Hybrid supported metallocene catalyst and method for producing the same

Abstract

This invention relates to a hybrid supported metallocene catalyst and a method for producing the same. By using a catalyst produced by altering the loading order of three transition metal compounds having specific content among four transition metal compounds, a polyolefin with a broad molecular weight distribution can be obtained.

Description

[Technical Field]

[0001] This invention relates to a hybrid supported metallocene catalyst and a method for producing the same. [Background technology]

[0002] Ziegler-Natta catalysts, which are widely used in existing commercial processes, are multi-site catalysts. As a result, when using them for olefin polymerization, a wide molecular weight distribution is observed in the resulting polymer. This means that the compositional distribution of the polymerized comonomer is not uniform, making it difficult to achieve olefin polymerization with the desired physical properties.

[0003] On the other hand, metallocene catalysts are single-site catalysts with only one type of active site, and have the advantage that the molecular weight, stereoregularity, crystallinity, and especially the reactivity of the comonmer of the resulting polymer can be greatly adjusted by the structure of the catalyst and ligand. However, polyolefins polymerized with metallocene catalysts have a narrow molecular weight distribution, and when applied to some products, they present problems in terms of practical application, such as a significant drop in productivity due to the effects of extrusion load.

[0004] To overcome these technical challenges, research is focused on developing catalysts or processes that can control the molecular weight distribution of polyolefins during polymerization.

[0005] In particular, while it is common to hybridize two types of catalysts, if the properties of the catalysts are very similar, it becomes difficult to achieve targets such as a broad molecular weight distribution. [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] KR10-2455178B [Overview of the Initiative] [Problems that the invention aims to solve]

[0007] The objective is to provide a method for producing a hybrid supported metallocene catalyst by changing the loading order for three of four transition metal compounds having specific formulas and specific contents, and to provide the hybrid supported metallocene catalyst produced by this method. [Means for solving the problem]

[0008] 1. One aspect of the present invention relates to a method for producing a hybrid supported metallocene catalyst. A method for producing a hybrid supported metallocene catalyst according to one embodiment includes the steps of: producing a first catalyst compound solution containing one or two selected from the group consisting of a first transition metal compound represented by formula 1, a second transition metal compound represented by formula 2, a third transition metal compound represented by formula 3, and a fourth transition metal compound represented by formula 4; producing a second catalyst compound solution containing one or two transition metal compounds from the group consisting of the first to fourth transition metal compounds that are not included in the first catalyst compound solution; producing a transition metal-carrier composite by supporting the first catalyst compound solution on a carrier; and further supporting the second catalyst compound solution on the transition metal-carrier composite.

[0009] The hybrid supported metallocene catalyst comprises three compounds selected from the first transition metal compound, the second transition metal compound, the third transition metal compound, and the fourth transition metal compound.

[0010] [Formula 1]

[0011] [ka]

[0012] (In the above formula 1, R 1 and R 2 These are, independently, hydrogen, substituted or unsubstituted C 1-20 Alkyl, substituted or unsubstituted C 2-20 Alkenyl, substituted or unsubstituted C 6-20 Aryl, substituted, or unsubstituted C 1-20 Alkyl, substituted or unsubstituted C1-20 heteroalkyl, substituted or unsubstituted C 3-20 heteroaryl, substituted or unsubstituted C 1-20 alkylamide, substituted or unsubstituted C 6-20 arylamide, substituted or unsubstituted C 1-20 alkylidene, or substituted or unsubstituted C 1-20 is silyl, X is independently halogen, C 1-20 alkyl, C 2-20 alkenyl, C 2-20 alkynyl, C 6-20 aryl, C 1-20 alkyl, C 1-20 alkylamide, C 6-20 arylamide, or C 1-20 alkylidene, M is titanium (Ti), zirconium (Zr), or hafnium (Hf), and n, m are independently integers from 0 to 5.)

[0013] [Formula 2]

[0014] [Chemical Formula]

[0015] (In the above Formula 2, R 3 and R 4 are independently hydrogen, substituted or unsubstituted C 1-20 alkyl, substituted or unsubstituted C 2-20 alkenyl, substituted or unsubstituted C 6-20 aryl, substituted or unsubstituted C 6-20 aryl C 1-20 alkyl, substituted or unsubstituted C 1-20 heteroalkyl, substituted or unsubstituted C 3-20 heteroaryl, substituted or unsubstituted C 1-20 alkylamide, substituted or unsubstituted C 6-20 arylamide, substituted or unsubstituted C 1-20 alkylidene, or substituted or unsubstituted C1-20 Cyril, X is independently halogen, C 1-20 Alkyl, C 2-20 Alkenil, C 2-20 Alkinyl, C 6-20 Ariel, C 6-20 Aryl C 1-20 Alkyl, C 1-20 Alkylamide, C 6-20 Arylamide, or C 1-20 It is alkyridene, M is titanium (Ti), zirconium (Zr), or hafnium (Hf), and (where l is an integer from 1 to 6, and k is an integer from 0 to 4) [Formula 3]

[0016] [ka]

[0017] (In the above formula 3, R 5 ~R 9 These are, independently, hydrogen, substituted or unsubstituted C 1-20 Alkyl, substituted or unsubstituted C 2-20 Alkenyl, substituted or unsubstituted C 6-20 Aryl, substituted, or unsubstituted C 6-20 Aryl C 1-20 Alkyl, substituted or unsubstituted C 1-20 Heteroalkyl, substituted or unsubstituted C 3-20 Heteroaryl, substituted or unsubstituted C 1-20 Alkylamide, substituted or unsubstituted C 6-20 Arylamides, substituted or unsubstituted C 1-20 Alkylidenes, or substituted or unsubstituted C 1-20 Cyril, X is independently halogen, C 1-20 Alkyl, C 2-20 Alkenil, C 2-20 Alkinyl, C 6-20 Ariel, C 6-20 Aryl C 1-20 Alkyl, C1-20 Alkylamide, C 6-20 Arylamide, or C 1-20 It is alkyridene, M is titanium (Ti), zirconium (Zr), or hafnium (Hf). A is carbon (C), silicon (Si), germanium (Ge), or tin (Sn), and i and j are independent integers between 0 and 4. [Formula 4]

[0018] [ka]

[0019] (In the above formula 4, R 10 ~R 13 These are, independently, hydrogen, substituted or unsubstituted C 1-20 Alkyl, substituted or unsubstituted C 2-20 Alkenyl, substituted or unsubstituted C 6-20 Aryl, substituted, or unsubstituted C 6-20 Aryl C 1-20 Alkyl, substituted or unsubstituted C 1-20 Heteroalkyl, substituted or unsubstituted C 3-20 Heteroaryl, substituted or unsubstituted C 1-20 Alkylamide, substituted or unsubstituted C 6-20 Arylamides, substituted or unsubstituted C 1-20 Alkylidenes, or substituted or unsubstituted C 1-20 Cyril, X is independently halogen, C 1-20 Alkyl, C 2-20 Alkenil, C 2-20 Alkinyl, C 6-20 Ariel, C 6-20 Aryl C 1-20 Alkyl, C 1-20 Alkylamide, C 6-20 Arylamide, or C 1-20 It is alkyridene, M is titanium (Ti), zirconium (Zr), or hafnium (Hf). A is carbon (C), silicon (Si), germanium (Ge), or tin (Sn), and h is an integer between 0 and 4.

[0020] 2. In the specific example of paragraph 1 above, the hybrid supported metallocene catalyst may include a first transition metal compound, a third transition metal compound, and a fourth transition metal compound.

[0021] 3. In the specific examples of 1 and 2 above, the method for producing the hybrid supported metallocene catalyst may have a molar ratio of the first transition metal compound:third transition metal compound:fourth transition metal compound of approximately 3 to 5:approximately 1 to 2:approximately 4 to 6. In the specific examples, the molar ratio of the first transition metal compound:third transition metal compound:fourth transition metal compound may be approximately 3.1 to 4.9:approximately 1.1 to 1.9:approximately 4.2 to 5.9, for example, approximately 3.2 to 3.8:approximately 1.6 to 1.9:approximately 5.3 to 5.9, approximately 3.8 to 4.4:approximately 1 to 1.6:approximately 4.8 to 5.3, and approximately 4.4 to 4.9:approximately 1.1 to 1.5:approximately 4.2 to 4.8.

[0022] 4. In the specific example of paragraph 1 above, the hybrid supported metallocene catalyst may include the second transition metal compound, the third transition metal compound, and the fourth transition metal compound.

[0023] 5. In the specific examples of 1 to 4 above, the method for producing the hybrid supported metallocene catalyst may have a molar ratio of the second transition metal compound:third transition metal compound:fourth transition metal compound of approximately 3 to 5:approximately 1 to 2:approximately 4 to 6. In the specific examples, the molar ratio of the second transition metal compound:third transition metal compound:fourth transition metal compound may be approximately 3.1 to 4.9:approximately 1.1 to 1.9:approximately 4.2 to 5.9, for example, approximately 3.2 to 3.8:approximately 1.6 to 1.9:approximately 5.3 to 5.9, approximately 3.8 to 4.4:approximately 1 to 1.6:approximately 4.8 to 5.3, and approximately 4.4 to 4.9:approximately 1.1 to 1.5:approximately 4.2 to 4.8.

[0024] 6. According to the specific examples in 1 to 5 above, in formula 1, R 1and R 2 is independently C 1-20 alkyl, X is independently halogen, and n is 1, m is 4; in said Formula 2, R 3 and R 4 are independently hydrogen, X is independently halogen, and k is 0, l is 2; in said Formula 3, R 5 and R 6 are independently C 6-20 aryl, R 7 ~R 9 are independently C 1-20 alkyl, X is independently halogen, and i and j are independently 1; and in said Formula 4, R 10 and R 11 are independently C 6-20 aryl, R 12 ~R 13 are independently C 1-20 alkyl, X is independently halogen, and h can be 1.

[0025] 7. According to the specific examples of 1 to 6 above, in said Formula 1, Formula 2, Formula 3, and Formula 4, M is zirconium (Zr); and in said Formula 3 and Formula 4, A can be carbon (C).

[0026] 8. Another aspect of the present invention relates to a hybrid-supported metallocene catalyst. The hybrid-supported metallocene catalyst is manufactured according to the specific examples of 1 to 7 above.

[0027] 9. In another specific example, the hybrid-supported metallocene catalyst is a hybrid-supported metallocene catalyst containing three compounds selected from the group consisting of a first transition metal compound represented by the following Formula 1; a second transition metal compound represented by the following Formula 2; a third transition metal compound represented by the following Formula 3; and a fourth transition metal compound represented by the following Formula :4, and the hybrid-supported metallocene catalyst can satisfy the following mathematical formula 2: [Formula 1]

[0028] [Chemical formula]

[0029] (In the above formula 1, R 1 and R 2 These are, independently, hydrogen, substituted or unsubstituted C 1-20 Alkyl, substituted or unsubstituted C 2-20 Alkenyl, substituted or unsubstituted C 6-20 Aryl, substituted, or unsubstituted C 6-20 Aryl C 1-20 Alkyl, substituted or unsubstituted C 1-20 Heteroalkyl, substituted or unsubstituted C 3-20 Heteroaryl, substituted or unsubstituted C 1-20 Alkylamide, substituted or unsubstituted C 6-20 Arylamides, substituted or unsubstituted C 1-20 Alkylidenes, or substituted or unsubstituted C 1-20 Cyril, X is independently halogen, C 1-20 Alkyl, C 2-20 Alkenil, C 2-20 Alkinyl, C 6-20 Ariel, C 6-20 Aryl C 1-20 Alkyl, C 1-20 Alkylamide, C 6-20 Arylamide, or C 1-20 It is alkyridene, M is titanium (Ti), zirconium (Zr), or hafnium (Hf), and n and m are independent integers between 0 and 5. [Formula 2]

[0030] [ka]

[0031] (In the above formula 2, R 3 and R 4 These are, independently, hydrogen, substituted or unsubstituted C 1-20 Alkyl, substituted or unsubstituted C 2-20 Alkenyl, substituted or unsubstituted C 6-20Aryl, substituted, or unsubstituted C 6-20 Aryl C 1-20 Alkyl, substituted or unsubstituted C 1-20 Heteroalkyl, substituted or unsubstituted C 3-20 Heteroaryl, substituted or unsubstituted C 1-20 Alkylamide, substituted or unsubstituted C 6-20 Arylamides, substituted or unsubstituted C 1-20 Alkylidenes, or substituted or unsubstituted C 1-20 Cyril, X is independently halogen, C 1-20 Alkyl, C 2-20 Alkenil, C 2-20 Alkinyl, C 6-20 Ariel, C 6-20 Aryl C 1-20 Alkyl, C 1-20 Alkylamide, C 6-20 Arylamide, or C 1-20 It is alkyridene, M is titanium (Ti), zirconium (Zr), or hafnium (Hf), and (where l is an integer from 1 to 6, and k is an integer from 0 to 4) [Formula 3]

[0032] [ka]

[0033] (In the above formula 3, R 5 ~R 9 These are, independently, hydrogen, substituted or unsubstituted C 1-20 Alkyl, substituted or unsubstituted C 2-20 Alkenyl, substituted or unsubstituted C 6-20 Aryl, substituted, or unsubstituted C 6-20 Aryl C 1-20 Alkyl, substituted or unsubstituted C 1-20 Heteroalkyl, substituted or unsubstituted C 3-20 Heteroaryl, substituted or unsubstituted C 1-20 Alkylamide, substituted or unsubstituted C 6-20Arylamides, substituted or unsubstituted C 1-20 Alkylidenes, or substituted or unsubstituted C 1-20 Cyril, X is independently halogen, C 1-20 Alkyl, C 2-20 Alkenil, C 2-20 Alkinyl, C 6-20 Ariel, C 6-20 Aryl C 1-20 Alkyl, C 1-20 Alkylamide, C 6-20 Arylamide, or C 1-20 It is alkyridene, M is titanium (Ti), zirconium (Zr), or hafnium (Hf). A is carbon (C), silicon (Si), germanium (Ge), or tin (Sn), and i and j are independent integers between 0 and 4. [Formula 4]

[0034] [ka]

[0035] (In the above formula 4, R 10 ~R 13 These are, independently, hydrogen, substituted or unsubstituted C 1-20 Alkyl, substituted or unsubstituted C 2-20 Alkenyl, substituted or unsubstituted C 6-20 Aryl, substituted, or unsubstituted C 6-20 Aryl C 1-20 Alkyl, substituted or unsubstituted C 1-20 Heteroalkyl, substituted or unsubstituted C 3-20 Heteroaryl, substituted or unsubstituted C 1-20 Alkylamide, substituted or unsubstituted C 6-20 Arylamides, substituted or unsubstituted C 1-20 Alkylidenes, or substituted or unsubstituted C 1-20 Cyril, X is independently halogen, C 1-20Alkyl, C 2-20 Alkenil, C 2-20 Alkinyl, C 6-20 Ariel, C 6-20 Aryl C 1-20 Alkyl, C 1-20 Alkylamide, C 6-20 Arylamide, or C 1-20 It is alkyridene, M is titanium (Ti), zirconium (Zr), or hafnium (Hf). A is carbon (C), silicon (Si), germanium (Ge), or tin (Sn), and (h is an integer between 0 and 4) (Math 2) PDI PE ≥31 (In the above formula 2, PDI PE This is the molecular weight distribution (PDI, Mw / Mn) value measured by gel permeation chromatography at a measurement temperature of 170°C for polyethylene polymerized using a hybrid supported metallocene catalyst. 10. In the specific example of the above 9, the hybrid supported metallocene catalyst may include the first transition metal compound, the third transition metal compound, and the fourth transition metal compound.

[0036] 11. In the specific examples of 9-10 above, the molar ratio of the first transition metal compound:third transition metal compound:fourth transition metal compound may be approximately 3-5:1-2:4-6. In the specific examples, the molar ratio of the first transition metal compound:third transition metal compound:fourth transition metal compound may be approximately 3.1-4.9:1.1-1.9:4.2-5.9, for example, approximately 3.2-3.8:1.6-1.9:5.3-5.9, approximately 3.8-4.4:1-1.6:4.8-5.3, and approximately 4.4-4.9:1.1-1.5:4.2-4.8.

[0037] 12. In the specific example of item 9 above, the hybrid supported metallocene catalyst may include a second transition metal compound, a third transition metal compound, and a fourth transition metal compound.

[0038] 13. In the specific example of 12 above, the molar ratio of the second transition metal compound:third transition metal compound:fourth transition metal compound may be approximately 3-5:1-2:4-6. In the specific example, the molar ratio of the second transition metal compound:third transition metal compound:fourth transition metal compound may be approximately 3.1-4.9:1.1-1.9:4.2-5.9, for example, approximately 3.2-3.8:1.6-1.9:5.3-5.9, approximately 3.8-4.4:1-1.6:4.8-5.3, and approximately 4.4-4.9:1.1-1.5:4.2-4.8.

[0039] 14. According to the specific examples in 9-13 above, in formula 1, R 1 and R 2 C is independent 1-20 Alkyl, where X is independently a halogen, and n is 1 and m is 4; in the above formula 2, R 3 and R 4 is independently hydrogen, X is independently a halogen, and k is 0 and l is 2; in the above equation 3, R 5 and R 6 C is independent 6-20 In aryl, R 7 ~R 9 C is independent 1-20 Alkyl, where X is independently a halogen, and i and j are independently 1; and in the above formula 4, R 10 and R 11 C is independent 6-20 In aryl, R 12 ~R 13 C is independent 1-20 It is an alkyl group, X is independently a halogen, and h can be 1.

[0040] 15. In the specific examples of 9 to 14 above, M is zirconium (Zr) in formulas 1 to 4; and A can be carbon (C) in formulas 3 and 4.

[0041] 16. Another aspect of the present invention relates to a method for producing polyolefins. The method for producing polyethylene includes the step of polymerizing an olefin having the following formula 5 in the presence of a hybrid supported metallocene catalyst of the specific examples of 1 to 15 above;

[0042] [Formula 5] CH2=CHR 14 In the above equation 5, R 14 is hydrogen or a C1-C6 alkyl or aryl group. 17. Another aspect of the present invention relates to polyethylene resin. The polyolefin resin is polymerized by adding ethylene monomers in the presence of a mixed-supported metallocene catalyst of the specific examples 1 to 15 above, and the MFR ratio (MFR 21.6 / MFR 2.16 ) is characterized by being approximately 58 to approximately 213. In a specific example, the MFR ratio (MFR 21.6 / MFR 2.16 ) can range from approximately 60 to 211, for example, approximately 61 to 80, approximately 80 to 100, approximately 100 to 120, approximately 120 to 140, approximately 140 to 160, approximately 160 to 180, approximately 180 to 200, and approximately 200 to 213.

[0043] 18. In the specific examples of 17 above, the olefin resin may have an MFR / MFR0 value less than approximately 0.980 or greater than approximately 1.10, according to the following formula 1. In one specific example, the MFR / MFR0 value may be, for example, less than approximately 0.77 to 0.81, approximately 0.81 to 0.84, or approximately 0.84 to 0.975. In another specific example, the MFR / MFR0 value may be greater than approximately 1.105 to 1.25, approximately 1.25 to 1.45, or approximately 1.45 to 1.55.

[0044] (Math 1) MFR / MFR0 (In the above formula 1, MFR is the MFR value of a resin produced with a hybrid supported metallocene catalyst that is supported in order according to the metallocene catalyst production method of the present invention, and MFR0 is the MFR of a resin produced with a hybrid supported metallocene catalyst that is supported simultaneously regardless of order.)

[0045] 19. The polyethylene resins according to the specific examples in 17-18 may have a molecular weight distribution (PDI, Mw / Mn) value of approximately 31 or higher, as measured by gel permeation chromatography at a measurement temperature of 170°C. In the specific examples, the molecular weight distribution (PDI, Mw / Mn) value may be, for example, approximately 31.5-38.5, approximately 38.5-45.5, approximately 45.5-52.5, or approximately 52.5-59.5 or higher.

[0046] 20. Another aspect of the present invention relates to a method for adjusting the physical properties of polyethylene resin using hybrid supported metallocene catalysts according to the specific examples of 9 to 15 above. The method comprises the steps of: setting a target PDI value, MFR value, and Mw value of the polyethylene resin; and selecting a hybrid supported metallocene catalyst that exhibits the set PDI value, MFR value, and Mw value; wherein the step of selecting the hybrid supported metallocene catalyst can be selected from a population of hybrid supported metallocene catalysts produced by changing the order in which three compounds selected from the first transition metal compound, the second transition metal compound, the third transition metal compound, and the fourth transition metal compound are introduced.

[0047] 21. In the specific example of 20 above, if the set Mw value is approximately 100,000 or more, a hybrid supported metallocene catalyst manufactured using the three compounds of the first transition metal compound, the third transition metal compound, and the fourth transition metal compound can be used. If the set Mw value is less than approximately 100,000, a hybrid supported metallocene catalyst manufactured using the three compounds of the second transition metal compound, the third transition metal compound, and the fourth transition metal compound can be used. [Effects of the Invention]

[0048] The method for producing hybrid supported metallocene catalysts has the advantage of being able to produce polyolefins with a broad molecular weight distribution by applying metallocene catalysts prepared by changing the loading order of three of the four transition metal compounds having specific formulas and specific contents, and thus being able to adjust the properties of polyethylene, allowing them to be provided as a variety of target products. [Brief explanation of the drawing]

[0049] [Figure 1] Figure 1 is a graph showing the molecular weight distribution of polyethylene for Examples 1 to 6 and Comparative Example 1.

[0050] [Figure 2] Figure 2 is a graph showing the molecular weight distribution of polyethylene for Examples 7 to 12 and Comparative Example 2. [Modes for carrying out the invention]

[0051] The above objectives, other objectives, features, and advantages will be readily apparent through the attached drawings and the following preferred embodiments. However, the embodiments described herein are not limited to those described herein and can be embodied in other forms. Rather, the embodiments presented herein are provided to ensure that the disclosed content is thorough and complete, and that the technical ideas are fully conveyed to the average person in the art.

[0052] In this specification, terms such as “includes” or “having” indicate the presence of features, numbers, stages, actions, components, parts, or combinations thereof described in the specification, without prejudice to the possibility of the presence or addition of one or more other features, numbers, stages, actions, components, parts, or combinations thereof. Furthermore, when a layer, film, region, plate, etc., is described as being “on top” of another part, this includes not only the case where it is “immediately above” the other part, but also the case where there is yet another part in between. Conversely, when a layer, film, region, plate, etc., is described as being “below” another part, this includes not only the case where it is “immediately below” the other part, but also the case where there is yet another part in between.

[0053] Unless otherwise explicitly stated, all numbers, values, and / or expressions used herein to describe the quantities of components, reaction conditions, polymer compositions, and formulations should be understood to be approximate in all cases, as they reflect the various uncertainties of measurement that arise when obtaining such values ​​among essentially different numbers. Furthermore, where numerical ranges are disclosed herein, such ranges are continuous and, unless otherwise noted, include all values ​​from the minimum to the maximum value within such range. Additionally, where such ranges refer to integers, unless otherwise noted, include all integers from the minimum to the maximum value within such range.

[0054] In this specification, when a range is given for a variable, it can be understood that the variable includes all values ​​within the given range, including the end point of the range. For example, the range "5 to 10" can be understood to include not only the values ​​5, 6, 7, 8, 9, and 10, but also any sub-ranges such as 6 to 10, 7 to 10, 6 to 9, 7 to 9, etc., and any values ​​between integers that are within the range specified, such as 5.5, 6.5, 7.5, 5.5 to 8.5, and 6.5 to 9. Similarly, the range "10% to 30%" can be understood to include not only all integers up to 30% and values ​​such as 10%, 11%, 12%, 13%, etc., but also any sub-ranges such as 10% to 15%, 12% to 18%, 20% to 30%, etc., and any values ​​between integers that are within the range specified, such as 10.5%, 15.5%, 25.5%, etc.

[0055] Conventionally, polyolefins polymerized with metallocene catalysts have a narrow molecular weight distribution, and when applied to certain products, they have problems that make on-site application difficult, such as a significant drop in productivity due to the effects of extrusion load.

[0056] Therefore, the inventors diligently conducted research to solve this problem and, as a result, determined four types of transition metal compounds having specific formula structures. They found that when a hybrid supported metallocene catalyst is produced by changing the loading order of three of these compounds having specific content, it is possible not only to suppress the uneven characteristics of the metallocene catalyst but also to adjust the physical properties of the produced polyolefin, such as the molecular weight distribution, and have now completed this process.

[0057] Unless otherwise specified herein, "C1-C n "Alkyl" refers to primary to tertiary alkyl groups having 1 to n carbon atoms. These alkyl groups can be functional groups such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, tert-butyl, and n-hexyl.

[0058] Unless otherwise specified herein, "aryl" means a monocyclic or polycyclic compound having 2 to 30 carbon atoms containing one or more benzene rings, and a chemical group obtained by removing one hydrogen atom from a derivative thereof. For example, the monocyclic or polycyclic compound containing a benzene ring includes a benzene ring, toluene or xylene with an alkyl side chain attached to a benzene ring, biphenyl in which two or more benzene rings are linked by a single bond, fluorene, xanthene or anthraquinone in which a benzene ring is condensed with a cycloalkyl group or heterocycloalkyl group, and naphthalene or anthracene in which two or more benzene rings are condensed.

[0059] Unless otherwise specified herein, the prefix "hetero" means that one to three heteroatoms selected from the group consisting of -N-, -O-, -S-, and -P- substitute for a carbon atom. For example, these could be pyridine, pyrrole, or carbazole containing a nitrogen atom as a heteroatom; furan or dibenzofuran containing an oxygen atom as a heteroatom; or dibenzothiophene, diphenylamine, etc.

[0060] Unless otherwise specified herein, “halogen” means a Group 17 element, which may be, for example, a fluoro group, a chloro group, a bromo group, or an iodine group.

[0061] A method for producing a hybrid supported metallocene catalyst according to one embodiment includes the steps of: producing a first catalyst compound solution containing one or two selected from the group consisting of a first transition metal compound represented by the following formula 1, a second transition metal compound represented by the following formula 2, a third transition metal compound represented by the following formula 3, and a fourth transition metal compound represented by the following formula 4; producing a second catalyst compound solution containing one or two transition metal compounds from the group consisting of the first to fourth transition metal compounds that are not included in the first catalyst compound solution; producing a transition metal-carrier composite by supporting the first catalyst compound solution on a carrier; and further supporting the second catalyst compound solution on the transition metal-carrier composite.

[0062] [Formula 1]

[0063] [ka]

[0064] (In the above formula 1, R 1 and R 2 These are, independently, hydrogen, substituted or unsubstituted C 1-20 Alkyl, substituted or unsubstituted C 2-20 Alkenyl, substituted or unsubstituted C 6-20 Aryl, substituted, or unsubstituted C 6-20 Aryl C 1-20 Alkyl, substituted or unsubstituted C 1-20 Heteroalkyl, substituted or unsubstituted C 3-20 Heteroaryl, substituted or unsubstituted C 1-20 Alkylamide, substituted or unsubstituted C 6-20 Arylamides, substituted or unsubstituted C 1-20 Alkylidenes, or substituted or unsubstituted C 1-20 Cyril, X is independently halogen, C 1-20 Alkyl, C 2-20 Alkenil, C 2-20 Alkinyl, C 6-20 Ariel, C6-20 Aryl C 1-20 Alkyl, C 1-20 Alkylamide, C 6-20 Arylamide, or C 1-20 It is alkyridene, M is titanium (Ti), zirconium (Zr), or hafnium (Hf), and n and m are independent integers between 0 and 5. [Formula 2]

[0065] [ka]

[0066] (In the above formula 2, R 3 and R 4 These are, independently, hydrogen, substituted or unsubstituted C 1-20 Alkyl, substituted or unsubstituted C 2-20 Alkenyl, substituted or unsubstituted C 6-20 Aryl, substituted, or unsubstituted C 6-20 Aryl C 1-20 Alkyl, substituted or unsubstituted C 1-20 Heteroalkyl, substituted or unsubstituted C 3-20 Heteroaryl, substituted or unsubstituted C 1-20 Alkylamide, substituted or unsubstituted C 6-20 Arylamides, substituted or unsubstituted C 1-20 Alkylidenes, or substituted or unsubstituted C 1-20 Cyril, X is independently halogen, C 1-20 Alkyl, C 2-20 Alkenil, C 2-20 Alkinyl, C 6-20 Ariel, C 6-20 Aryl C 1-20 Alkyl, C 1-20 Alkylamide, C 6-20 Arylamide, or C 1-20 It is alkyridene, M is titanium (Ti), zirconium (Zr), or hafnium (Hf), and (where l is an integer from 1 to 6, and k is an integer from 0 to 4) [Formula 3]

[0067] [ka]

[0068] (In the above formula 3, R 5 ~R 9 These are, independently, hydrogen, substituted or unsubstituted C 1-20 Alkyl, substituted or unsubstituted C 2-20 Alkenyl, substituted or unsubstituted C 6-20 Aryl, substituted, or unsubstituted C 6-20 Aryl C 1-20 Alkyl, substituted or unsubstituted C 1-20 Heteroalkyl, substituted or unsubstituted C 3-20 Heteroaryl, substituted or unsubstituted C 1-20 Alkylamide, substituted or unsubstituted C 6-20 Arylamides, substituted or unsubstituted C 1-20 Alkylidenes, or substituted or unsubstituted C 1-20 Cyril, X is independently halogen, C 1-20 Alkyl, C 2-20 Alkenil, C 2-20 Alkinyl, C 6-20 Ariel, C 6-20 Aryl C 1-20 Alkyl, C 1-20 Alkylamide, C 6-20 Arylamide, or C 1-20 It is alkyridene, M is titanium (Ti), zirconium (Zr), or hafnium (Hf). A is carbon (C), silicon (Si), germanium (Ge), or tin (Sn), and i and j are independent integers between 0 and 4. [Formula 4]

[0069] [ka]

[0070] (In the above formula 4, R 10 ~R 13 These are, independently, hydrogen, substituted or unsubstituted C 1-20 Alkyl, substituted or unsubstituted C 2-20 Alkenyl, substituted or unsubstituted C 6-20 Aryl, substituted, or unsubstituted C 6-20 Aryl C 1-20 Alkyl, substituted or unsubstituted C 1-20 Heteroalkyl, substituted or unsubstituted C 3-20 Heteroaryl, substituted or unsubstituted C 1-20 Alkylamide, substituted or unsubstituted C 6-20 Arylamides, substituted or unsubstituted C 1-20 Alkylidenes, or substituted or unsubstituted C 1-20 Cyril, X is independently halogen, C 1-20 Alkyl, C 2-20 Alkenil, C 2-20 Alkinyl, C 6-20 Ariel, C 6-20 Aryl C 1-20 Alkyl, C 1-20 Alkylamide, C 6-20 Arylamide, or C 1-20 It is alkyridene, M is titanium (Ti), zirconium (Zr), or hafnium (Hf). A is carbon (C), silicon (Si), germanium (Ge), or tin (Sn), and h is an integer between 0 and 4.

[0071] At this time, R 1 ~R 13 The substituents can independently be one or more selected from the group consisting of halogen groups, cyano groups, nitro groups, and C1-C8 alkyl groups.

[0072] According to one example, in formula 1 above, R1 and R 2 C is independent 1-20 It is an alkyl group, where X is independently a halogen, and n can be 1 and m can be 4.

[0073] In the above equation 2, R 3 and R 4 k is independently hydrogen, X is independently a halogen, and k can be 0 and l can be 2.

[0074] In the above equation 3, R 5 and R 6 C is independent 6-20 In aryl, R 7 ~R 9 C is independent 1-20 It is an alkyl group, where X is independently a halogen, and i and j can independently be 1.

[0075] In the above equation 4, R 10 and R 11 C is independent 6-20 In aryl, R 12 ~R 13 C is independent 1-20 It is an alkyl group, X is independently a halogen, and h can be 1.

[0076] In equations 1 to 4, M can be zirconium (Zr), and in equations 3 and 4, A can be carbon (C).

[0077] According to one embodiment, formulas 1 to 4 can become formulas 1-1 to 4-1, respectively.

[0078] [Formula 1-1]

[0079] [ka]

[0080] [Formula 2-1]

[0081] [ka]

[0082] [Formula 3-1]

[0083] [ka]

[0084] [Formula 4-1]

[0085] [ka]

[0086] In one embodiment, a method for producing a hybrid supported metallocene catalyst involves selecting three types of transition metal compounds from the first to fourth transition metal compounds, then separating them into a solution of the first catalyst compound and a solution of the second catalyst compound, and changing the supported order. In this case, the three transition metal compounds can be selected to produce the catalyst in the order of the first, third, and fourth transition metal compounds; or selected to produce the catalyst in the order of the second, third, and fourth transition metal compounds.

[0087] The step of preparing the first catalyst compound solution according to one embodiment is to add one or more compounds selected from the group consisting of first transition metal compounds, second transition metal compounds, third transition metal compounds, and fourth transition metal compounds, along with a co-catalyst compound, to a solvent, and then stir to prepare the solution.

[0088] In the case of selecting and producing a first transition metal compound, a third transition metal compound, and a fourth transition metal compound according to one embodiment, one or two selected from the group consisting of the first transition metal compound, the third transition metal compound, and the fourth transition metal compound can be included in the first catalyst compound solution, preferably containing only one of each of the first transition metal compound, the third transition metal compound, and the fourth transition metal compound; or containing the first transition metal compound and the third transition metal compound, the first transition metal compound and the fourth transition metal compound, or the third transition metal compound and the fourth transition metal compound.

[0089] In the case of selecting and producing a second transition metal compound, a third transition metal compound, and a fourth transition metal compound according to one embodiment, one or two selected from the group consisting of the second transition metal compound, the third transition metal compound, and the fourth transition metal compound can be included in the first catalyst compound solution, preferably containing only one of each of the second transition metal compound, the third transition metal compound, and the fourth transition metal compound; or containing the second transition metal compound and the third transition metal compound, the second transition metal compound and the fourth transition metal compound, or the third transition metal compound and the fourth transition metal compound.

[0090] According to one embodiment, the co-catalyst compound is one that activates the transition metal compound, and can be, for example, an aluminoxane compound, an organo-aluminum compound, or a bulky compound that activates the transition metal compound, and preferably a methylaluminoxane (MAO).

[0091] The content of the co-catalyst compounds may vary depending on the type of transition metal compound. Specifically, the molar ratio of each transition metal compound to the co-catalyst can be approximately 1:100 to 200. In specific examples, the molar ratio of each transition metal compound to the co-catalyst can be approximately 1:102 to 198, for example, approximately 1:105 to 120, approximately 1:120 to 135, approximately 1:135 to 150, approximately 1:150 to 165, approximately 1:165 to 180, and approximately 1:180 to 195. If the content of the co-catalyst compounds is too low, outside of the above range, each transition metal compound will not be sufficiently activated. If the content of the co-catalyst compounds is too high, there will be a shortage of transition metals in the supported catalyst, resulting in low activity of the supported catalyst system.

[0092] According to one embodiment, the solvent may be an aliphatic hydrocarbon solvent such as pentane, hexane, heptane, octane, nonane, decane, undecane, and dodecane; an aromatic hydrocarbon solvent such as benzene, monochlorobenzene, dichlorobenzene, trichlorobenzene, and toluene; a halogenated aliphatic hydrocarbon solvent such as dichloromethane, trichloromethane, dichloroethane, and trichloroethane; an ether solvent such as diethyl ether and tetrahydrofuran; or most organic solvents such as acetone and ethyl acetate; preferably toluene.

[0093] According to one embodiment, the first catalyst compound solution can be stirred for about 10 minutes to about 1 hour at a temperature range of about 0°C to about 100°C, preferably about 0°C to about 70°C, in order to produce the solution.

[0094] According to one example, the step of preparing the second catalyst compound solution can be carried out in the same manner as the preparation process for the first catalyst compound solution. That is, it may involve adding one or more compounds selected from the group consisting of first to fourth transition metal compounds and a co-catalyst compound to an organic solvent, and then stirring to prepare the solution. In this case, the explanation of the second catalyst compound solution may be omitted if it pertains to the first catalyst compound solution.

[0095] According to one embodiment, when selecting and manufacturing a first transition metal compound, a third transition metal compound, and a fourth transition metal compound, a transition metal compound not included in the first catalyst compound solution can be included in the second catalyst compound solution among the group consisting of the first transition metal compound, the third transition metal compound, and the fourth transition metal compound. Preferably, only one kind of each of the first transition metal compound, the third transition metal compound, and the fourth transition metal compound is included; or the first transition metal compound and the third transition metal compound, the first transition metal compound and the fourth transition metal compound, or the third transition metal compound and the fourth transition metal compound can be included.

[0096] According to one embodiment, when selecting and manufacturing a second transition metal compound, a third transition metal compound, and a fourth transition metal compound, a transition metal compound not included in the first catalyst compound solution can be included in the second catalyst compound solution among the group consisting of the second transition metal compound, the third transition metal compound, and the fourth transition metal compound. Preferably, only one kind of each of the second transition metal compound, the third transition metal compound, and the fourth transition metal compound is included; or the second transition metal compound and the third transition metal compound, the second transition metal compound and the fourth transition metal compound, or the third transition metal compound and the fourth transition metal compound can be included.

[0097] According to one embodiment, the content of the cocatalyst compound can vary depending on the type of the transition metal compound, similar to the content described for the first catalyst compound solution.

[0098] According to one embodiment, the production of the second catalyst compound solution can be stirred for about 10 minutes to about 1 hour in a temperature range of about 0 °C to about 100 °C, preferably about 0 °C to about 70 °C, similar to the production of the first catalyst compound solution. In a specific example, the temperature can be about 2 °C to about 98 °C, for example, about 5 °C to about 20 °C, about 20 °C to about 35 °C, about 35 °C to about 50 °C, about 50 °C to about 65 °C, about 65 °C to about 80 °C, about 80 °C to about 95 °C. Also, in a specific example, the time can be about 12 minutes to about 58 minutes, for example, about 15 minutes to about 25 minutes, about 25 minutes to about 35 minutes, about 35 minutes to about 45 minutes, about 45 minutes to about 55 minutes.

[0099] According to an embodiment, the step of manufacturing a transition metal - support composite is a step of supporting a transition metal on a support by introducing a first catalyst compound solution into the support to manufacture the transition metal - support composite.

[0100] According to an embodiment, the support used for manufacturing the transition metal - support composite is a porous material with a large surface area having fine pores on the surface or inside, for example, silica (SiO2), alumina (Al2O3), magnesium chloride (MgCl2), or a mixture thereof, and synthetic polymers (Polymers) and the like can be used. Further, the support may contain a small amount of carbonate, sulfate, or nitrate.

[0101] According to an example embodiment, the transition metal - support composite can be manufactured by stirring the first catalyst compound solution at a temperature of about 10°C to about 130°C, preferably about 50°C to about 100°C for about 30 minutes to about 6 hours, preferably about 1 hour to about 2 hours.

[0102] According to an embodiment, as a method for supporting a transition metal compound and a cocatalyst compound in the first catalyst compound solution on a support, there are methods such as directly supporting the main catalyst on a dehydrated support in the presence of a solvent, pretreating the support with the cocatalyst compound and then supporting the main catalyst, post - treating the support with the cocatalyst compound after supporting the main catalyst on the support, reacting the transition metal compound with the cocatalyst compound and then adding and reacting the support, etc. Preferably, it can be a method of reacting the transition metal compound with the cocatalyst compound to produce a first catalyst compound solution and then reacting with the support.

[0103] In one example, the step of adding the second catalyst compound solution to the transition metal-supported composite is the step of further supporting the transition metal compound from the second catalyst compound solution onto the transition metal-supported composite, on which the transition metal from the first catalyst compound solution is supported, thereby ultimately producing a hybrid supported metallocene catalyst. At this time, any part of the explanation in the additional supporting step that overlaps with the step of producing the transition metal-supported composite may be omitted.

[0104] According to one embodiment, the additional support step can be carried out in the same way as the step for producing the transition metal-support composite, by adding the second catalyst compound solution to the transition metal-support composite and stirring for about 30 minutes to about 6 hours, preferably about 1 hour to about 2 hours, under a temperature of about 10°C to about 130°C, preferably about 50°C to about 100°C.

[0105] In one embodiment, when a hybrid supported metallocene catalyst is produced after additional loading, and a first transition metal compound, a third transition metal compound, and a fourth transition metal compound are selected for production, the molar ratio of the first transition metal compound:third transition metal compound:fourth transition metal compound can be approximately 3-5:1-2:4-6. In a specific example, the molar ratio of the first transition metal compound:third transition metal compound:fourth transition metal compound can be approximately 3.1-4.9:1.1-1.9:4.2-5.9, for example, approximately 3.2-3.8:1.6-1.9:5.3-5.9, approximately 3.8-4.4:1-1.6:4.8-5.3, and approximately 4.4-4.9:1.1-1.5:4.2-4.8. Within the above range, the effect of suppressing the uneven characteristics of the metallocene catalyst is excellent. Furthermore, when selecting and manufacturing the second, third, and fourth transition metal compounds, the molar ratio of the second, third, and fourth transition metal compounds can be approximately 3-5:1-2:4-6. In specific examples, the molar ratio of the second, third, and fourth transition metal compounds can be approximately 3.1-4.9:1.1-1.9:4.2-5.9, for example, approximately 3.2-3.8:1.6-1.9:5.3-5.9, approximately 3.8-4.4:1-1.6:4.8-5.3, and approximately 4.4-4.9:1.1-1.5:4.2-4.8. Within this range, the effect of suppressing the uneven characteristics of the metallocene catalyst is excellent. A hybrid supported metallocene catalyst according to another embodiment may contain three or more compounds selected from the group consisting of a first transition metal compound represented by formula 1; a second transition metal compound represented by formula 2; a third transition metal compound represented by formula 3; and a fourth transition metal compound represented by formula 4.

[0106] In this case, explanations of hybrid-supported metallocene catalysts that overlap with the manufacturing method of the hybrid-supported metallocene catalyst may be omitted.

[0107] [Formula 1]

[0108] [ka]

[0109] (In the above formula 1, R 1 and R 2 These are, independently, hydrogen, substituted or unsubstituted C 1-20 Alkyl, substituted or unsubstituted C 2-20 Alkenyl, substituted or unsubstituted C 6-20 Aryl, substituted, or unsubstituted C 6-20 Aryl C 1-20 Alkyl, substituted or unsubstituted C 1-20 Heteroalkyl, substituted or unsubstituted C 3-20 Heteroaryl, substituted or unsubstituted C 1-20 Alkylamide, substituted or unsubstituted C 6-20 Arylamides, substituted or unsubstituted C 1-20 Alkylidenes, or substituted or unsubstituted C 1-20 Cyril, X is independently halogen, C 1-20 Alkyl, C 2-20 Alkenil, C 2-20 Alkinyl, C 6-20 Ariel, C 6-20 Aryl C 1-20 Alkyl, C 1-20 Alkylamide, C 6-20 Arylamide, or C 1-20 It is alkyridene, M is titanium (Ti), zirconium (Zr), or hafnium (Hf), and n and m are independent integers between 0 and 5. [Formula 2]

[0110] [ka]

[0111] (In the above formula 2, R 3 and R 4 These are, independently, hydrogen, substituted or unsubstituted C 1-20 Alkyl, substituted or unsubstituted C 2-20 Alkenyl, substituted or unsubstituted C 6-20Aryl, substituted, or unsubstituted C 6-20 Aryl C 1-20 Alkyl, substituted or unsubstituted C 1-20 Heteroalkyl, substituted or unsubstituted C 3-20 Heteroaryl, substituted or unsubstituted C 1-20 Alkylamide, substituted or unsubstituted C 6-20 Arylamides, substituted or unsubstituted C 1-20 Alkylidenes, or substituted or unsubstituted C 1-20 Cyril, X is independently halogen, C 1-20 Alkyl, C 2-20 Alkenil, C 2-20 Alkinyl, C 6-20 Ariel, C 6-20 Aryl C 1-20 Alkyl, C 1-20 Alkylamide, C 6-20 Arylamide, or C 1-20 It is alkyridene, M is titanium (Ti), zirconium (Zr), or hafnium (Hf), and (where l is an integer from 1 to 6, and k is an integer from 0 to 4) [Formula 3]

[0112] [ka]

[0113] (In the above formula 3, R 5 ~R 9 These are, independently, hydrogen, substituted or unsubstituted C 1-20 Alkyl, substituted or unsubstituted C 2-20 Alkenyl, substituted or unsubstituted C 6-20 Aryl, substituted, or unsubstituted C 6-20 Aryl C 1-20 Alkyl, substituted or unsubstituted C 1-20 Heteroalkyl, substituted or unsubstituted C 3-20 Heteroaryl, substituted or unsubstituted C 1-20 Alkylamide, substituted or unsubstituted C 6-20Aryl amide, substituted or unsubstituted C 1-20 alkylidene, or substituted or unsubstituted C 1-20 silyl, and X is independently halogen, C 1-20 alkyl, C 2-20 alkenyl, C 2-20 alkynyl, C 6-20 aryl, C 6-20 aryl C 1-20 alkyl, C 1-20 alkyl amide, C 6-20 aryl amide, or C 1-20 alkylidene, and M is titanium (Ti), zirconium (Zr), or hafnium (Hf), and A is carbon (C), silicon (Si), germanium (Ge), or tin (Sn), and i and j are independently integers from 0 to 4) [Formula 4]

[0114] [Chemical formula]

[0115] (In the said Formula 4, R 10 ~R 13 are independently hydrogen, substituted or unsubstituted C 1-20 alkyl, substituted or unsubstituted C 2-20 alkenyl, substituted or unsubstituted C 6-20 aryl, substituted or unsubstituted C 6-20 aryl C 1-20 alkyl, substituted or unsubstituted C 1-20 heteroalkyl, substituted or unsubstituted C 3-20 heteroaryl, substituted or unsubstituted C 1-20 alkyl amide, substituted or unsubstituted C 6-20 aryl amide, substituted or unsubstituted C 1-20 alkylidene, or substituted or unsubstituted C 1-20 silyl, and X is independently halogen, C 1-20Alkyl, C 2-20 Alkenil, C 2-20 Alkinyl, C 6-20 Ariel, C 6-20 Aryl C 1-20 Alkyl, C 1-20 Alkylamide, C 6-20 Arylamide, or C 1-20 It is alkyridene, M is titanium (Ti), zirconium (Zr), or hafnium (Hf). A is carbon (C), silicon (Si), germanium (Ge), or tin (Sn), and (h is an integer between 0 and 4) At this time, R 1 ~R 13 The substituents can independently be one or more selected from the group consisting of halogen groups, cyano groups, nitro groups, and C1-C8 alkyl groups.

[0116] According to one example, in formula 1 above, R 1 and R 2 C is independent 1-20 It is an alkyl group, where X is independently a halogen, and n can be 1 and m can be 4.

[0117] In the above equation 2, R 3 and R 4 k is independently hydrogen, X is independently a halogen, and k can be 0 and l can be 2.

[0118] In the above equation 3, R 5 and R 6 C is independent 6-20 In aryl, R 7 ~R 9 C is independent 1-20 It is an alkyl group, where X is independently a halogen, and i and j can independently be 1.

[0119] In the above equation 4, R 10 and R 11 C is independent 6-20 In aryl, R 12 ~R 13 C is independent1-20 It is an alkyl group, X is independently a halogen, and h can be 1.

[0120] In equations 1 to 4, M can be zirconium (Zr), and in equations 3 and 4, A can be carbon (C).

[0121] According to one embodiment, the hybrid supported metallocene catalyst may be a three-component hybrid catalyst, and its type may vary depending on the method of producing the hybrid supported metallocene catalyst. Preferably, it contains a first transition metal compound, a third transition metal compound, and a fourth transition metal compound; or it may contain a second transition metal compound, a third transition metal compound, and a fourth transition metal compound.

[0122] In one embodiment, when the hybrid supported metallocene catalyst contains a first transition metal compound, a third transition metal compound, and a fourth transition metal compound, the molar ratio of the first transition metal compound:third transition metal compound:fourth transition metal compound may be about 3-5:about 1-2:about 4-6. In a specific example, the molar ratio of the first transition metal compound:third transition metal compound:fourth transition metal compound may be about 3.1-4.9:about 1.1-1.9:about 4.2-5.9, for example, about 3.2-3.8:about 1.6-1.9:about 5.3-5.9, about 3.8-4.4:about 1-1.6:about 4.8-5.3, and about 4.4-4.9:about 1.1-1.5:about 4.2-4.8.

[0123] Furthermore, when a second transition metal compound, a third transition metal compound, and a fourth transition metal compound are included, the molar ratio of the second transition metal compound:third transition metal compound:fourth transition metal compound can be approximately 3-5:1-2:4-6. In specific examples, the molar ratio of the second transition metal compound:third transition metal compound:fourth transition metal compound can be approximately 3.1-4.9:1.1-1.9:4.2-5.9, for example, approximately 3.2-3.8:1.6-1.9:5.3-5.9, approximately 3.8-4.4:1-1.6:4.8-5.3, and approximately 4.4-4.9:1.1-1.5:4.2-4.8.

[0124] Another embodiment of the method for producing polyethylene includes the step of polymerizing an olefin having the following formula 5 in the presence of a hybrid supported metallocene catalyst; preferably, the step of polymerizing by adding an ethylene monomer;

[0125] [5] CH2=CHR 14 In the above equation 5, R 14 is hydrogen or a C1-C6 alkyl or aryl group. According to one embodiment, a method for producing polyethylene may include the step of polymerizing ethylene monomers in the presence of a hybrid supported metallocene catalyst, where the polymerization time can be about 0.5 hours to about 1.5 hours, preferably about 0.8 hours to about 1.2 hours.

[0126] On the other hand, some information related to polyethylene manufacturing methods that overlaps with information on hybrid supported metallocene catalysts may be omitted from the explanation.

[0127] In another embodiment, polyethylene produced by a method for producing polyethylene from a hybrid supported metallocene catalyst has an MFR ratio (MFR 21.6 / MFR 2.16 ) can range from approximately 58 to 213.

[0128] According to one embodiment, polyethylene produced by a method for producing polyethylene from a hybrid supported metallocene catalyst was measured at a temperature of 190°C and a load of 2.16 kg at MFR 2.16 The values ​​are approximately 0.05g / 10min to approximately 0.71g / 10min, and the MFR ratio (MFR 21.6 / MFR 2.16 ) is characterized by being approximately 58 to approximately 213. In a specific example, the MFR ratio (MFR 21.6 / MFR 2.16 ) can range from approximately 60 to 211, for example, approximately 61 to 80, approximately 80 to 100, approximately 100 to 120, approximately 120 to 140, approximately 140 to 160, approximately 160 to 180, approximately 180 to 200, and approximately 200 to 213.

[0129] In one embodiment, the MFR / MFR0 value of polyethylene produced from a hybrid supported metallocene catalyst manufactured by sequentially supporting it is a value that can be used to determine the catalyst molecular weight distribution change characteristics due to a change in the supporting method, and may be less than about 0.980 or greater than about 1.10, preferably less than about 0.940 or greater than about 1.50. In one specific example, the MFR / MFR0 value may be, for example, less than about 0.77 to 0.81, about 0.81 to 0.84, or about 0.84 to 0.975. In another specific example, the MFR / MFR0 value may be, for example, greater than about 1.105 to 1.25, about 1.25 to 1.45, or about 1.45 to 1.55.

[0130] (Math 1) MFR / MFR0 (In the above formula 1, MFR is the MFR value of a resin produced with a hybrid supported metallocene catalyst that is supported in order according to the metallocene catalyst production method of the present invention, and MFR0 is the MFR of a resin produced with a hybrid supported metallocene catalyst that is supported simultaneously regardless of order.) In other words, polyethylene produced according to the method for producing polyethylene from a hybrid supported metallocene catalyst has the advantage of a broad MFR ratio distribution, which allows for the fluid adjustment of both narrow and broad molecular weight distributions simultaneously, making it useful for developing target products.

[0131] Another aspect of the present invention relates to a method for modifying the physical properties of polyethylene resin using a hybrid supported metallocene catalyst.

[0132] The method includes the steps of setting the PDI value, MFR value, and Mw value of a target polyethylene resin; and selecting a hybrid supported metallocene catalyst that exhibits the set PDI value, MFR value, and Mw value.

[0133] The step of selecting the hybrid supported metallocene catalyst can be performed by selecting from a population of hybrid supported metallocene catalysts produced by changing the order in which three compounds selected from the first transition metal compound, the second transition metal compound, the third transition metal compound, and the fourth transition metal compound are added.

[0134] For example, if the set Mw value is approximately 100,000 or more, a hybrid supported metallocene catalyst manufactured using the three compounds, the first transition metal compound, the third transition metal compound, and the fourth transition metal compound, can be used. If the set Mw value is less than approximately 100,000, a hybrid supported metallocene catalyst manufactured using the three compounds, the second transition metal compound, the third transition metal compound, and the fourth transition metal compound, can be used.

[0135] The present invention will be described in more detail below with reference to examples. However, these examples are for illustrative purposes only, and the scope of the present invention is not limited to these examples.

[0136] Manufacturing Examples 1-1 to 2-6: Production of Hybrid Supported Metallocene Catalysts As shown in Tables 1 and 2, transition metal compounds and co-catalysts (10% MAO) were added to toluene and stirred at room temperature for 0.5 hours to produce the first and second catalyst compound solutions, respectively. Subsequently, the first catalyst compound solution was added to 3.2 g of SP2402 silica (the support) and stirred at 75°C for 1 hour to produce a transition metal-support composite. Then, the second catalyst compound solution was added to the transition metal-support composite slurry and stirred further at 75°C for 1 hour. After that, the stirred product was washed three times with 10 mL of toluene and dried under vacuum for 1 hour to obtain 4.3 g of hybrid supported metallocene catalyst in powder form.

[0137] At this time, the hybrid supported metallocene catalysts of Production Examples 1-1 to 1-6 contained the compound represented by formula 1-1, the compound represented by formula 3-1, and the compound represented by formula 4-1 in a molar ratio of 40:10:50, and the hybrid supported metallocene catalysts of Production Examples 2-1 to 2-6 contained the compound represented by formula 2-1, the compound represented by formula 3-1, and the compound represented by formula 4-1 in a molar ratio of 40:10:50.

[0138] [Formula 1-1]

[0139] [ka]

[0140] [Formula 2-1]

[0141] [ka]

[0142] [Formula 3-1]

[0143] [ka]

[0144] [Formula 4-1]

[0145] [ka]

[0146] Comparative manufacturing example 1: Production of hybrid supported metallocene catalysts mixed in any order. As shown in Table 1, 22 mg of Compound 1 transition metal compound, 10 mg of Compound 3 transition metal compound, 47 mg of Compound 4 transition metal compound, and a co-catalyst (10% MAO) were added to toluene at once, without distinguishing between primary and secondary addition orders, and stirred at room temperature to produce a catalyst compound solution. Subsequently, the catalyst compound solution was added to 3.2 g of SP2402 silica, which served as the support, and stirred at 75°C for 3 hours. After that, the stirred product was washed three times with 10 mL of toluene and dried under vacuum for 1 hour to obtain 4.4 g of hybrid supported metallocene catalyst in powder form.

[0147] Comparative manufacturing example 2: Production of hybrid supported metallocene catalysts mixed in any order. As shown in Table 2, 23 mg of Compound 2 transition metal compound, 10 mg of Compound 3 transition metal compound, 47 mg of Compound 4 transition metal compound, and a co-catalyst (10% MAO) were added to toluene at once, without distinguishing between primary and secondary addition orders, and stirred at room temperature to produce a catalyst compound solution. Subsequently, the catalyst compound solution was added to 3.2 g of SP2402 silica, which served as the support, and stirred at 75°C for 3 hours. After that, the stirred product was washed three times with 10 mL of toluene and dried under vacuum for 1 hour to obtain 4.4 g of hybrid supported metallocene catalyst in powder form.

[0148] [Table 1]

[0149] *Compound 1: Compound represented by formula 1-1 = (n-butylcyclopentadienyl)(tetramethylcyclopentadienyl)zirconium(IV)dichloride;purchased at MCN Compound 3: Compound represented by formula 3-1 = (Diphenylmethylidene(n-butylcyclopentadienyl)(2,7-tert-butyl fluoren-9-yl)zirconium dichloride;purchased at MCN Compound 4: Compound represented by formula 4-1 = (Diphenylmethylidene(cyclopentadienyl)(2,7-tert-butylfluoren-9-yl)zirconium dichloride;purchased at MCN *Carrier SP-2402 was purchased from Grace; co-catalyst MAO 10% was purchased from Lake Materials. *All substances are used without further purification unless otherwise specified.

[0150] [Table 2]

[0151] *Compound 2: Compound represented by formula 2-1 = [Rac-ethylenebis(indenyl)]zirconium(IV)dichloride; purchased from MCN. Compound 3: Compound represented by formula 3-1 = (Diphenylmethylidene(n-butylcyclopentadienyl)(2,7-tert-butyl fluoren-9-yl)zirconium dichloride;purchased at MCN Compound 4: Compound represented by formula 4-1 = (Diphenylmethylidene(cyclopentadienyl)(2,7-tert-butylfluoren-9-yl)zirconium dichloride;purchased at MCN *Carrier SP-2402 was purchased from Grace; co-catalyst MAO 10% was purchased from Lake Materials. *All substances are used without further purification unless otherwise specified. Example 1: Production of polyolefin (polyethylene) 30 mg of the hybrid-supported metallocene catalyst prepared according to Production Example 1-1, 1 L of hexane, and 0.6 ml of 1 M triisobutylaluminum (TIBAL) scavenger were added to a slurry reactor, and ethylene was copolymerized for 1 hour. At this time, the ethylene pressure was 14 kgf / cm². 2Then, 10 ml of 1-hexene was initially added, and 100 cc of hydrogen was added initially, followed by a continuous addition of 10 cc per minute to produce polyethylene.

[0152] Example 2: Production of polyolefin (polyethylene) The procedure was carried out in the same manner as in Example 1, except that a hybrid supported metallocene catalyst manufactured according to Manufacturing Example 1-2 was used.

[0153] Example 3: Production of polyolefin (polyethylene) The procedure was carried out in the same manner as in Example 1, except that a hybrid supported metallocene catalyst prepared according to Production Examples 1-5 was used.

[0154] Comparative Example 1: Production of Polyolefin (Polyethylene) The procedure was carried out in the same manner as in Example 1, except that a hybrid supported metallocene catalyst manufactured according to Comparative Manufacturing Example 1 was used.

[0155] Example 4: Production of polyolefin (polyethylene) 30 mg of the hybrid-supported metallocene catalyst prepared according to Production Example 2-1, 1 L of hexane, and 0.6 ml of 1 M triisobutylaluminum (TIBAL) scavenger were added to a slurry reactor, and ethylene was copolymerized for 1 hour. At this time, the ethylene pressure was 14 kgf / cm². 2 Then, 10 ml of 1-hexene was initially added, and 100 cc of hydrogen was added initially, followed by a continuous addition of 20 cc per minute to produce polyethylene.

[0156] Example 5: Production of polyolefin (polyethylene) The procedure was carried out in the same manner as in Example 4, except that a hybrid supported metallocene catalyst prepared according to Production Example 2-3 was used.

[0157] Example 6: Production of polyolefin (polyethylene) The procedure was carried out in the same manner as in Example 4, except that a hybrid supported metallocene catalyst prepared according to Production Example 2-6 was used.

[0158] Comparative Example 2: Production of Polyolefin (Polyethylene) The procedure was carried out in the same manner as in Example 4, except that a hybrid supported metallocene catalyst manufactured according to Comparative Manufacturing Example 2 was used.

[0159] Methods for analyzing the physical properties of polyethylene -Density: Measured according to ASTM D1505

[0160] -Activity (g PE / g cat ): Measure the mass of the polymer obtained in the polymerization experiment and the mass of the catalyst added during the polymerization experiment, and calculate their ratio.

[0161] -MI: Melt fluidity MI is the extrusion volume over 10 minutes under a load of 2.16 kg, measured according to ASTM 1238 at a measurement temperature of 190°C.

[0162] -MFR: This represents the ratio of MI to MFI, i.e., MFI / MI, where MFI is the extrusion volume over 10 minutes under a load of 21.6 kg, measured according to ASTM 1238 at a measurement temperature of 190°C.

[0163] - Molecular weight distribution (PDI): Number-average molecular weight (Mn) and weight-average molecular weight (Mw) were measured at a measurement temperature of 170°C using 3D gel permeation chromatography-FTIR (3D GPC-FTIR). The molecular weight distribution (PDI, Mw / Mn) was expressed as the ratio of weight-average molecular weight to number-average molecular weight.

[0164] -Thermal properties (T m ): Measured using a differential scanning calorimeter.

[0165]

number

[0166] Specifically, in the MFR / MFR0 of the resins in Examples 1 to 6, MFR0 is the MFR value of the resin in Comparative Example 1, and in the MFR / MFR0 of the resins in Examples 7 to 12, MFR0 is the MFR value of the resin in Comparative Example 2. In this case, unlike Examples 1 to 12, Comparative Examples 1 and 2 had all the catalyst compounds and co-catalysts reacted and supported in a single step.

[0167] -X(%): Crystallinity. The crystalline and amorphous regions were separated by the peaks on the differential scanning calorimeter, and the area occupied by the crystalline region was used as a reference to the total area.

[0168] Analysis results of the physical properties of polyethylene Polyethylene was produced according to Examples 1 to 12, Comparative Examples 1 and 2, and its physical properties were analyzed. The results are shown in Tables 3 and 4, and Figures 1 and 2. Specifically, Figure 1 is a graph showing the molecular weight distribution of polyethylene according to Examples 1 to 6 and Comparative Example 1, and Figure 2 is a graph showing the molecular weight distribution of polyethylene according to Examples 7 to 12 and Comparative Example 2.

[0169] [Table 3]

[0170] [Table 4]

[0171] Referring to Tables 3 and 4, and Figures 1 and 2, when producing polyethylene using catalysts manufactured by changing the loading order according to Production Examples 1-1 to 1-6, it is possible to adjust the PDI over a wide range of 31 or higher without changing the catalyst type or content. Similarly, when using catalysts manufactured by changing the loading order according to Production Examples 2-1 to 2-6, it is possible to ensure a PDI of 31 or higher.

[0172] Furthermore, MFR / MFR0 can be a value that allows us to determine the characteristics of catalyst molecular weight distribution change due to changes in the loading method. When examining the MFR / MFR0 values ​​for Examples 1 to 12, the MFR / MFR0 values ​​for Examples 1 to 6 are either less than 0.940 or greater than 1.150, and the MFR / MFR0 values ​​for Examples 7 to 12 are either less than 0.980 or greater than 1.10, indicating that resins with diverse molecular weight ranges can be manufactured. In particular, it can be confirmed that each example represents a wide range of differences, either greater than 1.5 or less than 0.8.

[0173] In other words, using a hybrid supported metallocene catalyst manufactured by changing the loading order has the advantage of being able to produce polyethylene with a broad molecular weight distribution compared to the catalysts in comparative manufacturing examples 1 and 2, which are loaded all at once regardless of the loading order.

[0174] Simple modifications or alterations of the present invention can be readily carried out by a person with ordinary skill in the art, and all such modifications or alterations can be considered to fall within the scope of the present invention. [Industrial applicability]

[0175] The method for producing hybrid supported metallocene catalysts has the advantage of being applicable to a wide range of target products because it is possible to obtain polyolefins with a broad molecular weight distribution by applying metallocene catalysts produced by changing the loading order for three of the four transition metal compounds having specific formulas and specific contents, and by adjusting the physical properties of polyethylene.

Claims

1. A step of preparing a first catalyst compound solution containing one or two compounds selected from the group consisting of a first transition metal compound represented by formula 1 below, a second transition metal compound represented by formula 2 below, a third transition metal compound represented by formula 3 below, and a fourth transition metal compound represented by formula 4 below; A step of producing a second catalyst compound solution containing one or two transition metal compounds from the group consisting of the first to fourth transition metal compounds that are not included in the first catalyst compound solution; A step of supporting the first catalyst compound solution onto a support to produce a transition metal-support composite; and A method for producing a hybrid supported metallocene catalyst, comprising the step of further supporting the second catalyst compound solution onto the transition metal-support composite, The hybrid supported metallocene catalyst comprises three compounds selected from the first transition metal compound, the second transition metal compound, the third transition metal compound, and the fourth transition metal compound. Method for producing the hybrid supported metallocene catalyst: [Formula 1] 【Chemistry 1】 (In the above formula 1, R １ and R ２ are, independently, hydrogen, substituted or unsubstituted C １－２０ alkyl, substituted or unsubstituted C ２－２０ alkenyl, substituted or unsubstituted C ６－２０ aryl, substituted or unsubstituted C ６－２０ aryl C １－２０ alkyl, substituted or unsubstituted C １－２０ heteroalkyl, substituted or unsubstituted C ３－２０ heteroaryl, substituted or unsubstituted C １－２０ alkylamide, substituted or unsubstituted C ６－２０ arylamide, substituted or unsubstituted C １－２０ alkylidene, or substituted or unsubstituted C １－２０ silyl, and X is independently halogen, C １－２０ Alkyl, C ２－２０ Alkenil, C ２－２０ Alkinyl, C ６－２０ Ariel, C ６－２０ Aryl C １－２０ Alkyl, C １－２０ Alkylamide, C ６－２０ Arylamide, or C １－２０ It is alkyridene, M is titanium (Ti), zirconium (Zr), or hafnium (Hf), and n and m are independent integers between 0 and 5. [Formula 2] 【Chemistry 2】 (In the above equation 2, R ３ and R ４ These are, independently, hydrogen, substituted or unsubstituted C １－２０ Alkyl, substituted, or unsubstituted C ２－２０ Alkenyl, substituted or unsubstituted C ６－２０ Aryl, substituted, or unsubstituted C ６－２０ Aryl C １－２０ Alkyl, substituted, or unsubstituted C １－２０ Heteroalkyl, substituted or unsubstituted C ３－２０ Heteroaryl, substituted or unsubstituted C １－２０ Alkylamide, substituted or unsubstituted C ６－２０ Arylamides, substituted or unsubstituted C １－２０ Alkylidenes, or substituted or unsubstituted C １－２０ Cyril, X is independently halogen, C １－２０ Alkyl, C ２－２０ Alkenil, C ２－２０ Alkinyl, C ６－２０ Ariel, C ６－２０ Aryl C １－２０ Alkyl, C １－２０ Alkylamide, C ６－２０ Arylamide, or C １－２０ It is alkyridene, M is titanium (Ti), zirconium (Zr), or hafnium (Hf), and (where l is an integer from 1 to 6, and k is an integer from 0 to 4) [Formula 3] 【Transformation 3】 (In the above equation 3, R ５ ~R ９ These are, independently, hydrogen, substituted or unsubstituted C １－２０ Alkyl, substituted, or unsubstituted C ２－２０ Alkenyl, substituted or unsubstituted C ６－２０ Aryl, substituted, or unsubstituted C ６－２０ Aryl C １－２０ Alkyl, substituted, or unsubstituted C １－２０ Heteroalkyl, substituted or unsubstituted C ３－２０ Heteroaryl, substituted or unsubstituted C １－２０ Alkylamide, substituted or unsubstituted C ６－２０ Arylamides, substituted or unsubstituted C １－２０ Alkylidenes, or substituted or unsubstituted C １－２０ Cyril, X is independently halogen, C １－２０ Alkyl, C ２－２０ Alkenil, C ２－２０ Alkinyl, C ６－２０ Ariel, C ６－２０ Aryl C １－２０ Alkyl, C １－２０ Alkylamide, C ６－２０ Arylamide, or C １－２０ It is alkyridene, M is titanium (Ti), zirconium (Zr), or hafnium (Hf). A is carbon (C), silicon (Si), germanium (Ge), or tin (Sn), and i and j are independent integers between 0 and 4. [Formula 4] 【Chemistry 4】 (In the above equation 4, R １０ ~R １３ These are, independently, hydrogen, substituted or unsubstituted C １－２０ Alkyl, substituted, or unsubstituted C ２－２０ Alkenyl, substituted or unsubstituted C ６－２０ Aryl, substituted, or unsubstituted C ６－２０ Aryl C １－２０ Alkyl, substituted, or unsubstituted C １－２０ Heteroalkyl, substituted or unsubstituted C ３－２０ Heteroaryl, substituted or unsubstituted C １－２０ Alkylamide, substituted or unsubstituted C ６－２０ Arylamides, substituted or unsubstituted C １－２０ Alkylidenes, or substituted or unsubstituted C １－２０ Cyril, X is independently halogen, C １－２０ Alkyl, C ２－２０ Alkenil, C ２－２０ Alkinyl, C ６－２０ Ariel, C ６－２０ Aryl C １－２０ Alkyl, C １－２０ Alkylamide, C ６－２０ Arylamide, or C １－２０ It is alkyridene, M is titanium (Ti), zirconium (Zr), or hafnium (Hf). A is carbon (C), silicon (Si), germanium (Ge), or tin (Sn), and h is an integer between 0 and 4.

2. The method for producing a hybrid supported metallocene catalyst according to claim 1, wherein the hybrid supported metallocene catalyst comprises a first transition metal compound, a third transition metal compound, and a fourth transition metal compound.

3. A method for producing a hybrid supported metallocene catalyst according to claim 2, wherein the molar ratio of the first transition metal compound: third transition metal compound: fourth transition metal compound is 3 to 5: 1 to 2: 4 to 6.

4. The method for producing a hybrid supported metallocene catalyst according to claim 1, wherein the hybrid supported metallocene catalyst comprises the second transition metal compound, the third transition metal compound, and the fourth transition metal compound.

5. The method for producing a hybrid supported metallocene catalyst according to claim 4, wherein the molar ratio of the second transition metal compound:third transition metal compound:fourth transition metal compound is 3-5:1-2:4-6.

6. In the above formula 1, R １ and R ２ are each independently C １－２０ alkyl X is independently, halogenated, and n is 1 and m is 4; In the above equation 2, R ３ and R ４ It operates independently, with hydrogen. X is independently, halogenated, and k is 0 and l is 2; In the above equation 3, R ５ and R ６ Independently, C ６－２０ In Ariel, R ７ ~R ９ are each independently C １－２０ alkyl, X is independently, halogenated, and i and j are independently 1; In the aforementioned equation 4, R １０ and R １１ Independently, C ６－２０ In Ariel, R １２ ~R １３ Independently, C １－２０ Alkyl, X is independently, halogenated, and h is 1; the method for producing a hybrid supported metallocene catalyst according to claim 1.

7. In the aforementioned equations 1, 2, 3, and 4, M is zirconium (Zr); and In equations 3 and 4 above, A is carbon (C); the method for producing a hybrid supported metallocene catalyst according to claim 1.

8. A hybrid supported metallocene catalyst manufactured according to the manufacturing method described in any one of claims 1 to 7.

9. The first transition metal compound represented by the following formula 1; Second transition metal compounds represented by the following formula 2; Third transition metal compounds represented by the following formula 3; and A hybrid supported metallocene catalyst comprising three compounds selected from the group consisting of the fourth transition metal compounds represented by the following formula 4; The aforementioned hybrid supported metallocene catalyst is a hybrid supported metallocene catalyst that satisfies the following equation 2: [Formula 1] 【Transformation 5】 (In the above formula 1, R １ and R ２ These are, independently, hydrogen, substituted or unsubstituted C １－２０ Alkyl, substituted, or unsubstituted C ２－２０ Alkenyl, substituted or unsubstituted C ６－２０ Aryl, substituted, or unsubstituted C ６－２０ Aryl C １－２０ Alkyl, substituted, or unsubstituted C １－２０ Heteroalkyl, substituted or unsubstituted C ３－２０ Heteroaryl, substituted or unsubstituted C １－２０ Alkylamide, substituted or unsubstituted C ６－２０ Arylamides, substituted or unsubstituted C １－２０ Alkylidenes, or substituted or unsubstituted C １－２０ Cyril, X is independently halogen, C １－２０ Alkyl, C ２－２０ Alkenil, C ２－２０ Alkinyl, C ６－２０ Ariel, C ６－２０ Aryl C １－２０ Alkyl, C １－２０ Alkylamide, C ６－２０ Arylamide, or C １－２０ It is alkyridene, M is titanium (Ti), zirconium (Zr), or hafnium (Hf), and n and m are independent integers between 0 and 5. [Formula 2] 【Transformation 6】 (In the above equation 2, R ３ and R ４ These are, independently, hydrogen, substituted or unsubstituted C １－２０ Alkyl, substituted, or unsubstituted C ２－２０ Alkenyl, substituted or unsubstituted C ６－２０ Aryl, substituted, or unsubstituted C ６－２０ Aryl C １－２０ Alkyl, substituted, or unsubstituted C １－２０ Heteroalkyl, substituted or unsubstituted C ３－２０ Heteroaryl, substituted or unsubstituted C １－２０ Alkylamide, substituted or unsubstituted C ６－２０ Arylamides, substituted or unsubstituted C １－２０ Alkylidenes, or substituted or unsubstituted C １－２０ Cyril, X is independently halogen, C １－２０ Alkyl, C ２－２０ Alkenil, C ２－２０ Alkinyl, C ６－２０ Ariel, C ６－２０ Aryl C １－２０ Alkyl, C １－２０ Alkylamide, C ６－２０ Arylamide, or C １－２０ It is alkyridene, M is titanium (Ti), zirconium (Zr), or hafnium (Hf), and (where l is an integer from 1 to 6, and k is an integer from 0 to 4) [Formula 3] 【Transformation 7】 (In the above equation 3, R ５ ~R ９ These are, independently, hydrogen, substituted or unsubstituted C １－２０ Alkyl, substituted, or unsubstituted C ２－２０ Alkenyl, substituted or unsubstituted C ６－２０ Aryl, substituted, or unsubstituted C ６－２０ Aryl C １－２０ Alkyl, substituted, or unsubstituted C １－２０ Heteroalkyl, substituted or unsubstituted C ３－２０ Heteroaryl, substituted or unsubstituted C １－２０ Alkylamide, substituted or unsubstituted C ６－２０ Arylamides, substituted or unsubstituted C １－２０ Alkylidenes, or substituted or unsubstituted C １－２０ Cyril, X is independently halogen, C １－２０ Alkyl, C ２－２０ Alkenil, C ２－２０ Alkinyl, C ６－２０ Ariel, C ６－２０ Aryl C １－２０ Alkyl, C １－２０ Alkylamide, C ６－２０ Arylamide, or C １－２０ It is alkyridene, M is titanium (Ti), zirconium (Zr), or hafnium (Hf). A is carbon (C), silicon (Si), germanium (Ge), or tin (Sn), and i and j are independent integers between 0 and 4. [Formula 4] 【Transformation 8】 (In the above equation 4, R １０ ~R １３ These are, independently, hydrogen, substituted or unsubstituted C １－２０ Alkyl, substituted, or unsubstituted C ２－２０ Alkenyl, substituted or unsubstituted C ６－２０ Aryl, substituted, or unsubstituted C ６－２０ Aryl C １－２０ Alkyl, substituted, or unsubstituted C １－２０ Heteroalkyl, substituted or unsubstituted C ３－２０ Heteroaryl, substituted or unsubstituted C １－２０ Alkylamide, substituted or unsubstituted C ６－２０ Arylamides, substituted or unsubstituted C １－２０ Alkylidenes, or substituted or unsubstituted C １－２０ Cyril, X is independently halogen, C １－２０ Alkyl, C ２－２０ Alkenil, C ２－２０ Alkinyl, C ６－２０ Ariel, C ６－２０ Aryl C １－２０ Alkyl, C １－２０ Alkylamide, C ６－２０ Arylamide, or C １－２０ It is alkyridene, M is titanium (Ti), zirconium (Zr), or hafnium (Hf). A is carbon (C), silicon (Si), germanium (Ge), or tin (Sn), and (h is an integer between 0 and 4) (Math 2) PDI ＰＥ ≧31 (In the above formula 2, PDI ＰＥ This is the molecular weight distribution (PDI, Mw / Mn) value measured by gel permeation chromatography at a measurement temperature of 170°C for polyethylene polymerized using a hybrid supported metallocene catalyst.

10. The hybrid supported metallocene catalyst according to claim 9, comprising the first transition metal compound, the third transition metal compound, and the fourth transition metal compound.

11. The hybrid supported metallocene catalyst according to claim 10, wherein the molar ratio of the first transition metal compound: third transition metal compound: fourth transition metal compound is 3-5:1-2:4-6.

12. The hybrid supported metallocene catalyst according to claim 9, comprising the second transition metal compound, the third transition metal compound, and the fourth transition metal compound.

13. The hybrid supported metallocene catalyst according to claim 12, wherein the molar ratio of the second transition metal compound:third transition metal compound:fourth transition metal compound is 3-5:1-2:4-6.

14. In the above formula 1, R １ and R ２ Independently, C １－２０ Alkyl, X is independently, halogenated, and n is 1 and m is 4; In the above equation 2, R ３ and R ４ It operates independently, with hydrogen. X is independently, halogenated, and k is 0 and l is 2; In the above equation 3, R ５ and R ６ Independently, C ６－２０ In Ariel, R ７ ~R ９ Independently, C １－２０ Alkyl, X is independently, halogenated, and i and j are independently 1; In the aforementioned equation 4, R １０ and R １１ Independently, C ６－２０ In Ariel, R １２ ~R １３ Independently, C １－２０ Alkyl, X is independently, halogenated, and h is 1; the hybrid supported metallocene catalyst according to claim 9.

15. In the aforementioned equations 1, 2, 3, and 4, M is zirconium (Zr); and In equations 3 and 4 above, A is carbon (C); the hybrid supported metallocene catalyst according to claim 9.

16. Polymerized in the presence of a hybrid supported metallocene catalyst according to any one of claims 9 to 15, and MFR (MFR ２１．６ / MFR ２．１６ A polyethylene resin characterized in that the ratio is 58 to 213.

17. MFR / MFR calculated using the formula 1 below ０ The polyethylene resin according to claim 16, wherein the value is less than 0.980 or greater than 1.10: (Math 1) MFR / MFR ０ (In the above formula 1, MFR is the MFR value described in claim 16, and MFR ０ This refers to the MFR of a resin produced with a hybrid supported metallocene catalyst that is simultaneously supported in any order.

18. The polyethylene resin according to claim 16, wherein the polyethylene resin has a molecular weight distribution (PDI, Mw / Mn) value of 31 or more, as measured by gel permeation chromatography at a measurement temperature of 170°C.

19. A method for adjusting the physical properties of a polyethylene resin using a hybrid supported metallocene catalyst according to any one of claims 9 to 15, wherein the method is: Set the target PDI value, MFR value, or Mw value for the polyethylene resin; and Select a hybrid supported metallocene catalyst that exhibits the aforementioned set PDI value, MFR value, or Mw value; The step of selecting the hybrid supported metallocene catalyst includes the following steps: A method for adjusting the physical properties of polyethylene resin, comprising selecting from a population of hybrid supported metallocene catalysts produced by changing the order in which three compounds selected from the first transition metal compound, the second transition metal compound, the third transition metal compound, and the fourth transition metal compound are added.

20. If the set Mw value is 100,000 or more, a hybrid supported metallocene catalyst manufactured using the three compounds, the first transition metal compound, the third transition metal compound, and the fourth transition metal compound, is used. A method for adjusting the physical properties of a polyethylene resin according to claim 19, wherein if the set Mw value is less than 100,000, a hybrid supported metallocene catalyst manufactured using three compounds, the second transition metal compound, the third transition metal compound, and the fourth transition metal compound, is used.

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