Metallocene catalyst for polyethylene polymerization, method for preparing polyethylene copolymer using same, and film prepared using polyethylene copolymer

Abstract

The present invention relates to a metallocene catalyst for polyethylene polymerization, a method for preparing a polyethylene copolymer using same, and a film prepared using the polyethylene copolymer. According to the present invention, it is possible to prepare polyethylene with a high molecular weight. In addition, according to the present invention, a film having improved transparency can be manufactured.

Description

Metallocene catalyst for polyethylene polymerization, method for producing polyethylene copolymer using the same, and film produced using the polyethylene copolymer

[0001] The present invention relates to a metallocene catalyst for polyethylene polymerization, a method for producing a polyethylene copolymer using the same, and a film produced using the polyethylene copolymer.

[0002] This application claims priority to and the benefit of Republic of Korea Patent Application No. 10-2023-0169843, filed November 29, 2023, which is incorporated herein by reference in its entirety.

[0003] Global demand for polyolefins, particularly polyethylene, is approaching 100 million metric tons per year, growing steadily at 3-5% annually.

[0004] Polyethylene is undergoing continuous change, centered around its existing product line. For example, production of low-density linear polyethylene is increasing, driven by the use of metallocene catalysts to enhance film properties. Efforts are also being made to diversify and develop new product lines and produce specialized products. Among these product lines, demand for ultra-high molecular weight polyethylene, which requires high properties, has been steadily increasing.

[0005] The present invention aims to provide a catalyst for producing a polyethylene copolymer having improved molecular weight.

[0006] In addition, the present invention aims to provide a film having excellent transparency from a polyethylene copolymer.

[0007] A metallocene catalyst for polyethylene polymerization according to one embodiment of the present invention comprises: (A) a transition metal compound; (B) a cocatalyst compound; and (C) a carrier supporting the transition metal compound (A) and the cocatalyst compound (B), wherein the transition metal compound (A) may be a mixture of a first metallocene catalyst compound represented by the following chemical formula 1 and a second metallocene catalyst compound represented by the following chemical formula 2.

[0008] [Chemical Formula 1]

[0009]

[0010] (In the above chemical formula 1,

[0011] M 1 is titanium (Ti), zirconium (Zr) or hafnium (Hf),

[0012] X 1 Silver halogen group, (C1-C 20 )alkyl group, (C2-C 20 )alkenyl group, (C2-C 20 )alkynyl group, (C6-C 20 )aryl group, (C1-C 20 )alkyl(C6-C 20 )aryl group, (C6-C 20 )aryl(C1-C 20 )alkyl group, (C1-C 20 )alkylamido group, (C6-C 20 )arylamido group, or (C1-C 20 ) is an alkylidene group,

[0013] R 1 and R 2 is a (C1-C6) alkyl group

[0014] n and k are integers from 0 to 2, but at least one is not 0.)

[0015] [Chemical Formula 2]

[0016]

[0017] (In the above chemical formula 2,

[0018] M 2is titanium (Ti), zirconium (Zr) or hafnium (Hf),

[0019] X 2 is a halogen group, (C1-C 20 )alkyl group, (C2-C 20 )alkenyl group, (C2-C 20 )alkynyl group, (C6-C 20 )aryl group, (C1-C 20 )alkyl(C6-C 20 )aryl group, (C6-C 20 )aryl(C1-C 20 )alkyl group, (C1-C 20 )alkylamido group, (C6-C 20 )arylamido group, or (C1-C 20 ) is an alkylidene group,

[0020] Q is carbon (C), silicon (Si), germanium (Ge), or tin (Sn),

[0021] R 3 Inland R 7 are each independently substituted or unsubstituted (C1-C 20 )alkyl group, substituted or unsubstituted (C2-C 20 )alkenyl group, substituted or unsubstituted (C6-C 20 )aryl group, substituted or unsubstituted (C1-C 20 )alkyl(C6-C 20 )aryl group, substituted or unsubstituted (C6-C 20 )aryl(C1-C 20 )alkyl group, substituted or unsubstituted (C1-C 20 )heteroalkyl group, substituted or unsubstituted (C3-C 20 )heteroaryl group, substituted or unsubstituted (C1-C 20 )alkylamido group, substituted or unsubstituted (C6-C 20 )arylamido group, substituted or unsubstituted (C1-C 20 )alkylidene group, or substituted or unsubstituted (C1-C 20 ) is a cylinder,

[0022] R 3 Inland R 7Each independently adjacent group is connected to a substituted or unsubstituted saturated or unsaturated C4-C 20 can form a ring,

[0023] m, l, and y are each integers from 0 to 4)

[0024] According to another embodiment of the present invention, a metallocene catalyst for polyethylene polymerization comprises, in the chemical formula 1, M is zirconium (Zr), X is halogen, and R 1 and R 2 is a (C1-C6) alkyl group, n and k are each 1 or 2, and in the above chemical formula 2, M is zirconium (Zr), X is halogen, Q is carbon (C), and R 3 Inland R 5 is unsubstituted (C1-C 20 ) is an alkyl group, and R 6 and R 7 is unsubstituted (C6-C 20 ) is an aryl group, and m and y can each be 1.

[0025] According to another embodiment of the present invention, a metallocene catalyst for polyethylene polymerization may be a first metallocene catalyst compound represented by the chemical formula 1, which may be represented by the following chemical formula 1-1, and a second metallocene catalyst compound represented by the chemical formula 2, which may be represented by the following chemical formula 2-1.

[0026] [Chemical Formula 1-1]

[0027]

[0028] [Chemical Formula 2-1]

[0029]

[0030] The cocatalyst compound (B) according to one embodiment of the present invention may be at least one selected from the group consisting of the following chemical formulas 3 to 5.

[0031] [Chemical Formula 3]

[0032]

[0033] (In the above chemical formula 3,

[0034] p is an integer greater than or equal to 2,

[0035] Ra is a halogen group; or (C1-C) substituted or unsubstituted with a halogen group 20 ) is a hydrocarbyl group),

[0036] [Chemical Formula 4]

[0037]

[0038] (In the above chemical formula 4,

[0039] Q is aluminum; or boron,

[0040] Rb are the same or different, and each independently represents a halogen group; or (C1-C) substituted or unsubstituted with a halogen group. 20 ) is a hydrocarbyl group),

[0041] [Chemical Formula 5]

[0042]

[0043] (In the above chemical formula 5,

[0044] [W] + is a cationic Lewis acid; or a cationic Lewis acid with a hydrogen atom attached,

[0045] Z is a group 13 element,

[0046] Rc are the same or different and each independently represents a halogen group, (C1-C 20 )substituted with one or more substituents selected from the group consisting of hydrocarbyl group, alkoxy group and phenoxy group (C6-C 20 )aryl group; or halogen group, (C1-C 20 )substituted with one or more substituents selected from the group consisting of hydrocarbyl group, alkoxy group and phenoxy group (C1-C 20 ) is an alkyl group)

[0047] A metallocene catalyst for polyethylene polymerization according to one embodiment of the present invention may include a first metallocene catalyst compound: a second metallocene catalyst compound in a molar ratio of 10:1 to 50:1.

[0048] The carrier (C) according to one embodiment of the present invention may be silica (SiO2), alumina (Al2O3), magnesium chloride (MgCl2), or a mixture thereof having fine pores on the surface or inside.

[0049] A method for producing a polyethylene copolymer according to one embodiment of the present invention may be to produce a polyethylene copolymer by reacting ethylene and an olefin monomer in the presence of a metallocene catalyst for polyethylene polymerization.

[0050] An olefin monomer according to one embodiment of the present invention is (C2~C 20 ) of α-olefins, (C4~C 20 ) of diolefins, (C3~C 20 ) cycloolefin, (C3~C 20 ) may be selected from the group consisting of cyclodiolefins, styrene and styrene derivatives.

[0051] According to another embodiment of the present invention, the olefin monomer may be an α-olefin of (C3 to C8).

[0052] According to one embodiment of the present invention, a polyethylene copolymer may have an Mz / Mn value of 4.5 or more and 6 or less, a density of 0.90 or more and 0.935 g / cm3 or less, and a melt flow rate ratio (MFRR) according to ASTM D1238 of 10 or more and 40 or less.

[0053] A film according to one embodiment of the present invention can be manufactured using a polyethylene copolymer.

[0054] A film according to one embodiment of the present invention may have an elasticity index calculated by the following mathematical formulas 1 to 4 of 20 or more and 40 or less, and a BOCD Index calculated by the following mathematical formula 5 of 0 or more and 3.0 or less.

[0055] [Mathematical Formula 1]

[0056] Elasticity Index = RSS X 1000

[0057] (In the above mathematical expression 1, RSS is Recovery Shear Strain (γ ∞ , and is calculated using mathematical formula 2.)

[0058] [Equation 2]

[0059]

[0060] (In the above mathematical expression 2, γΔ is RSS (Recovery Shear Strain), η* is complex viscosity, calculated using the following mathematical expression 3, G' is storage modulus, calculated using the following mathematical expression 4, and ω (Rad / s) is angular frequency, which is an arbitrary variable.)

[0061] [Equation 3]

[0062]

[0063] (In the above mathematical expression 3, η0(Pa·s) is the zero-shear viscosity, λ(s) is the relaxation time, ω(Rad / s) is the angular frequency, n is the shear-thinning index, and a is the fitting exponent.)

[0064] [Equation 4]

[0065]

[0066] (In the above mathematical expression 4, n is the number of Maxwell Equation modes, and g i (Pa) is the Plateau Modulus, and λ i (s) is the relaxation time and ω(Rad / s) is the angular frequency.)

[0067] [Equation 5]

[0068] BOCD Index = (short-chain branch content in high molecular weight components - short-chain branch content in low molecular weight components) / (short-chain branch content in low molecular weight components)

[0069] According to the present invention, the BOCD Index (Broad Orthogonal Comonomer Distribution Index) value of a polyethylene copolymer can be improved.

[0070] In addition, according to the present invention, the transparency of a film manufactured using a polyethylene copolymer can be improved.

[0071] Figure 1 is a drawing showing the molecular weight distribution and SCB distribution of the polyethylene copolymer manufactured in Example 1.

[0072] Figure 2 is a drawing showing the molecular weight distribution and SCB distribution of the polyethylene copolymer manufactured in Comparative Example 1.

[0073] Figure 3 is a graph showing the RSS (Recovery Shear Strain) of Example 1 and Comparative Examples 1 and 2.

[0074] Hereinafter, preferred embodiments of the present invention will be described. However, the embodiments of the present invention may be modified into various other forms, and the scope of the present invention is not limited to the embodiments described below.

[0075] The term "alkyl" described in the present invention means a monovalent straight-chain or branched saturated hydrocarbon radical composed only of carbon and hydrogen atoms, and examples of such alkyl radicals include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, hexyl, octyl, dodecyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, and the like.

[0076] In addition, the term "alkenyl" described in the present invention means a straight-chain or branched-chain hydrocarbon radical containing one or more carbon-carbon double bonds, including, but not limited to, ethenyl, propenyl, butenyl, pentenyl, etc.

[0077] In addition, the term "alkynyl" described in the present invention means a straight-chain or branched-chain hydrocarbon radical containing one or more carbon-carbon triple bonds, including, but not limited to, methynyl, ethynyl, propynyl, butynyl, pentynyl, hexynyl, heptynyl, octynyl, and the like.

[0078] In addition, the term "aryl" described in the present invention refers to an organic radical derived from an aromatic hydrocarbon by the removal of one hydrogen, and includes a single or fused ring system. Specific examples include, but are not limited to, phenyl, naphthyl, biphenyl, anthryl, fluorenyl, phenanthryl, triphenylenyl, pyrenyl, perylenyl, chrysenyl, naphthacenyl, fluoranthenyl, and the like.

[0079] In addition, the term “alkylaryl” described in the present invention means an organic group in which one or more hydrogens of an aryl group are replaced by an alkyl group, and includes, but is not limited to, methylphenyl, ethylphenyl, n-propylphenyl, isopropylphenyl, n-butylphenyl, isobutylphenyl, t-butylphenyl, etc.

[0080] In addition, the term “arylalkyl” described in the present invention means an organic group in which one or more hydrogens of an alkyl group are replaced by an aryl group, and includes, but is not limited to, phenylpropyl, phenylhexyl, etc.

[0081] In addition, the term "amido" described in the present invention means an amino group (-NH2) bonded to a carbonyl group (C=O), "alkylamido" means an organic group in which at least one hydrogen in -NH2 of the amido group is replaced with an alkyl group, and "arylamido" means an organic group in which at least one hydrogen in -NH2 of the amido group is replaced with an aryl group, and the alkyl group in the alkylamido group and the aryl group in the arylamido group may be the same as the examples of the alkyl group and aryl group described above, but are not limited thereto.

[0082] In addition, the term "alkylidene" described in the present invention means a divalent aliphatic hydrocarbon group in which two hydrogen atoms are removed from the same carbon atom of an alkyl group, and includes, but is not limited to, ethylidene, propylidene, isopropylidene, butylidene, and pentylidene.

[0083] In addition, the term "acetal" described in the present invention means an organic group formed by a bond between an alcohol and an aldehyde, that is, a substituent having two ether (-OR) bonds on one carbon, and includes, but is not limited to, methoxymethoxy, 1-methoxyethoxy, 1-methoxypropyloxy, 1-methoxybutyloxy, 1-ethoxyethoxy, 1-ethoxypropyloxy, 1-ethoxybutyloxy, 1-(n-butoxy)ethoxy, 1-(iso-butoxy)ethoxy, 1-(sec-butoxy)ethoxy, 1-(tert-butoxy)ethoxy, 1-(cyclohexyloxy)ethoxy, 1-methoxy-1-methylmethoxy, 1-methoxy-1-methylethoxy, etc.

[0084] In addition, the term "ether" described in the present invention is an organic group having at least one ether bond (-O-), and includes, but is not limited to, 2-methoxyethyl, 2-ethoxyethyl, 2-butoxyethyl, 2-phenoxyethyl, 2-(2-methoxyethoxy)ethyl, 3-methoxypropyl, 3-butoxypropyl, 3-phenoxypropyl, 2-methoxy-1-methylethyl, 2-methoxy-2-methylethyl, 2-methoxyethyl, 2-ethoxyethyl, 2-butoxyethyl, 2-phenoxyethyl, and the like.

[0085] In addition, the term "silyl" described in the present invention means a -SiH3 radical derived from silane, and at least one of the hydrogen atoms in the silyl group may be substituted with various organic groups such as alkyl and halogen, and specifically includes, but is not limited to, trimethylsilyl, triethylsilyl, t-butyldimethylsilyl, vinyldimethylsilyl, propyldimethylsilyl, triphenylsilyl, diphenylsilyl, phenylsilyl, trimethoxysilyl, methyldimethoxysilyl, ethyldiethoxysilyl, triethoxysilyl, vinyldimethoxysilyl, triphenoxysilyl, etc.

[0086] In addition, the term "alkoxy" described in the present invention means an -O-alkyl radical, wherein "alkyl" is as defined above. Examples of such alkoxy radicals include, but are not limited to, methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, t-butoxy, and the like.

[0087] Additionally, the term “halogen” described in the present invention means a fluorine, chlorine, bromine or iodine atom.

[0088] In addition, the term “C” described in the present invention n 」 means that the number of carbon atoms is n.

[0089] The present invention relates to a metallocene catalyst for polyethylene polymerization, comprising: (A) a transition metal compound; (B) a cocatalyst compound; and (C) a carrier supporting the transition metal compound (A) and the cocatalyst compound (B), wherein the transition metal compound (A) is a mixture of a first metallocene catalyst compound represented by the following chemical formula 1 and a second metallocene catalyst compound represented by the following chemical formula 2.

[0090] The above transition metal compound is a main catalyst of a metallocene catalyst for polyethylene polymerization.

[0091] [Chemical Formula 1]

[0092]

[0093] (In the above chemical formula 1,

[0094] M 1 is titanium (Ti), zirconium (Zr) or hafnium (Hf), and specifically, M can be zirconium (Zr),

[0095] X 1 Silver halogen group, (C1-C 20 )alkyl group, (C2-C 20 )alkenyl group, (C2-C 20 )alkynyl group, (C6-C 20 )aryl group, (C1-C 20 )alkyl(C6-C 20 )aryl group, (C6-C 20 )aryl(C1-C 20 )alkyl group, (C1-C 20 )alkylamido group, (C6-C 20 )arylamido group, or (C1-C 20 ) is an alkylidene group, and specifically X may be a halogen, and more specifically X may be chlorine (Cl),

[0096] R 1 and R 2 is a (C1-C6) alkyl group,

[0097] n and k are each integers from 0 to 2, but at least one is not 0, and specifically, n and k can each be 1 or 2).

[0098] [Chemical Formula 2]

[0099]

[0100] (In the above chemical formula 2,

[0101] M 2 is titanium (Ti), zirconium (Zr) or hafnium (Hf), and specifically, M can be zirconium (Zr),

[0102] X 2 is a halogen group, (C1-C 20 )alkyl group, (C2-C 20 )alkenyl group, (C2-C 20 )alkynyl group, (C6-C 20 )aryl group, (C1-C 20 )alkyl(C6-C20 )aryl group, (C6-C 20 )aryl(C1-C 20 )alkyl group, (C1-C 20 )alkylamido group, (C6-C 20 )arylamido group, or (C1-C 20 ) is an alkylidene group, and specifically X may be a halogen, and more specifically X may be chlorine (Cl),

[0103] Q is carbon (C), silicon (Si), germanium (Ge), or tin (Sn), and specifically, Q can be carbon (C),

[0104] R 3 Inland R 7 are each independently substituted or unsubstituted (C1-C 20 )alkyl group, substituted or unsubstituted (C2-C 20 )alkenyl group, substituted or unsubstituted (C6-C 20 )aryl group, substituted or unsubstituted (C1-C 20 )alkyl(C6-C 20 )aryl group, substituted or unsubstituted (C6-C 20 )aryl(C1-C 20 )alkyl group, substituted or unsubstituted (C1-C 20 )heteroalkyl group, substituted or unsubstituted (C3-C 20 )heteroaryl group, substituted or unsubstituted (C1-C 20 )alkylamido group, substituted or unsubstituted (C6-C 20 )arylamido group, substituted or unsubstituted (C1-C 20 )alkylidene group, or substituted or unsubstituted (C1-C 20 ) is a silyl group, and specifically R 3 Inland R 7 are each independently substituted or unsubstituted with an acetal group or an ether group (C1-C 20 ) substituted or unsubstituted with an alkyl group, acetal group or ether group (C2-C 20 ) substituted or unsubstituted with an alkenyl group, acetal group or ether group (C6-C 20) substituted or unsubstituted with an aryl group, acetal group or ether group (C1-C 20 )alkyl(C6-C 20 ) substituted or unsubstituted with an aryl group, acetal group or ether group (C6-C 20 )aryl(C1-C 20 ) substituted or unsubstituted with an alkyl group, acetal group or ether group (C1-C 20 ) substituted or unsubstituted with a heteroalkyl group, acetal group or ether group (C3-C 20 ) substituted or unsubstituted with a heteroaryl group, acetal group or ether group (C1-C 20 ) substituted or unsubstituted with an alkylamido group, an acetal group or an ether group (C6-C 20 ) substituted or unsubstituted with an arylamido group, an acetal group or an ether group (C1-C 20 ) substituted or unsubstituted with an alkylidene group, or an acetal group, or an ether group (C1-C 20 ) may be a cylinder,

[0105] Specifically R 3 Silver (C1-C 20 ) may be alkyl, more specifically R 3 can be (C1-C6)alkyl, more specifically R 3 can be n-butyl,

[0106] Specifically R 4 and R 5 are respectively (C1-C 20 ) may be alkyl, more specifically R 4 and R 5 Each can be (C1-C6)alkyl, and more specifically R 4 and R 5 can be t-butyl respectively,

[0107] Specifically R 6 and R 7 are each (C6-C 20 ) may be alkyl, more specifically R 6 and R 7 can each be phenyl,

[0108] R 3 Inland R 7 can be connected to each other to form a ring, specifically R 3 Inland R 7 Each independently adjacent group is connected to a substituted or unsubstituted saturated or unsaturated C4-C 20 It can form a ring, more specifically R 3 Inland R 7 Each independently adjacent group is connected to a saturated or unsaturated C4-C substituted or unsubstituted acetal or ether group. 20 can form a ring,

[0109] m, l, and y are each integers from 0 to 4, and specifically, m, l, and y can each be 1.

[0110] The first metallocene catalyst compound represented by the above chemical formula 1 can be represented by the following chemical formula 1-1.

[0111] [Chemical Formula 1-1]

[0112]

[0113] The second metallocene catalyst compound represented by the above chemical formula 2 can be represented by the following chemical formula 2-1.

[0114] [Chemical Formula 2-1]

[0115]

[0116] The above cocatalyst compound (B) may be at least one selected from the group consisting of the following chemical formulas 3 to 5.

[0117] [Chemical Formula 3]

[0118]

[0119] (In the above chemical formula 3,

[0120] p is an integer greater than or equal to 2,

[0121] Ra is a halogen group; or (C1-C) substituted or unsubstituted with a halogen group20 ) is a hydrocarbyl group)

[0122] [Chemical Formula 4]

[0123]

[0124] (In the above chemical formula 4,

[0125] Q is aluminum; or boron,

[0126] Rb are the same or different, and each independently represents a halogen group; or (C1-C) substituted or unsubstituted with a halogen group. 20 ) is a hydrocarbyl group),

[0127] [Chemical Formula 5]

[0128]

[0129] (In the above chemical formula 5,

[0130] [W] + is a cationic Lewis acid; or a cationic Lewis acid with a hydrogen atom attached,

[0131] Z is a group 13 element,

[0132] Rc are the same or different and each independently represents a halogen group, (C1-C 20 )substituted with one or more substituents selected from the group consisting of hydrocarbyl group, alkoxy group and phenoxy group (C6-C 20 )aryl group; or halogen group, (C1-C 20 )substituted with one or more substituents selected from the group consisting of hydrocarbyl group, alkoxy group and phenoxy group (C1-C 20 ) is an alkyl group)

[0133] The above cocatalyst compound is included in the catalyst composition together with the transition metal compound and serves to activate the transition metal compound. Specifically, in order for the transition metal compound to become an active catalyst component used in olefin polymerization, a compound including a unit represented by the above chemical formula 3 that can act as a counterion with weak binding force, i.e. an anion, is extracted from the ligand (Q1Q2) in the transition metal compound to cationize the central metal (M), a compound represented by the chemical formula 4, and a compound represented by the chemical formula 5 work together as cocatalysts.

[0134] The 'unit' represented by the above chemical formula 3 is a structure in which n structures within [ ] are connected within the compound. If it includes a unit represented by the chemical formula 3, other structures within the compound are not particularly limited, and it may be a cluster-type, for example, a spherical compound in which repeating units of the chemical formula 3 are connected to each other.

[0135] The compound containing the unit represented by Chemical Formula 3 is not particularly limited, and is preferably an alkylaluminoxane. Non-limiting examples include methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, butylaluminoxane, etc. Considering the activity of the above transition metal compound, methylaluminoxane can be preferably used.

[0136] In addition, the compound represented by the above chemical formula 4 is not particularly limited as an alkyl metal compound, and non-limiting examples thereof include trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, dimethylchloroaluminum, triisopropylaluminum, tri-s-butylaluminum, tricyclopentylaluminum, tripentylaluminum, triisopentylaluminum, trihexylaluminum, trioctylaluminum, ethyldimethylaluminum, methyldiethylaluminum, triphenylaluminum, tri-p-tolylaluminum, dimethylaluminum methoxide, dimethylaluminum ethoxide, trimethylboron, triethylboron, triisobutylboron, tripropylboron, tributylboron, etc. Considering the activity of the above transition metal compound, one or more selected from the group consisting of trimethylaluminum, triethylaluminum, and triisobutylaluminum can be preferably used.

[0137] The compound represented by chemical formula 5 is [W] when considering the activity of the above transition metal compound. + If it is a cationic Lewis acid with a hydrogen atom bonded to it, it is a dimethylanilinium cation, and [W] + If it is a cationic Lewis acid, [(C6H5)3C] + and the above [Z(Rc)4] - is [B(C6F5)4] - It can be used preferably.

[0138] The compound represented by chemical formula 5 is not particularly limited, but [W] +Non-limiting examples of cationic Lewis acids having hydrogen atoms bonded thereto include triethylammonium tetrakisphenylborate, tributylammonium tetrakisphenylborate, trimethylammonium tetrakisphenylborate, tripropylammonium tetrakisphenylborate, trimethylammonium tetrakis(p-tolyl)borate, tripropylammonium tetrakis(p-tolyl)borate, trimethylammonium tetrakis(o,p-dimethylphenyl)borate, triethylammonium tetrakis(o,p-dimethylphenyl)borate, tributylammonium tetrakis(p-trifluoromethylphenyl)borate, trimethylammonium tetrakis(p-trifluoromethylphenyl)borate, tributylammonium tetrakispentafluorophenylborate, anilinium tetrakisphenylborate, anilinium tetrakis(pentafluorophenyl)borate, N,N-dimethylanilinium There are tetrakis(pentafluorophenyl)borate, N,N-diethylaniliniumtetrakisphenylborate, N,N-diethylaniliniumtetrakisphenylborate, N,N-diethylaniliniumtetrakispentafluorophenylborate, diethylammoniumtetrakispentafluorophenylborate, triphenylphosphoniumtetrakisphenylborate, trimethylphosphoniumtetrakisphenylborate, triphenylcarboniumtetrakis(p-trifluoromethylphenyl)borate, triphenylcarboniumtetrakispentafluorophenylborate, dimethylaniliniumtetrakis(pentafluorophenyl)borate, etc.

[0139] The metallocene catalyst for polyethylene polymerization of the present invention may include a first metallocene catalyst compound: a second metallocene catalyst compound in a molar ratio of 10:1 to 50:1.

[0140] Meanwhile, in the present invention, the transition metal compound represented by chemical formula 1, or the transition metal compound and the cocatalyst compound may be supported on a carrier. As the above carrier, an inorganic or organic material carrier generally used in the manufacture of a catalyst can be used without limitation, for example, silica (SiO2), alumina (Al2O3), magnesia (MgO), magnesium chloride (MgCl2), calcium chloride (CaCl2), zirconia (ZrO2), titania (TiO2), boron trioxide (B2O3), calcium oxide (CaO), zinc oxide (ZnO), barium oxide (BaO), thorium dioxide (ThO2), silica-alumina (SiO2-Al2O3), silica-magnesia (SiO2-MgO), silica-titania (SiO2-TiO2), silica-vanadium pentoxide (SiO2-V2O5), silica-chromium oxide (SiO2-Cr2O3), silica-titania-magnesia (SiO2-TiO2-MgO), bauxite, zeolite, starch, Cyclodextrin, synthetic polymers, etc. can be used. Preferably, the carrier may be silica (SiO2), alumina (Al2O3), magnesium chloride (MgCl2), or a mixture thereof, which have a large surface area and fine pores on the surface or inside. Alternatively, the carrier may be at least one carrier selected from the group consisting of silica, silica-alumina, and silica-magnesia, which contains hydroxyl groups on the surface.

[0141] Methods for supporting a transition metal compound and a co-catalyst compound on a carrier may include a method of directly supporting the transition metal compound on a dehydrated carrier, a method of pretreating the carrier with the co-catalyst compound and then supporting the transition metal compound, a method of supporting the transition metal compound on the carrier and then post-treating it with the co-catalyst compound, a method of reacting the transition metal compound and the co-catalyst compound and then adding the carrier to cause a reaction, etc.

[0142] The solvent usable in the above-described supporting method may be an aliphatic hydrocarbon solvent, an aromatic hydrocarbon solvent, a halogenated aliphatic hydrocarbon solvent, or a mixture thereof. Here, non-limiting examples of the aliphatic hydrocarbon solvent include pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, etc. In addition, non-limiting examples of the aromatic hydrocarbon solvent include benzene, monochlorobenzene, dichlorobenzene, trichlorobenzene, toluene, etc. In addition, non-limiting examples of the above halogenated aliphatic hydrocarbon solvents include dichloromethane, trichloromethane, dichloroethane, and trichloroethane.

[0143] In addition, the process of supporting the above transition metal compound and the cocatalyst compound on the carrier is advantageous in terms of the efficiency of the supporting process when carried out at a temperature of -70 to 200°C, preferably -50 to 150°C, and more preferably 0 to 100°C.

[0144] In the transition metal catalyst composition of the present invention, the transition metal compound can be used as a homogeneous catalyst or a supported catalyst. That is, it can be used as a homogeneous catalyst in which the transition metal compound and the reactant react in the same phase, and as a heterogeneous catalyst in which the transition metal compound and the reactant react in different phases, the transition metal compound in the transition metal catalyst composition can be used as a supported catalyst in which the transition metal compound is supported on a carrier and dispersed.

[0145] The method for producing polyolefin according to the present invention includes a step of polymerizing an olefin monomer in the presence of a transition metal catalyst composition including the above transition metal compound.

[0146] The transition metal catalyst composition comprising the above transition metal compound is the same as described above.

[0147] The above olefin monomer may be ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-itocene, norbornene, norbornadiene, ethylidennorboden, phenylnorboden, vinylnorboden, dicyclopentadiene, 1,4-butadiene, 1,5-pentadiene, 1,6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene, 3-chloromethylstyrene, or a mixture thereof.

[0148] In the present invention, the polymer produced through a polymerization process carried out by directly contacting an olefin monomer compound can be prepared by olefin polymerization under conditions in which the catalyst site is relatively insoluble and / or immobile so that the polymer chain is rapidly immobilized according to these information. Such immobilization is achieved, for example, by using a solid insoluble catalyst, performing the polymerization in a medium in which the produced polymer is generally insoluble, and allowing the polymerization reactants and products to be heated to a temperature below the crystallization temperature (T) of the polymer. c ) can be performed by maintaining it below.

[0149] The aforementioned catalyst can be preferably applied to the copolymerization of olefin monomers, preferably ethylene or propylene. Below, a method for producing polyethylene, which includes a step of polymerizing an olefin monomer in the presence of the catalyst, is described.

[0150] Olefin polymerization processes are well known in the art and include liquid-phase polymerization, solution polymerization, slurry polymerization, and low-pressure gas-phase polymerization. Metallocene catalysts are particularly useful in known operational modes using fixed-bed, moving-bed, or slurry processes performed in single, series, or parallel reactors.

[0151] When the above polymerization reaction is carried out in a liquid or slurry phase, a solvent or the propylene or ethylene monomer itself can be used as a medium.

[0152] The solvent that can be used in the polymerization reaction may be an aliphatic hydrocarbon solvent, an aromatic hydrocarbon solvent, a halogenated aliphatic hydrocarbon solvent, or a mixture thereof. Here, non-limiting examples of the aliphatic hydrocarbon solvent include butane, isobutane, pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, cyclopentane, methylcyclopentane, cyclohexane, etc. In addition, non-limiting examples of the aromatic hydrocarbon solvent include benzene, monochlorobenzene, dichlorobenzene, trichlorobenzene, toluene, xylene, chlorobenzene, etc. In addition, non-limiting examples of the halogenated aliphatic hydrocarbon solvent include dichloromethane, trichloromethane, chloroethane, dichloroethane, trichloroethane, 1,2-dichloroethane, etc.

[0153] In the present invention, polyolefin can be produced by polymerizing olefin monomers in the presence of the above catalyst. At this time, the transition metal compound and cocatalyst component can be introduced separately into the reactor, or each component can be mixed in advance and introduced into the reactor. There are no specific restrictions on mixing conditions, such as the order of introduction, temperature, or concentration. The polyolefin in the present invention can be, for example, polyethylene.

[0154] Meanwhile, in the polymerization reaction of the present invention, the amount of the catalyst added can be determined within a range in which the polymerization reaction of the monomer can sufficiently occur depending on the slurry phase, liquid phase, gas phase, or solution process, and is therefore not particularly limited. However, the amount of the catalyst added is 10 based on the concentration of the central metal (M) in the transition metal compound per unit volume (L) of the monomer. -8 It is preferable that it is 1 mol / L, and 10 -7 10 inland -1 mol / L is more preferable, and 10 -7 10 inland -2 It is even more desirable to have mol / L.

[0155] In addition, the polymerization reaction of the present invention may be carried out as a batch type, semi-continuous type or continuous type reaction, and preferably as a continuous type reaction.

[0156] The temperature and pressure conditions of the polymerization reaction of the present invention can be determined in consideration of the efficiency of the polymerization reaction depending on the type of reaction to be applied and the type of reactor, but the polymerization temperature can be 40 to 150°C, preferably 60 to 100°C, and the pressure can be 1 to 100 atm, preferably 5 to 50 atm.

[0157] More specifically, the polyethylene production method of the present invention may be to produce a polyethylene copolymer by reacting ethylene and one or more olefin monomers in the presence of a metallocene catalyst for polyethylene polymerization. The olefin monomer is (C2~C 20 ) of α-olefins, (C4~C 20 ) of diolefins, (C3~C 20 ) cycloolefin, (C3~C 20 ) may be selected from the group consisting of cyclodiolefins, styrene and styrene derivatives. More specifically, the olefin equivalent may be an α-olefin of (C3~C8).

[0158] According to the present invention, a film manufactured using polyethylene and having improved transparency is provided. Specifically, a film having improved transparency and having an elasticity index of 20 or greater is provided. More specifically, a mLLDPE film having improved transparency and having an elasticity index of 20 or greater and 40 or less is provided.

[0159] RSS is a value obtained by quantifying the elasticity of a rubber-like liquid as a rheological property. RSS is a rheological property regarding the recovery characteristics of a material, and its value can be measured through a recovery experiment. For example, RSS can be approximated through an oscillatory experiment (Small Amplitude Oscillation Shear, SAOS). RSS (Recovery Shear Strain, γ∞) can be approximated in the low-shear region using the following mathematical equation 2 according to the Cox-Merz Rule. In order to minimize the error of the approximate value, the value at low shear (ω = 0.01 to 0.05) can be taken. By adjusting ω = 0.01 to 0.05, γ∞ can be obtained as a value of 0.01 to 0.1.

[0160] [Equation 2]

[0161]

[0162] Complex viscosity (η*) and storage modulus (G') can be measured using a small amplitude oscillation shear (SAOS) test using a rotational rheometer, a rheological analysis device. Through the SAOS test, data on η(ω) and G' are obtained as function graphs according to angular frequency (ω).

[0163] Complex viscosity (η*) was fitted using the following mathematical equation 3 (Carreau-Yasuda Model). The Carreau-Yasuda model is a graph model equation of η(ω) according to angular frequency (ω).

[0164] [Equation 3]

[0165]

[0166] η(ω): viscosity function, η0(Pa·s): zero-shear viscosity, λ(s): relaxation time, ω(Rad / s): angular frequency, n: shear-thinning index, a: fitting exponent

[0167] By fitting the mathematical equation 3 and graph data according to each frequency (ω) to the model equation using Excel's solver function, the variables λ, n, and a can be obtained.

[0168] The storage modulus (G') value was fitted using the following mathematical equation 4 (Maxwell Model). The Maxwell model is a model equation that fits well with the graph of G' according to angular frequency (ω).

[0169] [Equation 4]

[0170]

[0171] n: number of Maxwell Equation modes, g i (Pa): Plateau Modulus, λ i(s): Relaxation Time, ω(Rad / s): Angular Frequency

[0172] By fitting the mathematical equation 4 and graph data according to each frequency (ω) to the model equation using Excel's solver function, g i and λ i (i=1~7) can be obtained.

[0173] The elasticity index is the value obtained by multiplying the RSS (Recovery Shear Strain) value by 1000. In the present invention, the value obtained by multiplying the RSS by 1000 is used as the elasticity index and is used as an indicator for predicting the elasticity and film processing properties (haze) of the resin.

[0174] [Mathematical Formula 1]

[0175] Elasticity Index = RSS X 1000

[0176] The elasticity index, which is the RSS multiplied by 1,000, ranges from 10 to 100 for the film product group. As the RSS value increases, the melt elasticity of the resin increases. Therefore, during film molding, a fibrous crystal structure is formed rather than a spherical crystal structure, reducing the roughness of the film surface. Therefore, it is known that an increase in the RSS value reduces haze, thereby improving molding quality.

[0177] Haze in film indicates cloudiness and can be measured using a device called a haze meter. There is an inverse correlation between elasticity and haze. Therefore, elasticity can be used to predict haze.

[0178]

[0179] Example

[0180] Hereinafter, the present invention will be described in more detail with examples of metallocene catalyst synthesis and polymerization. However, the following examples are merely examples of implementing the present invention and are not intended to limit the present invention.

[0181] <Example of manufacturing a metallocene catalyst>

[0182] All synthetic reactions were carried out in an inert atmosphere such as nitrogen or argon, and standard Schlenk and glove box techniques were used.

[0183] Toluene was purchased as anhydrous grade from Sigma-Aldrich and further dried by passing through activated molecular sieves (4A) or activated alumina beds before use.

[0184] MAO (methylaluminoxane) was purchased as a 10% toluene solution (HS-MAO-10%) from Albemarle and used, and silica was used as XPO2402 from Grace without additional treatment.

[0185] Additionally, bis(1-butyl-3-methylcyclopentadienyl)zirconium dichloride and diphenylmethylene(n-Butyl-Cyclopentadienyl)(2,7-di-t-Butyl-9-Fluorenyl)zirconium dichloride were purchased and used without purification.

[0186] Bis(1-butyl-3-methylcyclopentadienyl)zirconium dichloride is represented by chemical formula 6, and diphenylmethylene(n-butyl-cyclopentadienyl)(2,7-di-t-butyl9-fluorenyl)zirconium dichloride is represented by chemical formula 7.

[0187] [Chemical Formula 6]

[0188]

[0189] [Chemical Formula 7]

[0190]

[0191] Bis(1-butyl-3-methylcyclopentadienyl)zirconium dichloride was purchased from WR Grace, and diphenylmethylene(n-butyl-cyclopentadienyl)(2,7-di-t-butyl9-fluorenyl)zirconium dichloride was purchased from MCN.

[0192] [Synthesis Example 1]

[0193] Inside a glove box, 1 g of silica was placed in a round-bottom flask and taken out of the glove box. 10 mL of toluene was added at room temperature to prepare a silica slurry. The temperature of the prepared silica slurry was lowered to 0°C, 8 mL of MAO (methylaluminoxane) was slowly added to the silica slurry, stirred for 1 hour, and then increased to 70°C to react for an additional 4 hours to prepare a silica slurry. The temperature of the obtained silica slurry was lowered again to 0°C.

[0194] In a glove box, bis(1-butyl-3-methylcyclopentadienyl)zirconium dichloride and diphenylmethylene(n-butyl-cyclopentadienyl)(2,7-di-t-butyl9-fluorenyl)zirconium dichloride were mixed in a molar ratio of 30:1 to prepare a mixture, and 100 μmol of the mixture was placed in a Schlenk flask and taken out of the glove box. Then, 10 mL of toluene was added to the Schlenk flask to completely dissolve it, thereby obtaining a catalyst compound solution.

[0195] The catalyst compound solution obtained above was slowly added to the silica slurry at room temperature, then the temperature was raised to 70°C and the reaction was continued for 1 hour. Thereafter, the temperature was lowered to room temperature, stirring was stopped, the toluene layer was separated and removed, and the mixture was washed three times with normal hexane, and then vacuum was applied to remove all solvent.

[0196] As a result, a free flowing powder of catalyst 1 with a pale yellow color was obtained. It was confirmed that the Zr loading rate of the obtained catalyst 1 was 0.4 wt% and the Al loading rate was 13.0 wt%.

[0197] [Synthesis Example 2]

[0198] Catalyst 2 was obtained in the same manner as in Synthesis Example 1, except that bis(1-butyl-3-methylcyclopentadienyl)zirconium dichloride was used alone instead of the mixture of bis(1-butyl-3-methylcyclopentadienyl)zirconium dichloride and diphenylmethylene(n-butyl-cyclopentadienyl)(2,7-di-t-butyl9-fluorenyl)zirconium dichloride in a molar ratio of 30:1.

[0199] <Manufacturing of polyethylene copolymer>

[0200] [Example 1]

[0201] The above catalyst 1 was placed in a well-dried catalyst injection cylinder (1.5 L, SUS) and transported to the pilot under a nitrogen atmosphere, and then diluted to 1.5 wt% by pushing it under nitrogen pressure into a catalyst tank (V-2400, pilot metallocene catalyst tank) containing a quantified mineral oil. Shell Ondina 68, a Yeosu oil product, was used as the mineral oil. The catalyst transport operation was performed by repeatedly purging the Teflon lines and valves used so that it could be performed under an HPN (high-purity nitrogen) atmosphere.

[0202] The operating conditions were common conditions of reactor temperature 85 ℃, total pressure 22 K / G, and ethylene partial pressure 12.1 K / G (ethylene concentration 55 mol%), and the input amounts of C6 / C2 and H2 / C2 were adjusted so that polyethylene copolymer could be produced. The production amount was checked and the catalyst input amount was adjusted so that the bed weight could be maintained at 45~50 kg and the powder discharge rate per hour could be maintained at 7~8 kg / hr.

[0203] [Comparative Example 1]

[0204] A polyethylene copolymer was prepared in the same manner as in Example 1, except that catalyst 2 was used instead of catalyst 1.

[0205] [Comparative Example 2]

[0206] A commercially available polyethylene copolymer (DL Chem, XP9200E) was used.

[0207] <Polyethylene copolymer analysis method>

[0208] The physical properties of polyethylene copolymers were measured according to the following method and are shown in Fig. 1, Fig. 2 and Table 1.

[0209] (1) Molecular weight (Mn, Mw, Mz), molecular weight distribution (MWD), Mz / Mn value (MZD)

[0210] The number-average molecular weight (Mn), weight-average molecular weight (Mw), and z-average molecular weight (Mz) were measured using a PL-GPC 220 GPC (Gel Permeation Chromatography) analyzer from Agilent.

[0211] The molecular weight distribution (MWD) was calculated by dividing the above weight average molecular weight (Mw) by the number average molecular weight (Mn).

[0212] The Mz / Mn value (Molecular z-Average weight Distribution (MZD)) was calculated by dividing the above z-average molecular weight (Mz) by the number average molecular weight (Mn).

[0213] (2) Melting point (Tm), crystallization temperature (Tc), and melting enthalpy (ΔH)

[0214] Melting point (Tm), crystallization temperature (Tc), and melting enthalpy (ΔH) were measured using TA's Q-200 Differential Scanning Calorimetry (DSC).

[0215] (3) Melt index (MI) and melt flow rate ratio (MFRR)

[0216] Melt index (MI) at 190℃ under a load of 2.16 kg according to ASTM D1238 2.16 ) was measured and the high-load melting index (MI) was measured at 190℃ with a load of 21.6 kg. 21.6 ) was measured.

[0217] The above high load melting index (MI) 21.6 ) is the melting index (MI) 2.16 ) was divided into the melt flow rate ratio (MFRR) and calculated.

[0218] (4) Content of low molecular weight components and high molecular weight components

[0219] The molecular weight distribution obtained through GPC was used to obtain the content of components using a peak fit analysis program.

[0220] (5) Biochemical CD Index (BOCD Index) and Short Chain Branch (SCB) content

[0221] The weight-average molecular weight and SCB content of the copolymer were measured using a cross-fractionation chromatography (CFC) device from Polymer Char. The SCB (short-chain branch content in high-molecular-weight components) at the top 30% of the copolymer weight based on the weight-average molecular weight (Mw) and the SCB (short-chain branch content in low-molecular-weight components) at the bottom 30% were substituted into the following mathematical equation 5 to obtain the Broad Orthogonal Comonomer Distribution Index (BOCD Index). The SCB above stands for Short Chain Branch.

[0222] [Equation 5]

[0223] BOCD Index = (short-chain branch content in high molecular weight components - short-chain branch content in low molecular weight components) / (short-chain branch content in low molecular weight components)

[0224] Classification MIMFRRTmTcΔHMnMwMzMWDMZDg / 10min(2.16kg)-℃℃J / gg / molg / molg / mol--Example 11.018.0108.83107.5118.744,341117,072223,0062.65.02Comparative Example 11.017.7107.18107.0120.347,156115,981201,9532.54.28

[0225] It can be confirmed that Example 1 has a higher number-average molecular weight (Mn) and weight-average molecular weight (Mw) compared to Comparative Example 1. In particular, the z-average molecular weight (Mz) of Comparative Example 1 is only 201,953 g / mol, whereas the -average molecular weight (Mz) of Example 1 is 223,006 g / mol. In addition, the MZD of Comparative Example 1 is only 4.28, whereas the MZD of Example 1 is 5.02, which is significantly higher. The BOCD Index of Example 1 was 0.08, whereas the BOCD Index of Comparative Example 1 was 0.03. In Example 1, it can be confirmed that the BOCD Index increased due to an increase in the comonomer content in the polymer region due to a change in the catalyst.

[0226] Film Manufacturing and Property Analysis

[0227] A film was manufactured using the polyethylene copolymers of Example 1 and Comparative Examples 1 and 2, and the physical properties of the film were measured according to the following method, and are shown in Tables 2 and 3 and Fig. 3.

[0228] (1) Calculation of RSS (Recovery Shear Strain, γ∞) value

[0229] The RSS (Recovery Shear Strain, γ∞) value was calculated using the complex viscosity (η*) and storage modulus (G') property values ​​using the following mathematical equation 2.

[0230] [Equation 2]

[0231]

[0232] Complex viscosity (η*) and storage modulus (G') were measured using a small amplitude oscillation shear (SAOS) test using a rotational rheometer, a rheological analysis device. Through the SAOS test, data on η(ω) and G' were obtained as function graphs according to angular frequency (ω).

[0233] Complex viscosity (η*) was fitted using the following mathematical equation 3 (Carreau-Yasuda Model). The Carreau-Yasuda model is a graph model equation of η(ω) according to angular frequency (ω).

[0234] [Equation 3]

[0235]

[0236] η(ω): viscosity function, η0(Pa·s): zero-shear viscosity, λ(s): relaxation time, ω(Rad / s): angular frequency, n: shear-thinning index, a: fitting exponent

[0237] By fitting the mathematical equation 3 and graph data according to each frequency (ω) to the model equation using Excel's solver function, the variables λ, n, and a can be obtained.

[0238] The storage modulus (G') value was fitted using the following mathematical equation 4 (Maxwell Model). The Maxwell model is a model equation that fits well with the graph of G' according to angular frequency (ω).

[0239] [Equation 4]

[0240]

[0241] n: number of Maxwell Equation modes, g i (Pa): Plateau Modulus, λ i (s): Relaxation Time, ω(Rad / s): Angular Frequency

[0242] By fitting the mathematical equation 4 and graph data according to each frequency (ω) to the model equation using Excel's solver function, g i and λ i (i=1~7) was obtained.

[0243] For Example 1, Comparative Examples 1 and 2, when ω = 0.03 Rad / s, η is calculated using Equations 3 and 4. * and G' values ​​were calculated respectively and are shown in Table 3. Each η * As a result of calculating the RSS value of mathematical formula 1 through the G' value, it was confirmed that Example 1, Comparative Examples 1 and 2 had RSS values ​​of 0.0227, 0.0106 and 0.0125, respectively. The elasticity index corresponding to 1000 times the RSS value is shown in Table 3.

[0244] [Mathematical Formula 1]

[0245] Elasticity Index = RSS X 1000

[0246] (2) Density

[0247] It was measured by the density gradient method according to ASTM D1505.

[0248] (3) Pressure, speed, load

[0249] Using the LLDPE Blown Film film forming machine of Shinkwang Co., Ltd., the data extruded during film forming was measured.

[0250] (4) Tensile strength (Tensile (Break)) and tensile elongation (Elongation)

[0251] Measurements were made in the machine direction (MD) and transverse direction (TD) using Instron equipment according to ASTM D638.

[0252] (5) Elementordorf tear strength

[0253] Both machine direction (MD) and transverse direction (TD) were measured using Elmendorf measuring equipment according to ASTM D1922.

[0254] (6) Dart Impact

[0255] Measured according to ASTM D1709 Method A using a Dart Impact Tester.

[0256] (7) Haze

[0257] After forming the film to a thickness of 30 μm, the haze was measured using a haze meter according to the ASTM D1003 test method. Specifically, haze can be calculated using the following equation.

[0258] [Equation 6]

[0259] Haze (%) = T d (diffuse transmitted light) / T t (Battle Overload) x 100(%)

[0260] Density Film Extrusion Data Tensile (Break) Elongation Elmendorf Dart Impact Haze Pressure Speed ​​Load MDT DMDT DMDT D g / cm 3 barrpmAkgf / cm 2 kgf / cm 2 %%gfgfg%Example 10.91869026.19360420600700400620>100020Comparative Example 10.91779025.89430440640690440550>100038Comparative Example 20.91873025.28360410620700480640>100035

[0261] Distinction η * G' elasticity index (RSSX1000) Haze (%) Example 179025.3922.720 Comparative example 174855.0310.638 Comparative example 264431.5212.535

[0262] It can be confirmed that the film manufactured by Example 1 has a significantly low haze value of 20%. The polyethylene copolymer of Example 1 has high molecular weight and molecular weight distribution (MWD), and it is believed that the transparency of the film increased due to this increase in molecular weight.

Claims

1. (A) Transition metal compound; (B) a cocatalyst compound; and (C) a carrier comprising the above transition metal compound (A) and a cocatalyst compound (B), The above transition metal compound (A) is a metallocene catalyst for polyethylene polymerization, which is a mixture of a first metallocene catalyst compound represented by the following chemical formula 1 and a second metallocene catalyst compound represented by the following chemical formula 2: [Chemical Formula 1] (In the above chemical formula 1, M 1 is titanium (Ti), zirconium (Zr) or hafnium (Hf), X 1 Silver halogen, (C 1 -C 20 )alkyl group, (C 2 -C 20 )alkenyl group, (C 2 -C 20 )alkynyl group, (C 6 -C 20 )aryl group, (C 1 -C 20 )alkyl(C 6 -C 20 )aryl group, (C 6 -C 20 )Aryl(C 1 -C 20 )alkyl group, (C 1 -C 20 )alkylamido group, (C 6 -C 20 )arylamido group, or (C 1 -C 20 ) is an alkylidene group, R 1 and R 2 is (C 1 -C 6 ) is an alkyl group n and k are integers from 0 to 2, but at least one is not 0). [Chemical formula 2] (In the above chemical formula 2, M 2 is titanium (Ti), zirconium (Zr) or hafnium (Hf), X 2 is a halogen group, (C 1 -C 20 )alkyl group, (C 2 -C 20 )alkenyl group, (C 2 -C 20 )alkynyl group, (C 6 -C 20 )aryl group, (C 1 -C 20 )alkyl(C 6 -C 20 )aryl group, (C 6 -C 20 )Aryl(C 1 -C 20 )alkyl group, (C 1 -C 20 )alkylamido group, (C 6 -C 20 )arylamido group, or (C 1 -C 20 ) is an alkylidene group, Q is carbon (C), silicon (Si), germanium (Ge), or tin (Sn), R 3 Inland R 7 are each independently substituted or unsubstituted (C 1 -C 20 )alkyl group, substituted or unsubstituted (C 2 -C 20 )alkenyl group, substituted or unsubstituted (C 6 -C 20 )aryl group, substituted or unsubstituted (C 1 -C 20 )alkyl(C 6 -C 20 )aryl group, substituted or unsubstituted (C 6 -C 20 )Aryl(C 1 -C 20 )alkyl group, substituted or unsubstituted (C 1 -C 20 )heteroalkyl group, substituted or unsubstituted (C 3 -C 20 )heteroaryl group, substituted or unsubstituted (C 1 -C 20 )alkylamido group, substituted or unsubstituted (C 6 -C 20 )arylamido group, substituted or unsubstituted (C 1 -C 20 )alkylidene group, or substituted or unsubstituted (C 1 -C 20 ) is a cylinder, R 3 Inland R 7 Each independently adjacent group is connected to a substituted or unsubstituted saturated or unsaturated C 4 -C 20 can form a ring, m, l, and y are each integers from 0 to 4).

2. In paragraph 1, In the above chemical formula 1, M is zirconium (Zr), X is halogen, and R 1 and R 2 is (C 1 -C 6 ) is an alkyl group, and n and k are each 1 or 2, In the above chemical formula 2, M is zirconium (Zr), X is halogen, Q is carbon (C), and R 3 Inland R 5 is unsubstituted (C 1 -C 20 ) is an alkyl group, and R 6 and R 7 is unsubstituted (C 6 -C 20 ) is an aryl group, and m, l, and y are each 1, a metallocene catalyst for polyethylene polymerization.

3. In paragraph 1, The first metallocene catalyst compound represented by the above chemical formula 1 is represented by the following chemical formula 1-1, A metallocene catalyst for polyethylene polymerization, wherein the second metallocene catalyst compound represented by the above chemical formula 2 is represented by the following chemical formula 2-1. [Chemical Formula 1-1] [Chemical Formula 2-1] 4. In paragraph 1, The above cocatalyst compound (B) is at least one metallocene catalyst for polyethylene polymerization selected from the group consisting of the following chemical formulas 3 to 5: [Chemical Formula 3] (In the above chemical formula 3, p is an integer greater than or equal to 2, Ra is a halogen group; or (C) substituted or unsubstituted with a halogen group 1 -C 20 ) is a hydrocarbyl group. [Chemical Formula 4] (In the above chemical formula 4, Q is aluminum; or boron, Rb are the same or different from each other, and each independently represents a halogen group; or (C) substituted or unsubstituted with a halogen group 1 -C 20 ) is a hydrocarbyl group. [Chemical Formula 5] (In the above chemical formula 5, [W] + is a cationic Lewis acid; or a cationic Lewis acid with a hydrogen atom attached, Z is a group 13 element, Rc are the same or different and each independently represents a halogen group, (C 1 -C 20 ) substituted with one or more substituents selected from the group consisting of hydrocarbyl groups, alkoxy groups and phenoxy groups (C 6 -C 20 )aryl group; or halogen group, (C 1 -C 20 ) substituted with one or more substituents selected from the group consisting of hydrocarbyl groups, alkoxy groups and phenoxy groups (C 1 -C 20 ) is an alkyl group.

5. In paragraph 1, A metallocene catalyst for polyethylene polymerization, wherein the first metallocene catalyst compound and the second metallocene catalyst compound are present in a molar ratio of 10:1 to 50:

1.

6. In paragraph 1, The above carrier (C) is silica (SiO) having fine pores on the surface or inside. 2 ), alumina (Al 2 O 3 ), magnesium chloride (MgCl 2 ), or a mixture thereof, a metallocene catalyst for polyethylene polymerization.

7. A method for producing a polyethylene copolymer, wherein ethylene and an olefin monomer are reacted in the presence of a metallocene catalyst for polyethylene polymerization according to any one of claims 1 to 6.

8. In paragraph 7, The above olefin monomer is (C 2 ~C 20 ) of α-olefin, (C 4 ~C 20 ) of diolefin, (C 3 ~C 20 ) of cycloolefin, (C 3 ~C 20 ) A method for producing a polyethylene copolymer, wherein the polyethylene copolymer is selected from the group consisting of cyclodiolefins, styrene and styrene derivatives.

9. In paragraph 7, The above olefin monomer is (C 3 ~C 8 ) A method for producing a polyethylene copolymer, which is an α-olefin.

10. A polyethylene copolymer manufactured by the manufacturing method of Article 7.

11. In paragraph 10, The Mz / Mn value is 4.5 or more and 6 or less, and the density is 0.90 or more and 0.935 g / cm3 or less. A polyethylene copolymer having a melt flow rate ratio (MFRR) of 10 to 40 according to ASTM D1238.

12. A film manufactured using the polyethylene copolymer of Article 10.

13. In paragraph 12, The elasticity index calculated by the following mathematical formulas 1 to 4 is 20 or more and 40 or less, A film having a BOCD Index of 0 or more and 3.0 or less, calculated using the following mathematical formula 5. [Mathematical Formula 1] Elasticity Index = RSS X 1000 (In the above mathematical expression 1, RSS is Recovery Shear Strain (γ ∞ , and is calculated using mathematical formula 2.) [Mathematical formula 2] (In the above mathematical expression 2, γ ∞ is the RSS (Recovery Shear Strain), η* is the complex viscosity, which is calculated by the following mathematical formula 3, G' is the storage modulus, which is calculated by the following mathematical formula 4, and ω (Rad / s) is the angular frequency, which is an arbitrary variable.) [Mathematical Formula 3] (In the above mathematical expression 3, η 0 (Pa s) is the zero-shear viscosity, λ(s) is the relaxation time, ω(Rad / s) is the angular frequency, n is the shear-thinning index, and a is the fitting exponent.) [Mathematical Formula 4] (In the above mathematical expression 4, n is the number of Maxwell Equation modes, and g i (Pa) is the Plateau Modulus, and λ i (s) is the relaxation time and ω(Rad / s) is the angular frequency.) [Mathematical Formula 5] BOCD Index = (short-chain branch content in high molecular weight component - short-chain branch content in low molecular weight component) / (short-chain branch content in low molecular weight component)

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