Ziegler-Natta catalyst for olefin polymerization and method for producing polyolefins

Abstract

This invention relates to a Ziegler-Natta catalyst for olefin polymerization and a method for producing polyolefins with excellent processability using the same. The Ziegler-Natta catalyst for olefin polymerization is characterized by its ability to produce polyolefins with excellent processability because it contains at least one external electron donor that satisfies a specific formula based on an alkoxysilane (silicate), thereby increasing the number of active sites of the titanium compound.

Description

[Technical Field]

[0001] This invention relates to a Ziegler-Natta catalyst for olefin polymerization and a method for producing polyolefins with excellent processability using the same. [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. Such 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. As a result, 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.

[0004] (Patent Document 1) KR10-2423660B [Overview of the project] [Problems that the invention aims to solve]

[0005] The objective is to provide a Ziegler-Natta catalyst for olefin polymerization comprising at least one external electron donor satisfying a specific formula; a method for producing polyolefins using the catalyst; and a polyolefin with excellent processability produced thereby. [Means for solving the problem]

[0006] The Ziegler-Natta catalyst for olefin polymerization on one side includes a Ziegler-Natta pro-catalyst for olefin polymerization containing a titanium compound represented by the following formula 1, a magnesium compound represented by the following formula 2, and an internal electron donor represented by the following formula 3; an organoaluminum compound represented by the following formula 4; and an external electron donor represented by the following formula 5.

[0007] [Formula 1] TiX (OR 1 ) 4-n (In the above formula 1, R 1 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, X is a halogen atom, n is an integer from 0 to 4, and 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) [Formula 2] Mg(OR 2 [[ID=​​​​​​​​​​​​​​​​​​​​​​​

[0008] [ka]

[0009] (In the above formula 3, R 3 This includes hydrogen atoms, halogen atoms, and substituted or unsubstituted C1-C atoms. 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, 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, m is an integer from 0 to 4, and 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. [Formula 4] Al(R 6 ) p X 3-p (In formula 4 above, R 6 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 One of the groups selected from the group consisting of aryl groups, X is a halogen atom, p is an integer between 0 and 3, and 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. [Formula 5]

[0010] [ka]

[0011] (In formula 5 above, R 7 , R 8 , R 9 and R 10 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 It is one selected from the group consisting of aryl groups, and 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. The internal electron donor may be one or more selected from the group consisting of diisobutyl phthalate, diethyl phthalate, di-n-butyl phthalate, di-n-octyl phthalate, and diisooctyl phthalate.

[0012] The aforementioned external electron donor may be one or more compounds selected from the group consisting of compounds represented by the following formulas 5-1 and 5-2.

[0013] [Formula 5-1]

[0014] [ka]

[0015] (In the above formula 5-1, R 11 , R 12 , and R 13 These are independently substituted or unsubstituted C1-C2 alkyl groups, R 14 and R 15 These are independently of substitution or non-substitution of C1-C 20 Alkyl, substituted or unsubstituted C3-C 20Cycloalkyl groups, and substituted or unsubstituted C3-C 20 One of the groups selected from the group consisting of aryl groups, R 16 This consists of a hydrogen atom, a halogen group, and a substituted or unsubstituted C1-C group. 20 Alkyl, substituted or unsubstituted C3-C 20 Cycloalkyl groups, and substituted or unsubstituted C3-C 20 It is one selected from the group consisting of aryl groups, and 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. [Formula 5-2]

[0016] [ka]

[0017] (In equation 5-2 above, R 11 and R 12 These are independently substituted or unsubstituted C1-C2 alkyl groups, R 17 , R 18 , and R 20 ~R 22 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, R 19 This consists of a hydrogen atom, a halogen group, and a substituted or unsubstituted C1-C group. 20 Alkyl, substituted or unsubstituted C3-C 20 Cycloalkyl groups, and substituted or unsubstituted C3-C 20 It is one selected from the group consisting of aryl groups, and 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. The external electron donor may be one or more compounds selected from the group consisting of compounds represented by the following formulas 5-1a, 5-1b, 5-1c, 5-1d, 5-2a, and 5-2b.

[0018] [Formula 5-1a]

[0019] [ka]

[0020] [Formula 5-1b]

[0021] [ka]

[0022] [Formula 5-1c]

[0023] [ka]

[0024] [Formula 5-1d]

[0025] [ka]

[0026] [Formula 5-2a]

[0027] [ka]

[0028] [Formula 5-2b]

[0029] [ka]

[0030] In another specific example, the external electron donor may be two compounds selected from those represented by formulas 5-1a, 5-1b, 5-1c, 5-1d, 5-2a, and 5-2b.

[0031] The molar ratio of the titanium compound to the external electron donor in the Ziegler-Natta main catalyst for olefin polymerization can be approximately 1:3 to 9. In specific examples, the molar ratio of the titanium compound to the external electron donor in the Ziegler-Natta main catalyst for olefin polymerization can be approximately 1:3.1 to 8.8, for example, approximately 1:3.5, 1:4, 1:4.5, 1:5, 1:5.5, 1:6, 1:6.5, 1:7, 1:7.5, 1:8, and 1:8.5.

[0032] Another aspect of the method for producing polyolefins includes the step of polymerizing an olefin having the following formula 6 in the presence of a Ziegler-Natta catalyst for olefin polymerization containing an external electron donor represented by the following formula 5;

[0033] [Formula 5]

[0034] [ka]

[0035] (In formula 5 above, R 7 , R 8 , R 9 , and R 10 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 It is one selected from the group consisting of aryl groups, and 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. [Formula 6] CH2=CHR 23 (In formula 6 above, R 23 (These are hydrogen or a C1-C6 alkyl or aryl group.) The aforementioned external electron donor may be one or more compounds selected from the group consisting of compounds represented by the following formulas 5-1 and 5-2.

[0036] [Formula 5-1]

[0037] [ka]

[0038] (In the above formula 5-1, R 11 , R 12 , and R 13 These are independently substituted or unsubstituted C1-C2 alkyl groups, R 14 and R 15 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, R 16 This consists of a hydrogen atom, a halogen group, and a substituted or unsubstituted C1-C group. 20 Alkyl, substituted or unsubstituted C3-C 20 Cycloalkyl groups, and substituted or unsubstituted C3-C 20 It is one selected from the group consisting of aryl groups, and 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. [Formula 5-2]

[0039] [ka]

[0040] (In equation 5-2 above, R11 and R 12 is, independently, a substituted or unsubstituted C1-C2 alkyl group, R 17 R 18 and R 20 ~R 22 is, independently, 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, R 19 is a hydrogen atom, a halogen group, 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 in the above substituted or unsubstituted, 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) The external electron donor can be one or more selected from the group consisting of compounds represented by the following formula 5-1a, formula 5-1b, formula 5-1c, formula 5-1d, formula 5-2a, and formula 5-2b.

[0041] [Formula 5-1a]

[0042] [Chemical formula]<​​​​​​​​​​​​​​​​​​​​​​​​​

[0047] [Formula 5-1d]

[0048] [ka]

[0049] [Formula 5-2a]

[0050] [ka]

[0051] [Formula 5-2b]

[0052] [ka]

[0053] In another specific example, the external electron donor may be two compounds selected from those represented by formulas 5-1a, 5-1b, 5-1c, 5-1d, 5-2a, and 5-2b.

[0054] The molar ratio of the titanium compound to the external electron donor in the Ziegler-Natta main catalyst for olefin polymerization contained in the aforementioned Ziegler-Natta catalyst for olefin polymerization can be approximately 1:3 to 9. In specific examples, the molar ratio of the titanium compound to the external electron donor in the Ziegler-Natta main catalyst for olefin polymerization can be approximately 1:3.1 to 8.8, for example, approximately 1:3.5, 1:4, 1:4.5, 1:5, 1:5.5, 1:6, 1:6.5, 1:7, 1:7.5, 1:8, and 1:8.5.

[0055] The polymerization described above can be carried out by supplying the olefin at a pressure of approximately 6 bar to approximately 8 bar and polymerizing it at a temperature of approximately 80°C to approximately 90°C for approximately 0.5 hours to approximately 1.5 hours.

[0056] The polyolefin resin according to another aspect is manufactured by the method for manufacturing polyolefin according to the present invention, and is characterized in that the MFR ratio (MFR 21.6 / MFR 2.16 ) is about 33.0 to about 44.0. In a specific example, the MFR ratio (MFR 21.6 / MFR 2.16 ) can be about 33.1 to 43.2, for example, 33.8, 36.5, 39.2, 40.2.

Advantages of the Invention

[0057] The Ziegler-Natta catalyst for olefin polymerization can increase the number of active sites of the titanium compound by containing at least one external electron donor satisfying a specific formula based on alkoxysilane (silicate), and thus has the characteristic of being able to produce a polyolefin with excellent processability.

Modes for Carrying Out the Invention

[0058] The above objects, other objects, features, and advantages are considered to be easily understood through the following preferred embodiments related to the accompanying drawings. However, it is not limited to the embodiments described here and can be embodied in other forms. Rather, the embodiments introduced here are provided so that the disclosed content becomes thorough and complete, and the technical idea can be sufficiently conveyed to an ordinary technician.

[0059] Each drawing is described, and similar reference numerals are used for similar components. In the accompanying drawings, the dimensions of 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 to distinguish one component from another. For example, a first component may be named a second component, and a similar second component may also be named a first component, without falling outside the scope of the invention. Singular expressions include plural expressions unless the context clearly indicates otherwise.

[0060] 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.

[0061] 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.

[0062] 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.

[0063] 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.

[0064] In response to this problem, the inventors diligently conducted research and discovered that in the case of a Ziegler-Natta catalyst for olefin polymerization containing at least one external electron donor that satisfies a specific formula based on alkoxysilane (silicate), it is possible to increase the number of active sites of the titanium compound and produce polyolefins with excellent processability, and have now completed this process.

[0065] Unless otherwise specified, "C1-C n "Alkyl group" refers to 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.

[0066] 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.

[0067] 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.

[0068] Unless otherwise specified, halogen groups refer to Group 17 elements, and can include, for example, fluoro groups, chloro groups, bromo groups, or iodine groups.

[0069] A Ziegler-Natta catalyst for olefin polymerization according to one embodiment comprises a Ziegler-Natta pro-catalyst for olefin polymerization containing a titanium compound represented by formula 1, a magnesium compound represented by formula 2, and an internal electron donor represented by formula 3; an organoaluminum compound represented by formula 4; and an external electron donor represented by formula 5.

[0070] [Formula 1] TiX n (OR 1 ) 4-n In Equation 1, R 1 C1-C is either substituted or non-substituted. 20Alkyl, 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, X is a halogen atom, n is an integer from 0 to 4, and In the substituted or unsubstituted configurations described above, 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.

[0071] [Formula 2] Mg(OR 2 ) k X 2-k In equation 2, 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, X is a halogen atom, k is an integer between 0 and 2, and In the substituted or unsubstituted configurations described above, 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] [Formula 3]

[0073] [ka]

[0074] In equation 3, R 3 This includes hydrogen atoms, halogen atoms, and substituted or unsubstituted C1-C atoms. 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, R 4 and R5 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, m is an integer from 0 to 4, and In the substituted or unsubstituted configurations described above, 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.

[0075] [Formula 4] Al(R 6 ) p X 3-p In equation 4, R 6 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 One of the groups selected from the group consisting of aryl groups, X is a halogen atom, p is an integer between 0 and 3, and In the substituted or unsubstituted configurations described above, 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.

[0076] [Formula 5]

[0077] [ka]

[0078] In equation 5, R 7 , R 8 , R 9 , and R 10 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-C20 One selected from the group consisting of aryl groups, and In the substituted or unsubstituted configurations described above, 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.

[0079] According to one embodiment, the Ziegler-Natta Pro-catalyst for olefin polymerization is a catalyst component comprising a titanium compound having active sites, a magnesium compound serving as a catalyst support, and an internal electron donor that binds to the catalyst support and activates the active sites of the titanium compound, and preferably exists in powder form. According to one embodiment, the Ziegler-Natta catalyst for olefin polymerization may further contain an organoaluminum compound serving as a co-catalyst and an external electron donor that further activates the active sites, thereby including a titanium compound with more activated active sites.

[0080] According to one embodiment, the titanium compound is an active center metal, that is, a metal having an active site through which a substantial polymerization reaction can be carried out. According to one embodiment, the titanium compound may be one or more selected from the group consisting of tetravalent titanium halides and titanium alkoxides, preferably titanium tetrachloride (TiCl4), titanium trichloride (TiCl3), etc.

[0081] According to one embodiment, magnesium compounds have the characteristic that, as catalyst supports, they can later control properties such as the activity of active center metals having active sites, like titanium compounds, and stereoregularity, according to their molecular structure and bond strength through bonding with electron donors. According to one embodiment, the magnesium compound is 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 become magnesium diethoxide, which has the advantage of being well soluble in the solvent during catalyst synthesis.

[0082] According to one embodiment, the internal electron donor has the characteristic of being able to adjust the activity and stereoregularity of the titanium compound through bonding with the magnesium compound that serves as the catalyst support. According to one embodiment, the internal electron donor may be one or more selected from the group consisting of diisobutyl phthalate, diethyl phthalate, di-n-butyl phthalate, di-n-octyl phthalate, and diisooctyl phthalate, and preferably diisobutyl phthalate, which competitively bonds to the catalyst support with the TiCl4 catalytic active site, thereby preventing the TiCl4 active site from sticking together and helping to ensure uniform support.

[0083] According to one embodiment, the organoaluminum compound can act as a co-catalyst to activate the TiCl4 active site. According to one example, it 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, and preferably triethylaluminum, which can increase polymerization activity and facilitate adjustment of the molecular weight of the polymerized resin.

[0084] According to one embodiment, the external electron donor can bind to the site where the internal electron donor has been removed by the co-catalyst triethylaluminum, thereby performing a role in maintaining catalytic activity and stability, and can be one or more compounds selected from the group consisting of compounds represented by the following formulas 5-1 and 5-2.

[0085] [Formula 5-1]

[0086] [ka]

[0087] In equation 5-1, R 11 , R 12 , and R 13 These are independently substituted or unsubstituted C1-C2 alkyl groups, R 14 and R 15 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, R 16 This consists of a hydrogen atom, a halogen group, and a substituted or unsubstituted C1-C group. 20 Alkyl, substituted or unsubstituted C3-C 20 Cycloalkyl groups, and substituted or unsubstituted C3-C 20 It is one selected from the group consisting of aryl groups, and In the substituted or unsubstituted configurations described above, 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.

[0088] [Formula 5-2]

[0089] [ka]

[0090] In equation 5-2, R 11 and R 12 These are independently substituted or unsubstituted C1-C2 alkyl groups, R 17 , R 18 , and R 20 ~R 22 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, R 19 This consists of a hydrogen atom, a halogen group, and a substituted or unsubstituted C1-C group. 20 Alkyl, substituted or unsubstituted C3-C 20 Cycloalkyl groups, and substituted or unsubstituted C3-C 20 It is one selected from the group consisting of aryl groups, and In the substituted or unsubstituted configurations described above, 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.

[0091] According to one embodiment, the external electron donor may be one or more compounds selected from the group consisting of compounds represented by formulas 5-1a to 5-1d and formulas 5-2a to 5-2b below.

[0092] [Formula 5-1a]

[0093] [ka]

[0094] [Formula 5-1b]

[0095] [ka]

[0096] [Formula 5-1c]

[0097] [ka]

[0098] [Formula 5-1d]

[0099] [ka]

[0100] [Formula 5-2a]

[0101] [ka]

[0102] [Formula 5-2b]

[0103] [ka]

[0104] In other words, formula 5-1a can be triethoxy-(1,3-dichloroisopropoxy)-silane, formula 5-1b can be triethoxy-(t-butoxy)-silane, formula 5-1c can be triethoxy-[3-chloro-1-(2-chloroethyl)propoxy]silane, formula 5-1d can be triethoxy-(1,1-diethylpropoxy)-silane, formula 5-2a can be diethoxyisopropoxy-(t-butoxy)-silane, and formula 5-2b can be diethoxy-(1-ethylpropoxy)-(1,1-diethylpropoxy)-silane.

[0105] In other words, according to the present invention, the external electron donors contained in the Ziegler-Natta catalyst for olefin polymerization have specific structures, such as the compounds represented by formulas 5-1a to 5-1d and 5-2a to 5-2b. The more functional groups with different structures contained in a single external electron donor, the more binding modes of the external electron donors increase on the magnesium chloride crystal surface, increasing the active sites of the titanium compound and improving the processability of the polyolefin produced through olefin polymerization.

[0106] According to one embodiment, the external electron donor may contain one of the compounds represented by formulas 5-1a to 5-1d and formulas 5-2a to 5-2b, or two compounds selected from the group consisting of the compounds represented by formulas 5-1a to 5-1d and formulas 5-2a to 5-2b. Preferably, if two compounds are included, a high MFR ratio of 39 or more (MFR 21.6 / MFR 2.16 ) can be ensured. For example, if the external electron donor contains two types, the external electron donor may contain the compound represented by formula 5-1a and one of the compounds represented by formulas 5-1b to 5-1d, and formulas 5-2a to 5-2b, or the compound represented by formula 5-1b and one of the compounds represented by formulas 5-1c to 5-1d, and formulas 5-2a to 5-2b, or the compound represented by formula 5-1c and one of the compounds represented by formulas 5-1d and 5-2a to 5-2b, or the compound represented by formula 5-1d and one of the compounds represented by formulas 5-2a to 5-2b, or the compound represented by formula 5-2a and the compound represented by formula 5-2b.

[0107] In one embodiment, when the external electron donor contains two compounds, the first and second compounds are selected from the compounds represented by formulas 5-1a, 5-1b, 5-1c, 5-1d, 5-2a, and 5-2b, and the molar ratio of the first to second compounds can be approximately 1:0.8 to 1.2. In this case, the first and second compounds can be different from each other. For example, the compound represented by formula 5-1a contained in the external electron donor can be the first compound, and any one of the compounds represented by formulas 5-1b to 5-1d and formulas 5-2a to 5-2b can be the second compound. In this case, the molar ratio of the first compound to the second compound can be approximately 1:0.8 to 1.2. In a specific example, the molar ratio of the first compound to the second compound can be, for example, 1:0.9, 1:1, or 1:1.1.

[0108] Within the aforementioned range, the catalytic active site exhibits excellent stability, and poisoning of the catalytic active site can be prevented.

[0109] According to one embodiment, the external electron donor can be included in an amount of about 40% to about 60% by weight, based on 100% by weight of the Ziegler-Natta catalyst for total olefin polymerization. Within this range, the stability of the catalytic active sites is excellent, and poisoning can be prevented.

[0110] In other words, Ziegler-Natta catalysts for olefin polymerization have the characteristic that, as the external electron donors have specific structures such as those shown in formulas 5-1a to 5-1d and 5-2a to 5-2b, with alkoxysilane (silicate) as the base material, the number of binding modes of the external electron donors to the magnesium chloride crystal surface increases as the number of functional groups with different structures in a single external electron donor increases. Thus, the number of active sites of the titanium compound increases, and the processability of the polyolefin produced through olefin polymerization can be increased.

[0111] Another embodiment of the method for producing a Ziegler-Natta Pro-catalyst for olefin polymerization includes the steps of: mixing a titanium compound represented by formula 1 and a magnesium compound represented by formula 2 and stirring for the first time; adding an internal electron donor represented by formula 3 to the result of the first stirring and stirring for the second time; and vacuum drying the result of the second stirring. In this case, any content that overlaps with the Ziegler-Natta catalyst for olefin polymerization in the content related to the method for producing a Ziegler-Natta Pro-catalyst for olefin polymerization will be omitted from the explanation.

[0112] According to one example, the first stirring step involves adding the titanium compound and magnesium compound to the organic solvent and then stirring at a heating rate of approximately 0.5°C / min to approximately 1.5°C / min from room temperature to a first temperature.

[0113] According to one embodiment, the organic solvent may be toluene, ether, acetone, alcohol, etc., and preferably toluene.

[0114] According to one embodiment, the first temperature can be approximately 70°C to approximately 90°C, preferably approximately 75°C to approximately 85°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.

[0115] According to one example, the second stirring step involves adding an internal electron donor to the product resulting from the first stirring, raising the temperature to a second temperature, and stirring for approximately 1.8 hours to approximately 2.2 hours.

[0116] In one embodiment, the second temperature can be approximately 100°C to approximately 120°C, preferably approximately 105°C to approximately 115°C. If the second temperature is outside this range and is too low, there is the disadvantage that TiCl4 will not be supported on the support, and if the second temperature is too high, there is the disadvantage that the solvent will evaporate.

[0117] According to one embodiment, a third stirring step may be further included after the second stirring step. A specific example is the step of removing the organic solvent and titanium compound, adding a new organic solvent and titanium compound, raising the temperature from room temperature to the third temperature, and stirring for approximately 1.8 to 2.2 hours. The step of washing the product resulting from the third stirring through an organic solvent or the like may be further included.

[0118] According to one embodiment, the third temperature can be about 100°C to about 120°C, preferably about 105°C to about 115°C.

[0119] According to one embodiment, the vacuum drying step involves drying the second or third stirring result under vacuum to obtain a Ziegler-Natta main catalyst for olefin polymerization supported in powder form. This step may further include washing the second or third stirring result with an organic solvent or the like before vacuum drying.

[0120] Another embodiment of 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 4, and an external electron donor represented by formula 5 to an organic solvent and then stirring. In this case, the explanation of the Ziegler-Natta catalyst for olefin polymerization, which overlaps with the Ziegler-Natta catalyst for olefin polymerization in the content related to the method for producing the Ziegler-Natta catalyst (Pro-catalyst), may be omitted.

[0121] According to one embodiment, the organic solvent may be hexane, toluene, ether, acetone, alcohol, etc., and preferably hexane.

[0122] In one embodiment, the stirring speed may be approximately 280 rpm to approximately 320 rpm, preferably approximately 290 rpm to approximately 310 rpm. In a specific example, the stirring speed may be approximately 285 rpm to 315 rpm, for example, approximately 290, 295, 300, 305, or 310 rpm.

[0123] According to one embodiment, the titanium compound and external electron donor of the Ziegler-Natta main catalyst for olefin polymerization can be added in a molar ratio of about 1:3 to 9, preferably 1:4 to 8. In specific examples, the molar ratio of the titanium compound to the external electron donor of the Ziegler-Natta main catalyst for olefin polymerization can be about 1:3.1 to 8.8, for example, about 1:3.5, 1:4, 1:4.5, 1:5, 1:5.5, 1:6, 1:6.5, 1:7, 1:7.5, 1:8, or 1:8.5.

[0124] Within the aforementioned molar ratio, the catalytic active site exhibits excellent stability, preventing a decrease in activity due to poisoning.

[0125] Another embodiment of the method for producing polyolefins may include the step of polymerizing an olefin having the following formula 6 in the presence of a Ziegler-Natta catalyst for olefin polymerization; preferably, the olefin can be polymerized in the presence of a Ziegler-Natta catalyst for olefin polymerization that includes an external electron donor represented by formula 5.

[0126] [Formula 6] CH2=CHR 23 In equation 6, R 23 This can be hydrogen or a C1-C6 alkyl or aryl group.

[0127] According to one embodiment, a method for producing polyolefins can be a method for producing polyethylene. Therefore, it may include the step of polymerizing the olefin, preferably an ethylene monomer, in the presence of a Ziegler-Natta catalyst for olefin polymerization.

[0128] According to one embodiment, the polyolefin can be polymerized under conditions of a hydrogen gas atmosphere at a pressure of approximately 6 bar to approximately 8 bar and a temperature of approximately 80°C to approximately 90°C. However, if the temperature is outside these conditions, there is a disadvantage that polymerization will not occur if the temperature is too low, as the catalyst activity cannot be utilized, and if the temperature is too high, there is a disadvantage that catalyst overreaction occurs and the activity decreases rapidly.

[0129] According to one embodiment, the polymerization time can be about 0.5 hours to about 1.5 hours, preferably about 0.8 hours to about 1.2 hours.

[0130] In another embodiment, a polyolefin, preferably polyethylene, produced according to a method for producing polyolefins from a Ziegler-Natta catalyst for olefin polymerization, is obtained, with an MFR ratio (MFR 21.6 / MFR 2.16 ) could be approximately 33.0 to 44.0.

[0131] According to one example, a polyolefin, preferably polyethylene, produced according to a method for producing polyolefins from a Ziegler-Natta catalyst for olefin polymerization, was subjected to a MFR at a temperature of 190°C and a load of 21.6 kg. 21.6 The MFR was approximately 29.0g / 10min to 48.0g / 10min at a temperature of 190℃ and a load of 2.16kg. 2.16 This is approximately 0.5g / 10min to approximately 1.5g / 10min, and the MFR ratio (MFR 21.6 / MFR 2.16 ) is characterized by being approximately 33.0 to 44.0. In a specific example, the MFR ratio (MFR 21.6 / MFR 2.16The ratio can be approximately 33.1 to 43.2, for example, 33.8, 36.5, 39.2, or 40.2. In other words, in the case of polyolefins produced according to the method for producing polyolefins from the Ziegler-Natta catalyst for olefin polymerization, the external electron donors contained in the catalyst have a specific structure. The more functional groups with different structures are contained in a single external electron donor, the more binding modes of the external electron donors to the magnesium chloride crystal surface increase. Therefore, the number of active sites of the titanium compound increases, resulting in a high MFR ratio, which has the advantage of excellent processability and improved productivity of polyolefin resins.

[0132] The present invention will be described in more detail below through examples. However, these examples are for illustrative purposes only, and the scope of the present invention is not limited to these examples.

[0133] Example 1: Production of polyethylene using Ziegler-Natta catalyst for olefin polymerization Manufacturing Example 1: Production of Ziegler-Natta Pro-catalyst for Olefin Polymerization 4 g of magnesium compound Mg(OC2H5)2 (magnesium ethoxide) support and 8 ml of titanium compound TiCl4 were added to 12 ml of organic solvent toluene, and the mixture was heated to 80°C at room temperature at a rate of 1°C / min, followed by a first stirring at 300 RPM. After the reaction temperature reached 80°C, diisobutyl phthalate (catalyst A) (4.5 mmol), an internal electron donor, was added to the first stirring result, and the mixture was heated to 110°C at a rate of 1°C / min, followed by a second stirring for 2 hours. Then, the TiCl4 + Toluene solution was removed, and a new TiCl4 (10 ml) + toluene (30 ml) solution was added, followed by a third stirring at room temperature at a rate of 1°C / min, followed by a third stirring for 2 hours. Subsequently, the supported catalyst, which was the result of the third stirring, was washed twice with 100 ml of toluene and twice with 100 ml of hexane, and dried under vacuum to obtain a powdered Ziegler-Natta main catalyst (supported catalyst) for olefin polymerization.

[0134] Manufacturing Example 2: Production of Ziegler-Natta catalyst and polyethylene for olefin polymerization A 2-liter high-pressure reactor was dried in an oven, assembled while still hot, and the reactor was subjected to a nitrogen atmosphere by alternating nitrogen and vacuum three times. Then, 1000 ml of hexane, an organic solvent, was added to the reactor, followed by 15 mg of Ziegler-Natta main catalyst for olefin polymerization (Preparation Example 1), 0.24 ml of the external electron donor [triethoxy-(1,3-dichloroisopropoxy)-silane; ED1; formula 5-1a] (a solution diluted in hexane at a 1 / 20 volume ratio), and 2 mmol of triethylaluminum, an organoaluminum compound (co-catalyst). Subsequently, the Ziegler-Natta catalyst for olefin polymerization was prepared while stirring at 300 rpm. After that, the reactor temperature was raised to 85°C, hydrogen was injected once at a pressure of 3 bar, and polyethylene polymerization was carried out for 1 hour while continuously supplying ethylene at a constant pressure of 7 bar. Subsequently, the reactor temperature was lowered to room temperature, and the resulting polymer was separated, collected, and dried to obtain a white powder polyethylene polymer.

[0135] Example 2: Production of polyethylene by changing the external electron donor Compared to Example 1, in Production Example 2, a polyethylene polymer was obtained in the same manner as in Example 1, except that triethoxy-(t-butoxy)-silane (ED2; formula 5-1b) was used as the external electron donor.

[0136] Example 3: Production of polyethylene by changing the external electron donor Compared to Example 1, in Production Example 2, a polyethylene polymer was obtained in the same manner as in Example 1, except that diethoxyisopropoxy-(t-butoxy)-silane (ED3; formula 5-2a) was used as the external electron donor.

[0137] Example 4: Production of polyethylene using an external electron donor In comparison with Example 1, the polyethylene polymer was obtained in the same manner as in Example 1, except that in Production Example 2, triethoxy-(t-butoxy)-silane (ED2; formula 5-1b) and diethoxyisopropoxy-(t-butoxy)-silane (ED3; formula 5-2a) were used as external electron donors in a 1:1 molar ratio.

[0138] Example 5: Production of polyethylene using an external electron donor In comparison with Example 1, the polyethylene polymer was obtained in the same manner as in Example 1, except that in Production Example 2, diethoxyisopropoxy-(t-butoxy)-silane (ED3; Formula 5-2a) and triethoxy-[3-chloro-1-(2-chloroethyl)propoxy]silane (ED4; Formula 5-1c) were used as external electron donors in a 1:1 molar ratio.

[0139] Example 6: Production of polyethylene using an external electron donor In comparison with Example 1, the polyethylene polymer was obtained in the same manner as in Example 1, except that in Production Example 2, a mixture of diethoxyisopropoxy-(t-butoxy)-silane (ED3; formula 5-2a) and diethoxy-(1-ethylpropoxy)-(1,1-diethylpropoxy)-silane (ED5; formula 5-2b) was used as the external electron donor in a 1:1 molar ratio.

[0140] Comparative Example 1: Polyethylene production by changing the external electron donor Compared to Example 1, in Production Example 2, the polyethylene polymer was obtained in the same manner as in Example 1, except that cyclohexylmethyldimethoxysilane (C-donor) (ED6) was used as the external electron donor.

[0141] Comparative Example 2: Polyethylene production by changing the internal and external electron donors Compared to Example 1, the polyethylene polymer was produced in the same manner as in Example 1, except that in Production Example 1, a commercial Ziegler-Natta catalyst Z-213 (manufactured by Lyondellbasell, catalyst B) was used as the internal electron donor, and in Production Example 2, cyclohexylmethyldimethoxysilane (C-donor) (ED6) was used as the external electron donor.

[0142] Methods for evaluating the physical properties of polyethylene -Activity (g PE / g cat Measurement: Weight of resin obtained (g) / Weight of catalyst (g) -MFR 2.16 (g / 10min) and -MFR 21.6 Measurement of (g / 10min): According to ASTM D 1238, with a load of 2.16 kg at 190°C (MI 2.16 ) and a load of 21.6 kg (MI 21.6 ) Measured.

[0143] - Melt flow ratio (MFR): Melt index MFR 21.6 and MFR 2.16 Each is measured, and the ratio is calculated as MFR = (MFR 21.6 / MFR 2.16 ) -Density (g / cm 3 Measurement: Measured according to ASTM D1505 Methods for evaluating the physical properties of polyethylene

[0144] [Table 1]

[0145] Referring to Table 1, in the case of polyethylene according to Examples 1 to 3, compared to the polyethylene according to Comparative Examples 1 and 2, even if other physical properties are similar, polyethylene is produced using a catalyst containing external electron donors having a specific structure, and the more functional groups with different structures are contained in a single external electron donor, the more the bonding modes of the external electron donors on the magnesium chloride crystal surface increase, and therefore, in order to improve the number of active sites of the titanium compound, the MFR ratio (MFR 21.6 / MFR 2.16 It was confirmed that the MFR ratio (MFR) was higher, ranging from 33.1 to 36.5. Furthermore, in the case of polyethylene according to Examples 4 to 6, it contains two or more types of external electron donors, and the binding modes of the external electron donors to the magnesium chloride crystal surface are increased, and therefore the number of active sites of the titanium compound is further improved, thus increasing the MFR ratio (MFR 21.6 / MFR 2.16 It was also confirmed that ) had a higher value.

[0146] In other words, polyethylene produced using the Ziegler-Natta catalyst for olefin polymerization has the advantage of a high MFR ratio, resulting in excellent processability and improved polyethylene resin productivity.

[0147] 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]

[0148] Ziegler-Natta catalysts for olefin polymerization are characterized by their ability to produce polyolefins with excellent processability because they increase the number of active sites in the titanium compound by including at least one external electron donor that satisfies a specific formula based on an alkoxysilane (silicate).

Claims

1. A Ziegler-Natta procatalyst 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 represented by formula 3 below; Organic aluminum compounds represented by the following formula 4; and External electron donor represented by the following equation 5; Ziegler-Natta catalysts for olefin polymerization, including: [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 from 0 to 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.) [Formula 3] 【Chemistry 1】 (In the above equation 3, R ３ This includes hydrogen atoms, halogen atoms, and substituted or unsubstituted C atoms. 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, 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, m 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 4] Al(R ６ ) ｐ X ３－ｐ (In the above equation 4, R ６ 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 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.) [Formula 5] 【Chemistry 2】 (In the above formula 5, R ７ , R ８ , R ９ and R １０ 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 It is one selected from the group consisting of aryl groups, 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 internal electron donor is one or more selected from the group consisting of diisobutyl phthalate, diethyl phthalate, di-n-butyl phthalate, di-n-octyl phthalate, and diisooctyl phthalate.

3. The Ziegler-Natta catalyst for olefin polymerization according to claim 1, wherein the external electron donor is one or more compounds selected from the group consisting of compounds represented by the following formulas 5-1 and 5-2: [Formula 5-1] 【Transformation 3】 (In the above formula 5-1, R １１ , R １２ , and R １３ Independently, C is either substituted or non-substituted. １ -C ２ With an alkyl group, R １４ and R １５ 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, R １６ This includes hydrogen atoms, halogen groups, and substituted or unsubstituted C atoms. １ -C ２０ Alkyl, substituted or unsubstituted C ３ -C ２０ Cycloalkyl groups, and substituted or unsubstituted C ３ -C ２０ It is one selected from the group consisting of aryl groups, 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 5-2] 【Chemistry 4】 (In the above equation 5-2, R １１ and R １２ are, independently, a substituted or unsubstituted C １ -C ２ alkyl group, R １７ 、 R １８ 、 and R ２０ ~R ２２ is independently 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, R １９ This includes hydrogen atoms, halogen groups, and substituted or unsubstituted C atoms. １ -C ２０ Alkyl, substituted or unsubstituted C ３ -C ２０ Cycloalkyl groups, and substituted or unsubstituted C ３ -C ２０ It is one selected from the group consisting of aryl groups, 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).

4. The Ziegler-Natta catalyst for olefin polymerization according to claim 1, wherein the external electron donor is one or more compounds selected from the group consisting of compounds represented by the following formulas 5-1a, 5-1b, 5-1c, 5-1d, 5-2a, and 5-2b: [Formula 5-1a] 【Transformation 5】 [Formula 5-1b] 【Transformation 6】 [Formula 5-1c] 【Transformation 7】 [Formula 5-1d] 【Transformation 8】 [Formula 5-2a] 【Chemistry 9】 [Formula 5-2b] 【Chemistry 10】 。

5. The Ziegler-Natta catalyst for olefin polymerization according to claim 4, wherein the external electron donor is two compounds selected from those represented by formulas 5-1a, 5-1b, 5-1c, 5-1d, 5-2a, and 5-2b.

6. The Ziegler-natta catalyst for olefin polymerization according to claim 1, wherein the molar ratio of the titanium compound to the external electron donor of the Ziegler-natta main catalyst for olefin polymerization is 1:3 to 9.

7. A main catalyst containing an internal electron donor represented by the following formula 3; and A method for producing polyolefins, comprising the step of polymerizing an olefin having the following formula 6 in the presence of a Ziegler-Natta catalyst for olefin polymerization containing an external electron donor represented by the following formula 5; [Formula 3] 【Chemistry 11】 (In the above equation 3, R ３ This includes hydrogen atoms, halogen atoms, and substituted or unsubstituted C atoms. 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, 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, m 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 5] 【Chemistry 12】 (In the above formula 5, R ７ , R ８ , R ９ , and R １０ 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 It is one selected from the group consisting of aryl groups, 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 6] CH ２ =CHR ２３ (In the above equation 6, R ２３ is hydrogen or C １ -C ６ (An alkyl or aryl group).

8. The method for producing polyolefin according to claim 7, wherein the external electron donor is one or more compounds selected from the group consisting of compounds represented by the following formulas 5-1 and 5-2: [Formula 5-1] 【Chemistry 13】 (In the above formula 5-1, R １１ , R １２ , and R １３ Independently, C is either substituted or non-substituted. １ -C ２ With an alkyl group, R １４ and R １５ 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, R １６ This includes hydrogen atoms, halogen groups, and substituted or unsubstituted C atoms. １ -C ２０ Alkyl, substituted or unsubstituted C ３ -C ２０ Cycloalkyl groups, and substituted or unsubstituted C ３ -C ２０ It is one selected from the group consisting of aryl groups, 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 5-2] 【Chemistry 14】 (In the above equation 5-2, R １１ and R １２ Independently, C is either substituted or non-substituted. １ -C ２ With an alkyl group, R １７ , R １８ , and R ２０ ~R ２２ 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, R １９ This includes hydrogen atoms, halogen groups, and substituted or unsubstituted C atoms. １ -C ２０ Alkyl, substituted or unsubstituted C ３ -C ２０ Cycloalkyl groups, and substituted or unsubstituted C ３ -C ２０ It is one selected from the group consisting of aryl groups, 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).

9. The method for producing polyolefin according to claim 7, wherein the external electron donor is one or more compounds selected from the group consisting of compounds represented by the following formulas 5-1a, 5-1b, 5-1c, 5-1d, 5-2a, and 5-2b: [Formula 5-1a] 【Chemistry 15】 [Formula 5-1b] 【Chemistry 16】 [Formula 5-1c] 【Chemistry 17】 [Formula 5-1d] [Chemistry 18] [Formula 5-2a] 【Chemistry 19】 [Formula 5-2b] 【Chemistry 20】 。

10. The method for producing a polyolefin according to claim 9, wherein the external electron donor is two compounds selected from those represented by formulas 5-1a, 5-1b, 5-1c, 5-1d, 5-2a, and 5-2b.

11. The method for producing polyolefins according to claim 7, wherein the molar ratio of the titanium compound to the external electron donor in the Ziegler-natta main catalyst for olefin polymerization contained in the Ziegler-natta catalyst for olefin polymerization is 1:3 to 9.

12. The method for producing a polyolefin according to claim 7, wherein the polymerization is carried out by supplying the olefin at a pressure of 6 bar to 8 bar and polymerizing it at a temperature of 80°C to 90°C for 0.5 hours to 1.5 hours.

13. Manufactured by the manufacturing method described in claim 7, with an MFR ratio (MFR ２１．６ / MFR ２．１６ A polyolefin resin characterized in that the ratio is 33.0 to 44.0.

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