Ziegler-Natta catalyst for olefin polymerization, method for producing polyolefins, and polyolefin resins

Abstract

The present invention provides a Ziegler-Natta catalyst for olefin polymerization, a method for producing polyolefins, and a polyolefin resin. Specifically, the present invention provides a Ziegler-Natta main catalyst for olefin polymerization comprising a titanium compound represented by formula 1, a magnesium compound represented by formula 2, and an internal electron donor; an organoaluminum compound represented by formula 7; and an external electron donor represented by formula 3, wherein the internal electron donor is a mixture of a first internal electron donor selected from formulas 4 to 6 and a second internal electron donor selected from formulas 4 to 6 and different from the first internal electron donor, wherein in 10 moles of the mixture, the first internal electron donor and the second internal electron donor are present in a molar ratio of 3:7 to 7:3. The present invention provides a Ziegler-Natta catalyst for olefin polymerization, a method for producing polyolefins using the same, and a polyolefin resin produced using the same.

Description

[Technical Field]

[0001] This invention relates to a Ziegler-Natta catalyst for olefin polymerization, a method for producing polyolefins with excellent processability using the same, and polyolefin resins. [Background technology]

[0002] Polyolefins are a class of polymers derived from simple olefins. Known methods for producing polyolefins include the use of Ziegler-Natta polymerization catalysts. Ziegler-Natta polymerization catalysts use transition metal halides to polymerize vinyl monomers, providing polymers with a highly isotactic stereochemical configuration.

[0003] In particular, polyethylene, a type of polyolefin, has seen a diversification of applications in recent years, making it preferable to produce polyethylene resins with excellent processability in order to improve the productivity of the resin. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Korean Patent Publication No. 10-2423660 [Overview of the project] [Problems that the invention aims to solve]

[0005] The objective of this specification is to provide a catalyst for producing polyolefins with excellent processability and a method for producing polyolefins with excellent processability, by satisfying all of the density, melt index, and melt index ratio described herein. [Means for solving the problem]

[0006] We provide a Ziegler-Natta catalyst for olefin polymerization.

[0007] According to one example, the Ziegler-Natta catalyst for olefin polymerization comprises a titanium compound represented by formula 1 below, a magnesium compound represented by formula 2 below, and an internal electron donor; an organoaluminum compound represented by formula 7 below; and an external electron donor represented by formula 3 below, wherein the internal electron donor is a mixture of a first internal electron donor selected from formulas 4 to 6 below, and a second internal electron donor selected from formulas 4 to 6 but different from the first internal electron donor, wherein in 10 moles of the mixture, the ratio of the first internal electron donor to the second internal electron donor is 3:7 to 7:3. In a specific example, the molar ratio may be approximately 3.5:6.5 to approximately 6.5:3.5, for example, approximately 4:6 to approximately 6:4, approximately 4.5:5.5 to approximately 5.5:4.5, or approximately 5:5.

[0008] [Formula 1] TiX n (OR 1 ) 4-n

[0009] (In the above formula 1,

[0010] R 1 C1-C is either substituted or non-substituted. 20 Alkyl, substituted or unsubstituted C3-C 20 Cycloalkyl groups, and substituted or unsubstituted C3-C 20 One of the groups selected from the group consisting of aryl groups,

[0011] X is a halogen atom,

[0012] n is an integer from 0 to 4, and

[0013] In the aforementioned substituted or unsubstituted configurations, the substituent is independently one or more selected from the group consisting of halogen groups, cyano groups, nitro groups, and C1-C8 alkyl groups.

[0014] [Formula 2] Mg(OR 2 ) k X 2-k

[0015] (In the above Formula 2,

[0016] R 2 is one selected from the group consisting of a substituted or unsubstituted C1-C 20 alkyl group, a substituted or unsubstituted C3-C 20 cycloalkyl group, and a substituted or unsubstituted C3-C 20 aryl group, and

[0017] X is a halogen atom, and

[0018] k is an integer from 0 to 2, and

[0019] the above-mentioned substituted or unsubstituted, and the substituents are independently one or more selected from the group consisting of a halogen group, a cyano group, a nitro group, and a C1-C8 alkyl group)

[0020] [Chemical formula]

[0021] (In the above Formula 3,

[0022] L1 and L2 are each independently a substituted or unsubstituted C1-C 20 alkyl group, the above-mentioned substituted or unsubstituted, and the substituents are independently one or more selected from the group consisting of a halogen group, a cyano group, a nitro group, and a C1-C8 alkyl group, and

[0023] L3 and L4 are each independently a substituted or unsubstituted C1-C 20 alkyl group, and one selected from the group consisting of a substituted or unsubstituted C3-C 20 cycloalkyl group, and

[0024] In the aforementioned substituted or unsubstituted configurations, the substituent is independently one or more selected from the group consisting of halogen groups, cyano groups, nitro groups, and C1-C8 alkyl groups.

[0025] [ka]

[0026] (In the above formula 4,

[0027] R 31 ,R 32 ,R 33 , and R 34 These are, independently, hydrogen, substituted or unsubstituted C1-C 20 Alkyl, substituted or unsubstituted C3-C 20 Cycloalkyl groups, and substituted or unsubstituted C3-C 20 One selected from the group consisting of aryl groups, or R 31 and R 33 These are C3-C that are linked together and can be substituted or not substituted. 20 It can form a cycloalkyl group,

[0028] R 4 and R 5 These are independently of substitution or non-substitution of C1-C 20 Alkyl, substituted or unsubstituted C3-C 20 Cycloalkyl groups, and substituted or unsubstituted C3-C 20 One of the groups selected from the group consisting of aryl groups,

[0029] In the aforementioned substituted or unsubstituted configurations, the substituent is independently one or more selected from the group consisting of halogen groups, cyano groups, nitro groups, and C1-C8 alkyl groups.

[0030] [ka]

[0031] (In formula 5 above,

[0032] R 6 ,R 7 , and R 8 These are independently of substitution or non-substitution of C1-C 20 Alkyl, substituted or unsubstituted C3-C 20 Cycloalkyl groups, and substituted or unsubstituted C3-C 20 One of the groups selected from the group consisting of aryl groups,

[0033] n is an integer from 0 to 4, and

[0034] In the aforementioned substituted or unsubstituted configurations, the substituent is independently one or more selected from the group consisting of halogen groups, cyano groups, nitro groups, and C1-C8 alkyl groups.

[0035] [ka]

[0036] (In formula 6 above,

[0037] R 9 and R 10 These are, independently, hydrogen, substituted or unsubstituted C1-C 20 Alkyl, substituted or unsubstituted C3-C 20 Cycloalkyl groups, and substituted or unsubstituted C3-C 20 One selected from the group consisting of aryl groups, or R 9 and R 10 These are C3-C that are linked together and can be substituted or not substituted. 20 It can form a cycloalkyl group,

[0038] R 11 and R 12 These are, independently, substituted or non-substituted C1-C 20 Alkyl, substituted or unsubstituted C3-C 20 Cycloalkyl groups, and substituted or unsubstituted C3-C 20 One of the groups selected from the group consisting of aryl groups,

[0039] In the aforementioned substituted or unsubstituted configurations, the substituent is independently one or more selected from the group consisting of halogen groups, cyano groups, nitro groups, and C1-C8 alkyl groups.

[0040] [Formula 7] Al(R 13 ) p X 3-p

[0041] (In formula 7 above,

[0042] R 13 This is a hydrogen atom, substituted or unsubstituted C1-C 20 Alkyl, substituted or unsubstituted C3-C 20 Cycloalkyl groups, and substituted or unsubstituted C3-C 20 It is one of the groups selected from the group consisting of aryl groups,

[0043] X is a halogen atom,

[0044] p is an integer from 0 to 3, and

[0045] In the aforementioned substituted or unsubstituted configurations, the substituent is independently one or more selected from the group consisting of halogen groups, cyano groups, nitro groups, and C1-C8 alkyl groups.

[0046] A method for producing polyolefins is provided.

[0047] According to one example, a method for producing polyolefins includes the step of polymerizing an olefin monomer in the presence of the Ziegler-Natta catalyst for olefin polymerization:

[0048] Polyolefin resin is provided.

[0049] According to one example, the product is manufactured by the above manufacturing method, and the MFR ratio (MI) is 21.6 / MI 2.16 ) is approximately 30.0 to approximately 50.0. In a specific example, the MFR ratio (MI 21.6 / MI2.16 ) can range from approximately 30.5 to approximately 49.5, for example, approximately 30.5 to approximately 33.5, approximately 33.5 to approximately 36.5, approximately 36.5 to approximately 39.5, approximately 39.5 to approximately 42.5, approximately 42.5 to approximately 45.5, and approximately 45.5 to approximately 48.5. [Effects of the Invention]

[0050] The Ziegler-Natta catalyst for olefin polymerization produces polyolefins with excellent processability by containing two specific internal electron donors in a specific weight ratio with a specific external electron donor, thereby satisfying all the density, melt index, and melt index ratios described in this specification. [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 communicated to the average person in the art.

[0052] Each drawing is described, and similar reference numerals are used for similar components. In the accompanying drawings, the dimensions of the structures are enlarged for clarity of the invention. Terms such as "first," "second," etc., can be used to describe various components, but the components should not be limited by such terms. The terms are used solely for the purpose of distinguishing one component from another. For example, a first component may be named a second component, and similarly, a second component may be named a first component, without falling outside the scope of the invention.

[0053] A singular expression includes plural expressions unless the context clearly indicates otherwise.

[0054] In this specification, terms such as “includes” or “have” indicate the presence of features, figures, stages, actions, components, parts, or combinations thereof described in the specification, and should be understood not to preclude the possibility of the presence or addition of one or more other features, figures, stages, actions, components, parts, or combinations thereof.

[0055] 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.

[0056] 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 given 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 of the given range, 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 of the given range, such as 10.5%, 15.5%, 25.5%, etc.

[0057] In recent years, as polyethylene has become more diverse in its applications, there has been a need for catalysts and manufacturing methods to produce polyethylene resins with excellent processability in order to improve the productivity of the resin.

[0058] In response to this problem, the present inventors conducted intensive research and, as a result, have provided an olefin-Ziegler-Natta catalyst and a method for producing polyolefins, which produce polyethylene with excellent processability by mixing two specific internal electron donors in the main catalyst with a specific molar ratio in relation to a specific external electron donor. Here, "excellent processability" can mean a high melt flow ratio.

[0059] Here, "polyethylene with excellent processability" can be a polyolefin that satisfies the following physical properties:

[0060] (i) Density: 0.950g / cm 3 ~0.965g / cm 3

[0061] (ii) Melting index: 0.1g / 10min to 10.0g / 10min

[0062] (iii) Melt flow ratio: 30.0~50.0

[0063] The density was measured according to ASTM D1505.

[0064] The melting index mentioned above is the value at a load of 2.16 kg, and was measured at 190°C with a load of 2.16 kg according to ASTM D1238.

[0065] The aforementioned melt flow ratio (MFR) is defined by ASTM D1238 as the melting index (MI) of 2.16 kg at 190°C. 2.16 ), and according to ASTM D1238, the melting index (MI) at 190°C in 21.6 kg. 21.6 ) measure the ratio between these MI 21.6 / MI 2.16 This is the calculated value.

[0066] Unless otherwise specified, "C1-C n "Alkyl group" refers to linear or branched primary alkyl groups, secondary alkyl groups (n≧3), and tertiary alkyl groups (n≧4) having 1 to n carbon atoms. For example, they can be functional groups such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, tert-butyl, and n-hexyl.

[0067] Unless otherwise specified, the aryl group refers to 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 such a derivative. For example, the monocyclic or polycyclic compounds containing benzene rings include benzene rings, toluene or xylene with alkyl side chains attached to benzene rings, biphenyls in which two or more benzene rings are linked by a single bond, fluorene, xanthene or anthraquinones in which benzene rings are condensed with cycloalkyl or heterocycloalkyl groups, and naphthalene or anthracene in which two or more benzene rings are condensed.

[0068] Unless otherwise specified, 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, this could include pyridine, pyrrole, or carbazole, which contain a nitrogen atom as a heteroatom; furan or dibenzofuran, which contain an oxygen atom as a heteroatom; or dibenzothiophene, diphenylamine, etc.

[0069] Unless otherwise specified, halogen groups refer to Group 17 elements, and can include, for example, fluoro groups, chloro groups, bromo groups, or iodine groups.

[0070] According to one example, the Ziegler-Natta catalyst for olefin polymerization includes a main catalyst comprising a titanium compound as described below, a magnesium compound as described below, and an internal electron donor; an organoaluminum compound as described below; and an external electron donor as described below, but containing two types of internal electron donors as described below in specific molar ratios.

[0071] Specifically, the Ziegler-Natta catalyst for olefin polymerization contains, in a specific molar ratio, an external electron donor represented by formula 3 below, and a first internal electron donor and a second internal electron donor, selected from formulas 4 to 6 below and having different chemical structures.

[0072] [External electron donor]

[0073] External electron donors can play a role in stabilizing the catalytic active sites of the titanium compound in the main catalyst. When the siloxane-based external electron donor represented by formula 3 below is applied to the first and second internal electron donors described below, it may facilitate the production of polyolefins with excellent processability.

[0074] The external electron donor can be represented by the following equation 3:

[0075] [ka]

[0076] (In the above formula 3,

[0077] L1 and L2 are independently substituted or non-substituted C1-C 20 The alkyl group, whether substituted or unsubstituted, has substituents that are independently one or more selected from the group consisting of halogen groups, cyano groups, nitro groups, and C1-C8 alkyl groups.

[0078] L3 and L4 are independently substituted or non-substituted C1-C 20 Alkyl groups, and substituted or unsubstituted C3-C 20It is one selected from the group consisting of cycloalkyl groups, and whether substituted or unsubstituted, the substituent is independently one or more selected from the group consisting of halogen groups, cyano groups, nitro groups, and C1-C8 alkyl groups.

[0079] In one specific example, at least one of L3 and L4 is a substituted or non-substituted C3-C 20 It can become a cycloalkyl group. In this case, when applied to the first internal electron donor and the second internal electron donor described below, it may be possible to easily produce polyolefins with excellent processability.

[0080] For example, either L3 or L4 is a substitute or non-substitute C3-C. 20 Cycloalkyl groups, e.g., substituted or unsubstituted C3-C 10 It can be a cycloalkyl group, a substituted or unsubstituted C5-C6 cycloalkyl group (first external electron donor).

[0081] For example, both L3 and L4 are C3-C with substitution or non-substitution. 20 Cycloalkyl groups, e.g., substituted or unsubstituted C3-C 10 It can be a cycloalkyl group, a substituted or unsubstituted C5-C6 cycloalkyl group (second external electron donor).

[0082] According to one example, the catalyst may include one type of external electron donor represented by formula 3, that is, either a first external electron donor alone or a second external electron donor alone.

[0083] In one embodiment, the catalyst may be a mixture containing two types of external electron donors represented by formula 3. In one specific example, the catalyst may be a mixture of the first external electron donor and the second external electron donor. For example, in 10 moles of the mixture, the ratio of the first external electron donor to the second external electron donor may be approximately 3:7 to 7:3, approximately 3.5:6.5 to 6.5:3.5, approximately 4:6 to 6:4, approximately 4.5:5.5 to 5.5:4.5, and approximately 5:5.

[0084] In one specific example, L1 and L2 are independently substituted or non-substituted C1-C 10 This can be an alkyl group, such as a substituted or unsubstituted C1-C5 alkyl group.

[0085] In one specific example, the external electron donor may include one or more of the following equations 3-1 and 3-2:

[0086] [ka]

[0087] [ka]

[0088] According to one example, the external electron donor may be included in a content of approximately 40% to 60% by weight, based on 100% by weight of the Ziegler-Natta catalyst for total olefin polymerization. In specific examples, the content may be approximately 42% to 58% by weight, for example, approximately 44% to 56%, approximately 46% to 54%, or approximately 48% to 52%. Within this content range, the stability of the catalytic active sites is high, and the problem of reduced activity due to poisoning of the catalytic active sites can be eliminated.

[0089] According to one example, the external electron donor represented by formula 3 may be present in the Ziegler-Natta catalyst for olefin polymerization in an amount of about 95% by weight or more, preferably about 99% to 100% by weight, and more preferably 100% by weight, based on 100% by weight of the total external electron donors contained. Within this range, the effects of the present invention can be easily realized. Here, "total external electron donor" may mean a compound that is independently contained in the olefin Ziegler-Natta catalyst in relation to the main catalyst, and is known to those skilled in the art to play a role in stabilizing the catalytic active sites of the titanium compound.

[0090] [Internal electron donor]

[0091] When the external electron donor is included in the olefin-Ziegler-Natta catalyst, the internal electron donor is selected so as to satisfy the above-described polyolefin excellent in processability, that is, a specific range of density, melt index, and melt index ratio. When the external electron donor is applied, the internal electron donor can provide various active sites, thereby enabling the production of a polyolefin resin excellent in processability.

[0092] The internal electron donor is a mixture of a first internal electron donor selected from the following formulas 4 to 6; and a second internal electron donor selected from the formulas 4 to 6 and different from the first internal electron donor. In 10 moles of the mixture, the first internal electron donor: the second internal electron donor is contained in a molar ratio of about 3:7 to about 7:3. In a specific example, the molar ratio can be about 3.5:6.5 to about 6.5:3.5, for example, about 4:6 to about 6:4, about 4.5:5.5 to about 5.5:4.5, about 5:5.

[0093]

Chemical formula

[0094] (In the formula 4,

[0095] R 31 ,R 32 ,R 33 , and R 34 are each independently one selected from the group consisting of hydrogen, a substituted or unsubstituted C1-C 20 alkyl group, a substituted or unsubstituted C3-C 20 cycloalkyl group, and a substituted or unsubstituted C3-C 20 aryl group, or R 31 and R 33 can be linked to each other to form a substituted or unsubstituted C3-C 20 cycloalkyl group,

[0096] R 4 and R 5 are independently a substituted or unsubstituted C1-C 20An alkyl group, a substituted or unsubstituted C3-C 20 cycloalkyl group, and a substituted or unsubstituted C3-C 20 aryl group, selected from the group consisting of one kind,

[0097] (wherein the substitution or non-substitution, the substituents are independently one or more selected from the group consisting of a halogen group, a cyano group, a nitro group, and a C1-C8 alkyl group)

[0098]

Chemical formula

[0099] (In the formula 5,

[0100] R 6 , R 7 , and R 8 are independently a substituted or unsubstituted C1-C 20 alkyl group, a substituted or unsubstituted C3-C 20 cycloalkyl group, and a substituted or unsubstituted C3-C 20 aryl group, selected from the group consisting of one kind,

[0101] n is an integer from 0 to 4, and

[0102] (wherein the substitution or non-substitution, the substituents are independently one or more selected from the group consisting of a halogen group, a cyano group, a nitro group, and a C1-C8 alkyl group)

[0103]

Chemical formula

[0104] (In the formula 6,

[0105] R 9 and R 10 are each independently hydrogen, a substituted or unsubstituted C1-C 20 alkyl group, a substituted or unsubstituted C3-C 20 It should be noted that there may be some inaccuracies in the original text, especially in the part where the chemical formula-related content is not very clear in terms of specific chemical structure representation. And the "六亲不认" in the translation of ID=51 seems to be an incorrect or misspelled content in the original. If possible, it is recommended to check and correct the original text for a more accurate translation.Cycloalkyl groups, and substituted or unsubstituted C3-C 20 It is one selected from the group consisting of aryl groups, or R 9 and R 10 These are C3-C that are linked together and can be substituted or not substituted. 20 It can form a cycloalkyl group,

[0106] R 11 and R 12 These are, independently, substituted or non-substituted C1-C 20 Alkyl, substituted or unsubstituted C3-C 20 Cycloalkyl groups, and substituted or unsubstituted C3-C 20 One of the groups selected from the group consisting of aryl groups,

[0107] In the aforementioned substituted or unsubstituted configurations, the substituent is independently one or more selected from the group consisting of halogen groups, cyano groups, nitro groups, and C1-C8 alkyl groups.

[0108] The mixture contains both a first internal electron donor and a second internal electron donor. With respect to the external electron donor, olefin-Ziegler-Natta catalysts containing either the first internal electron donor alone or the second internal electron donor alone may make it difficult to produce polyolefins that satisfy all of the above-mentioned density, melting index, and melting index ratio. In particular, it may be difficult to satisfy the above-mentioned melting index ratio, which may result in poor processability.

[0109] The mixture contains both a first internal electron donor and a second internal electron donor, but in 10 moles of the mixture, the ratio of the first internal electron donor to the second internal electron donor can be approximately 3:7 to 7:3 molars. In specific examples, the molar ratio can be approximately 3.5:6.5 to 6.5:3.5, for example, approximately 4:6 to 6:4, approximately 4.5:5.5 to 5.5:4.5, or approximately 5:5. At molar ratios less than approximately 3:7, for example, approximately 1:9 or 2:8, it may be difficult to produce polyolefins that satisfy all of the above-mentioned density, melting index, and melting index ratio, or the effect of adding internal electron donors on producing polyolefins with excellent processability may be weak. At molar ratios exceeding approximately 7:3, for example, approximately 8:2 or 9:1, it becomes difficult to produce polyolefins that satisfy all of the above-mentioned density, melt index, and melt index ratio requirements, or the effect of adding internal electron donors to produce polyolefins with excellent processability may be weak.

[0110] In one specific example, the mixture may contain the first internal electron donor and the second internal electron donor in molar ratios of approximately 3:7, approximately 3.5:6.5, approximately 4:6, approximately 4.5:5.5, approximately 5:5, approximately 5.5:4.5, approximately 6:4, approximately 6.5:3.5, and approximately 7:3.

[0111] In one specific example, in equation 4, R 4 and R 5 These are independently substituted or unsubstituted linear or branched C1-C 20 Alkyl groups, for example, C1-C 10 It can be an alkyl group or a C1-C5 alkyl group. For example, the compound of formula 4 may include one or more compounds represented by any of the following formulas 4-1 to 4-7 as a diethyl diester compound:

[0112] [ka] [ka]

[0113] In one specific example, in equation 5, R7 and R 8 These are independently substituted or unsubstituted linear or branched C1-C 20 Alkyl groups, for example, branched C1-C 10 It can be an alkyl group or a branched C1-C5 alkyl group. For example, the compound of formula 5 may include one or more compounds represented by the following formulas 5-1 to 5-2 as a diisopropyl diester compound:

[0114] [ka]

[0115] In one specific example, in equation 6, R 9 ,R 10 ,R 11 , and R 12 These are, independently, substituted or unsubstituted linear or branched C1-C 20 Alkyl groups, for example, linear C1-C 10 It can be an alkyl group, or a linear C1-C5 alkyl group. For example, the compound of formula 6 may include one or more compounds represented by any of the following formulas 6-1 to 6-4 as a diethyl diester compound:

[0116] [ka]

[0117] According to one example, the internal electron donor, i.e., the mixture, may be present in an amount of about 0.002 moles to about 0.008 moles, preferably about 0.003 moles to about 0.004 moles, or about 0.007 moles to about 0.008 moles, per mole of the external electron donor. Within this range, it may be easier to produce polyethylene that satisfies the density, melting index, and melting index ratio described above.

[0118] In one specific example, the mixture is a mixture of the compound of formula 4 and the compound of formula 5, and in 10 moles of the mixture of the compound of formula 4 and the compound of formula 5, the ratio of the compound of formula 4 to the compound of formula 5 may be about 3:7 to about 7:3 (first embodiment). In specific examples, the molar ratio may be about 3.5:6.5 to about 6.5:3.5, for example, about 4:6 to about 6:4, about 4.5:5.5 to about 5.5:4.5, or about 5:5.

[0119] In this first embodiment, the compound of formula 4 may be present in an amount of 0.001 to 0.007 moles, preferably 0.003 to 0.004 moles, and the compound of formula 5 may be present in an amount of 0.001 to 0.007 moles, preferably 0.003 to 0.004 moles, per mole of the external electron donor. Within this range, it may be possible to easily produce polyethylene with excellent processability.

[0120] In one specific example, the mixture is a mixture of the compound of formula 4 and the compound of formula 6, and in 10 moles of the mixture of the compound of formula 4 and the compound of formula 6, the ratio of the compound of formula 4 to the compound of formula 6 may be about 3:7 to about 7:3 (second embodiment). In a specific example, the molar ratio may be about 3.5:6.5 to about 6.5:3.5, for example, about 4:6 to about 6:4, about 4.5:5.5 to about 5.5:4.5, or about 5:5.

[0121] In this second embodiment, the compound of formula 4 may be present in an amount of 0.001 to 0.007 moles, preferably 0.003 to 0.004 moles, per mole of the external electron donor, and the compound of formula 6 may be present in an amount of 0.001 to 0.007 moles, preferably 0.003 to 0.004 moles. Within this range, it may be possible to easily produce polyethylene with excellent processability.

[0122] In one specific example, the mixture is a mixture of the compound of formula 5 and the compound of formula 6, and in 10 moles of the mixture of the compound of formula 5 and the compound of formula 6, the ratio of the compound of formula 5 to the compound of formula 6 may be about 3:7 to about 7:3 (third embodiment). In a specific example, the molar ratio may be about 3.5:6.5 to about 6.5:3.5, for example, about 4:6 to about 6:4, about 4.5:5.5 to about 5.5:4.5, or about 5:5.

[0123] In this third embodiment, the compound of formula 5 may be present in an amount of 0.001 to 0.007 moles, preferably 0.003 to 0.004 moles, per mole of the external electron donor, and the compound of formula 6 may be present in an amount of 0.001 to 0.007 moles, preferably 0.003 to 0.004 moles. Within this range, it may be possible to easily produce polyethylene with excellent processability.

[0124] According to one example, the mixture of the first internal electron donor and the second internal electron donor may be present in the Ziegler-Natta catalyst for olefin polymerization in an amount of about 95% by weight or more, preferably about 99% to 100% by weight, and more preferably 100% by weight, based on 100% by weight of the total internal electron donors contained in the Ziegler-Natta catalyst for olefin polymerization. Within this range, the production of polyethylene with excellent processability may be facilitated. Here, "total internal electron donor" may mean a compound contained in the main catalyst of the olefin Ziegler-Natta catalyst, which is known to those skilled in the art to play a role in stabilizing the catalytic active sites of the titanium compound.

[0125] [Titanium compounds]

[0126] Titanium compounds can be compounds containing an active center metal, that is, a metal with an active site. Titanium compounds can provide polyolefins by catalyzing the substantial polymerization reaction of olefin monomers.

[0127] Titanium compounds are compounds represented by the following formula 1.

[0128] [Formula 1] TiX n (OR 1 ) 4-n

[0129] (In the above formula 1,

[0130] R 1 C1-C is either substituted or non-substituted. 20 Alkyl, substituted or unsubstituted C3-C 20 Cycloalkyl groups, and substituted or unsubstituted C3-C 20 One of the groups selected from the group consisting of aryl groups,

[0131] X is a halogen atom,

[0132] n is an integer from 0 to 4, and

[0133] In the aforementioned substituted or unsubstituted configurations, the substituent is independently one or more selected from the group consisting of halogen groups, cyano groups, nitro groups, and C1-C8 alkyl groups.

[0134] For example, the titanium compound may be one or more selected from the group consisting of tetravalent titanium halides and tetravalent titanium alkoxides. Preferably, the titanium compound may be titanium tetrachloride (TiCl4).

[0135] [Magnesium compounds]

[0136] Magnesium compounds, as catalyst supports, can regulate properties such as the activity of active center metals with active sites, like titanium compounds, and stereoregularity, through bonding with electron donors, according to their molecular structure and bonding strength.

[0137] Magnesium compounds are compounds represented by the following formula 2:

[0138] [Formula 2] Mg(OR 2 ) k X 2-k

[0139] (In the above formula 2,

[0140] R 2 C1-C is either substituted or non-substituted. 20 Alkyl, substituted or unsubstituted C3-C 20 Cycloalkyl groups, and substituted or unsubstituted C3-C 20 One of the groups selected from the group consisting of aryl groups,

[0141] X is a halogen atom,

[0142] k is an integer between 0 and 2, and

[0143] In the aforementioned substituted or unsubstituted configurations, the substituent is independently one or more selected from the group consisting of halogen groups, cyano groups, nitro groups, and C1-C8 alkyl groups.

[0144] For example, the magnesium compound can be magnesium dialkoxide, magnesium diaryloxide, or magnesium chloride (MgCl2), and preferably magnesium dialkoxide, which can reduce impurities in the final synthesized catalyst with high purity and can be magnesium diethoxide, which has the advantage of being well soluble in the solvent during catalyst synthesis.

[0145] [Organoaluminum compounds]

[0146] Organoaluminum compounds can act as co-catalysts, activating the active sites of titanium compounds.

[0147] Organoaluminum compounds may include compounds of the following formula 7:

[0148] [Formula 7] Al(R 13 ) p X 3-p

[0149] (In formula 7 above,

[0150] R 13 This is a hydrogen atom, substituted or unsubstituted C1-C 20 Alkyl, substituted or unsubstituted C3-C 20 Cycloalkyl groups, and substituted or unsubstituted C3-C 20 It is one of the groups selected from the group consisting of aryl groups,

[0151] X is a halogen atom,

[0152] p is an integer from 0 to 3, and

[0153] In the aforementioned substituted or unsubstituted configurations, the substituent is independently one or more selected from the group consisting of halogen groups, cyano groups, nitro groups, and C1-C8 alkyl groups.

[0154] According to one example, the organoaluminum compound may be one or more selected from the group consisting of trimethylaluminum, triethylaluminum, triisobutylaluminum, trioctylaluminum, diethylaluminum hydride, diisobutylaluminum hydride, diethylaluminum chloride, diisobutylaluminum chloride, sesquiethylaluminum chloride, and ethylaluminum dichloride. Preferably, the organoaluminum compound may be triethylaluminum, which increases polymerization activity and facilitates the adjustment of the weight-average molecular weight of the polymerized polyolefin.

[0155] [Main catalyst]

[0156] The main catalyst includes a titanium compound represented by formula 1, a magnesium compound represented by formula 2, and an internal electron donor, wherein the titanium compound represented by formula 1 and the internal electron donor may be supported on the magnesium compound represented by formula 2.

[0157] According to one example, the main catalyst can be in powder form. As described below, the Ziegler-Natta catalyst for olefin polymerization according to one example can be produced by mixing the main catalyst with an organoaluminum compound and an external electron donor.

[0158] The main catalyst in powder form can be uniformly coated with the organoaluminum compound and the external electron donor. This facilitates the production of polyolefins having the aforementioned density, melt index, and melt index ratio by ensuring that the main catalyst in powder form is well dispersed in the organoaluminum compound and the external electron donor, thereby increasing dispersion stability.

[0159] A method for producing a Ziegler-Natta main catalyst for olefin polymerization may include the steps of: mixing a titanium compound represented by formula 1 and a magnesium compound represented by formula 2 and performing a first stirring; adding an internal electron donor to the result of the first stirring and performing a second stirring; and vacuum drying the result of the second stirring.

[0160] The first stirring step involves adding the titanium compound and magnesium compound to the organic solvent and then stirring them at room temperature until they reach a first temperature at a heating rate of 0.5°C / min to 1.5°C / min.

[0161] The organic solvent can be toluene, ether, acetone, alcohol, etc., and preferably toluene.

[0162] The first temperature can be approximately 70°C to 90°C, preferably approximately 75°C to 85°C. In specific examples, the first temperature can be approximately 72°C to 88°C, for example, approximately 72°C to 75°C, approximately 75°C to 80°C, approximately 80°C to 85°C, or approximately 85°C to 88°C. If the first temperature is outside this range and is too low, the internal electron donor will not dissolve in the solvent, which is a disadvantage. If the first temperature is too high, side reactions of the internal electron donor will occur, which is a disadvantage.

[0163] The second stirring step involves adding an internal electron donor to the first stirring result, raising the temperature to a second temperature, and stirring for approximately 1.8 hours to approximately 2.2 hours. In specific examples, this could be approximately 1.82 hours to approximately 1.9 hours, approximately 1.9 hours to approximately 2 hours, or approximately 2 hours to approximately 2.2 hours.

[0164] The second temperature can be about 100°C to about 120°C, preferably about 105°C to about 115°C. In specific examples, the second temperature can be about 102°C to about 118°C, for example, about 102°C to about 110°C or about 110°C to about 118°C. If the second temperature is outside this range and is too low, the titanium compound will not be supported on the magnesium compound, and if the second temperature is too high, the solvent will evaporate, which is another disadvantage.

[0165] After the second stirring step, a third stirring step may be further included. Specifically, this step involves removing the organic solvent and titanium compound, adding a new organic solvent and titanium compound, raising the temperature to a third temperature at room temperature, and stirring for approximately 1.8 to 2.2 hours. In specific examples, this could be approximately 1.82 to 1.9 hours, approximately 1.9 hours to 2 hours, or approximately 2 hours to 2.2 hours. After stirring, a step of washing the result of the third stirring with an organic solvent or the like may be further included.

[0166] The third temperature can be about 100°C to about 120°C, preferably about 105°C to about 115°C. In specific examples, the third temperature can be about 102°C to about 118°C, for example, about 102°C to about 110°C, or about 110°C to about 118°C.

[0167] The vacuum drying step involves drying the second or third stirring result under vacuum to obtain a powdered Ziegler-Natta main catalyst for olefin polymerization supported on a support. This step may further include washing the second or third stirring result with an organic solvent before vacuum drying.

[0168] [Ziegler-Natta catalyst for olefin polymerization]

[0169] The titanium compound and external electron donor in the Ziegler-Natta main catalyst for olefin polymerization may be present in a molar ratio of about 1:60 to about 1:380, preferably about 1:120 to about 1:190. In specific examples, the molar ratio may be about 1:62 to about 1:378, for example, about 1:62 to about 1:150, about 1:150 to about 1:250, or about 1:250 to about 1:378. Within this molar ratio range, the stability of the catalytic active site is excellent, and the problem of reduced catalyst activity due to poisoning of the catalytic active site can be eliminated.

[0170] The organoaluminum compounds and external electron donors of the Ziegler-Natta main catalyst for olefin polymerization are in a ratio of approximately 1:3.0 x 10⁻⁶. -7 ~Approx. 1:9.0x10 -7 Preferably about 1:5.0x10 -7 ~Approx. 1:7.0x10 -7 It may be included in the following molar ratio. In a specific example, the molar ratio is approximately 1:3.2 x 10 -7 ~Approx. 1:8.8x10 -7 For example, approximately 1:3.2x10 -7 ~About 1:5.0x10 -7 , about 1:5.0x10 -7 ~Approx. 1:7.0x10 -7 , about 1:7.0x10 -7 ~Approx. 1:8.8x10 -7 This can be achieved. Within the aforementioned molar ratio range, it may become easier to produce polyolefins with excellent processability.

[0171] The magnesium compound and external electron donor of the Ziegler-Natta main catalyst for olefin polymerization may be present in a molar ratio of about 1:9 to about 1:13, preferably about 1:10 to about 1:12. In specific examples, the molar ratio may be 1:9.2 to about 1:12.8, for example, about 1:9.2 to about 1:10.0, about 1:10.0 to about 1:11.0, or about 1:11.0 to about 1:12.8. Within this molar ratio range, the production of polyolefins with excellent processability can be facilitated.

[0172] The method for producing a Ziegler-Natta catalyst for olefin polymerization includes the step of adding a Ziegler-Natta main catalyst for olefin polymerization, an organoaluminum compound represented by formula 7, and an external electron donor represented by formula 3 to an organic solvent, followed by stirring. At this time, explanations of the method for producing a Ziegler-Natta catalyst for olefin polymerization that overlap with the explanation of the Ziegler-Natta catalyst for olefin polymerization may be omitted.

[0173] The organic solvent can be hexane, toluene, ether, acetone, alcohol, etc., and is preferably hexane.

[0174] The stirring speed can be approximately 280 rpm to approximately 320 rpm, preferably approximately 290 rpm to approximately 310 rpm. In specific examples, the stirring speed can be approximately 285 rpm to approximately 315 rpm, for example, approximately 285 rpm to approximately 295 rpm, approximately 295 rpm to approximately 305 rpm, or approximately 305 rpm to approximately 315 rpm.

[0175] [Method for producing polyolefins]

[0176] According to one example, a method for producing polyolefins includes the step of polymerizing an olefin monomer in the presence of the Ziegler-Natta catalyst for olefin polymerization.

[0177] According to one example, an olefin monomer may include an olefin monomer having the following formula 8:

[0178] [Formula 8] CH2=CHR 14

[0179] (In formula 8 above,

[0180] R 14 (These are hydrogen or a C1-C6 alkyl or aryl group.)

[0181] According to one embodiment, a method for producing polyolefins can be a method for producing polyethylene. Therefore, it may include the step of adding the olefin monomer, preferably ethylene, in the presence of a Ziegler-Natta catalyst for olefin polymerization and polymerizing it.

[0182] Polyolefins can be polymerized under conditions of approximately 6 bar to 8 bar pressure and approximately 80°C to 90°C in a hydrogen gas atmosphere. However, deviating from these temperature conditions has disadvantages: if the temperature is too low, the catalyst's activity cannot be utilized, and polymerization will not occur; if the temperature is too high, catalyst overreaction occurs, and the activity decreases rapidly.

[0183] The polymerization time can be approximately 0.5 hours to approximately 1.5 hours, preferably approximately 0.8 hours to approximately 1.2 hours.

[0184] According to one example, for every mole of an olefin monomer, the Ziegler-Natta catalyst for olefin polymerization contains approximately 1.0 x 10⁻¹⁶ molecules. -5 Moles ~ approximately 3.0 x 10 -5 Moles, preferably about 1.5 x 10⁻⁶ -5 Moles ~ approximately 2.5 x 10 -5 It may be contained in moles. In a specific example, for 1 mole of the olefin monomer, the Ziegler-Natta catalyst for olefin polymerization is present in approximately 1.2 x 10⁻¹⁶ units. -5 Moles ~ approximately 2.9 x 10 -5 moles, for example, about 1.2 x 10⁻⁶ -5 ~about 1.5x10 -5 , about 1.5x10 -5 ~about 2x10 -5 , about 2x10 -5 ~about 2.5x10 -5 , about 2.5x10 -5 ~Approximately 2.9 x 10 -5 This can be achieved. Within the aforementioned range, the polymerization yield of polyolefins from olefin monomers can be increased.

[0185] [Polyolefin resin]

[0186] According to one example, a polyolefin resin is provided. The polyolefin resin is produced by the above-mentioned manufacturing method, and has an MFR ratio (MI 21.6 / MI 2.16 ) is approximately 30.0 to approximately 50.0. In a specific example, the MFR ratio (MI 21.6 / MI 2.16 ) can range from approximately 30.5 to approximately 49.5, for example, approximately 30.5 to approximately 33.5, approximately 33.5 to approximately 36.5, approximately 36.5 to approximately 39.5, approximately 39.5 to approximately 42.5, approximately 42.5 to approximately 45.5, and approximately 45.5 to approximately 48.5.

[0187] 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.

[0188] The specific specifications of the components used in the following examples and comparative examples are as follows:

[0189] External electron donor:

[0190] [ka]

[0191] Internal electron donor:

[0192] [ka]

[0193] [ka]

[0194] [ka]

[0195] Example 1

[0196] Manufacturing Example 1: Production of Ziegler-Natta main catalyst for olefin polymerization

[0197] 4 g of magnesium compound Mg(OC2H5)2 support and 45 ml of titanium compound TiCl were placed in 35 ml of toluene, and the temperature was raised to 80°C at room temperature at a rate of 1°C / min, with first stirring at 300 rpm. After the reaction temperature reached 80°C, 1.4 mmol of formula 4-1, which is an internal electron donor, and 0.6 mmol of formula 5-1 were added to the first stirring result, and the temperature was raised to 110°C at a rate of 1°C / min, followed by second stirring while maintaining the temperature for 2 hours. Then, the TiCl4 + Toluene solution was removed, and a new TiCl4 (13 ml) + toluene (20 ml) solution was added, and the temperature was raised to 100°C at room temperature at a rate of 1°C / min, followed by third stirring while maintaining the temperature for 2 hours. Subsequently, the supported catalyst, which was the result of the third stirring, was washed four times with 50 ml of toluene at 100°C and twice with 50 ml of hexane at 60°C, and then dried under vacuum to obtain a powdered Ziegler-Natta main catalyst (supported catalyst) for olefin polymerization.

[0198] Manufacturing Example 2: Production of Ziegler-Natta catalyst and polyethylene for olefin polymerization

[0199] After drying a 2-liter high-pressure reactor in an oven, it was assembled while still hot, and the reactor was subjected to a nitrogen atmosphere by alternating between nitrogen and vacuum three times. Then, 1000 ml of hexane, an organic solvent, was added to the reactor, followed by 15 mg of the Ziegler-Natta main catalyst for olefin polymerization (Production Example 1), 0.24 ml of the external electron donor formula 3-1 (a solution diluted in hexane at a 1 / 20 volume ratio), and 2 mmol of triethylaluminum (a co-catalyst) (2 ml of 1 M hexane solution). The Ziegler-Natta catalyst for olefin polymerization was then produced while stirring at 300 rpm.

[0200] Subsequently, the reactor temperature was raised to 85°C, and after a single injection of 3 bar of hydrogen, polyethylene polymerization was carried out for 1 hour while continuously supplying ethylene at a constant pressure of 7 bar. After that, the reactor temperature was lowered to room temperature, and the resulting polymer was separated, collected, and dried to obtain a white powder polyethylene polymer.

[0201] Examples 2 to 27

[0202] In Example 1, except that the internal electron donor and the external electron donor were changed as shown in Table 1 below, a Ziegler-Natta main catalyst for olefin polymerization and a Ziegler-Natta catalyst for olefin polymerization were produced in the same manner as in Example 1, and polyethylene was produced.

[0203] Comparative Example 1

[0204] Manufacturing Example 1: Production of Ziegler-Natta main catalyst for olefin polymerization

[0205] 4 g of a magnesium compound Mg(OC2H5)2 support and 5 ml of a titanium compound TiCl4 were placed in 35 ml of toluene, and the temperature was raised from room temperature to 80 °C at a rate of 1 °C / min, and the first stirring was carried out at 300 rpm. Next, when the reaction temperature reached 80 °C, 2.0 mmol of Formula 4-1, which is an internal electron donor, was added to the product of the first stirring, and after raising the temperature to 110 °C at a rate of 1 °C, the second stirring was carried out for (maintained for) 2 hours while maintaining the temperature. Then, the TiCl4 + toluene solution was removed, and after adding new TiCl4 (13 ml) + toluene (20 ml), the temperature was raised from room temperature to 100 °C at a rate of 1 °C / min, and the third stirring was carried out for 2 hours while maintaining the temperature. Next, the supported catalyst, which is the product of the third stirring, was washed four times with 50 ml of toluene at 100 °C and twice with 50 ml of hexane at 60 °C, and dried in vacuo to obtain a powdery Ziegler-Natta main catalyst for olefin polymerization (supported catalyst).

[0206] Manufacturing Example 2: Production of Ziegler-Natta catalyst and polyethylene for olefin polymerization

[0207] After drying a 2-liter capacity high-pressure reactor in an oven, it was assembled while still hot, and the reactor was subjected to a nitrogen atmosphere by alternating between nitrogen and vacuum three times. Then, 1000 ml of hexane, an organic solvent, was added to the reactor, followed by 15 mg of the Ziegler-Natta main catalyst for olefin polymerization (Production Example 1), 0.24 ml of the external electron donor formula 3-1 (a solution diluted in hexane at a 1 / 20 volume ratio), and 2 mmol of triethylaluminum (a co-catalyst) (2 ml of 1 M hexane solution). The Ziegler-Natta catalyst for olefin polymerization was then produced while stirring at 300 rpm.

[0208] Subsequently, the reactor temperature was raised to 85°C, and after injecting 3 bar of hydrogen once, the ethylene pressure was continuously maintained at a constant pressure of 7 bar. (For every 1 mole of ethylene, the Ziegler-Natta catalyst for olefin polymerization was 2.0 x 10⁻¹⁰.) -5 Polyethylene polymerization was carried out for 1 hour while adding (in moles). After that, the reactor temperature was lowered to room temperature, and the resulting polymer was separated, collected, and dried to obtain a white powder polyethylene polymer.

[0209] Comparative Examples 2 to 15

[0210] In Comparative Example 1, the internal and external electron donors were changed as shown in Table 1 below, but the Ziegler-Natta main catalyst for olefin polymerization and the Ziegler-Natta catalyst for olefin polymerization were produced in the same manner as in Comparative Example 1, and polyethylene was produced.

[0211] Methods for evaluating the physical properties of polyethylene

[0212] Activity (G PE / Gcat) (Unit: none): Weight of resin obtained (g) / Weight of catalyst (g)

[0213] MI 2.16 (Unit: g / 10min) and MI 21.6(Unit: g / 10min): Using the TOYOSEIKI MELT INDEXER P-101 measuring device, a load of 2.16 kg was applied at 190°C according to ASTM D1238 (MI). 2.16 ) and a load of 21.6 kg (MI 21.6 ) Measured

[0214] Melt flow ratio: Melt index MI 21.6 and MI 2.16 Each was measured according to ASTM D1238, and the ratio was used to determine the MFR = (MI 21.6 / MI 2.16 )

[0215] Density (unit: g / cm³) 3 ): Measured by ASTM D1505

[0216] [Table 1] [ka]

[0217] *In Table 1 above,

[0218] The total number of moles of internal electron donors is 0.0038 mmol.

[0219] The total number of moles of the external electron donor is 1.2 mmol.

[0220] In the external electron donor, in equation 3-1 + equation 3-2, the molar ratio of equation 3-1 to equation 3-2 is 1:1

[0221] Referring to Table 1 above, the Ziegler-Natta catalyst for olefin polymerization in the examples produced polyolefins that simultaneously satisfied the density, melting index, and melting index ratio of this application.

[0222] On the other hand, Ziegler-Natta catalysts for olefin polymerization that do not meet the configuration of the present application were unable to produce polyolefins that simultaneously meet the density, melt index, and melt index ratio of the present application.

[0223] Simple modifications or changes of the present invention can be easily implemented by those with ordinary knowledge in this field, and all such modifications and changes can be regarded as being included in the scope of the present invention.

Industrial Applicability

[0224] The Ziegler-Natta catalyst for olefin polymerization contains two specific internal electron donors in a specific weight ratio with a specific external electron donor, and by satisfying all of the density, melt index, and melt index ratio described in the specification of the present application, a polyolefin with excellent processability was produced.

Claims

1. A Ziegler-Natta main catalyst for olefin polymerization comprising a titanium compound represented by formula 1 below, a magnesium compound represented by formula 2 below, and an internal electron donor; Organic aluminum compounds represented by the following formula 7; and Includes an external electron donor represented by the following formula 3; The internal electron donor is a mixture of a first internal electron donor selected from compounds represented by the following formulas 4 to 6, and a second internal electron donor selected from compounds represented by the following formulas 4 to 6, which is different from the first internal electron donor. A Ziegler-Natta catalyst for olefin polymerization, comprising 10 moles of the aforementioned mixture, wherein the first internal electron donor and the second internal electron donor are present in a molar ratio of 3:7 to 7:

3. [Formula 1] TiX ｎ (OR １ ) ４－ｎ (In the above formula 1, R １ is one selected from the group consisting of a substituted or unsubstituted C １ -C ２０ alkyl group, a substituted or unsubstituted C ３ -C ２０ cycloalkyl group, and a substituted or unsubstituted C ３ -C ２０ aryl group X is a halogen atom, n is an integer from 0 to 4, and In the aforementioned substituted or unsubstituted configurations, the substituents are independently halogen groups, cyano groups, nitro groups, and C １ -C ８ (One or more alkyl groups selected from the group consisting of alkyl groups.) [Formula 2] Mg(OR ２ ) ｋ X ２－ｋ (In the above equation 2, R ２ C is either substituted or non-substituted. １ -C ２０ Alkyl, substituted or unsubstituted C ３ -C ２０ Cycloalkyl groups, and substituted or unsubstituted C ３ -C ２０ One of the groups selected from the group consisting of aryl groups, X is a halogen atom, k is an integer between 0 and 2, and In the aforementioned substituted or unsubstituted configurations, the substituents are independently halogen groups, cyano groups, nitro groups, and C １ -C ８ (One or more alkyl groups selected from the group consisting of alkyl groups.) 【Chemistry 1】 (In the above equation 3, L １ and L ２ These are, independently, substitute or non-substitute C. １ -C ２０ With an alkyl group, In the aforementioned substituted or unsubstituted configurations, the substituents are independently halogen groups, cyano groups, nitro groups, and C １ -C ８ One or more alkyl groups selected from the group consisting of alkyl groups, L ３ and L ４ These are, independently, substitute or non-substitute C. １ -C ２０ Alkyl alkyl groups, and substituted or unsubstituted C ３ -C ２０ It is one of the types selected from the group consisting of cycloalkyl groups, In the aforementioned substituted or unsubstituted configurations, the substituents are independently halogen groups, cyano groups, nitro groups, and C １ -C ８ (One or more alkyl groups selected from the group consisting of alkyl groups). 【Chemistry 2】 (In the above equation 4, R ３１ , R ３２ , R ３３ , and R ３４ These are, independently, hydrogen, substituted or unsubstituted C １ -C ２０ Alkyl, substituted or unsubstituted C ３ -C ２０ Cycloalkyl groups, and substituted or unsubstituted C ３ -C ２０ One selected from the group consisting of aryl groups, or R ３１ and R ３３ These are C's that can be linked together to be substituted or non-substituted. ３ -C ２０ It can form a cycloalkyl group, R ４ and R ５ Independently, C is either substituted or non-substituted. １ -C ２０ Alkyl, substituted or unsubstituted C ３ -C ２０ Cycloalkyl groups, and substituted or unsubstituted C ３ -C ２０ One of the groups selected from the group consisting of aryl groups, In the aforementioned substituted or unsubstituted configurations, the substituents are independently halogen groups, cyano groups, nitro groups, and C １ -C ８ (One or more alkyl groups selected from the group consisting of alkyl groups.) 【Transformation 3】 (In the above equation 5, R ６ , R ７ , and R ８ Independently, C is either substituted or non-substituted. １ -C ２０ Alkyl, substituted or unsubstituted C ３ -C ２０ Cycloalkyl groups, and substituted or unsubstituted C ３ -C ２０ One of the groups selected from the group consisting of aryl groups, n is an integer from 0 to 4, and In the aforementioned substituted or unsubstituted configurations, the substituents are independently halogen groups, cyano groups, nitro groups, and C １ -C ８ (One or more alkyl groups selected from the group consisting of alkyl groups.) 【Chemistry 4】 (In the above equation 6, R ９ and R １０ These are, independently, hydrogen, substituted or unsubstituted C １ -C ２０ Alkyl, substituted or unsubstituted C ３ -C ２０ Cycloalkyl groups, and substituted or unsubstituted C ３ -C ２０ One selected from the group consisting of aryl groups, or R ９ and R １０ These are C's that can be linked together to be substituted or non-substituted. ３ -C ２０ It can form a cycloalkyl group, R １１ and R １２ each independently represents a substituted or unsubstituted C １ -C ２０ alkyl group, a substituted or unsubstituted C ３ -C ２０ cycloalkyl group, and a substituted or unsubstituted C ３ -C ２０ aryl group, and is selected from the group consisting of one kind thereof In the aforementioned substituted or unsubstituted configurations, the substituents are independently halogen groups, cyano groups, nitro groups, and C １ -C ８ (One or more selected from the group consisting of alkyl groups) [Formula 7] Al(R １３ ) ｐ X ３－ｐ (In the above formula 7, R １３ C is a hydrogen atom, substituted or unsubstituted. １ -C ２０ Alkyl, substituted or unsubstituted C ３ -C ２０ Cycloalkyl groups, and substituted or unsubstituted C ３ -C ２０ It is one of the groups selected from the group consisting of aryl groups, X is a halogen atom, p is an integer from 0 to 3, and In the aforementioned substituted or unsubstituted configurations, the substituents are independently halogen groups, cyano groups, nitro groups, and C １ -C ８ (One or more alkyl groups selected from the group consisting of alkyl groups).

2. The Ziegler-Natta catalyst for olefin polymerization according to claim 1, wherein the mixture is a mixture of the compound of formula 4 and the compound of formula 5, and in 10 moles of the mixture of the compound of formula 4 and the compound of formula 5, the compound of formula 4 and the compound of formula 5 are contained in a molar ratio of 3:7 to 7:

3.

3. The Ziegler-Natta catalyst for olefin polymerization according to claim 1, wherein the mixture is a mixture of the compound of formula 4 and the compound of formula 6, and in 10 moles of the mixture of the compound of formula 4 and the compound of formula 6, the compound of formula 4 and the compound of formula 6 are contained in a molar ratio of 3:7 to 7:

3.

4. The Ziegler-Natta catalyst for olefin polymerization according to claim 1, wherein the mixture is a mixture of the compound of formula 5 and the compound of formula 6, and in 10 moles of the mixture of the compound of formula 5 and the compound of formula 6, the compound of formula 5 and the compound of formula 6 are contained in a molar ratio of 3:7 to 7:

3.

5. The Ziegler-Natta catalyst for olefin polymerization according to claim 1, wherein the compound of formula 4 comprises one or more compounds represented by any one of the following formulas 4-1 to 4-7, the compound of formula 5 comprises one or more compounds represented by the following formulas 5-1 to 5-2, and the compound of formula 6 comprises one or more compounds represented by any one of the following formulas 6-1 to 6-4. 【Transformation 5】 【Transformation 6】 【Transformation 7】

6. The Ziegler-Natta catalyst for olefin polymerization according to claim 1, wherein the internal electron donor is contained in an amount of 0.002 moles to 0.008 moles per mole of the external electron donor.

7. The external electron donor is L in formula 3. ３ and L ４ At least one of them is a substituted or unsubstituted C ３ -C ２０ The Ziegler-Natta catalyst for olefin polymerization according to claim 1, wherein the catalyst is a cycloalkyl group.

8. The external electron donor is L in formula 3. ３ and L ４ One of these is a substitution or non-substitution C. ３ -C ２０ The first external electron donor is a cycloalkyl group, and L in formula 3. ３ and L ４ Both are substitutional or non-substitutional C ３ -C ２０ The Ziegler-Natta catalyst for olefin polymerization according to claim 7, comprising a mixture of second external electron donors, which are cycloalkyl groups.

9. The Ziegler-Natta catalyst for olefin polymerization according to claim 8, wherein the first external electron donor and the second external electron donor are present in a molar ratio of 3:7 to 7:3 in 10 moles of the mixture.

10. The Ziegler-Natta catalyst for olefin polymerization according to claim 7, wherein the external electron donor comprises one or more compounds selected from those represented by the following formulas 3-1 and 3-2. 【Transformation 8】

11. The Ziegler-Natta catalyst for olefin polymerization according to claim 1, wherein the external electron donor is contained in an amount of 40% to 60% by weight based on 100% by weight of the Ziegler-Natta catalyst for olefin polymerization.

12. The Ziegler-Natta catalyst for olefin polymerization according to claim 1, wherein the mixture of the first internal electron donor and the second internal electron donor is present in an amount of 95% by weight or more, based on 100% by weight of all internal electron donors contained in the Ziegler-Natta catalyst for olefin polymerization.

13. A method for producing polyolefins, comprising the step of polymerizing an olefin monomer in the presence of a Ziegler-Natta catalyst for olefin polymerization according to any one of claims 1 to 12.

14. For every 1 mole of the olefin monomer, the amount of the Ziegler-Natta catalyst for olefin polymerization is 1.0 x 10⁻¹⁶. －５ ~3.0 x 10 －５ A method for producing polyolefin according to claim 13, which is contained in moles.

15. Manufactured by the manufacturing method described in claim 13, with an MFR ratio (MI ２１．６ / MI ２．１６ A polyolefin resin characterized in that the ratio is 30.0 to 50.0.

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