, and the 1-hexene comonomer content was 1.5 weight % based on the ethylene content.

[0363] Thereafter, ethylene was added at a reactor temperature of 82°C and a flow rate of 7.0 kg / cm 2 Up to 7.5kg / cm 2 The reaction was continued in a hexane slurry state under a pressure of . Then, the solvent was removed and dried to prepare the high-density polyethylene of Examples 1-3 in powder form.

[0364] Examples 1-4

[0365] The high density polyethylene of Examples 1-4 was prepared in the same manner as Examples 1-3, except that the supported catalyst prepared in Preparation Example 2 was added to the single slurry polymerization process instead of the supported catalyst prepared in Preparation Example 1.

[0366] Comparative Example 1-1

[0367] The melt index (MI) prepared using a Ziegler-Natta (Z / N) catalyst (CE2030K, manufactured by LG Chem) was 2.16 A commercially available high-density polyethylene (HDPE) with a molecular weight of 0.37 g / 10 min (190°C, 2.16 kg) was used as Comparative Example 1-1.

[0368] Comparative Example 1-2

[0369] The melt index (MI) prepared using a Ziegler-Natta (Z / N) catalyst (CE2080, manufactured by LG Chem) was 2.16 A commercially available high-density polyethylene (HDPE) with a molecular weight of 0.35 g / 10 min (190°C, 2.16 kg) was used as Comparative Example 1-2.

[0370] Comparative Examples 1-3

[0371] The high density polyethylene of Comparative Example 1-3 was prepared in the same manner as Example 1-1, except that the supported catalyst of Comparative Preparation Example 1 without the metallocene compound of Synthesis Example 3 was added to the single slurry polymerization process instead of the supported catalyst prepared in Preparation Example 1.

[0372] Comparative Examples 1-4

[0373] The melt index (MI) of the prepared Ziegler-Natta (Z / N) catalyst was 2.16 , 190°C, 2.16kg) of 0.59g / 10min high density polyethylene (HDPE) was used as Comparative Examples 1-4.

[0374] Comparative Examples 1-5

[0375] High density polyethylenes of Comparative Examples 1-5 were prepared in the same manner as Example 1, except that the supported catalyst of Comparative Preparation Example 2 without the metallocene compound of Synthesis Example 2 was added to the single slurry polymerization process instead of the supported catalyst prepared in Preparation Example 1.

[0376] Comparative Examples 1-6

[0377] The high density polyethylene of Comparative Examples 1 to 6 was prepared using the mixed supported metallocene catalyst of Comparative Preparation Example 3 and 1-butene as a comonomer using a hexane slurry stirred tank polymerization reactor. Here, two reactors (reactors R1 and R2) were used for bimodal operation.

[0378] Specifically, in the first reactor R1, the ethylene input was 7.0 kg / hr and the pressure was 7.5 kg / cm 2 , the temperature was 84.4°C, the hydrogen input was 3.1 g / hr, in the second reactor R2, the ethylene input was 6.0 kg / hr, and the pressure was 4.7 kg / cm 2 , the temperature was 75.2°C, and the comonomer 1-butene input was 18.0 g / hr.

[0379] <Test Example 1: Evaluation of Physical Properties of Polyethylene>

[0380] The physical properties of the polyethylenes prepared in Examples and Comparative Examples were measured by the following methods and are shown in Table 1.

[0381] (1) Melt index

[0382] Melt Index (MI 2.16 ) and melt index (MI 21.6) are measured according to ASTM D 1238 (Condition E) of the American Society for Testing and Materials at 190°C under loads of 2.16 kg and 21.6, respectively, and are expressed as the weight (g) of the polymer melted for 10 minutes.

[0383] (2) Melt flow rate ratio

[0384] Melt flow rate ratio (MI 21.6 / MI 2.16 , MFRR) by dividing MI 21.6 Melt index (MI, 21.6 kg load) divided by MI 2.16 (MI, 2.16 kg load).

[0385] (3) Density

[0386] The density of polyethylene (g / cm2) was measured according to ASTM D 1505. 3 ).

[0387] (4)ESCR

[0388] The time required to reach F50 (50% failure) was measured according to ASTM D 1693 using a 10% Igepal CO-630 solution at a temperature of 50°C.

[0389] (5)NCLS

[0390] The time required to reach F50 (50% failure) was measured according to ASTM F 2136 using a 10% Igepal CO-630 solution at a temperature of 50°C.

[0391] (6) Weight average molecular weight, polydispersity index (PDI, Mw / Mn), and Log MW (5.0 or more and 4.0 or less) ratio by GPC analysis

[0392] The weight average molecular weight (Mw) and the number average molecular weight (Mn) were measured by gel permeation chromatography (GPC, manufactured by Water), and the molecular weight distribution (PDI, Mw / Mn) was determined by dividing the weight average molecular weight by the number average molecular weight.

[0393] Specifically, a PL-GPC220 manufactured by Waters was used as a gel permeation chromatography (GPC) instrument, and a Polymer Laboratories PLgelMIX-B 300 mm long column was used. The evaluation temperature was 160 ° C, and the solvent used 1,2,4-trichlorobenzene at a flow rate of 1 mL / min. Each polymer sample of the embodiment and the comparative example was pretreated by dissolving in 1,2,4-trichlorobenzene containing 0.0125% butylated hydroxytoluene (BHT) at 160 ° C for 10 hours using a GPC analyzer (PL-GP220), and a sample with a concentration of 10 mg / 10 mL was supplied in an amount of 200 μL. Mw and Mn were obtained using a calibration curve formed using a polystyrene standard. Nine polystyrene standards were used with molecular weights of 2000 g / mol, 10000 g / mol, 30000 g / mol, 70000 g / mol, 200000 g / mol, 700000 g / mol, 2000000 g / mol, 4000000 g / mol and 10000000 g / mol.

[0394] In addition, in the log diagram of the weight average molecular weight (Mw) of the polyethylene measured in this manner, that is, in the GPC curve diagram with logMW on the x-axis and dw / dlogMw on the y-axis, the ratio of the integrated value in the region where Log MW is 5.0 or more to the total integrated value (HHw, unit: %) and the ratio of the integrated value in the region where Log MW is 4.0 or less to the total integrated value (LMw, unit: %) were calculated and shown in the following Table 1.

[0395] [Table 1]

[0396]

[0397] Referring to Table 1, it was confirmed that the polyethylene of Examples 1-1 to 1-4 of the present disclosure used a catalyst containing all three metallocene compounds of Synthesis Examples 1 to 3 to enhance the high molecular area ratio and maintain the low molecular area ratio in the molecular structure, thereby optimizing the molecular weight distribution and the weight average molecular weight.

[0398] [Preparation of polyethylene composition mixed with recycled polyethylene]

[0399] The high-density polyethylene prepared in one of the examples and comparative examples and a recycled polyethylene resin (PCR, manufactured by Byucksan Plastics, with a melt index MI measured at 190° C. and a load of 2.16 kg) were mixed. 2.16 : 0.4 to 0.7 g / 10min, density: 0.940 to 0.960 g / cm 3) were mixed at 30 wt % to 50 wt % and 70 wt % to 50 wt %, respectively. Then, the physical properties were evaluated in the same manner as previously described in the evaluation of the physical properties of polyethylene, and the measurement results are shown in Table 2 below.

[0400] [Table 2]

[0401]

[0402] Referring to Table 2, it can be seen that when polyethylene prepared using a catalyst containing all three metallocene compounds of Synthesis Examples 1 to 3 is used in Examples 2-1 to 2-8 of the present disclosure, the molecular weight distribution and weight average molecular weight can be optimized while enhancing the high molecular area ratio and maintaining the low molecular area ratio in the molecular structure. Therefore, even if the content of recycled polyethylene resin (PCR) is increased, the notched constant toughness stress (NCLS), which is an indicator of mechanical properties such as environmental stress crack resistance (ESCR), can be significantly improved, while the compatibility with recycled polyethylene is excellent.

Claims

1. A polyethylene that meets the following conditions: The integrated value in the region where log Mw is 5.0 or more in the GPC graph where the x-axis is logMw and the y-axis is dw / dlogMw is 60% or more of the total integrated value, The molecular weight distribution (Mw / Mn) is 7 or more, and The weight average molecular weight is 300000 g / mol or more.

2. The polyethylene according to claim 1, in, The polyethylene is an ethylene homopolymer or an ethylene / α-olefin copolymer.

3. The polyethylene according to claim 1, in, The polyethylene has an integrated value in a region where Log Mw is 5.0 or more in a GPC graph where the x-axis represents logMw and the y-axis represents dw / dlogMw, which is 60% or more and less than 90% of the total integrated value.

4. The polyethylene according to claim 1, in, The polyethylene has an integrated value in a region where Log Mw is 4.0 or less in a GPC graph where the x-axis is logMw and the y-axis is dw / dlogMw, which is 20% or less and 10% or more of the total integrated value.

5. The polyethylene according to claim 1, in, The molecular weight distribution (Mw / Mn) of the polyethylene is 7 to 13.

6. The polyethylene according to claim 1, in, The weight average molecular weight of the polyethylene is 300,000 g / mol to 1,000,000 g / mol.

7. The polyethylene according to claim 1, in, The melt index (MI) of the polyethylene measured according to ASTM D 1238 at 190°C and a load of 2.16 kg is 2.16 ) is 0.1g / 10min to 0.7g / 10min.

8. The polyethylene according to claim 1, in, The melt flow rate ratio (MFR) of the polyethylene measured at 190°C according to ASTM D 1238 is 21.6 / MI 2.16 ) is 40 to 80.

9. The polyethylene according to claim 1, in, The density of the polyethylene is 0.940 g / cm 3 Up to 0.957g / cm 3 .

10. The polyethylene according to claim 1, in, The polyethylene has an ESCR measured according to ASTM D 1693 of 120 hours or more.

11. The polyethylene according to claim 1, in, The polyethylene has an NCLS of 11.5 hours or more measured according to ASTM F 2136.

12. A method for preparing polyethylene, the polyethylene being the polyethylene described in any one of claims 1 to 11, the method comprising the step of polymerizing ethylene in the presence of a catalyst, the catalyst comprising at least one first metallocene compound represented by the following chemical formula 1, at least one second metallocene compound represented by the following chemical formula 2, and at least one third metallocene compound represented by the following chemical formula 3: [Chemical formula 1] In Chemical Formula 1, At least one of R1 to R8 is -(CH2) n -OR, where R is C 1-6 A linear or branched alkyl group, wherein n is an integer from 2 to 6, The other R1 to R8 are the same as or different from each other and are each independently selected from hydrogen, halogen, C 1-20 Alkyl, C 2-20 Alkenyl, C 6-20 Aryl, C 7-40 Alkyl aryl and C 7-40 The functional groups in the group consisting of arylalkyl or two or more substituents adjacent to each other may be linked to each other to form a group having no substituent or substituted with C 1-10 Hydrocarbon C 6-20 aliphatic or aromatic ring, Q1 and Q2 are the same or different from each other and are each independently hydrogen, halogen, C 1-20 Alkyl, C 2-20 Alkenyl, C 2-20 Alkoxyalkyl, C 6-20 Aryl, C 7-40 Alkyl aryl or C 7-40 Arylalkyl; A1 is carbon (C), silicon (Si) or germanium (Ge); M1 is a Group IV transition metal; X1 and X2 are the same or different from each other and are each independently halogen, C 1-20 Alkyl, C 2-20 Alkenyl, C 6-20 Aryl, nitro, acylamino, C 1-20 Alkylsilyl, C 1-20 Alkoxy or C 1-20 a sulfonate group; and m is 0 or 1, [Chemical formula 2] In chemical formula 2, Q3 and Q4 are the same or different from each other and are each independently hydrogen, halogen, C 1-20 Alkyl, C 2-20 Alkenyl, C 2-20 Alkoxyalkyl, C 6-20 Aryl, C 7-40 Alkyl aryl or C 7-40 Arylalkyl; A2 is carbon (C), silicon (Si) or germanium (Ge); M2 is a Group IV transition metal; X3 and X4 are the same or different from each other and are each independently halogen, C 1-20 Alkyl, C 2-20 Alkenyl, C 6-20 Aryl, nitro, acylamino, C 1-20 Alkylsilyl, C 1-20 Alkoxy or C 1-20 a sulfonate group; and Either one of C1 and C2 is represented by the following chemical formula 2a or 2b, and the other of C1 and C2 is represented by the following chemical formula 2c, 2d or 2e, [Chemical formula 2a] [Chemical formula 2b] [Chemical formula 2c] [Chemical formula 2d] [Chemical formula 2e] In Formulae 2a, 2b, 2c, 2d and 2e, R9 to R 39 and R9' to R 21 ' are the same or different from each other and are each independently hydrogen, halogen, C 1-20 Alkyl, C 1-20 Haloalkyl, C 2-20 Alkenyl, C 1-20 Alkylsilyl, C 1-20 Alkylsilylalkylene, C 1-20 Alkoxysilyl, C 1-20 Alkoxy, C 6-20 Aryl, C 7-40 Alkyl aryl or C 7-40 Arylalkyl, provided that R 17 To R 21 and R 17 'To R 21 At least one of them is C 1-20 Haloalkyl, R 22 To R 39 Two or more substituents adjacent to each other in the formula may be linked to each other to form a group having no substituent or substituted with C 1-10 Hydrocarbon C 6-20 an aliphatic or aromatic ring; and * indicates the sites that bind to A2 and M2, [Chemical formula 3] In chemical formula 3, Q5 and Q6 are the same or different from each other and are each independently hydrogen, halogen, C 1-20 Alkyl, C 2-20 Alkenyl, C 2-20 Alkoxyalkyl, C 6-20 Aryl, C 7-40 Alkyl aryl or C 7-40 Arylalkyl; A3 is carbon (C), silicon (Si) or germanium (Ge); M3 is a Group IV transition metal; X5 and X6 are the same or different from each other and are each independently halogen, C 1-20 Alkyl, C 2-20 Alkenyl, C 6-20 Aryl, nitro, acylamino, C 1-20 Alkylsilyl, C 1-20 Alkoxy or C 1-20 a sulfonate group; and Any one of C3 and C4 is represented by Chemical Formula 3a, 3b or 3c, provided that at least one of C3 and C4 is not represented by Chemical Formula 3c, [Chemical formula 3a] [Chemical formula 3b] [Chemical formula 3c] In Formulae 3a and 3b, R 40 To R 47 and R 40 'To R 47 ' are the same or different from each other and are each independently hydrogen, halogen, C 1-20 Alkyl, C 1-20 Haloalkyl, C 2-20 Alkenyl, C 1-20 Alkylsilyl, C 1-20 Alkylsilylalkylene, C 1-20 Alkoxysilyl, C 1-20 Alkoxy, C 6-20 Aryl, C 7-40 Alkyl aryl or C 7-40 arylalkyl, and R 48 and R 48 ' are the same or different from each other and are each independently C 1-20 Alkyl, C 1-20 Alkylsilyl, C 1-20 Alkylsilylalkylene, C 1-20 Alkoxysilyl or C 1-20 Alkoxy; In Formula 3c, R 49 To R 56 are the same or different from each other and are each independently hydrogen, halogen, C 1-20 Alkyl, C 1-20 Haloalkyl, C 2-20 Alkenyl, C 1-20 Alkylsilyl, C 1-20 Alkylsilylalkylene, C 1-20 Alkoxysilyl, C 1-20 Alkoxy, C 6-20 Aryl, C 7-40 Alkyl aryl or C 7-40 Arylalkyl, or R 49 To R 56 Two or more substituents adjacent to each other in the ring may be connected to each other to form an aliphatic ring which may be substituted or not substituted, or an aromatic ring which may be substituted or not substituted; and * indicates the sites binding to A3 and M3.

13. The method for preparing polyethylene according to claim 12, in, The first metallocene compound is represented by any one of the following chemical formulas 1-1 to 1-4: [Chemical formula 1-1] [Chemical formula 1-2] [Chemical formula 1-3] [Chemical formula 1-4] In Chemical Formulas 1-1 to 1-4, Q1, Q2, A1, M1, X1, X2 and R1 to R8 are as defined in claim 12, and R' and R" are the same or different from each other and are each independently hydrogen or C 1-10 Hydrocarbon.

14. The method for preparing polyethylene according to claim 12, in, R3 and R6 are C 1-6 Alkyl, or C 1-6 Alkoxy substituted C 2-6 alkyl.

15. The method for preparing polyethylene according to claim 12, in, The second metallocene compound is represented by the following chemical formula 2-1: [Chemical formula 2-1] In chemical formula 2-1, Q3, Q4, A2, M2, X3, X4, R 11 , R 17 To R 21 and R 22 To R 29 As defined in claim 12.

16. The method for preparing polyethylene according to claim 12, in, R 17 To R 21 and R 17 'To R 21 'Each is hydrogen or C 1-6 haloalkyl, provided that R 17 To R 21 and R 17 'To R 21 At least one of them is C 1-6 Halogenated alkyl.

17. The method for preparing polyethylene according to claim 12, in, The third metallocene compound is represented by the following chemical formula 3-1: [Chemical formula 3-1] In chemical formula 3-1, Q5, Q6, A3, M3, X5, X6, R 45 , R 48 and R 49 To R 56 As defined in claim 12.

18. The method for preparing polyethylene according to claim 12, in, R 45 and R 45 'Each is hydrogen, halogen, C 1-6 Alkyl or C 1-6 Alkoxy.

19. The method for preparing polyethylene according to claim 12, in, R 48 and R 48 'Each is C 1-6 Alkyl, C 1-6 Alkylsilyl, C 1-6 Alkylsilylalkylene or C 6-12 Aryl.

20. The method for preparing polyethylene according to claim 12, in, The molar ratio of the second metallocene compound based on the mole number of the first metallocene compound is 1:1 to 1:3, and A molar ratio of the third metallocene compound based on the mole number of the first metallocene compound is 1:2 to 1:

8.

21. The method for preparing polyethylene according to claim 12, in, The polymerization step is carried out by introducing 70 ppm to 120 ppm of hydrogen based on the ethylene content.

22. A polyethylene composition comprising the polyethylene of any one of claims 1 to 11 and a recycled polyethylene resin (PCR).

23. The polyethylene composition according to claim 22, in, The content of the recycled polyethylene resin (PCR) is 10 wt % to 90 wt %.

24. The polyethylene composition according to claim 22, in, The density of the recycled polyethylene resin (PCR) is 0.940 g / cm 3 Up to 0.960g / cm 3 .

25. The polyethylene composition according to claim 22, in, The polyethylene composition has a NCLS of 7 hours or more measured according to ASTM F 2136.

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