Ziegler–natta catalyst for olefin polymerization, method for producing polyolefin, and polyolefin resin

Abstract

The present invention provides a Ziegler–Natta catalyst for olefin polymerization, a method for producing a polyolefin, and a polyolefin resin, wherein the Ziegler–Natta catalyst for olefin polymerization includes: (i) a Ziegler–Natta pro-catalyst for olefin polymerization comprising a titanium compound represented by chemical formula 1, a magnesium compound represented by chemical formula 2, a first internal electron donor represented by chemical formula 3, and a second internal electron donor that is at least one selected from the group consisting of compounds represented by chemical formula 4 and chemical formula 5; (ii) an organoaluminum compound represented by chemical formula 6; and (iii) an external electron donor represented by chemical formula 7.

Description

Ziegler-Natta catalyst for olefin polymerization, method for manufacturing polyolefin, and polyolefin resin

[0001] The present invention relates to a Ziegler-Natta catalyst for olefin polymerization, a method for producing polyolefins, and a polyolefin resin. More specifically, the present invention relates to a Ziegler-Natta catalyst for olefin polymerization, a method for producing polyolefins with excellent processability and hydrogen reactivity using the same, and a polyolefin resin.

[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 and provide polymers having a highly isotactic stereochemical configuration.

[0003] In particular, as the applications of polyethylene, a type of polyolefin, have recently diversified, there was a need for catalysts with excellent activity and hydrogen reactivity, as well as methods for manufacturing the same, in order to produce polyethylene resins with excellent processability, which significantly impacts product productivity.

[0004] Related prior art is Korean Patent Publication No. 10-2015-0034768.

[0005] The object of the present invention is to provide a Ziegler-Natta catalyst for ethylene polymerization that increases the number of active sites of a titanium compound by including an internal electron donor and an external electron donor satisfying a specific chemical formula.

[0006] Another objective of the present invention is to provide a method for manufacturing a polyolefin and a polyolefin resin that can bond with magnesium compounds at various strengths and has excellent processability by using internal electron donors satisfying specific chemical formulas with different functional groups and structures.

[0007] Another objective of the present invention is to provide a method for manufacturing a polyolefin and a polyolefin resin capable of controlling hydrogen reactivity and processability by varying the ratio between internal electron donors.

[0008] The above and other objectives of the present invention can all be achieved by the present invention described below.

[0009] 1. One aspect of the present invention relates to a Ziegler-Natta catalyst for olefin polymerization. The Ziegler-Natta catalyst for olefin polymerization comprises: a Ziegler-Natta pro-catalyst comprising a titanium compound represented by the following chemical formula 1, a magnesium compound represented by the following chemical formula 2, a first internal electron donor represented by the following chemical formula 3, and a second internal electron donor selected from the group consisting of one or more compounds represented by the following chemical formulas 4 and 5; an organoaluminum compound represented by the following chemical formula 5; and an external electron donor represented by the following chemical formula 6:

[0010] [Chemical Formula 1]

[0011] TiX n (OR 1 ) 4-n

[0012] (In the above chemical formula 1,

[0013] R 1 C1-C of substituted or non-substituted 20 Alkyl groups, substituted or unsubstituted C3-C 20 Cycloalkyl groups, and substituted or unsubstituted C6-C 20 It is one species selected from the group composed of aryls, and

[0014] X is a halogen atom, and

[0015] n is an integer from 0 to 4, and

[0016] In the above substitution or non-substitution, the substituent is independently one selected from the group consisting of halogen groups, cyano groups, nitro groups, and C1-C8 alkyl groups.

[0017] [Chemical Formula 2]

[0018] Mg(OR 2 ) k X 2-k

[0019] (In the above chemical formula 2,

[0020] R 2 C1-C of substituted or non-substituted 20 Alkyl groups, substituted or unsubstituted C3-C 20 Cycloalkyl groups, and substituted or unsubstituted C6-C 20 It is one species selected from the group composed of aryls, and

[0021] X is a halogen atom, and

[0022] k is an integer from 0 to 2, and

[0023] In the above substitution or non-substitution, the substituent is independently one selected from the group consisting of halogen groups, cyano groups, nitro groups, and C1-C8 alkyl groups.

[0024] [Chemical Formula 3]

[0025]

[0026] (In the above chemical formula 3,

[0027] R 3 and R 4 Each is independently a substituted or non-substituted C1-C 20 Alkyl groups, substituted or unsubstituted C3-C 20 Cycloalkyl groups, and substituted or unsubstituted C6-C 20 It is one species selected from the group consisting of aryl groups, or R 3 and R 4 They are connected to each other, resulting in substitutive or non-substitutive C3-C 20 Forming a cycloaliphatic ring or an aromatic ring,

[0028] R5 and R 6 Each is independently a substituted or non-substituted C1-C 20 It is an alkyl group, and

[0029] In the above substitution or non-substitution, the substituent is independently one selected from the group consisting of halogen groups, cyano groups, nitro groups, phenyl groups, and C1-C8 alkyl groups.

[0030] [Chemical Formula 4]

[0031]

[0032] (In the above chemical formula 4,

[0033] R 7 , R 8 and R 9 Each is independently a substituted or non-substituted C1-C 20 Alkyl groups, substituted or unsubstituted C3-C 20 Cycloalkyl groups, and substituted or unsubstituted C6-C 20 It is one species selected from the group composed of aryls, and

[0034] m is an integer from 0 to 4, and

[0035] In the above substitution or non-substitution, the substituent is independently one selected from the group consisting of halogen groups, cyano groups, nitro groups, and C1-C8 alkyl groups.

[0036] [Chemical Formula 5]

[0037]

[0038] (In the above chemical formula 5,

[0039] R 10 , R 11 , R 12 and R 13 Each is independently a hydrogen atom, a substituted or unsubstituted C1-C 20 Alkyl groups, substituted or unsubstituted C3-C 20 Cycloalkyl groups, and substituted or unsubstituted C6-C 20It is one species selected from the group composed of aryls, and

[0040] R 14 and R 15 Each is independently a substituted or non-substituted C1-C 20 Alkyl groups, substituted or unsubstituted C3-C 20 Cycloalkyl groups, and substituted or unsubstituted C6-C 20 It is one type selected from the group consisting of aryl groups, and

[0041] In the above substitution or non-substitution, the substituent is independently one selected from the group consisting of halogen groups, cyano groups, nitro groups, and C1-C8 alkyl groups.

[0042] [Chemical Formula 6]

[0043] Al(R 16 ) p X 3-p

[0044] (In the above chemical formula 6,

[0045] R 16 hydrogen atoms, substituted or non-substituted C1-C 20 Alkyl groups, substituted or unsubstituted C3-C 20 Cycloalkyl groups, and substituted or unsubstituted C6-C 20 It is one species selected from the group composed of aryls, and

[0046] X is a halogen atom, and

[0047] p is an integer from 0 to 3, and

[0048] In the above substitution or non-substitution, the substituent is independently one selected from the group consisting of halogen groups, cyano groups, nitro groups, and C1-C8 alkyl groups.

[0049] [Chemical Formula 7]

[0050]

[0051] (In the above chemical formula 7,

[0052] R 17 and R 18Each is independently a substituted or non-substituted C1-C 20 It is an alkyl group, and

[0053] R 19 and R 20 Each is independently a substituted or non-substituted C1-C 20 Alkyl groups and substituted or unsubstituted C3-C 20 It is one selected from the group consisting of cycloalkyl groups, and

[0054] In the above substitution or non-substitution, the substituent is independently one selected from the group consisting of halogen groups, cyano groups, nitro groups, and C1-C8 alkyl groups).

[0055] 2. In the above 1 embodiment, R of Chemical Formula 3 3 and R 4 It may not be the same.

[0056] 3. In the above 1 to 2 embodiments, the first internal electron donor may be one or more selected from the group consisting of compounds represented by the following chemical formulas 3-1 to 3-6:

[0057] [Chemical Formula 3-1]

[0058]

[0059] [Chemical Formula 3-2]

[0060]

[0061] [Chemical Formula 3-3]

[0062]

[0063] [Chemical Formula 3-4]

[0064]

[0065] [Chemical Formula 3-5]

[0066]

[0067] [Chemical Formula 3-6]

[0068]

[0069] 4. In the above 1 to 3 embodiments, R of Formula 4 8 and R 9 Each is independently a linear C1-C 20 Alkyl groups and branched chain type C1-C 20 It may be one selected from the group consisting of alkyl groups.

[0070] 5. In the above 1 to 4 embodiments, R of Formula 5 14 and R 15 Each is independently a linear C1-C 20 Alkyl groups and branched chain type C1-C 20 It may be one selected from the group consisting of alkyl groups.

[0071] 6. In the above embodiments 1 to 5, the second internal electron donor may be one or more selected from the group consisting of compounds represented by the following formulas 4-1 and 5-1 to 5-6:

[0072] [Chemical Formula 4-1]

[0073]

[0074] [Chemical Formula 5-1]

[0075]

[0076] [Chemical Formula 5-2]

[0077]

[0078] [Chemical Formula 5-3]

[0079]

[0080] [Chemical Formula 5-4]

[0081]

[0082] [Chemical Formula 5-5]

[0083]

[0084] [Chemical Formula 5-6]

[0085]

[0086] 7. In the above 1 to 6 embodiments, the external electron donor may be one or more selected from the group consisting of compounds represented by the following chemical formulas 7-1 to 7-6:

[0087] [Chemical Formula 7-1]

[0088]

[0089] [Chemical Formula 7-2]

[0090]

[0091] [Chemical Formula 7-3]

[0092]

[0093] [Chemical Formula 7-4]

[0094]

[0095] [Chemical Formula 7-5]

[0096]

[0097] [Chemical Formula 7-6]

[0098]

[0099] 8. In the above 1 to 7 embodiments, the Ziegler-Natta catalyst for olefin polymerization may include the first internal electron donor and the second internal electron donor in a molar ratio of about 8:2 to 2:8.

[0100] 9. In the above 1 to 8 embodiments, a mixture including the first internal electron donor and the second internal electron donor may be included in an amount of about 1 to 30 weight% of the 100 weight% of the Ziegler-Natta catalyst for olefin polymerization.

[0101] 10. In the above 1 to 9 embodiments, the molar ratio of the external electron donor to the mixture containing the first internal electron donor and the second internal electron donor of the Ziegler-Natta main catalyst for olefin polymerization may be about 2 to 15.

[0102] 11. In the above 1 to 10 embodiments, the molar ratio of the external electron donor to the titanium compound of the Ziegler-Natta main catalyst for olefin polymerization may be about 2 to 7.

[0103] 12. Another aspect of the present invention relates to a method for producing a polyolefin comprising the step of polymerizing an olefin monomer in the presence of an olefin polymerization Ziegler-Natta catalyst of the 1 to 11 embodiments above.

[0104] 13. In the above 12 embodiments, the molar ratio of the Ziegler-Natta catalyst for olefin polymerization to the olefin monomer is approximately 3 x 10 -6 Up to 7 x 10 -6 It could be.

[0105] 14. Another aspect of the present invention is manufactured by the method of manufacturing the above 12 embodiments, and MFR (MFI 21.6 / MFI 2.16 The present invention relates to a polyolefin resin characterized by having a value of approximately 20.0 to 50.0.

[0106] 15. Another aspect of the present invention relates to a polyolefin resin polymerized by a Ziegler-Natta catalyst for olefin polymerization comprising: a main catalyst supported on a carrier, wherein a first internal electron donor represented by the following chemical formula 3; a second internal electron donor selected from the group consisting of one or more compounds represented by the following chemical formulas 4 and 5; an organoaluminum compound represented by the following chemical formula 6; and an external electron donor represented by the following chemical formula 7; wherein the carrier comprises titanium and magnesium, and the polyolefin resin is MFR (MFI 21.6 / MFI 2.16 It is characterized by ) being approximately 20.0 to 50.0:

[0107] [Chemical Formula 3]

[0108]

[0109] (In the above chemical formula 3,

[0110] R 3 and R 4 Each is independently a substituted or non-substituted C1-C 20 Alkyl groups, substituted or unsubstituted C3-C 20 Cycloalkyl groups, and substituted or unsubstituted C6-C 20 It is one species selected from the group consisting of aryl groups, or R 3 and R 4 They are connected to each other, resulting in substitutive or non-substitutive C3-C 20 Forming a cycloaliphatic ring or an aromatic ring,

[0111] R 5 and R 6 Each is independently a substituted or non-substituted C1-C 20 It is an alkyl group, and

[0112] In the above substitution or non-substitution, the substituent is independently one selected from the group consisting of halogen groups, cyano groups, nitro groups, phenyl groups, and C1-C8 alkyl groups.

[0113] [Chemical Formula 4]

[0114]

[0115] (In the above chemical formula 4,

[0116] R 7 , R 8 and R 9 Each is independently a substituted or non-substituted C1-C 20 Alkyl groups, substituted or unsubstituted C3-C 20 Cycloalkyl groups, and substituted or unsubstituted C6-C 20 It is one species selected from the group composed of aryls, and

[0117] m is an integer from 0 to 4, and

[0118] In the above substitution or non-substitution, the substituent is independently one selected from the group consisting of halogen groups, cyano groups, nitro groups, and C1-C8 alkyl groups.

[0119] [Chemical Formula 5]

[0120]

[0121] (In the above chemical formula 5,

[0122] R 10 , R 11 , R 12 and R 13 Each is independently a hydrogen atom, a substituted or unsubstituted C1-C 20 Alkyl groups, substituted or unsubstituted C3-C 20 Cycloalkyl groups, and substituted or unsubstituted C6-C 20 It is one species selected from the group composed of aryls, and

[0123] R 14 and R 15 Each is independently a substituted or non-substituted C1-C 20 Alkyl groups, substituted or unsubstituted C3-C 20 Cycloalkyl groups, and substituted or unsubstituted C6-C 20 It is one type selected from the group consisting of aryl groups, and

[0124] In the above substitution or non-substitution, the substituent is independently one selected from the group consisting of halogen groups, cyano groups, nitro groups, and C1-C8 alkyl groups.

[0125] [Chemical Formula 6]

[0126] Al(R 16 ) p X 3-p

[0127] (In the above chemical formula 6,

[0128] R 16 hydrogen atoms, substituted or non-substituted C1-C 20 Alkyl groups, substituted or unsubstituted C3-C 20 Cycloalkyl groups, and substituted or unsubstituted C6-C 20 It is one species selected from the group composed of aryls, and

[0129] X is a halogen atom, and

[0130] p is an integer from 0 to 3, and

[0131] In the above substitution or non-substitution, the substituent is independently one selected from the group consisting of halogen groups, cyano groups, nitro groups, and C1-C8 alkyl groups.

[0132] [Chemical Formula 7]

[0133]

[0134] (In the above chemical formula 7,

[0135] R 17 and R 18 Each is independently a substituted or non-substituted C1-C 20 It is an alkyl group, and

[0136] R 19 and R 20 Each is independently a substituted or non-substituted C1-C 20 Alkyl groups and substituted or unsubstituted C3-C 20 It is one selected from the group consisting of cycloalkyl groups, and

[0137] In the above substitution or non-substitution, the substituent is independently one selected from the group consisting of halogen groups, cyano groups, nitro groups, and C1-C8 alkyl groups).

[0138] 16. In the above 15 embodiments, the titanium may be represented by the following chemical formula 1, and the magnesium may be represented by the following chemical formula 2:

[0139] [Chemical Formula 1]

[0140] TiX n (OR 1 ) 4-n

[0141] (In the above chemical formula 1,

[0142] R 1 C1-C of substituted or non-substituted 20 Alkyl groups, substituted or unsubstituted C3-C 20 Cycloalkyl groups, and substituted or unsubstituted C6-C 20It is one species selected from the group composed of aryls, and

[0143] X is a halogen atom, and

[0144] n is an integer from 0 to 4, and

[0145] In the above substitution or non-substitution, the substituent is independently one selected from the group consisting of halogen groups, cyano groups, nitro groups, and C1-C8 alkyl groups.

[0146] [Chemical Formula 2]

[0147] Mg(OR 2 ) k X 2-k

[0148] (In the above chemical formula 2,

[0149] R 2 C1-C of substituted or non-substituted 20 Alkyl groups, substituted or unsubstituted C3-C 20 Cycloalkyl groups, and substituted or unsubstituted C6-C 20 It is one species selected from the group composed of aryls, and

[0150] X is a halogen atom, and

[0151] k is an integer from 0 to 2, and

[0152] In the above substitution or non-substitution, the substituent is independently one selected from the group consisting of halogen groups, cyano groups, nitro groups, and C1-C8 alkyl groups).

[0153] 17. In the above 15 to 16 embodiments, the first internal electron donor may be one or more selected from the group consisting of compounds represented by the following chemical formulas 3-1 to 3-6:

[0154] [Chemical Formula 3-1]

[0155]

[0156] [Chemical Formula 3-2]

[0157]

[0158] [Chemical Formula 3-3]

[0159]

[0160] [Chemical Formula 3-4]

[0161]

[0162] [Chemical Formula 3-5]

[0163]

[0164] [Chemical Formula 3-6]

[0165]

[0166] 18. In the above embodiments 15 to 17, the second internal electron donor may be one or more selected from the group consisting of compounds represented by the following formulas 4-1 and 5-1 to 5-6:

[0167] [Chemical Formula 4-1]

[0168]

[0169] [Chemical Formula 5-1]

[0170]

[0171] [Chemical Formula 5-2]

[0172]

[0173] [Chemical Formula 5-3]

[0174]

[0175] [Chemical Formula 5-4]

[0176]

[0177] [Chemical Formula 5-5]

[0178]

[0179] [Chemical Formula 5-6]

[0180]

[0181] 19. In the above 15 to 18 embodiments, the external electron donor may be one or more selected from the group consisting of compounds represented by the following chemical formulas 7-1 to 7-6:

[0182] [Chemical Formula 7-1]

[0183]

[0184] [Chemical Formula 7-2]

[0185]

[0186] [Chemical Formula 7-3]

[0187]

[0188] [Chemical Formula 7-4]

[0189]

[0190] [Chemical Formula 7-5]

[0191]

[0192] [Chemical Formula 7-6]

[0193]

[0194] 20. In the above 15 to 19 embodiments, the Ziegler-Natta catalyst for olefin polymerization may contain the first internal electron donor and the second internal electron donor in a molar ratio of about 8:2 to 2:8.

[0195] 21. In the above 15 to 20 embodiments, the molar ratio of the external electron donor to the mixture containing the first internal electron donor and the second internal electron donor of the Ziegler-Natta main catalyst for olefin polymerization may be about 2 to 15.

[0196] The present invention has the effect of being able to produce polyethylene in which the Ziegler-Natta catalyst for ethylene polymerization includes an internal electron donor and an external electron donor satisfying a specific chemical formula, thereby increasing the number of active sites of a titanium compound, and by using internal electron donors satisfying a specific chemical formula with different functional groups and structures, it is possible to bond with a magnesium compound with varying strengths, and hydrogen reactivity and processability can be controlled by varying the ratio between internal electron donors.

[0197] The above objectives, other objectives, features, and advantages will be easily understood through the following preferred embodiments associated with the accompanying drawings. However, the embodiments described herein are not limited to those described herein and may be embodied in other forms. Rather, the embodiments introduced herein are provided to ensure that the disclosed content is thorough and complete and that the technical concept is sufficiently conveyed to a person skilled in the art.

[0198] In describing each drawing, similar reference numerals have been used for similar components. In the attached drawings, the dimensions of the structures are depicted enlarged from their actual size for clarity of the invention. Terms such as "first," "second," etc., may be used to describe various components, but said components should not be limited by said terms. These terms are used solely for the purpose of distinguishing one component from another. For example, without departing from the scope of the invention, the first component may be named the second component, and similarly, the second component may be named the first component.

[0199] A singular expression includes a plural expression unless the context clearly indicates otherwise.

[0200] In this specification, terms such as “comprising” or “having” are intended to specify the existence of the features, numbers, steps, actions, components, parts, or combinations thereof described in the specification, and should not be understood as precluding the existence or addition of one or more other features, numbers, steps, actions, components, parts, or combinations thereof.

[0201] Unless otherwise specified, all numbers, values, and / or expressions used herein to represent amounts of ingredients, reaction conditions, polymer compositions, and formulations should be understood to be modified by the term "approximately" in all cases, as these numbers are essentially approximations reflecting the various uncertainties of measurement that occur in obtaining these values ​​among other things. Furthermore, where a numerical range is disclosed herein, such range is continuous and, unless otherwise indicated, includes all values ​​from the minimum value of such range to the maximum value including the maximum value. Moreover, where such range refers to an integer, it includes all integers from the minimum value to the maximum value including the maximum value, unless otherwise indicated.

[0202] In this specification, where a range is described for a variable, it will be understood that the variable includes all values ​​within the described range, including the described endpoints of the range. For example, the range “5 to 10” will 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 valid for the category of the described range, such as 5.5, 6.5, 7.5, 5.5 to 8.5, and 6.5 to 9. Also, for example, the range “10% to 30%” will be understood to include all integers including values ​​such as 10%, 11%, 12%, 13%, etc. and up to 30%, as well as any sub-range such as 10% to 15%, 12% to 18%, 20% to 30%, etc., and any value between valid integers within the stated range category such as 10.5%, 15.5%, 25.5%, etc.

[0203] Recently, as the applications of polyethylene have diversified, there was a need for catalysts and methods for manufacturing the same to produce polyethylene resins with excellent processability and hydrogen reactivity, which significantly affect resin properties.

[0204] Accordingly, the inventors of the present invention, as a result of research to solve the above problem, discovered and completed the following: when polyethylene is manufactured using a Ziegler-Natta pro-catalyst for ethylene polymerization containing a first internal electron donor and a second internal electron donor satisfying a specific chemical formula, and a Ziegler-Natta catalyst for ethylene polymerization containing an external electron donor satisfying a specific chemical formula, each internal electron donor and external electron donor increases the active sites of the titanium compound, and by using internal electron donors satisfying a specific chemical formula with different functional groups and structures, it is possible to bond with the magnesium compound with varying strengths, and hydrogen reactivity and processability can be controlled by varying the ratio between the internal electron donors.

[0205] Unless otherwise noted, "C1-C n "Alkyl group" means a primary alkyl group having 1 to n carbon atoms, a secondary alkyl group (n ≥ 3), and a tertiary alkyl group (n ≥ 4). For example, it may be a functional group such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, tert-butyl, n-hexyl, etc., but is not limited thereto.

[0206] Unless otherwise noted, "straight chain" in alkyl groups means that the carbon atom chains forming the alkyl group consist only of straight chains without any branching.

[0207] Unless otherwise noted, "branched chain type" in alkyl groups means that at least one part of the carbon atom chain forming the alkyl group has a branched chain.

[0208] Unless otherwise noted, an aryl group refers to a monovalent substituent derived from an aromatic hydrocarbon, and refers to a pendant form or a condensed form in which two or more rings are simply connected. For example, an aryl may be, but is not limited to, phenyl, biphenyl, terphenyl, stilbene, naphthyl, anthracenyl, phenanthrenyl, pyrenyl, perylenyl, chrysenyl, tetrahydronaphthyl, etc.

[0209] Unless otherwise noted, the prefix hetero means that one to three heteroatoms selected from the group consisting of -N-, -O-, -S- and -P- substitute a carbon atom. For example, it may be pyridine, pyrrole, or carbazole containing a nitrogen atom as a heteroatom, furan or dibenzofuran containing an oxygen atom as a heteroatom, or dibenzothiophene, diphenylamine, etc., but is not limited thereto.

[0210] Unless otherwise noted, a halogen group refers to a group 17 element, and may be, for example, a fluoro group, a chloro group, a bromo group, or an iodo group, but is not limited thereto.

[0211]

[0212] A Ziegler-Natta catalyst for olefin polymerization according to one embodiment comprises: a Ziegler-Natta pro-catalyst for olefin polymerization comprising a titanium compound represented by the following chemical formula 1, a magnesium compound represented by the following chemical formula 2, a first internal electron donor represented by the following chemical formula 3, and a second internal electron donor selected from the group consisting of one or more compounds represented by the following chemical formulas 4 and 5; an organoaluminum compound represented by the following chemical formula 6; and an external electron donor represented by the following chemical formula 7.

[0213]

[0214] (A) Titanium compound

[0215] A titanium compound according to one embodiment may be a compound comprising an active center metal, that is, a metal having an active site. The titanium compound can produce a polyolefin by catalyzing a substantial polymerization reaction of an olefin monomer.

[0216] The above titanium compound is a compound represented by the following chemical formula 1:

[0217] [Chemical Formula 1]

[0218] TiX n (OR 1 ) 4-n

[0219] (In the above chemical formula 1,

[0220] R 1 C1-C of substituted or non-substituted 20 Alkyl groups, substituted or unsubstituted C3-C 20 Cycloalkyl groups, and substituted or unsubstituted C6-C 20 It is one species selected from the group composed of aryls, and

[0221] X is a halogen atom, and

[0222] n is an integer from 0 to 4, and

[0223] In the above substitution or non-substitution, the substituent is independently one selected from the group consisting of halogen groups, cyano groups, nitro groups, and C1-C8 alkyl groups).

[0224] In a specific example, the titanium compound may be one or more selected from the group consisting of halides of tetravalent titanium and alkoxides of tetravalent titanium. The titanium compound may preferably be titanium tetrachloride (TiCl4), titanium trichloride ethoxide (Ti(OC2H5)Cl3), titanium trichloride (TiCl3), etc.

[0225]

[0226] (B) Magnesium compound

[0227] According to one embodiment, a magnesium compound can control properties such as the activity and stereoregularity of an active center metal having an active site, such as a titanium compound, through bonding with an electron donor as a catalyst support, depending on the molecular structure and bonding strength.

[0228] The above magnesium compound is a compound represented by the following chemical formula 2:

[0229] [Chemical Formula 2]

[0230] Mg(OR 2 ) k X 2-k

[0231] (In the above chemical formula 2,

[0232] R 2 C1-C of substituted or non-substituted 20 Alkyl groups, substituted or unsubstituted C3-C 20 Cycloalkyl groups, and substituted or unsubstituted C6-C 20 It is one species selected from the group composed of aryls, and

[0233] X is a halogen atom, and

[0234] k is an integer from 0 to 2, and

[0235] In the above substitution or non-substitution, the substituent is independently one selected from the group consisting of halogen groups, cyano groups, nitro groups, and C1-C8 alkyl groups).

[0236] In a specific example, the magnesium compound may be magnesium dialkoxide, magnesium diaryloxide, or magnesium chloride (MgCl2), etc. The magnesium dialkoxide may have high purity and reduce impurities in the finally synthesized catalyst, and the magnesium diethoxide may be well soluble in a solvent during catalyst synthesis. The magnesium compound may preferably be magnesium diethoxide, which has high purity and can reduce impurities in the finally synthesized catalyst, and is easily soluble in a solvent during catalyst synthesis.

[0237]

[0238] (C) Internal electron donor

[0239] According to one embodiment, an internal electron donor can control properties such as the activity and stereoregularity of a titanium compound through bonding with a magnesium compound that serves as a catalyst support. When an external electron donor is included in an olefin-Ziegler-Natta catalyst, the internal electron donor can provide various active sites and can produce a polyolefin satisfying a specific range of density, melt index, and melt index ratio.

[0240]

[0241] (C-1) First internal electron donor

[0242] The above first internal electron donor is a compound represented by the following chemical formula 3:

[0243] [Chemical Formula 3]

[0244]

[0245] (In the above chemical formula 3,

[0246] R 3 and R 4 Each is independently a substituted or non-substituted C1-C 20 Alkyl groups, substituted or unsubstituted C3-C 20 Cycloalkyl groups, and substituted or unsubstituted C6-C 20 It is one species selected from the group consisting of aryl groups, or R 3 and R 4 They are connected to each other, resulting in substitutive or non-substitutive C3-C 20 Forming a cycloaliphatic ring or an aromatic ring,

[0247] R 5 and R 6 Each is independently a substituted or non-substituted C1-C 20 It is an alkyl group, and

[0248] In the above substitution or non-substitution, the substituent is independently one selected from the group consisting of halogen groups, cyano groups, nitro groups, phenyl groups, and C1-C8 alkyl groups.

[0249] In a specific example, R of the above chemical formula 3 3 and R 4 Is Each independently substituted or non-substituted C1-C 10 Alkyl groups, substituted or unsubstituted C3-C 10 Cycloalkyl groups, substituted or unsubstituted C6-C 15 Aryl group or R 3 and R 4 They are connected to each other, resulting in substitutive or non-substitutive C3-C 10 It can form a cycloaliphatic ring or an aromatic ring. For example, in the above chemical formula 3, R 3 and R 4 Is Each independently a substituted or unsubstituted C1-C5 alkyl group, a substituted or unsubstituted C5-C6 cycloalkyl group, and a substituted or unsubstituted C6-C 10 It can form aryl groups or interconnected substituted or non-substituted C3-C6 cycloaliphatic rings or aromatic rings.

[0250] In a specific example, R of the above chemical formula 3 3 and R 4 It may not be the same.

[0251] In a specific example, R of the above chemical formula 3 5 and R 6 Is Each independently substituted or non-substituted C1-C 10 It may be an alkyl group, for example, a substituted or unsubstituted C1-C5 alkyl group.

[0252] The first internal electron donor may be one or more selected from the group consisting of compounds represented by the following chemical formulas 3-1 to 3-6:

[0253] [Chemical Formula 3-1]

[0254]

[0255] [Chemical Formula 3-2]

[0256]

[0257] [Chemical Formula 3-3]

[0258]

[0259] [Chemical Formula 3-4]

[0260]

[0261] [Chemical Formula 3-5]

[0262]

[0263] [Chemical Formula 3-6]

[0264]

[0265] The first internal electron donor may be two types selected from the compounds represented by Chemical Formulas 3-1 to 3-6. In a specific example, the molar ratio of the first compound selected from the compounds represented by Chemical Formulas 3-1 to 3-6 and the second compound selected from the compounds represented by Chemical Formulas 3-1 to 3-6 may be about 3:7 to 7:3, for example, about 4:6 to 6:4 or 5:5. Within this range, the stability of the catalytic active site is high, and there may be no problem of reduced activity due to poisoning of the catalytic active site.

[0266] The first internal electron donor is included in an amount of about 0.5 to 15 weight% of 100 weight% of the total Ziegler-Natta catalyst for olefin polymerization. In a specific example, the internal electron donor may be included in an amount of about 1 to 12 weight%, for example, about 3 to 10 weight%. Within this range, the stability of the catalyst active site is high, and there may be no problem of reduced activity due to poisoning of the catalyst active site.

[0267]

[0268] (C-2) Second internal electron donor

[0269] The above second internal electron donor is one or more selected from the group consisting of compounds represented by the following chemical formulas 4 and 5:

[0270] [Chemical Formula 4]

[0271]

[0272] (In the above chemical formula 4,

[0273] R 7 , R 8 and R 9 Each is independently a substituted or non-substituted C1-C 20 Alkyl groups, substituted or unsubstituted C3-C 20 Cycloalkyl groups, and substituted or unsubstituted C6-C 20 It is one species selected from the group composed of aryls, and

[0274] m is an integer from 0 to 4, and

[0275] In the above substitution or non-substitution, the substituent is independently one selected from the group consisting of halogen groups, cyano groups, nitro groups, and C1-C8 alkyl groups.

[0276] In a specific example, R of the above chemical formula 4 7 , R 8 and R 9 Is Each independently substituted or non-substituted C1-C 10 Alkyl groups, substituted or unsubstituted C3-C 10 Cycloalkyl groups, substituted or unsubstituted C6-C 15 It may be an aryl group. For example, R of the above chemical formula 4. 7 , R 8 and R 9 Is Each independently a substituted or unsubstituted C1-C5 alkyl group, a substituted or unsubstituted C5-C6 cycloalkyl group, and a substituted or unsubstituted C6-C 10 It could be Arilgi.

[0277] In a specific example, R of the above chemical formula 4 8 and R 9 Each is independently a linear C1-C 20 Alkyl groups and branched chain type C1-C 20It may be one selected from the group consisting of alkyl groups. For example, R of Chemical Formula 4 above. 8 and R 9 Is Each independently linear C1-C 10 Alkyl group, branched chain C1-C 10 It can be an alkyl group.

[0278] [Chemical Formula 5]

[0279]

[0280] (In the above chemical formula 5,

[0281] R 10 , R 11 , R 12 and R 13 Each is independently a hydrogen atom, a substituted or unsubstituted C1-C 20 Alkyl groups, substituted or unsubstituted C3-C 20 Cycloalkyl groups, and substituted or unsubstituted C6-C 20 It is one species selected from the group composed of aryls, and

[0282] R 14 and R 15 Each is independently a substituted or non-substituted C1-C 20 Alkyl groups, substituted or unsubstituted C3-C 20 Cycloalkyl groups, and substituted or unsubstituted C6-C 20 It is one type selected from the group consisting of aryl groups, and

[0283] In the above substitution or non-substitution, the substituent is independently one selected from the group consisting of halogen groups, cyano groups, nitro groups, and C1-C8 alkyl groups.

[0284] In a specific example, R of the above chemical formula 5 10 , R 11 , R 12 and R 13 Is Each independently a hydrogen atom, a substituted or non-substituted C1-C10 Alkyl groups, substituted or unsubstituted C3-C 10 Cycloalkyl groups, substituted or unsubstituted C6-C 15 It may be an aryl group. For example, R of the above chemical formula 5. 10 , R 11 , R 12 and R 13 Is Each independently a hydrogen atom, a substituted or unsubstituted C1-C5 alkyl group, a substituted or unsubstituted C5-C6 cycloalkyl group, a substituted or unsubstituted C6-C 10 It could be Arilgi.

[0285] In a specific example, R of the above chemical formula 5 14 and R 15 Each is independently a linear C1-C 20 Alkyl groups and branched chain type C1-C 20 It may be one selected from the group consisting of alkyl groups. For example, R of Chemical Formula 5 above. 14 and R 15 Is Each independently linear C1-C 10 Alkyl group, branched chain C1-C 10 It can be an alkyl group.

[0286] The second internal electron donor may be one or more selected from the group consisting of compounds represented by the following chemical formulas 4-1 and 5-1 to 5-6:

[0287] [Chemical Formula 4-1]

[0288]

[0289] [Chemical Formula 5-1]

[0290]

[0291] [Chemical Formula 5-2]

[0292]

[0293] [Chemical Formula 5-3]

[0294]

[0295] [Chemical Formula 5-4]

[0296]

[0297] [Chemical Formula 5-5]

[0298]

[0299] [Chemical Formula 5-6]

[0300]

[0301] The second internal electron donor may be two types selected from compounds represented by Formula 4-1 and Formulas 5-1 to 5-6. In a specific example, the molar ratio of the first compound selected from compounds represented by Formula 4-1 and Formulas 5-1 to 5-6 and the second compound selected from compounds represented by Formula 4-1 and Formulas 5-1 to 5-6 may be about 3:7 to 7:3, for example, about 4:6 to 6:4 or about 5:5. Within this range, the stability of the catalytic active site is high, and there may be no problem of reduced activity due to poisoning of the catalytic active site.

[0302] The second internal electron donor is included in an amount of about 0.5 to 15 weight% of 100 weight% of the total Ziegler-Natta catalyst for olefin polymerization. In a specific example, the internal electron donor may be included in an amount of about 1.5 to 12 weight%, for example, about 3.5 to 10 weight%. Within this range, the stability of the catalyst active sites is high, and there may be no problem of reduced activity due to poisoning of the catalyst active sites.

[0303] The molar ratio of the first internal electron donor and the second internal electron donor may be about 8:2 to 2:8. In a specific example, the molar ratio may be about 7:3 to 3:7, for example, about 6:4 to 4:6 or 5:5. The first internal electron donor and the second internal electron donor, which have different functional groups and structures, can bond with the magnesium compound with varying strengths, and the hydrogen reactivity and processability of the polyolefin resin can be controlled by varying the ratio between the internal electron donors.

[0304] A mixture comprising a first internal electron donor represented by Chemical Formula 3 and a second internal electron donor represented by Chemical Formulas 4 and 5 may be included in an amount of about 95% by weight or more, preferably about 99% to 100% by weight, and more preferably about 100% by weight, of the total internal electron donors contained in the Ziegler-Natta catalyst for olefin polymerization. Within this range, the number of active sites of the titanium compound can be increased. Here, 'total internal electron donor' may refer to a compound included in the main catalyst of the olefin Ziegler-Natta catalyst, which is known to those skilled in the art to perform the role of stabilizing the catalytic active sites of the titanium compound.

[0305]

[0306] (D) Organoaluminum compounds

[0307] An organic aluminum compound according to one embodiment can activate the active site of a titanium compound.

[0308] The above organoaluminum compound is a compound represented by the following chemical formula 6:

[0309] [Chemical Formula 6]

[0310] Al(R 16 ) p X 3-p

[0311] (In the above chemical formula 6,

[0312] R16 hydrogen atoms, substituted or non-substituted C1-C 20 Alkyl groups, substituted or unsubstituted C3-C 20 Cycloalkyl groups, and substituted or unsubstituted C6-C 20 It is one species selected from the group composed of aryls, and

[0313] X is a halogen atom, and

[0314] p is an integer from 0 to 3, and

[0315] In the above substitution or non-substitution, the substituent is independently one selected from the group consisting of halogen groups, cyano groups, nitro groups, and C1-C8 alkyl groups.

[0316] In a specific example, the organoaluminum compound may be one or more selected from the group consisting of trimethylaluminum, triethylaluminum, triisobutylaluminum, trioctylaluminum, trihexylaluminum, diethylaluminum hydride, diisobutylaluminum hydride, diethylaluminum chloride, diisobutylaluminum chloride, sesquiethylaluminum chloride, and ethylaluminum dichloride. The organoaluminum compound may preferably be triethylaluminum, which can increase polymerization activity.

[0317]

[0318] (E) External electronic donor

[0319] An external electron donor according to one embodiment can stabilize the catalytic active site of a titanium compound among the main catalysts. A siloxane-based external electron donor represented by the following chemical formula 7 can produce a polyolefin satisfying a specific range of density, melt index, and melt index ratio when applied to an internal electron donor. For example, the external electron donor can maintain catalytic activity and stability by binding to the site where the internal electron donor was removed by triethylaluminum.

[0320] The above external electron donor is a compound represented by the following chemical formula 7:

[0321] [Chemical Formula 7]

[0322]

[0323] (In the above chemical formula 7,

[0324] R 17 and R 18 Each is independently a substituted or non-substituted C1-C 20 It is an alkyl group, and

[0325] R 19 and R 20 Each is independently a substituted or non-substituted C1-C 20 Alkyl groups and substituted or unsubstituted C3-C 20 It is one selected from the group consisting of cycloalkyl groups, and

[0326] In the above substitution or non-substitution, the substituent is independently one selected from the group consisting of halogen groups, cyano groups, nitro groups, and C1-C8 alkyl groups).

[0327] In a specific example, R of the above chemical formula 7 17 and R 18 Is Each independently substituted or non-substituted C1-C 10 It may be an alkyl group, for example, a substituted or unsubstituted C1-C5 alkyl group.

[0328] In a specific example, R of the above chemical formula 7 19 and R 20 Each independently Substituted or non-substituted C1-C 10 Alkyl groups, substituted or unsubstituted C3-C 10 It may be a cycloalkyl group. For example, R of Chemical Formula 7 above. 13 and R 14 It may be a substituted or unsubstituted C1-C5 alkyl group, or a substituted or unsubstituted C5-C6 cycloalkyl group.

[0329] The above external electron donor may be one or more selected from the group consisting of compounds represented by the following chemical formulas 7-1 to 7-6:

[0330] [Chemical Formula 7-1]

[0331]

[0332] [Chemical Formula 7-2]

[0333]

[0334] [Chemical Formula 7-3]

[0335]

[0336] [Chemical Formula 7-4]

[0337]

[0338] [Chemical Formula 7-5]

[0339]

[0340] [Chemical Formula 7-6]

[0341]

[0342]

[0343] The above external electron donor can facilitate the production of polyolefins with excellent processability when applied to internal electron donors. In addition, the above external electron donor binds more strongly to the crystal planes of the magnesium compound, thereby reducing the number of final active sites and reducing the melt index ratio, making it easy to reach a melt index ratio of about 20.0 to less than 50.0.

[0344] The above external electron donor is included in an amount of about 20 to 50 weight percent of 100 weight percent of the total Ziegler-Natta catalyst for olefin polymerization. In a specific example, the above external electron donor may be included in an amount of about 30 to 40 weight percent, for example, about 33 to 38 weight percent. Within this range, the stability of the catalyst active sites is high, and there may be no problem of reduced activity due to poisoning of the catalyst active sites.

[0345] The external electron donor represented by Chemical Formula 7 above may be included in an amount of about 95% by weight or more, preferably about 99% to 100% by weight, and more preferably about 100% by weight, of the total external electron donor contained in the Ziegler-Natta catalyst for olefin polymerization. Within this range, the number of active sites of the titanium compound can be increased. Here, 'total external electron donor' may refer to a compound included independently of the main catalyst in the olefin Ziegler-Natta catalyst, and may mean a compound known to those skilled in the art to perform the role of stabilizing the catalytic active sites of the titanium compound.

[0346]

[0347] Ziegler-Natta main catalyst for olefin polymerization

[0348] A Ziegler-Natta main catalyst for olefin polymerization according to one embodiment comprises a titanium compound represented by Formula 1, a magnesium compound represented by Formula 2, a first internal electron donor represented by Formula 3, and a second internal electron donor selected from the group consisting of compounds represented by Formulas 4 and 5, wherein the titanium compound, the first internal electron donor, and the second internal electron donor may be supported on the magnesium compound.

[0349] The above-described Ziegler-Natta main catalyst for olefin polymerization may be in a powder state. A Ziegler-Natta catalyst for olefin polymerization according to one embodiment may be prepared by mixing an organic aluminum compound and an external electron donor with the above-described Ziegler-Natta main catalyst for olefin polymerization. The above-described powdered Ziegler-Natta main catalyst for olefin polymerization can be uniformly coated with the organic aluminum compound and the external electron donor. This allows the powdered Ziegler-Natta main catalyst for olefin polymerization to be well dispersed in the organic aluminum compound and the external electron donor, thereby increasing dispersion stability and facilitating the production of polyolefins having the density, melt index, and melt index ratio described above.

[0350] The method for preparing the above-described Ziegler-Natta main catalyst for olefin polymerization may include: a step of mixing a titanium compound represented by Chemical Formula 1 and a magnesium compound represented by Chemical Formula 2 and stirring them first; a step of sequentially adding an internal electron donor represented by Chemical Formula 3 and an internal electron donor represented by Chemical Formula 4 to the result of the first stirring and stirring second; and a step of vacuum drying the result of the second stirring.

[0351] The first stirring step above can be performed by adding the titanium compound and the magnesium compound to an organic solvent, and then stirring at a heating rate of about 0.5°C to 1.5°C in the specific example, or about 0.7°C to 1.3°C, for example, about 0.8°C to 1.2°C from room temperature to the first temperature.

[0352] The above organic solvent may be toluene, ether, acetone, alcohol, etc., and preferably may be toluene.

[0353] The first temperature may be about 70°C to 90°C, for example, about 72°C to 88°C, preferably about 75°C to 85°C. Within this range, the internal electron donor may be dissolved in the solvent, and side reactions of the internal electron donor may not occur.

[0354] The first stirring speed may be about 200 rpm to 400 rpm, for example, about 210 rpm to 390 rpm, preferably about 220 rpm to 380 rpm.

[0355] The second stirring step above may involve introducing an internal electron donor into the first stirring result and then stirring for about 1.8 to 2.2 hours at a heating rate of about 0.5°C to 1.5°C up to a second temperature. In a specific example, stirring may be performed for about 1.85 to 2.15 hours, for example, about 1.9 to 2.1 hours, at a heating rate of about 0.7°C to 1.3°C, for example, about 0.8°C to 1.2°C.

[0356] The second temperature may be about 100°C to 120°C, for example, about 102°C to 118°C, preferably about 105°C to 115°C. In this range, the titanium compound can be well supported on the magnesium compound, and the solvent may not evaporate.

[0357] After the second stirring step above, a third stirring step may be additionally included. In a specific example, after removing the organic solvent and titanium compound, a new organic solvent and titanium compound are added, and then stirring is performed at a heating rate of about 0.5°C to 1.5°C from room temperature to a third temperature and maintained for about 1.8 hours to 2.2 hours. In a specific example, stirring is performed at a heating rate of about 0.7°C to 1.3°C, for example, about 0.8°C to 1.2°C, and maintained for about 1.85 hours to 2.15 hours, for example, about 1.9 hours to 2.1 hours.

[0358] The third temperature above may be about 90°C to 110°C, for example, about 92°C to 108°C, preferably about 95°C to 105°C.

[0359] The vacuum drying step described above may involve drying the second stirring product or the third stirring product under vacuum to obtain a Ziegler-Natta main catalyst for olefin polymerization supported in powder form. At this time, a step of washing the second stirring product or the third stirring product with an organic solvent, etc., before vacuum drying may be further included.

[0360] The temperature during the above washing may be about 50°C to 120°C, for example, about 60°C to 110°C, preferably about 70°C to 100°C.

[0361]

[0362] Ziegler-Natta catalyst for olefin polymerization

[0363] A Ziegler-Natta catalyst for olefin polymerization according to one embodiment comprises a titanium compound having an active site, a magnesium compound serving as a catalyst support, and a first internal electron donor and a second internal electron donor that combine with the catalyst support to activate the active site of the titanium compound, and additionally includes an organoaluminum compound and an external electron donor that activates the active site.

[0364] The molar ratio of the external electron donor to the titanium compound of the above-mentioned Ziegler-Natta main catalyst for olefin polymerization may be about 2 to 7, for example, about 3 to 6, preferably about 4 to 5. Within this range, the stability of the catalyst active site is excellent, and there may be no problem of reduced catalyst activity due to poisoning of the catalyst active site.

[0365] The molar ratio of the external electron donor to the magnesium compound of the above-mentioned Ziegler-Natta catalyst for olefin polymerization may be about 2 to 7, for example, about 3 to 6, preferably about 4 to 5. Within this range, it may be easy to manufacture polyolefins with excellent processability and hydrogen reactivity.

[0366] The molar ratio of the external electron donor to the mixture containing the first internal electron donor and the second internal electron donor of the above-mentioned Ziegler-Natta main catalyst for olefin polymerization may be about 2 to 15, for example, about 5 to 10, preferably about 6 to 7. Within this range, it may be easy to manufacture polyolefins with excellent processability and hydrogen reactivity.

[0367] The molar ratio of the external electron donor to the organoaluminum compound of the Ziegler-Natta catalyst for olefin polymerization may be about 0.01 to 0.08, for example, about 0.01 to 0.06, preferably about 0.02 to 0.06. Within this range, it may be easy to manufacture polyolefins with excellent processability and hydrogen reactivity.

[0368] The method for preparing the above-mentioned Ziegler-Natta catalyst for olefin polymerization may include the step of introducing the main Ziegler-Natta catalyst for olefin polymerization, an organoaluminum compound represented by Chemical Formula 6, and an external electron donor represented by Chemical Formula 7 into an organic solvent and then stirring. Any content related to the method for preparing the above-mentioned Ziegler-Natta catalyst for olefin polymerization that overlaps with the Ziegler-Natta catalyst for olefin polymerization may be omitted from the explanation.

[0369] The above organic solvent may be hexane, toluene, ether, acetone, alcohol, etc., and preferably may be hexane.

[0370] The above stirring can be carried out at a speed of about 280 rpm to 320 rpm, for example, about 285 rpm to 315 rpm, preferably about 290 rpm to 310 rpm.

[0371]

[0372] Polyolefin manufacturing method

[0373] A method for manufacturing a polyolefin according to one embodiment includes the step of polymerizing an olefin monomer in the presence of a Ziegler-Natta catalyst for olefin polymerization.

[0374] The above olefin monomer may include an olefin monomer having the following chemical formula 8:

[0375] [Chemical Formula 8]

[0376] CH2=CHR 21

[0377] (In the above chemical formula 8,

[0378] R 21 is hydrogen or a C1-C6 alkyl or aryl group)

[0379] The above method for manufacturing a polyolefin may be a method for manufacturing polyethylene. Accordingly, it may include the step of polymerizing by introducing the olefin monomer, preferably ethylene, in the presence of a Ziegler-Natta catalyst for olefin polymerization.

[0380] The above method for manufacturing a polyolefin can be polymerized in a hydrogen gas atmosphere at a pressure of about 2 bar to 4 bar and a temperature of about 80°C to 90°C for about 0.5 hours to 1.5 hours. In a specific example, the pressure may be about 2.2 bar to 3.8 bar, for example, about 2.5 bar to 3.5 bar. In a specific example, the temperature may be about 82°C to 88°C, for example, about 83°C to 86°C. In a specific example, the time may be about 0.7 hours to 1.4 hours, for example, about 0.8 hours to 1.2 hours. Within this range, the catalyst activity is excellent, making polymerization easy, and the disadvantage of rapid decrease in activity due to catalyst overreaction can be reduced.

[0381] The molar ratio of the Ziegler-Natta catalyst for olefin polymerization to the olefin monomer is approximately 3 x 10 -6 Up to 7 x 10 -6 It can be. In a specific example, about 4 x 10 -6 Up to 6 x 10 -6 Moles, for example, preferably about 4 x 10 -6 Up to 5 x 10 -6It may be possible. Within the above range, the polymerization yield of polyolefin from olefin monomers may be high.

[0382]

[0383] Polyolefin resin

[0384] A polyolefin resin according to one embodiment has a density of about 0.940 to 0.965 g / cm³ as measured according to ASTM D1505. 3 , in a specific example, about 0.950 to 0.962 g / cm² 3 , for example Approximately 0.952 to 0.960 g / cm³ 3 It could be.

[0385] A polyolefin resin according to one embodiment is manufactured by the manufacturing method described above, and the MFI at a temperature of 190°C and a load of 21.6 kg in accordance with ASTM D1238 21.6 This is approximately 35.0g / 10min to 60.0g / 10min, and MFI at a temperature of 190℃ and a load of 2.16kg. 2.16 This may be approximately 0.1g / 10min to 30.0g / 10min.

[0386] In a specific example, the above MFI 21.6 is about It may be 38.0g / 10min to 56.5g / 10min, for example, about 40.0g / 10min to 50.0g / 10min. In addition, in a specific example, the MFI 2.16 This can be about 0.5 g / 10 min to 25.0 g / 10 min, for example, about 1.0 g / 10 min to 20.0 g / 10 min. Polyethylene with excellent processability and hydrogen reactivity can be produced within the above range.

[0387] A polyolefin resin according to one embodiment is manufactured by the manufacturing method described above, and MFR (MFI according to ASTM D1238 21.6 / MFI 2.16 ) is approximately 20.0 to 50.0. In a specific example, the MFR (MFI21.6 / MFI 2.16 ) can be about 23.0 to 45.0, for example, about 25.0 to 40.0. Polyethylene with excellent processability and hydrogen reactivity can be produced within the above range.

[0388]

[0389] The present invention will be explained in more detail below through examples. However, these examples are intended to illustrate the invention and the scope of the invention is not limited to these examples.

[0390]

[0391] Examples

[0392] The components used in each of the following examples and comparative examples are as follows:

[0393] (a) First internal electron donor

[0394] [Chemical Formula 3-6]

[0395]

[0396]

[0397] (b) Second internal electron donor

[0398] [Chemical Formula 4-1]

[0399]

[0400] [Chemical Formula 5-1]

[0401]

[0402]

[0403] (c) Third internal electronic donor

[0404] [Chemical Formula 9-1]

[0405]

[0406]

[0407] (d) External electron donor

[0408] [Chemical Formula 7-1]

[0409]

[0410]

[0411] Example 1

[0412] Preparation Example 1: Preparation of Ziegler-Natta Main Catalyst for Olefin Polymerization

[0413] 4g of magnesium compound Mg(OC2H5)2 carrier and 45ml of titanium compound TiCl were added to 35ml of toluene and stirred at 300rpm at room temperature for 80 o 1 up to C o The temperature was increased at a heating rate of C / min. Subsequently, when the reaction temperature reached 80℃, the first internal electron donor and the second internal electron donor were added sequentially to the first stirred product, and 110 o 1 up to C o After heating at a heating rate of C / min, the second stirring was performed for 2 hours while maintaining the temperature. Subsequently, the TiCl4+toluene solution was removed, and a new TiCl4 (13 ml) + toluene (20 ml) solution was added. Then, the temperature was raised from room temperature to 100°C at a heating rate of 1°C / min while stirring for the third time, and maintained for 2 hours. Afterward, the supported catalyst resulting from the third stirring was washed 4 times with 50 ml of toluene at 100°C and 2 times with 50 ml of hexane at 60°C, and dried under vacuum to obtain a powder form of Ziegler-Natta catalyst (supported catalyst) for olefin polymerization.

[0414] The first internal electron donor used was 4.0 mmol (0.87 g) of Formula 3-6, and the second internal electron donor used was 1.0 mmol (0.22 g) of Formula 4-1.

[0415]

[0416] Preparation Example 2: Preparation of Ziegler-Natta catalyst for olefin polymerization and polyethylene

[0417] A 2L high-pressure reactor was dried in an oven and assembled while hot, and the inside of the reactor was made into a nitrogen atmosphere by alternately operating nitrogen and vacuum three times. Subsequently, 1000 ml of hexane, an organic solvent, was added to the reactor, and 15 mg of the main Ziegler-Natta catalyst for olefin polymerization (Preparation Example 1), 0.24 mmol (0.045 g) of the external electron donor of Formula 7-1, and 2 mmol of triethylaluminum (2 ml of 1 M hexane solution) were additionally added. Then, the temperature of the reactor was raised to 85°C while stirring the catalyst slurry solution in the reactor at 300 rpm, and after introducing 3 bar of hydrogen once, the Ziegler-Natta catalyst for olefin polymerization was prepared. Subsequently, polyethylene polymerization was carried out for 1 hour while continuously introducing ethylene at a constant pressure of 7 bar. Subsequently, the temperature of the reactor was lowered to room temperature, and the generated polymer was separated, collected, and dried to produce white powder polyethylene resin.

[0418]

[0419] Example 2

[0420] Polyethylene resin was prepared in the same manner as in Example 1, except that 2.5 mmol (0.54 g) of the first internal electron donor and 2.5 mmol (0.57 g) of the second internal electron donor were used in Preparation Example 1.

[0421]

[0422] Example 3

[0423] Polyethylene resin was prepared in the same manner as in Example 1, except that 1.0 mmol (0.22 g) of the first internal electron donor and 4.0 mmol (0.91 g) of the second internal electron donor were used in Preparation Example 1.

[0424]

[0425] Example 4

[0426] In Preparation Example 1, a polyethylene resin was prepared in the same manner as in Example 1, except that the second internal electron donor used Chemical Formula 5-1.

[0427]

[0428] Comparative Example 1

[0429] Polyethylene resin was prepared in the same manner as in Example 1, except that the second internal electron donor was not used in Preparation Example 1.

[0430]

[0431] Comparative Example 2

[0432] Polyethylene resin was prepared in the same manner as in Example 1, except that the second internal electron donor was not used in Preparation Example 1 and the external electron donor was not used in Preparation Example 2.

[0433]

[0434] Comparative Example 3

[0435] Polyethylene resin was prepared in the same manner as in Example 1, except that the first internal electron donor was not used in Preparation Example 1 and 4.0 mmol (0.91 g) of the second internal electron donor was used.

[0436]

[0437] Comparative Example 4

[0438] Polyethylene resin was prepared in the same manner as in Example 1, except that 4.0 mmol (1.11 g) of the third internal electron donor of Formula 9-1 was used instead of the first internal electron donor and the second internal electron donor in Preparation Example 1.

[0439]

[0440] Comparative Example 5

[0441] Polyethylene resin was prepared in the same manner as in Example 1, except that 4.0 mmol (1.11 g) of the third internal electron donor of Formula 9-1 was used instead of the first internal electron donor and the second internal electron donor in Preparation Example 1, and the external electron donor was not used in Preparation Example 2.

[0442]

[0443] Comparative Example 6

[0444] Polyethylene resin was prepared in the same manner as in Example 1, except that 4.5 mmol (0.97 g) of the first internal electron donor was used and 0.5 mmol (0.11 g) of the second internal electron donor was used in Preparation Example 1, and the external electron donor was not used in Preparation Example 2.

[0445]

[0446] Comparative Example 7

[0447] Polyethylene resin was prepared in the same manner as in Example 1, except that 0.5 mmol (0.11 g) of the first internal electron donor was used and 4.5 mmol (1.03 g) of the second internal electron donor was used in Preparation Example 1, and the external electron donor was not used in Preparation Example 2.

[0448]

[0449] The physical properties of the manufactured polyethylene resin were evaluated using the following methods, and the results are shown in Tables 1, 2, and 3:

[0450]

[0451] Methods for evaluating physical properties

[0452] (1) Activity (g PE / g cat )

[0453] It was calculated as the weight of the obtained polyethylene (g) / the weight of the catalyst used (g).

[0454]

[0455] (2) MFI 2.16(g / 10min) and MFI 21.6 (g / 10min)

[0456] Using the TOYOSEIKI MELT INDEXER P-101 measuring device, and in accordance with ASTM D1238, a load of 2.16 kg at 190°C (MFI 2.16 ) and a load of 21.6 kg (MFI 21.6 ) was measured.

[0457]

[0458] (3) MFR

[0459] Using the TOYOSEIKI MELT INDEXER P-101 measuring device, in accordance with ASTM D1238, MFI 21.6 and MFI 2.16 Measure each and the ratio, MFI 21.6 / MFI 2.16 I obtained MFR.

[0460]

[0461] (4) Density (g / cm³) 3 )

[0462] Measured according to ASTM D1505.

[0463]

[0464] Classification Ti (Atomic Wt%) Mg (Atomic Wt%) 1st Internal Electron Donor (Wt%) 2nd Internal Electron Donor (Wt%) 3rd Internal Electron Donor (Wt%) Example 1 2.7 19.3 9.1 1.6 - Example 2 3.3 18.9 3.5 3.4 - Example 3 3.0 18.8 1.2 9.1 - Example 4 2.9 18.9 8.8 2.0 Comparative Example 1 3.1 19.1 10.1 - Comparative Example 2 3.1 18.9 10.1 - Comparative Example 3 2.4 20.3 - 7.6 - Comparative Example 4 3.7 17.7 - 11.1 Comparative Example 5 3.7 17.6 - 11.1 Comparative Example 6 3.5 18.3 9.8 0.4 - Comparative Example 7 3.6 18.8 0.7 7.2 -

[0465] * In Table 1 above, 'weight%' is the weight% of the content of each component in the Ziegler-Natta catalyst for olefin polymerization.

[0466] Classification 1 Internal Electron Donor System 2 Internal Electron Donor System 3 Internal Electron Donor System 1 Molar Ratio of Internal Electron Donor to Second Internal Electron Donor External Electron Donor Example 1 Chemical Formula 3-6 Chemical Formula 4-1-8:2 Chemical Formula 7-1 Example 2 Chemical Formula 3-6 Chemical Formula 4-1-5:5 Chemical Formula 7-1 Example 3 Chemical Formula 3-6 Chemical Formula 4-1-2:8 Chemical Formula 7-1 Example 4 Chemical Formula 3-6 Chemical Formula 5-1-8:2 Chemical Formula 7-1 Comparative Example 1 Chemical Formula 3-6 --- Chemical Formula 7-1 Comparative Example 2 Chemical Formula 3-6 ---- Comparative Example 3- Chemical Formula 4-1 --- Chemical Formula 7-1 Comparative Example 4-- Chemical Formula 9-1 --- Chemical Formula 7-1 Comparative Example 5-- Chemical Formula 9-1 --- Comparative Example 6 Chemical Formula 3-6 Chemical Formula 4-1-9:1-Comparative Example 7 Chemical Formula 3-6 Chemical Formula 4-1-1:9-

[0467] Differential activity (g PE / g cat )MFI 2.16 (g / 10min)MFI 21.6 (g / 10min)MFR density (g / cm³) 3 Example 1 30671.235.529.60.954 Example 2 20671.035.235.20.955 Example 3 16671.241.334.40.964 Example 4 32671.235.329.40.954 Comparative Example 1 46000.717.725.30.955 Comparative Example 2 57331.3 33.725.90.956 Comparative Example 3206 70.927.330.30.957 Comparative Example 4426 71.027.827.80.961 Comparative Example 53333 1.028.728.70.958 Comparative Example 632001.133.430.40.957 Comparative Example 7226 70.928.331.40.956

[0468] Referring to Table 3 above, it can be confirmed that the Ziegler-Natta catalyst for olefin polymerization of Examples 1-4 can produce a polyolefin that simultaneously satisfies the melt index, melt index ratio, and density of the present invention. On the other hand, it can be confirmed that the Ziegler-Natta catalyst for olefin polymerization of Comparative Examples 1-7 cannot produce a polyolefin that simultaneously satisfies the melt index, melt index ratio, and density of the present invention.

[0469] Simple variations or modifications of the present invention can be easily implemented by those skilled in the art, and all such variations or modifications are considered to be included within the scope of the present invention.

[0470] A Ziegler-Natta catalyst for olefin polymerization according to one embodiment of the present invention is industrially available.

Claims

A Ziegler-Natta pro-catalyst for olefin polymerization comprising a titanium compound represented by the following chemical formula 1, a magnesium compound represented by the following chemical formula 2, a first internal electron donor represented by the following chemical formula 3, and a second internal electron donor selected from the group consisting of one or more compounds represented by the following chemical formulas 4 and 5; An organoaluminum compound represented by the following chemical formula 6; and A Ziegler-Natta catalyst for olefin polymerization comprising an external electron donor represented by the following chemical formula 7: [Chemical Formula 1] TiX n (OR 1 ) 4-n (In the above chemical formula 1, R 1 C1-C of substituted or non-substituted 20 Alkyl groups, substituted or unsubstituted C3-C 20 Cycloalkyl groups, and substituted or unsubstituted C6-C 20 It is one species selected from the group composed of aryls, and X is a halogen atom, and n is an integer from 0 to 4, and In the above substitution or non-substitution, the substituent is independently one selected from the group consisting of halogen groups, cyano groups, nitro groups, and C1-C8 alkyl groups. [Chemical Formula 2] Mg(OR 2 ) k X 2-k (In the above chemical formula 2, R 2 C1-C of substituted or non-substituted 20 Alkyl groups, substituted or unsubstituted C3-C 20 Cycloalkyl groups, and substituted or unsubstituted C6-C 20 It is one species selected from the group composed of aryls, and X is a halogen atom, and k is an integer from 0 to 2, and In the above substitution or non-substitution, the substituent is independently one selected from the group consisting of halogen groups, cyano groups, nitro groups, and C1-C8 alkyl groups. [Chemical Formula 3] (In the above chemical formula 3, R 3 and R 4 Each is independently a substituted or non-substituted C1-C 20 Alkyl groups, substituted or unsubstituted C3-C 20 Cycloalkyl groups, and substituted or unsubstituted C6-C 20 It is one species selected from the group consisting of aryl groups, or R 3 and R 4 They are connected to each other, resulting in substitutive or non-substitutive C3-C 20 Forming a cycloaliphatic ring or an aromatic ring, R 5 and R 6 Each is independently a substituted or non-substituted C1-C 20 It is an alkyl group, and In the above substitution or non-substitution, the substituent is independently one selected from the group consisting of halogen groups, cyano groups, nitro groups, phenyl groups, and C1-C8 alkyl groups. [Chemical Formula 4] (In the above chemical formula 4, R 7 , R 8 and R 9 Each is independently a substituted or non-substituted C1-C 20 Alkyl groups, substituted or unsubstituted C3-C 20 Cycloalkyl groups, and substituted or unsubstituted C6-C 20 It is one species selected from the group composed of aryls, and m is an integer from 0 to 4, and In the above substitution or non-substitution, the substituent is independently one selected from the group consisting of halogen groups, cyano groups, nitro groups, and C1-C8 alkyl groups. [Chemical Formula 5] (In the above chemical formula 5, R 10 , R 11 , R 12 and R 13 Each is independently a hydrogen atom, a substituted or unsubstituted C1-C 20 Alkyl groups, substituted or unsubstituted C3-C 20 Cycloalkyl groups, and substituted or unsubstituted C6-C 20 It is one species selected from the group composed of aryls, and R 14 and R 15 Each is independently a substituted or non-substituted C1-C 20 Alkyl groups, substituted or unsubstituted C3-C 20 Cycloalkyl groups, and substituted or unsubstituted C6-C 20 It is one type selected from the group consisting of aryl groups, and In the above substitution or non-substitution, the substituent is independently one selected from the group consisting of halogen groups, cyano groups, nitro groups, and C1-C8 alkyl groups. [Chemical Formula 6] Al(R 16 ) p X 3-p (In the above chemical formula 6, R 16 hydrogen atoms, substituted or non-substituted C1-C 20 Alkyl groups, substituted or unsubstituted C3-C 20 Cycloalkyl groups, and substituted or unsubstituted C6-C 20 It is one species selected from the group composed of aryls, and X is a halogen atom, and p is an integer from 0 to 3, and In the above substitution or non-substitution, the substituent is independently one selected from the group consisting of halogen groups, cyano groups, nitro groups, and C1-C8 alkyl groups. [Chemical Formula 7] (In the above chemical formula 7, R 17 and R 18 Each is independently a substituted or non-substituted C1-C 20 It is an alkyl group, and R 19 and R 20 Each is independently a substituted or non-substituted C1-C 20 Alkyl groups and substituted or unsubstituted C3-C 20 It is one selected from the group consisting of cycloalkyl groups, and In the above substitution or non-substitution, the substituent is independently one selected from the group consisting of halogen groups, cyano groups, nitro groups, and C1-C8 alkyl groups). In paragraph 1, R of the above chemical formula 3 3 and R 4 A Ziegler-Natta catalyst for olefin polymerization that is not identical. In paragraph 1, The above-mentioned first internal electron donor is one or more selected from the group consisting of compounds represented by the following chemical formulas 3-1 to 3-6, a Ziegler-Natta catalyst for olefin polymerization: [Chemical Formula 3-1] [Chemical Formula 3-2] [Chemical Formula 3-3] [Chemical Formula 3-4] [Chemical Formula 3-5] [Chemical Formula 3-6] In paragraph 1, R of the above chemical formula 4 8 and R 9 Each is independently a linear C1-C 20 Alkyl groups and branched chain type C1-C 20 A Ziegler-Natta catalyst for olefin polymerization, which is one selected from the group consisting of alkyl groups. In paragraph 1, R of the above chemical formula 5 14 and R 15 Each is independently a linear C1-C 20 Alkyl groups and branched chain type C1-C 20 A Ziegler-Natta catalyst for olefin polymerization, which is one selected from the group consisting of alkyl groups. In paragraph 1, The above second internal electron donor is one or more selected from the group consisting of compounds represented by the following Formula 4-1 and Formulas 5-1 to 5-6, a Ziegler-Natta catalyst for olefin polymerization: [Chemical Formula 4-1] [Chemical Formula 5-1] [Chemical Formula 5-2] [Chemical Formula 5-3] [Chemical Formula 5-4] [Chemical Formula 5-5] [Chemical Formula 5-6] In paragraph 1, The above external electron donor is one or more selected from the group consisting of compounds represented by the following chemical formulas 7-1 to 7-6, a Ziegler-Natta catalyst for olefin polymerization: [Chemical Formula 7-1] [Chemical Formula 7-2] [Chemical Formula 7-3] [Chemical Formula 7-4] [Chemical Formula 7-5] [Chemical Formula 7-6] In paragraph 1, The above Ziegler-Natta catalyst for olefin polymerization comprises the first internal electron donor and the second internal electron donor in a molar ratio of 8:2 to 2:

8. In paragraph 1, A Ziegler-Natta catalyst for olefin polymerization, comprising 1 to 30 weight% of a mixture including the first internal electron donor and the second internal electron donor in 100 weight% of the above olefin polymerization Ziegler-Natta catalyst. In paragraph 1, A Ziegler-Natta catalyst for olefin polymerization, wherein the molar ratio of the external electron donor to a mixture comprising the first internal electron donor and the second internal electron donor of the Ziegler-Natta main catalyst for olefin polymerization is 2 to 15. In paragraph 1, A Ziegler-Natta catalyst for olefin polymerization, wherein the molar ratio of the external electron donor to the titanium compound of the Ziegler-Natta main catalyst for olefin polymerization is 2 to 7. A method for producing a polyolefin, 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 11. In Paragraph 12, The molar ratio of the Ziegler-Natta catalyst for olefin polymerization to the olefin monomer is 3 x 10 -6 Up to 7 x 10 -6 A method for manufacturing polyolefins. Manufactured by the manufacturing method of Paragraph 12, and MFR (MFI 21.6 / MFI 2.16 A polyolefin resin characterized by having ) 20.0 to 50.

0. A polyolefin resin polymerized by a Ziegler-Natta catalyst for olefin polymerization comprising: a main catalyst in which a first internal electron donor represented by the following chemical formula 3 and a second internal electron donor selected from the group consisting of one or more compounds represented by the following chemical formulas 4 and 5 are supported on a carrier, an organoaluminum compound represented by the following chemical formula 6 and an external electron donor represented by the following chemical formula 7; and The above carrier comprises titanium and magnesium, and The above polyolefin resin is MFR (MFI 21.6 / MFI 2.16 Polyolefin resin characterized by ) being 20.0 to 50.0: [Chemical Formula 3] (In the above chemical formula 3, R 3 and R 4 Each is independently a substituted or non-substituted C1-C 20 Alkyl groups, substituted or unsubstituted C3-C 20 Cycloalkyl groups, and substituted or unsubstituted C6-C 20 It is one species selected from the group consisting of aryl groups, or R 3 and R 4 They are connected to each other, resulting in substitutive or non-substitutive C3-C 20 Forming a cycloaliphatic ring or an aromatic ring, R 5 and R 6 Each is independently a substituted or non-substituted C1-C 20 It is an alkyl group, and In the above substitution or non-substitution, the substituent is independently one selected from the group consisting of halogen groups, cyano groups, nitro groups, phenyl groups, and C1-C8 alkyl groups. [Chemical Formula 4] (In the above chemical formula 4, R 7 , R 8 and R 9 Each is independently a substituted or non-substituted C1-C 20 Alkyl groups, substituted or unsubstituted C3-C 20 Cycloalkyl groups, and substituted or unsubstituted C6-C 20 It is one species selected from the group composed of aryls, and m is an integer from 0 to 4, and In the above substitution or non-substitution, the substituent is independently one selected from the group consisting of halogen groups, cyano groups, nitro groups, and C1-C8 alkyl groups. [Chemical Formula 5] (In the above chemical formula 5, R 10 , R 11 , R 12 and R 13 Each is independently a hydrogen atom, a substituted or unsubstituted C1-C 20 Alkyl groups, substituted or unsubstituted C3-C 20 Cycloalkyl groups, and substituted or unsubstituted C6-C 20 It is one species selected from the group composed of aryls, and R 14 and R 15 Each is independently a substituted or non-substituted C1-C 20 Alkyl groups, substituted or unsubstituted C3-C 20 Cycloalkyl groups, and substituted or unsubstituted C6-C 20 It is one type selected from the group consisting of aryl groups, and In the above substitution or non-substitution, the substituent is independently one selected from the group consisting of halogen groups, cyano groups, nitro groups, and C1-C8 alkyl groups. [Chemical Formula 6] Al(R 16 ) p X 3-p (In the above chemical formula 6, R 16 hydrogen atoms, substituted or non-substituted C1-C 20 Alkyl groups, substituted or unsubstituted C3-C 20 Cycloalkyl groups, and substituted or unsubstituted C6-C 20 It is one species selected from the group composed of aryls, and X is a halogen atom, and p is an integer from 0 to 3, and In the above substitution or non-substitution, the substituent is independently one selected from the group consisting of halogen groups, cyano groups, nitro groups, and C1-C8 alkyl groups. [Chemical Formula 7] (In the above chemical formula 7, R 17 and R 18 Each is independently a substituted or non-substituted C1-C 20 It is an alkyl group, and R 19 and R 20 Each is independently a substituted or non-substituted C1-C 20 Alkyl groups and substituted or unsubstituted C3-C 20 It is one selected from the group consisting of cycloalkyl groups, and In the above substitution or non-substitution, the substituent is independently one selected from the group consisting of halogen groups, cyano groups, nitro groups, and C1-C8 alkyl groups). In paragraph 15, The above titanium is represented by the following chemical formula 1, and Polyolefin resin in which the magnesium is represented by the following chemical formula 2: [Chemical Formula 1] TiX n (OR 1 ) 4-n (In the above chemical formula 1, R 1 C1-C of substituted or non-substituted 20 Alkyl groups, substituted or unsubstituted C3-C 20 Cycloalkyl groups, and substituted or unsubstituted C6-C 20 It is one species selected from the group composed of aryls, and X is a halogen atom, and n is an integer from 0 to 4, and In the above substitution or non-substitution, the substituent is independently one selected from the group consisting of halogen groups, cyano groups, nitro groups, and C1-C8 alkyl groups. [Chemical Formula 2] Mg(OR 2 ) k X 2-k (In the above chemical formula 2, R 2 C1-C of substituted or non-substituted 20 Alkyl groups, substituted or unsubstituted C3-C 20 Cycloalkyl groups, and substituted or unsubstituted C6-C 20 It is one species selected from the group composed of aryls, and X is a halogen atom, and k is an integer from 0 to 2, and In the above substitution or non-substitution, the substituent is independently one selected from the group consisting of halogen groups, cyano groups, nitro groups, and C1-C8 alkyl groups). In paragraph 15, A polyolefin resin wherein the first internal electron donor is one or more selected from the group consisting of compounds represented by the following chemical formulas 3-1 to 3-6: [Chemical Formula 3-1] [Chemical Formula 3-2] [Chemical Formula 3-3] [Chemical Formula 3-4] [Chemical Formula 3-5] [Chemical Formula 3-6] In paragraph 15, The above-mentioned second internal electron donor is a polyolefin resin, wherein the second internal electron donor is one or more selected from the group consisting of compounds represented by the following chemical formulas 4-1 and 5-1 to 5-6: [Chemical Formula 4-1] [Chemical Formula 5-1] [Chemical Formula 5-2] [Chemical Formula 5-3] [Chemical Formula 5-4] [Chemical Formula 5-5] [Chemical Formula 5-6] In paragraph 15, The above-mentioned external electron donor is a polyolefin resin selected from the group consisting of one or more compounds represented by the following chemical formulas 7-1 to 7-6: [Chemical Formula 7-1] [Chemical Formula 7-2] [Chemical Formula 7-3] [Chemical Formula 7-4] [Chemical Formula 7-5] [Chemical Formula 7-6] In paragraph 15, The above-described Ziegler-Natta catalyst for olefin polymerization comprises the first internal electron donor and the second internal electron donor in a molar ratio of 8:2 to 2:8, a polyolefin resin. In paragraph 15, A polyolefin resin in which the molar ratio of the external electron donor to the mixture comprising the first internal electron donor and the second internal electron donor of the Ziegler-Natta main catalyst for olefin polymerization is 2 to 15.

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