Ziegler-natta catalyst for olefin polymerization, method for preparing polyolefin, and polyolefin resin

Abstract

The present invention provides a ziegler-natta catalyst for olefin polymerization, a method for preparing polyolefin, and a polyolefin resin, the ziegler-natta catalyst for olefin polymerization comprising: (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, and an internal electron donor represented by chemical formula 3; (ii) an organoaluminum compound represented by chemical formula 4; and (iii) an external electron donor represented by chemical formula 5, wherein the internal electron donor and the external electron donor are included in a molar ratio of 1: 0.07 to 1: 0.09.

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 reduced low molecular weight content 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 and methods for manufacturing the same to produce polyethylene resin with reduced low molecular weight content, which significantly affects resin properties.

[0004] Related prior art is Korean Patent Publication No. 10-2015-0044902.

[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 producing a polyolefin and a polyolefin resin in which the oxidation state of the active site of a titanium compound can be controlled by using a co-catalyst satisfying a specific chemical formula, and the low molecular weight content is reduced by narrowing the molecular weight distribution.

[0007] The above and other objectives of the present invention can all be achieved by the present invention described below.

[0008] 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 titanium compound represented by the following Chemical Formula 1; a magnesium compound represented by the following Chemical Formula 2; and an internal electron donor represented by the following Chemical Formula 3; an organoaluminum compound represented by the following Chemical Formula 4; and an external electron donor represented by the following Chemical Formula 5; wherein the internal electron donor and the external electron donor are included in a molar ratio of 1:0.07 to 1:0.09:

[0009] [Chemical Formula 1]

[0010] TiX n (OR 1 ) 4-n

[0011] (In the above chemical formula 1,

[0012] 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

[0013] X is a halogen atom, and

[0014] n is an integer from 0 to 4, and

[0015] 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.

[0016] [Chemical Formula 2]

[0017] Mg(OR 2 )k X 2-k

[0018] (In the above chemical formula 2,

[0019] 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

[0020] X is a halogen atom, and

[0021] k is an integer from 0 to 2, and

[0022] 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.

[0023] [Chemical Formula 3]

[0024]

[0025] (In the above chemical formula 3,

[0026] 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 One selected from the group consisting of aryl groups, or a C3-C of interconnected substitutions or non-substitutions 20 It forms a cycloaliphatic ring or an aromatic ring,

[0027] R 5 and R 6 Each is independently a substituted or non-substituted C1-C 20 It is an alkyl group, and

[0028] 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.

[0029] [Chemical Formula 4]

[0030] Al(R 7 ) p X 3-p

[0031] (In the above chemical formula 4,

[0032] R 7 Silver is a hydrogen atom, substituted or non-substituted C5-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

[0033] X is a halogen atom, and

[0034] p is an integer from 0 to 3, 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 8 and R 9 Each is independently a substituted or non-substituted C1-C 20 It is an alkyl group, and

[0040] R 10 and R 11 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] 2. In the above 1 embodiment, R of Chemical Formula 3 3 and R 4 It may not be the same.

[0043] 3. In the above 1 to 2 embodiments, the 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:

[0044] [Chemical Formula 3-1]

[0045]

[0046] [Chemical Formula 3-2]

[0047]

[0048] [Chemical Formula 3-3]

[0049]

[0050] [Chemical Formula 3-4]

[0051]

[0052] [Chemical Formula 3-5]

[0053]

[0054] [Chemical Formula 3-6]

[0055]

[0056] 4. In the above 1 to 3 embodiments, the internal electron donor may be two types selected from the compounds represented by Chemical Formulas 3-1 to 3-6.

[0057] 5. In the above 1 to 4 embodiments, the external electron donor may be one or more selected from the group consisting of compounds represented by the following chemical formulas 5-1 to 5-3:

[0058] [Chemical Formula 5-1]

[0059]

[0060] [Chemical Formula 5-2]

[0061]

[0062] [Chemical Formula 5-3]

[0063]

[0064] 6. In the above 1 to 5 embodiments, the titanium compound and the external electron donor of the Ziegler-Natta catalyst for olefin polymerization may be included in a molar ratio of 1:25 to 1:40.

[0065] 7. 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 6 embodiments above.

[0066] 8. In the above 7 embodiments, for every 1 mole of the olefin monomer, the Ziegler-Natta catalyst for olefin polymerization is 1 x 10⁻⁶ -5 Up to 3 x 10 -5 It can be included in the mole.

[0067] 9. Another aspect of the present invention is manufactured by the manufacturing method of the above 7 embodiments, and MFR (MFI 21.6 / MFI 2.16 The present invention relates to a polyolefin resin characterized by having a value of less than approximately 27.0.

[0068] 10. Another aspect of the present invention relates to a polyolefin resin produced by the method of the above-described 7 embodiments and characterized by having a xylene solubility (XS) of about 5 weight% or less.

[0069] 11. Another aspect of the present invention relates to a polyolefin resin polymerized by a Ziegler-Natta catalyst for olefin polymerization comprising a main catalyst, a co-catalyst, and an external electron donor represented by the following chemical formula 5, wherein the internal electron donor represented by the following chemical formula 3 is supported on a carrier, the carrier comprises titanium and magnesium, the co-catalyst is represented by the following chemical formula 4, and the polyolefin resin satisfies the following physical properties (i) to (ii):

[0070] (i) MFR(MFI 21.6 / MFI 2.16 ) is less than 27.0

[0071] (ii) Xylene Solubility (XS) is 5 wt% or less

[0072] [Chemical Formula 3]

[0073]

[0074] (In the above chemical formula 3,

[0075] 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 One selected from the group consisting of aryl groups, or a C3-C of interconnected substitutions or non-substitutions 20 Forming a cycloaliphatic ring or an aromatic ring,

[0076] R 5 and R 6 Each is independently a substituted or non-substituted C1-C 20 It is an alkyl group, and

[0077] 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.

[0078] [Chemical Formula 4]

[0079] Al(R 7 ) p X 3-p

[0080] (In the above chemical formula 4,

[0081] R 7 Silver is a hydrogen atom, substituted or non-substituted C5-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

[0082] X is a halogen atom, and

[0083] p is an integer from 0 to 3, and

[0084] 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.

[0085] [Chemical Formula 5]

[0086]

[0087] (In the above chemical formula 5,

[0088] R 8 and R 9 Each is independently a substituted or non-substituted C1-C 20 It is an alkyl group, and

[0089] R 10 and R 11 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

[0090] 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).

[0091] 12. In the above 11 embodiments, the internal electron donor and the external electron donor may be included in a molar ratio of 1:0.07 to 1:0.09.

[0092] 13. In the above 11 to 12 embodiments, the titanium may be represented by the following chemical formula 1, and the magnesium may be represented by the following chemical formula 2:

[0093] [Chemical Formula 1]

[0094] TiX n (OR 1 ) 4-n

[0095] (In the above chemical formula 1,

[0096] 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

[0097] X is a halogen atom, and

[0098] n is an integer from 0 to 4, and

[0099] 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.

[0100] [Chemical Formula 2]

[0101] Mg(OR 2 ) k X 2-k

[0102] (In the above chemical formula 2,

[0103] 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

[0104] X is a halogen atom, and

[0105] k is an integer from 0 to 2, and

[0106] 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).

[0107] 14. In the above embodiments 11 to 13, the 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:

[0108] [Chemical Formula 3-1]

[0109]

[0110] [Chemical Formula 3-2]

[0111]

[0112] [Chemical Formula 3-3]

[0113]

[0114] [Chemical Formula 3-4]

[0115]

[0116] [Chemical Formula 3-5]

[0117]

[0118] [Chemical Formula 3-6]

[0119]

[0120] 15. In the above 12 to 14 embodiments, the external electron donor may be one or more selected from the group consisting of compounds represented by the following chemical formulas 5-1 to 5-3:

[0121] [Chemical Formula 5-1]

[0122]

[0123] [Chemical Formula 5-2]

[0124]

[0125] [Chemical Formula 5-3]

[0126]

[0127] 16. In the above 12 to 15 embodiments, the titanium compound and the external electron donor of the Ziegler-Natta catalyst for olefin polymerization may be included in a molar ratio of 1:25 to 1:40.

[0128] The present invention has the effect of enabling the production of polyethylene with reduced low molecular weight content by narrowing the molecular weight distribution, and by using a Ziegler-Natta catalyst for ethylene polymerization that includes an internal electron donor and an external electron donor satisfying a specific chemical formula to increase the number of active sites of a titanium compound, and by using a co-catalyst satisfying a specific chemical formula to control the oxidation state of the active sites of the titanium compound.

[0129] 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.

[0130] 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.

[0131] A singular expression includes a plural expression unless the context clearly indicates otherwise.

[0132] 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.

[0133] Unless otherwise specified, all numbers, values, and / or expressions used herein to denote amounts of ingredients, reaction conditions, polymer compositions, and formulations shall 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 others.

[0134] Additionally, where a numerical range is disclosed in this description, such range is continuous and, unless otherwise indicated, includes all values ​​from the minimum value of such range up to the maximum value including the maximum value. Furthermore, where such range refers to an integer, unless otherwise indicated, it includes all integers from the minimum value up to the maximum value including the maximum value.

[0135] 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.

[0136] Recently, as the applications of polyethylene have diversified, there has been a need for catalysts and methods for manufacturing polyethylene resins with reduced low molecular weight content, which significantly affects resin properties.

[0137] Accordingly, the inventors of the present invention, as a result of research to solve the above problem, discovered that when polyethylene is manufactured using a Ziegler-Natta pro-catalyst for ethylene polymerization containing an 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 a co-catalyst satisfying a specific chemical formula, the oxidation state of the active sites of the titanium compound can be controlled, and the molecular weight distribution can be narrowed to manufacture polyethylene with reduced low molecular weight content, and thus completed this.

[0138] Unless otherwise noted, "C1-C n "Alkyl group" refers to 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.

[0139] 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.

[0140] 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.

[0141] 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.

[0142] 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.

[0143] 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.

[0144]

[0145] A Ziegler-Natta catalyst for olefin polymerization according to one embodiment comprises: a titanium compound represented by the following chemical formula 1, a magnesium compound represented by the following chemical formula 2, and an internal electron donor represented by the following chemical formula 3; an organoaluminum compound represented by the following chemical formula 4; and an external electron donor represented by the following chemical formula 5.

[0146]

[0147] (A) Titanium compound

[0148] 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.

[0149] The above titanium compound is a compound represented by the following chemical formula 1:

[0150] [Chemical Formula 1]

[0151] TiX n (OR 1 ) 4-n

[0152] (In the above chemical formula 1,

[0153] 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

[0154] X is a halogen atom, and

[0155] n is an integer from 0 to 4, and

[0156] 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).

[0157] 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.

[0158]

[0159] (B) Magnesium compound

[0160] 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.

[0161] The above magnesium compound is a compound represented by the following chemical formula 2:

[0162] [Chemical Formula 2]

[0163] Mg(OR 2 ) k X 2-k

[0164] (In the above chemical formula 2,

[0165] R 2 C1-C of substituted or non-substituted20 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

[0166] X is a halogen atom, and

[0167] k is an integer from 0 to 2, and

[0168] 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).

[0169] In a specific example, the magnesium compound may be magnesium dialkoxide, magnesium diaryloxide, magnesium diethoxide, or magnesium chloride (MgCl2), etc. The magnesium dialkoxide has high purity and can reduce impurities in the finally synthesized catalyst, and the magnesium diethoxide can be well dissolved in a solvent during catalyst synthesis. The magnesium compound may preferably be magnesium chloride, which can increase the number of active sites of the catalyst and control the molecular weight distribution of polyethylene.

[0170]

[0171] (C) Internal electron donor

[0172] 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.

[0173] The above internal electron donor is a compound represented by the following chemical formula 3:

[0174] [Chemical Formula 3]

[0175]

[0176] (In the above chemical formula 3,

[0177] 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 One selected from the group consisting of aryl groups, or a C3-C of interconnected substitutions or non-substitutions 20 Forming a cycloaliphatic ring or an aromatic ring,

[0178] R 5 and R 6 Each is independently a substituted or non-substituted C1-C 20 It is an alkyl group, and

[0179] 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).

[0180] 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 C3-C of aryl groups or interconnected substitutions or non-substitutions 10 It can form a cycloaliphatic ring. For example, R of Chemical Formula 3 above. 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 substituent or non-substituent C3-C6 cyclic rings.

[0181] In a specific example, R of the above chemical formula 3 3 and R4 It may not be the same.

[0182] 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.

[0183] The above 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:

[0184] [Chemical Formula 3-1]

[0185]

[0186] [Chemical Formula 3-2]

[0187]

[0188] [Chemical Formula 3-3]

[0189]

[0190] [Chemical Formula 3-4]

[0191]

[0192] [Chemical Formula 3-5]

[0193]

[0194] [Chemical Formula 3-6]

[0195]

[0196] The above internal electron donor is included in an amount of about 13 to 28 weight percent of 100 weight percent of the total Ziegler-Natta catalyst for olefin polymerization. In a specific example, the above internal electron donor may be included in an amount of about 14 to 24 weight percent, for example, about 15 to 20 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.

[0197] The internal electron donor represented by Chemical Formula 3 above may be included in an amount of about 95% by weight or more, preferably about 99% to 100% by weight, and more preferably 100% by weight, of the total internal 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 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.

[0198]

[0199] (D) Organoaluminum compounds

[0200] An organic aluminum compound according to one embodiment can control the oxidation state of the active site of a titanium compound as a co-catalyst and can reduce the low molecular weight content of the polyolefin by narrowing the molecular weight distribution.

[0201] The above organoaluminum compound is a compound represented by the following chemical formula 4:

[0202] [Chemical Formula 4]

[0203] Al(R 7 ) p X 3-p

[0204] (In the above chemical formula 4,

[0205] R 7 Silver is a hydrogen atom, substituted or non-substituted C5-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

[0206] X is a halogen atom, and

[0207] p is an integer from 0 to 3, and

[0208] 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).

[0209] 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 tri-n-hexylaluminum, which can increase polymerization activity and reduce the low molecular weight content of the polymerized polyolefin.

[0210]

[0211] (E) External electronic donor

[0212] 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 5 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 the co-catalyst tri-n-hexylaluminum.

[0213] The above external electron donor is a compound represented by the following chemical formula 5:

[0214] [Chemical Formula 5]

[0215]

[0216] (In the above chemical formula 5,

[0217] R 8 and R 9 Each is independently a substituted or non-substituted C1-C 20 It is an alkyl group, and

[0218] R 10 and R 11 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

[0219] 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).

[0220] In a specific example, R of the above chemical formula 5 8 and R 9 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.

[0221] In a specific example, R of the above chemical formula 5 10 and R 11 Each is independently a 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 5. 10 and R 11 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.

[0222] The above external electron donor may be one or more selected from the group consisting of compounds represented by the following chemical formulas 5-1 to 5-3:

[0223] [Chemical Formula 5-1]

[0224]

[0225] [Chemical Formula 5-2]

[0226]

[0227] [Chemical Formula 5-3]

[0228]

[0229] The above external electron donor binds more strongly to the crystal plane of the magnesium compound, reducing the number of final active sites and decreasing the melt index ratio, so that a melt index ratio of about 23 or more and less than 27 can be easily reached.

[0230] The above external electron donor is included in an amount of about 35 to 85 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 40 to 80 weight percent, for example, about 45 to 75 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.

[0231] The external electron donor represented by Chemical Formula 5 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.

[0232]

[0233] Ziegler-Natta main catalyst for olefin polymerization

[0234] A Ziegler-Natta main catalyst for olefin polymerization according to one embodiment comprises a titanium compound represented by Chemical Formula 1, a magnesium compound represented by Chemical Formula 2, and an internal electron donor represented by Chemical Formula 3, wherein the titanium compound and the internal electron donor may be supported on the magnesium compound.

[0235] 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.

[0236] 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 for the first time; a step of adding a mixture of an internal electron donor represented by Chemical Formula 3 to the result of the first stirring and stirring for the second time; and a step of vacuum drying the result of the second stirring.

[0237] 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 from room temperature to a first temperature, about 0.7°C to 1.3°C in a specific example, for example, about 0.8°C to 1.2°C.

[0238] The above organic solvent may be toluene, ether, acetone, alcohol, etc., and preferably may be toluene.

[0239] 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.

[0240] The second stirring step above may involve introducing an internal electron donor into the first stirring result, raising the temperature to a second temperature, and then stirring for about 1.8 to 2.2 hours, about 1.85 to 2.15 hours in a specific example, for example, about 1.9 to 2.1 hours.

[0241] 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.

[0242] After the second stirring step described 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 the temperature is raised from room temperature to a third temperature, and stirring may be performed for about 1.8 to 2.2 hours, or in a specific example, about 1.85 to 2.15 hours, for example, about 1.9 to 2.1 hours. Afterward, a step of washing the result of the third stirring with an organic solvent, etc. may be further included.

[0243] The third temperature may be about 100°C to 120°C, for example, about 102°C to 118°C, preferably about 105°C to 115°C.

[0244] 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.

[0245]

[0246] Ziegler-Natta catalyst for olefin polymerization

[0247] 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 an internal electron donor that combines with the catalyst support to activate the active site of the titanium compound, and additionally includes an organoaluminum compound serving as a co-catalyst and an external electron donor that activates the active site.

[0248] The titanium compound and the external electron donor of the Ziegler-Natta main catalyst for olefin polymerization may be included in a molar ratio of about 1:25 to 1:40, for example, about 1:27 to 1:38, preferably about 1:28 to 1:36. Within the above range, the stability of the catalyst active sites is excellent, and there may be no problem of reduced catalyst activity due to poisoning of the catalyst active sites.

[0249] The magnesium compound and the external electron donor of the Ziegler-Natta main catalyst for olefin polymerization may be included in a molar ratio of about 1:4 to 1:12, for example, about 1:5 to 1:10, preferably about 1:6 to 1:9. Within this range, it may be easy to produce polyolefins with reduced low molecular weight content.

[0250] The internal electron donor and external electron donor of the Ziegler-Natta main catalyst for olefin polymerization may be included in a molar ratio of about 1:0.07 to 1:0.09, for example, about 1:0.072 to 1:0.088, preferably about 1:0.075 to 1:0.085. Within this range, it may be easy to produce polyolefins with reduced low molecular weight content.

[0251] The organoaluminum compound and the external electron donor of the Ziegler-Natta catalyst for olefin polymerization may be included in a molar ratio of about 1:0.01 to 1:0.08, for example, about 1:0.01 to 1:0.06, preferably about 1:0.02 to 1:0.06. Within this range, it may be easy to produce polyolefins with reduced low molecular weight content.

[0252] 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 4, and an external electron donor represented by Chemical Formula 5 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.

[0253] The above organic solvent may be hexane, toluene, ether, acetone, alcohol, etc., and preferably may be hexane.

[0254] 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.

[0255]

[0256] Polyolefin manufacturing method

[0257] 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.

[0258] The above olefin monomer may include an olefin monomer having the following chemical formula 6:

[0259] [Chemical Formula 6]

[0260] CH2=CHR 12

[0261] (In the above chemical formula 6,

[0262] R 12 is hydrogen or a C1-C6 alkyl or aryl group)

[0263] 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.

[0264] The above method for manufacturing a polyolefin can be polymerized in a hydrogen gas atmosphere at a pressure of about 6 bar to 8 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 6.2 bar to 7.8 bar, for example, about 6.5 bar to 7.5 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.

[0265] For 1 mole of the above olefin monomer, the Ziegler-Natta catalyst for olefin polymerization is approximately 1 x 10⁻⁶ -5 Up to 3 x 10 -5 It may be included in moles. In a specific example, about 1.2 x 10⁻⁶ -5 Up to 2.8 x 10 -5 Moles, for example, preferably about 1.5 x 10⁻⁶ -5 Up to 2.5 x 10-5 It can be included in molar amounts. Within the above range, the polymerization yield of polyolefin from olefin monomers can be high.

[0266]

[0267] Polyolefin resin

[0268] A polyolefin resin according to one embodiment has a density of about 0.915 to 0.930 g / cm³ as measured according to ASTM D1505. 3 , in a specific example, about 0.917 to 0.928 g / cm³ 3 , for example, medicine 0.919 to 0.926 g / cm³ 3 It could be.

[0269] 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 20g / 10min to 70g / 10min, and the MFI at a temperature of 190℃ and a load of 2.16kg 2.16 This may be approximately 0.5g / 10min to 1.5g / 10min. In a specific example, the MFI 21.6 Is It may be about 25g / 10min to 65g / 10min, for example, about 30g / 10min to 60g / 10min. In addition, in a specific example, the MFI 2.16 This approximately 0.6g / 10min to 1.3g / 10min, e.g., MFI 2.16 This may be approximately 0.7g / 10min to 1.2g / 10min. By narrowing the molecular weight distribution within the above range, polyethylene with reduced low molecular weight content can be produced.

[0270] 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 less than approximately 27.0. In a specific example, the above MFR (MFI 21.6 / MFI 2.16 The molecular weight distribution can be about 23.0 to 26.8, for example, about 23.2 to 26.6. By narrowing the molecular weight distribution within the above range, polyethylene with reduced low molecular weight content can be produced.

[0271] A polyolefin resin according to one embodiment is manufactured by the manufacturing method described above, and has a xylene solubility (XS) of about 5 wt% or less in accordance with ASTM D5492-17. In a specific embodiment, the xylene solubility may be about 0.05 wt% to 5 wt%, for example, about 0.1 wt% to 4.9 wt%, preferably about 0.15 wt% to 4.8 wt%.

[0272]

[0273] 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.

[0274]

[0275] Examples

[0276] The components used in each of the following examples and comparative examples are as follows:

[0277] (a) Internal electron donor

[0278] [Chemical Formula 3-1]

[0279]

[0280] [Chemical Formula 3-4]

[0281]

[0282] [Chemical Formula 3-6]

[0283]

[0284] [Chemical Formula 3-7]

[0285]

[0286] (b) organoaluminum compounds

[0287] [Chemical Formula 4-1]

[0288]

[0289] [Chemical Formula 4-1']

[0290]

[0291] [Chemical Formula 4-2']

[0292]

[0293] (c) External electron donor

[0294] [Chemical Formula 5-1]

[0295]

[0296]

[0297] Example 1

[0298] Preparation Example 1: Preparation of Ziegler-Natta Main Catalyst for Olefin Polymerization

[0299] 4g of magnesium compound Mg(Cl)2 carrier and 8ml of titanium compound TiCl4 were added to 12ml of toluene, and the first stirring was performed while increasing the temperature from room temperature to 80℃ at a heating rate of 1℃ / min. Afterward, when the reaction temperature reached 80℃, an internal electron donor was added to the product of the first stirring, and the second stirring was performed for 2 hours while increasing the temperature to 110℃ at a heating rate of 1℃ / min and maintaining it. Afterward, the TiCl4+Toluene solution was removed, and a new TiCl4 (10ml)+Toluene (30ml) solution was added, and the third stirring was performed for 2 hours while increasing the temperature from room temperature to 110℃ at a heating rate of 1℃ / min and maintaining it. Subsequently, the supported catalyst, which is the result of the third stirring, was washed twice with 100 ml of toluene at 100°C and twice with 100 ml of hexane at 60°C, and dried under vacuum to obtain a powder form of Ziegler-Natta catalyst (supported catalyst) for olefin polymerization.

[0300] The above internal electron donor used 4.5 mmol of chemical formula 3-6.

[0301]

[0302] Preparation Example 2: Preparation of Ziegler-Natta catalyst for olefin polymerization and polyethylene

[0303] A 2L high-pressure reactor was dried in an oven and assembled while hot, and then 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 introduced into the reactor, and 15 mg of the main Ziegler-Natta catalyst for olefin polymerization (Preparation Example 1), 0.36 mmol of the external electron donor of Formula 5-1, and 2 mmol of the co-catalyst tri-n-hexylaluminum (2 ml of 1M hexane solution) were additionally introduced, followed by the introduction of 3 bar of hydrogen once, and the Ziegler-Natta catalyst for olefin polymerization was prepared by stirring at 300 rpm.

[0304] Afterwards, the temperature of the reactor was raised to 85°C, and polyethylene polymerization was carried out for 1 hour while continuously supplying ethylene at a constant pressure of 7 bar. Afterwards, the temperature of the reactor was lowered to room temperature, and the resulting polymer was separated, collected, and dried to produce a white powder polyethylene resin.

[0305]

[0306] Example 2

[0307] Polyethylene resin was prepared in the same manner as in Example 1, except that the internal electron donor in Preparation Example 1 was formulated as 3-1.

[0308]

[0309] Example 3

[0310] Polyethylene resin was prepared in the same manner as in Example 1, except that the internal electron donor in Preparation Example 1 was formulated as 3-4.

[0311]

[0312] Example 4

[0313] Polyethylene resin was prepared in the same manner as in Example 1, except that 5.1 mmol of the internal electron donor was used in Preparation Example 1.

[0314]

[0315] Example 5

[0316] Polyethylene resin was prepared in the same manner as in Example 1, except that 4.0 mmol of the internal electron donor was used in Preparation Example 1.

[0317]

[0318] Comparative Example 1

[0319] Polyethylene resin was prepared in the same manner as in Example 1, except that 0.18 mmol of the external electron donor was used in Preparation Example 2.

[0320]

[0321] Comparative Example 2

[0322] Polyethylene resin was prepared in the same manner as in Example 1, except that 0.09 mmol of the external electron donor was used in Preparation Example 2.

[0323]

[0324] Comparative Example 3

[0325] Polyethylene resin was prepared in the same manner as in Example 1, except that the above external electron donor was not applied in Preparation Example 2.

[0326]

[0327] Comparative Example 4

[0328] A polyethylene polymer was obtained in the same manner as in Example 1, except that 3.5 mmol of the internal electron donor was used in Preparation Example 1.

[0329]

[0330] Comparative Example 5

[0331] Polyethylene resin was prepared in the same manner as in Example 1, except that 2.5 mmol of the internal electron donor was used in Preparation Example 1.

[0332]

[0333] Comparative Example 6

[0334] Polyethylene resin was prepared in the same manner as in Example 1, except that the internal electron donor in Example 1 was formulated as 3-7.

[0335]

[0336] Comparative Example 7

[0337] Polyethylene resin was prepared in the same manner as in Example 1, except that the above-mentioned co-catalyst in Example 2 was of the formula 4-1'.

[0338]

[0339] Comparative Example 8

[0340] Polyethylene resin was prepared in the same manner as in Example 1, except that the above-mentioned co-catalyst in Example 2 was of the formula 4-2'.

[0341]

[0342] Comparative Example 9

[0343] Polyethylene resin was prepared in the same manner as in Example 1, except that 15 mmol of the internal electron donor was used in Preparation Example 1.

[0344]

[0345] The physical properties of the manufactured polyethylene resin were evaluated using the following methods, and the results are shown in Tables 1 and 2:

[0346]

[0347] Physical property evaluation method

[0348] (1) Activity (g PE / g cat )

[0349] It was calculated as the weight of the obtained polyethylene (g) / the weight of the catalyst used (g).

[0350]

[0351] (2) MFI 2.16 (g / 10min) and MFI 21.6(g / 10min)

[0352] 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.

[0353]

[0354] (3) MFR

[0355] 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.

[0356]

[0357] (4) Density (g / cm³) 3 )

[0358] Measured according to ASTM D1505.

[0359]

[0360] (5) Xylene Solubility (XS) (Weight%)

[0361] In accordance with ASTM D5492-17, the obtained polyethylene was placed in xylene and dissolved at a concentration of 1% at 140°C for 1 hour. After 2 hours at room temperature, the undissolved material was filtered and extracted. Subsequently, the weight of the extracted material was measured and calculated as a percentage of the total weight of the polypropylene.

[0362]

[0363] Classification Ti (Atomic Wt%) Mg (Atomic Wt%) Internal Electron Donor (Wt%) Example 1 3.5 19 15.0 Example 2 3.3 18 16.1 Example 3 3.2 18 15.5 Example 4 3.1 19 18.2 Example 5 4.0 19 12.5 Comparative Example 1 3.5 19 15.0 Comparative Example 2 3.5 19 15.0 Comparative Example 3 3.5 19 15.0 Comparative Example 4 3.7 19 12.6 Comparative Example 5 4.0 18.9 9.1 Comparative Example 6 2.5 19 28.1 Comparative Example 7 3.5 19 15.0 Comparative Example 8 3.5 19 15.0 Comparative Example 9 2.5 19 29

[0364] * In Table 1 above, 'weight%' is the weight% of the content of each component in the Ziegler-Natta catalyst for olefin polymerization.

[0365] Classification Internal electron donor External electron donor Co-catalytic activity (g PE / g cat )MFI 2.16 (g / 10min)MFI 21.6 (g / 10min)MFR density (g / cm³) 3) Xylene Solubility (Weight%) Example 1 Chemical Formula 3-6 (4.5 mmol) Chemical Formula 5-1 (0.36 mmol) Chemical Formula 4-1 (2 mmol) 4,632 1.1 26.2 23.8 0.9 223.7 Example 2 Chemical Formula 3-1 (4.5 mmol) Chemical Formula 5-1 (0.36 mmol) Chemical Formula 4-1 (2 mmol) 4,521 1.0 24.2 24.2 0.9 224.1 Example 3 Chemical Formula 3-4 (4.5 mmol) Chemical Formula 5-1 (0.36 mmol) Chemical Formula 4-1 (2 mmol) 4,654 1.1 26.3 23.9 0.9 223.8 Example 4 Chemical Formula 3-6 (5.1 mmol) Chemical Formula 5-1 (0.36 mmol) Chemical Formula 4-1 (2 mmol) 4125 1.02 4.02 4.00.922 4.2 Example 5 Chemical Formula 3-6 (4.0 mmol) Chemical Formula 5-1 (0.36 mmol) Chemical Formula 4-1 (2 mmol) 425 40.92 1.52 3.90.922 4.1 Comparative Example 1 Chemical Formula 3-6 (4.5 mmol) Chemical Formula 5-1 (0.18 mmol) Chemical Formula 4-1 (2 mmol) 4,421 1.33 4.62 6.60.922 5.6 Comparative Example 2 Chemical Formula 3-6 (4.5 mmol) Chemical Formula 5-1 (0.09 mmol) Chemical Formula 4-1 (2 mmol) 4,129 1.64 5.62 8.50.922 6.9 Comparative Example 3 Chemical Formula 3-6 (4.5 mmol) - Chemical Formula 4-1 (2 mmol)3,621 1.96 0.23 1.7 0.922 10.5 Comparative Example 4 Chemical Formula 3-6 (3.5 mmol) Chemical Formula 5-1 (0.36 mmol) Chemical Formula 4-1 (2 mmol) 4,215 1.33 4.22 6.3 0.922 5.3 Comparative Example 5 Chemical Formula 3-6 (2.5 mmol) Chemical Formula 5-1 (0.36 mmol) Chemical Formula 4-1 (2 mmol) 4,057 1.33 5.82 7.5 0.922 6.3 Comparative Example 6 Chemical Formula 3-7 (4.5 mmol) Chemical Formula 5-1 (0.36 mmol) Chemical Formula 4-1 (2 mmol) 3,821 1.33 7.82 9.1 0.922 9.8 Comparative Example 7 Chemical Formula 3-6 (4.5 mmol) Chemical Formula 5-1 (0.36 mmol) Chemical Formula 4-1'(2 mmol)4,378 1.23 1.42 6.2 0.92 25.2 Comparative Example 8 Chemical Formula 3-6(4.5 mmol) Chemical Formula 5-1(0.36 mmol) Chemical Formula 4-2'(2 mmol)4.298 1.23 2.2.326.90.9225.5 Comparative Example 9 Chemical Formula 3-6 (15 mmol) Chemical Formula 5-1 (0.36 mmol) Chemical Formula 4-1 (2 mmol) 2,6721.335.827.50.9226.3.

[0366] Referring to Table 2 above, it can be confirmed that the Ziegler-Natta catalyst for olefin polymerization of the example can produce a polyolefin that simultaneously satisfies the melt index, melt index ratio, density, and xylene solubility of the present invention. On the other hand, it can be confirmed that the Ziegler-Natta catalyst for olefin polymerization of the comparative example cannot produce a polyolefin that simultaneously satisfies the melt index, melt index ratio, density, and xylene solubility of the present invention.

[0367]

[0368] 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.

Claims

A Ziegler-Natta main catalyst (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, and an internal electron donor represented by the following Chemical Formula 3; An organoaluminum compound represented by the following chemical formula 4; and A Ziegler-Natta catalyst for olefin polymerization comprising an external electron donor represented by the following chemical formula 5; and A Ziegler-Natta catalyst for olefin polymerization, wherein the above internal electron donor and external electron donor are included in a molar ratio of 1:0.07 to 1:0.09: [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 One selected from the group consisting of aryl groups, or a C3-C of interconnected substitutions or non-substitutions 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] Al(R 7 ) p X 3-p (In the above chemical formula 4, R 7 Silver is a hydrogen atom, substituted or non-substituted C5-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 5] (In the above chemical formula 5, R 8 and R 9 Each is independently a substituted or non-substituted C1-C 20 It is an alkyl group, and R 10 and R 11 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 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, Ziegler-Natta catalyst for olefin polymerization, wherein the 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 3, A Ziegler-Natta catalyst for olefin polymerization, wherein the internal electron donor is two types selected from the compounds represented by Chemical Formulas 3-1 to 3-6. 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 5-1 to 5-3, a Ziegler-Natta catalyst for olefin polymerization: [Chemical Formula 5-1] [Chemical Formula 5-2] [Chemical Formula 5-3] In paragraph 1, A Ziegler-Natta catalyst for olefin polymerization, wherein the titanium compound and the external electron donor of the above-mentioned Ziegler-Natta main catalyst for olefin polymerization are included in a molar ratio of 1:25 to 1:

40. A method for producing 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 6. In Paragraph 7, For every 1 mole of the above olefin monomer, the above Ziegler-Natta catalyst for olefin polymerization is 1 x 10 -5 Up to 3 x 10 -5 A method for manufacturing polyolefins containing molar. Manufactured by the manufacturing method of claim 7, and MFR (MFI 21.6 / MFI 2.16 Polyolefin resin characterized by ) being less than 27.

0. A polyolefin resin manufactured by the method of claim 7 and characterized by having a xylene solubility (XS) of 5 weight% or less. A polyolefin resin polymerized by a Ziegler-Natta catalyst for olefin polymerization comprising a main catalyst, a co-catalyst, and an external electron donor represented by the following chemical formula 5, wherein an internal electron donor represented by the following chemical formula 3 is supported on a carrier; and The above carrier comprises titanium and magnesium, and The above co-catalyst is represented by the following chemical formula 4, and The above polyolefin resin is a polyolefin resin satisfying the following physical properties (i) to (ii): (i) MFR(MFI 21.6 / MFI 2.16 ) is less than 27.0 (ii) Xylene Solubility (XS) is 5 wt% or less [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 One selected from the group consisting of aryl groups, or a C3-C of interconnected substitutions or non-substitutions 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] Al(R 7 ) p X 3-p (In the above chemical formula 4, R 7 Silver is a hydrogen atom, substituted or non-substituted C5-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 5] (In the above chemical formula 5, R 8 and R 9 Each is independently a substituted or non-substituted C1-C 20 It is an alkyl group, and R 10 and R 11 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 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 11, A polyolefin resin comprising the internal electron donor and the external electron donor in a molar ratio of 1:0.07 to 1:0.

09. In Paragraph 11, 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 11, A polyolefin resin wherein the 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 11, A polyolefin resin wherein the above external electron donor is one or more selected from the group consisting of compounds represented by the following chemical formulas 5-1 to 5-3: [Chemical Formula 5-1] [Chemical Formula 5-2] [Chemical Formula 5-3] In Paragraph 11, A polyolefin resin comprising a titanium compound and an external electron donor of the above-mentioned Ziegler-Natta main catalyst for olefin polymerization in a molar ratio of 1:25 to 1:40.

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