Process for producing olefin polymer and olefin polymer produced thereby and having excellent processability

Abstract

The present invention relates to a method for producing an olefin polymer and an olefin polymer produced thereby, which has excellent processability. The olefin polymer produced by using a hybrid metallocene catalyst according to an embodiment of the present invention has a wide molecular weight distribution of a bimodal or multimodal type, and therefore has excellent high-speed processability. Furthermore, the olefin polymer film produced by molding the same exhibits suppressed gel formation and exhibits excellent quality.

Description

[Technical Field]

[0001] The present invention relates to a method for producing an olefin polymer and an olefin polymer produced thereby, which has excellent processability. Specifically, the present invention relates to a method for producing an olefin polymer in the presence of a mixed metallocene catalyst and an olefin polymer produced thereby, which can be used to produce a film having a bimodal or multimodal broad molecular weight distribution, excellent processability, and suppressed gel formation. [Background technology]

[0002] Polyolefin polymers are widely used in everyday life as materials for a variety of products, including shopping bags, greenhouses, fishing nets, cigarette wrappers, ramen noodle bags, yogurt bottles, battery cases, car bumpers, interior materials, shoe soles, and washing machines.

[0003] Traditionally, polyolefin polymers such as polyethylene, polypropylene, and ethylene-alpha-olefin copolymers and their copolymers have been produced using heterogeneous catalysts such as Ziegler-Natta catalysts, which consist of titanium compounds and alkylaluminum compounds.

[0004] Recently, research has been conducted into the production of polyolefins using metallocene catalysts, which are homogeneous catalysts with extremely high catalytic activity. Metallocene catalysts are compounds in which a transition metal or a transition metal halide is coordinated with a ligand such as cyclopentadienyl, indenyl, or cycloheptadienyl, and have a basic sandwich structure. The molecular structure varies depending on the type of ligand and the type of central metal.

[0005] In the heterogeneous catalyst Ziegler-Natta catalyst, the metal components that act as active sites are dispersed on the surface of an inert solid, and the properties of the active sites are not uniform. In contrast, metallocene catalysts are single-site catalysts, in which all active sites have the same polymerization properties because they are a single compound with a predetermined structure.

[0006] Such metallocene catalysts are easy to copolymerize and can control the steric structure of the polymer depending on the symmetry of the catalyst. The polymers produced by these catalysts have the advantages of narrow molecular weight distribution and uniform comonomer distribution.

[0007] On the other hand, polymers produced using metallocene catalysts have excellent mechanical strength due to their narrow molecular weight distribution, but suffer from poor processability. To address this issue, various methods have been proposed, such as modifying the molecular structure of the polymer or widening the molecular weight distribution. For example, U.S. Patent No. 5,272,236 proposes improving polymer processability by using a catalyst that introduces long chain branches (LCBs) as side chains to the polymer main chain. However, entanglement of the long chain branches can lead to the formation of gels.

[0008] It is generally known that the larger the molecular weight distribution (MWD) and melt flow rate (MFR) of a polyolefin, the better its processability. However, a polyolefin with a large MWD or MFR does not necessarily have excellent processability at high speeds.

[0009] Therefore, there is a demand for an olefin polymer that has a wide bimodal or multimodal molecular weight distribution, is excellent in high-speed processability, and can be used to produce a film in which gel formation is suppressed. Summary of the Invention [Problem to be solved by the invention]

[0010] The present invention aims to provide a method for producing an olefin polymer in the presence of a hybrid metallocene catalyst, and an olefin polymer produced thereby that has a broad bimodal or multimodal molecular weight distribution and can be used to produce a film that has excellent processability and suppresses gel formation. [Means for solving the problem]

[0011] In one embodiment of the present invention to achieve the above object, a method for producing an olefin polymer includes the steps of: (a) polymerizing ethylene and at least one alpha-olefin in the presence of a mixed metallocene catalyst comprising: (a) at least one first transition metal compound selected from the transition metal compounds represented by the following chemical formulas 1 to 4; (b) at least one second transition metal compound selected from the transition metal compounds represented by the following chemical formula 5; and (c) a co-catalyst compound; 3 and the melt index (I) measured at 190°C under a load of 2.16 kg 2.16 ) is 0.1~2.0g / 10min, the weight average molecular weight is 100,000~150,000g / mol, and melt fracture or shark skin phenomenon occurs when measured with a capillary rheometer. The shear rate is defined by the following mathematical formula 1. -1 Thus, there is provided a method for producing an olefin polymer.

number

number

[0012] In an embodiment of the present invention, the molar ratio of the first transition metal compound to the second transition metal compound may be in the range of 10:1 to 1:10.

[0013] In a specific example of the present invention, the transition metal compound of Chemical Formula 1 may be at least one of the transition metal compounds represented by Chemical Formulas 1-1 to 1-4 below, the transition metal compound of Chemical Formula 2 may be at least one of the transition metal compounds represented by Chemical Formulas 2-1 to 2-3 below, the transition metal compound of Chemical Formula 3 may be a transition metal compound represented by Chemical Formula 3-1 below, and the transition metal compound of Chemical Formula 4 may be a transition metal compound represented by Chemical Formula 4-1 below. [ka] In the above chemical formula, n-Bu is n-butyl, t-Bu is t-butyl, and Ph is phenyl. In an embodiment of the present invention, the transition metal compound of the above Chemical Formula 5 may be a transition metal compound represented by the following Chemical Formula 5-1. [ka] In an embodiment of the present invention, the co-catalyst compound may include at least one selected from the group consisting of a compound represented by the following Chemical Formula 6, a compound represented by the following Chemical Formula 7, and a compound represented by the following Chemical Formula 8. [ka] [Chemical formula 8] [LH] + [Z(A)4] - or [L] + [Z(A)4] - In the above chemical formula 6, n is an integer of 2 or more, and R a is a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group having 1 to 20 carbon atoms substituted with a halogen atom, In the above formula 7, D is aluminum (Al) or boron (B), and R b , R c and R d are each independently a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms substituted with a halogen atom, or an alkoxy group having 1 to 20 carbon atoms, In the above formula 8, L is a neutral or cationic Lewis base, [LH] + and [L] + is a Bronsted acid, Z is a Group 13 element, and each A is independently a substituted or unsubstituted aryl group having 6 to 20 carbon atoms or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms.

[0014] In a preferred embodiment of the present invention, the compound represented by Chemical Formula 6 is at least one selected from the group consisting of methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, and butylaluminoxane.

[0015] In a preferred embodiment of the present invention, the compound represented by Chemical Formula 7 is at least one selected from the group consisting of 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, and tributylboron.

[0016] In a preferred embodiment of the present invention, the compound represented by Chemical Formula 8 is selected from the group consisting of triethylammonium tetraphenylborate, tributylammonium tetraphenylborate, trimethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, trimethylammonium tetra(p-tolyl)borate, trimethylammonium tetra(o,p-dimethylphenyl)borate, tributylammonium tetra(p-trifluoromethylphenyl)borate, trimethylammonium tetra(p-trifluoromethylphenyl)borate, tributylammonium tetrapentafluorophenylborate, N,N-diethylanilinium tetraphenylborate, N,N-diethylanilinium tetrapentafluorophenylborate, diethylammonium tetrapentafluorophenylborate, triphenylphosphonium tetraphenylborate, trimethylphosphonium tetraphenylborate, triethylammonium tetraphenylaluminum, tributylammonium tetrapentafluorophenylborate, N,N-diethylanilinium ...ammonium tetraphenylborate, triethylammonium tetraphenylaluminum, tributylammonium tetrapentafluorophenylborate, N,N-diethylanilinium tetrapentafluorophenylborate, N,N-diethylanilinium tetrapentafluorophenylborate, triphenylphosphonium tetraphenylborate, trimethylammonium tetraphenylborate, tri ammonium tetraphenylaluminate, trimethylammonium tetraphenylaluminate, tripropylammonium tetraphenylaluminate, trimethylammonium tetra(p-tolyl)aluminate, tripropylammonium tetra(p-tolyl)aluminate, triethylammonium tetra(o,p-dimethylphenyl)aluminate, tributylammonium tetra(p-trifluoromethylphenyl)aluminate, trimethylammonium tetra(p-trifluoromethylphenyl)aluminate, tributylammonium tetrapentafluorophenylaluminate, N,N-diethylanilinium tetraphenylaluminate, N,N-diethylanilinium tetrapentafluorophenylaluminate, diethylammonium tetrapentatetraphenylaluminate, triphenylphosphonium tetraphenylaluminate, trimethylphosphonium tetraphenylaluminate, tripropylammonium tetra(p-tolyl)borate, triethylammonium tetra(o,At least one selected from the group consisting of triphenylcarbonium tetra(p-dimethylphenyl)borate, triphenylcarbonium tetra(p-trifluoromethylphenyl)borate, and triphenylcarbonium tetrapentafluorophenylborate.

[0017] In an embodiment of the present invention, the hybrid metallocene catalyst may further comprise a support that supports the hybrid transition metal compound, the cocatalyst compound, or both.

[0018] In an embodiment of the present invention, the support may comprise at least one selected from the group consisting of silica, alumina, and magnesia.

[0019] Here, the total amount of the mixed transition metal compounds supported on the carrier is 0.001 to 1 mmole per 1 g of the carrier, and the total amount of the promoter compounds supported on the carrier is 2 to 15 mmole per 1 g of the carrier.

[0020] In an embodiment of the present invention, the alpha-olefin may be at least one selected from the group consisting of propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, and 1-hexadecene. Preferably, the alpha-olefin may be 1-hexene.

[0021] In an embodiment of the present invention, the polymerization of ethylene and at least one alpha-olefin may be carried out by gas phase polymerization, specifically, the polymerization of ethylene and at least one alpha-olefin may be carried out in a gas phase fluidized bed reactor.

[0022] According to another embodiment of the present invention, a sintered body having a density of 0.930 to 0.970 g / cm3 produced by the above-mentioned production method is 3 and the melt index (I) measured at 190°C under a load of 2.16 kg 2.16) is 0.1 to 2.0 g / 10 min, the weight average molecular weight is 100,000 to 150,000 g / mol, and when measured with a capillary rheometer, melt fracture or shark skin phenomenon occurs. -1 The above olefin polymer is provided.

[0023] In an embodiment of the present invention, the olefin polymer has a melt index (I ) measured at 190° C. under a load of 21.6 kg. 21.6 ) and the melt index (I 2.16 The melt flow ratio (MFR) may be 30 to 200.

[0024] In an embodiment of the present invention, an inflection point may exist when the olefin polymer is plotted on a Van Gurp-Palmen graph.

[0025] In a specific example of the present invention, when the olefin polymer is formed into a film having a thickness of 30 to 60 μm by blow film molding, the gel index, which is defined as the number of gels having a size of 0.05 mm or more present in an arbitrary 5 cm × 5 cm film area, may be 1 or less.

[0026] According to another embodiment of the present invention, there is provided an olefin polymer film produced by molding the above-mentioned olefin polymer, wherein when the olefin polymer is blown into a film having a thickness of 30 to 60 μm, the gel index, defined as the number of gels of 0.05 mm or more present in an arbitrary 5 cm × 5 cm film area, is 1 or less. [Effects of the Invention]

[0027] The olefin polymer produced by the hybrid metallocene catalyst according to the embodiment of the present invention has a wide bimodal or multimodal molecular weight distribution, and therefore has excellent high-speed processability. Furthermore, the olefin polymer film produced by molding the same exhibits excellent quality with suppressed gel formation. [Brief explanation of the drawings]

[0028] [Figure 1] 1 is a Van Gurp-Palmen graph of the olefin polymers of Example 3, Comparative Examples 6 and 7, and Control Example 1. [Figure 2] 1 is a graph showing the results of GPC analysis of the olefin polymers of Example 3, Comparative Examples 6 and 7, and Control Example 1. DETAILED DESCRIPTION OF THE INVENTION

[0029] The present invention will now be described in more detail.

[0030] Method for producing olefin polymer According to one embodiment of the present invention, there is provided a method for producing an olefin polymer, comprising the steps of: (a) polymerizing ethylene and at least one alpha-olefin in the presence of a mixed metallocene catalyst comprising at least one first transition metal compound selected from the transition metal compounds represented by the following chemical formulas 1 to 4; (b) polymerizing at least one second transition metal compound selected from the transition metal compounds represented by the following chemical formula 5; and (c) polymerizing at least one alpha-olefin in the presence of a mixed metallocene catalyst comprising a co-catalyst compound.

[0031] [ka]

[0032] [ka]

[0033] [ka]

[0034] In the above chemical formula, l1 and m1 each independently represent an integer of 0 to 5. Preferably, l1 is 1 and m1 each independently represent an integer of 1 to 5.

[0035] l2, l3, l4 and m2 are each independently an integer of 0 to 4. Preferably, l2, l3, l4 and m2 are each independently 0 or 1.

[0036] m3 and m4 each independently represent an integer of 0 to 2. Preferably, m3 and m4 each independently represent 0 or 1.

[0037] p is the oxidation state of M and is +3, +4 or +5.

[0038] q is the formal charge of the YZL ligand and can be 0, −1, −2, or −3.

[0039] M is a group 4 element of the periodic table of elements, and specifically, M may be titanium (Ti), zirconium (Zr) or hafnium (Hf), and more specifically, M may be zirconium.

[0040] X is independently a halogen, C 1-20 Alkyl, C 2-20 Alkenyl, C 2-20 Alkynyl, C 6-20 Aryl, C 1-20 Alkyl C 6-20 Aryl, C 6-20 Aryl C 1-20 Alkyl, C 1-20 Alkylamide or C 6-20 Specifically, each X may independently represent a halogen, more specifically, chlorine (Cl).

[0041] Each Q is independently carbon (C), silicon (Si), germanium (Ge), or tin (Sn). Specifically, each Q may be independently carbon (C) or silicon (Si).

[0042] Q' are each independently hydrogen, substituted or unsubstituted C as an anionic leaving group. 1-40 Hydrocarbon groups, substituted or unsubstituted C 1-40 Q' is a heterohydrocarbon group, a heteroatom, or a halogen. Specifically, Q' may be a linear or branched alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an aryl group, an acyl group, an aroyl group, an alkoxy group, an aryloxy group, an alkylthio group, a dialkylamino group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkyl- or dialkyl-carbamoyl group, an acyloxy group, an acylamino group, an aroylamino group, a linear, branched, or cyclic alkylene group, or a combination thereof.

[0043] Q'' is a substituted or unsubstituted C 2-4 It is an alkylene group. Preferably, Q'' may be an ethylene group (-CH2-CH2-).

[0044] L is a Group 15 or 16 element, preferably nitrogen.

[0045] Y is a Group 15 element, preferably nitrogen or phosphorus, more preferably nitrogen.

[0046] Z is a Group 15 element, preferably nitrogen or phosphorus, more preferably nitrogen.

[0047] R1~R4, R7, R8, R 18 , R 19 are each independently a substituted or unsubstituted C 1-20 Alkyl, substituted or unsubstituted C 2-20 Alkenyl, substituted or unsubstituted C 6-20 Aryl, substituted or unsubstituted C 1-20 Alkyl C6-20 Aryl, substituted or unsubstituted C 6-20 Aryl C 1-20 Alkyl, substituted or unsubstituted C 1-20 Heteroalkyl, substituted or unsubstituted C 3-20 Heteroaryl, substituted or unsubstituted C 1-20 Alkylamides, substituted or unsubstituted C 6-20 Arylamide, or substituted or unsubstituted C 1-20 silyl, each of which independently connects adjacent groups to form a substituted or unsubstituted saturated or unsaturated C 4-20 A ring may or may not be formed. Specifically, R1 to R4, R7, R8, and R 18 , R 19 are each independently a substituted or unsubstituted C 1-20 Alkyl, or substituted or unsubstituted C 6-20 It may also be aryl.

[0048] R5, R6, R9 and R 10 are each independently a substituted or unsubstituted C 1-20 Alkyl, substituted or unsubstituted C 2-20 Alkenyl, substituted or unsubstituted C 6-20 Aryl, substituted or unsubstituted C 1-20 Alkyl C 6-20 Aryl, substituted or unsubstituted C 6-20 Aryl C 1-20 Alkyl, substituted or unsubstituted C 1-20 Heteroalkyl, substituted or unsubstituted C 3-20 Heteroaryl, substituted or unsubstituted C 1-20 Alkylamides, substituted or unsubstituted C 6-20 Arylamide, or substituted or unsubstituted C 1-20 Cyril, but R5 and R6, R9 and R 10 are each independently linked to each other to form a substituted or unsubstituted saturated or unsaturated C 2-20 A ring may or may not be formed. Specifically, R5 and R6, R9 and R 10 are each independently a substituted or unsubstituted C 1-20 Alkyl, substituted or unsubstituted C2-20 Alkenyl or substituted or unsubstituted C 6-20 It may also be aryl.

[0049] R 11 and R 12 are each independently 1-20 a hydrocarbon group or a heteroatom-containing group, where the heteroatom is silicon, germanium, tin, lead, or phosphorus, or R 11 and R 12 may be linked together. Specifically, R 11 and R 12 are each independently 1-6 It may also be a hydrocarbon group.

[0050] R 13 is absent or hydrogen, C 1-20 It may be an alkyl, halogen, or heteroatom-containing group. Specifically, R 13 may be hydrogen or methyl.

[0051] R 14 and R 15 are each independently an alkyl group, an aryl group, a substituted aryl group, a cyclic alkyl group, a substituted cyclic alkyl group, or a polycyclic ring system. 14 and R 15 may each independently be a substituted aryl group.

[0052] R 16 and R 17 may each independently be absent, a hydrogen, an alkyl group, a halogen, a heteroatom, a hydrocarbon group, or a heteroatom-containing group.

[0053] In the mixed metallocene catalyst for olefin polymerization according to an embodiment of the present invention, the molar ratio of the first transition metal compound to the second transition metal compound may be in the range of 10:1 to 1:10. When the molar ratio of the first transition metal compound to the second transition metal compound is within the above range, a polyolefin polymer having excellent high-speed processability can be obtained, and gel formation in the produced film can be suppressed.

[0054] In a specific example of the present invention, the transition metal compound of Chemical Formula 1 may be at least one of the transition metal compounds represented by Chemical Formulas 1-1 to 1-4 below, the transition metal compound of Chemical Formula 2 may be at least one of the transition metal compounds represented by Chemical Formulas 2-1 to 2-3 below, the transition metal compound of Chemical Formula 3 may be a transition metal compound represented by Chemical Formula 3-1 below, and the transition metal compound of Chemical Formula 4 may be a transition metal compound represented by Chemical Formula 4-1 below.

[0055] [ka]

[0056] [ka]

[0057] [ka]

[0058] [ka]

[0059] In the above chemical formula, n-Bu is n-butyl, t-Bu is t-butyl, and Ph is phenyl.

[0060] In an embodiment of the present invention, the transition metal compound of the above Chemical Formula 5 may be a transition metal compound represented by the following Chemical Formula 5-1.

[0061] [ka]

[0062] In an embodiment of the present invention, the co-catalyst compound may include at least one selected from the group consisting of a compound represented by the following Chemical Formula 6, a compound represented by the following Chemical Formula 7, and a compound represented by the following Chemical Formula 8.

[0063] [ka]

[0064] In the above chemical formula 6, n is an integer of 2 or more, and R a may be a halogen atom, a hydrocarbon having 1 to 20 carbon atoms, or a hydrocarbon having 1 to 20 carbon atoms substituted with a halogen atom. a may be methyl, ethyl, n-butyl or isobutyl.

[0065] [ka]

[0066] In the above formula 7, D is aluminum (Al) or boron (B), and R b , R c and R d are each independently a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms substituted with a halogen atom, or an alkoxy group having 1 to 20 carbon atoms. Specifically, when D is aluminum (Al), R b , R c and R d may each independently be methyl or isobutyl, and when D is boron (B), R b , R c and R d may each be pentafluorophenyl.

[0067] [Chemical formula 8] [LH] + [Z(A)4] - or [L] + [Z(A)4] -

[0068] In the above formula 8, L is a neutral or cationic Lewis base, [LH] + and [L] + is a Bronsted acid, Z is a Group 13 element, and each A is independently a substituted or unsubstituted aryl group having 6 to 20 carbon atoms or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms. Specifically, [LH] + may be a dimethylanilinium cation, [Z(A)4] - is [B(C6F5)4] - [L] + is [(C6H5)3C] + may be.

[0069] Examples of the compound represented by Chemical Formula 6 include methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, butylaluminoxane, etc., with methylaluminoxane being preferred, but not limited thereto.

[0070] Examples of the compound represented by Chemical Formula 7 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, and tributylboron, of which trimethylaluminum, triethylaluminum, and triisobutylaluminum are preferred, but not limited thereto.

[0071] Examples of the compound represented by the chemical formula 8 include triethylammonium tetraphenylborate, tributylammonium tetraphenylborate, trimethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, trimethylammonium tetra(p-tolyl)borate, trimethylammonium tetra(o,p-dimethylphenyl)borate, tributylammonium tetra(p-trifluoromethylphenyl)borate, trimethylammonium tetra(p-trifluoromethylphenyl)borate, tributylammonium tetrapentafluorophenylborate, N,N-diethylanilinium tetraphenylborate, N,N-diethylanilinium tetrapentafluorophenylborate, diethylammonium tetrapentafluorophenylborate, triphenylphosphonium tetraphenylborate, trimethylphosphonium tetraphenylborate, triethylammonium tetraphenylaluminate, tributylammonium tetraphenylaluminate, trimethylammonium tetraphenylaluminate, tripropylammonium trimethylammonium tetraphenylaluminate, trimethylammonium tetra(p-tolyl)aluminate, tripropylammonium tetra(p-tolyl)aluminate, triethylammonium tetra(o,p-dimethylphenyl)aluminate, tributylammonium tetra(p-trifluoromethylphenyl)aluminate, trimethylammonium tetra(p-trifluoromethylphenyl)aluminate, tributylammonium tetrapentafluorophenylaluminate, N,N-diethylanilinium tetraphenylaluminate, N,N-diethylanilinium tetrapentafluorophenylaluminate, diethylammonium tetrapentatetraphenylaluminate, triphenylphosphonium tetraphenylaluminate, trimethylphosphonium tetraphenylaluminate, tripropylammonium tetra(p-tolyl)borate, triethylammonium tetra(o,p-dimethylphenyl)borate, triphenylcarbonium tetra(p-trifluoromethylphenyl)borate, triphenylcarbonium tetrapentafluorophenylborate, and the like.

[0072] In an embodiment of the present invention, the hybrid metallocene catalyst for olefin polymerization may further comprise a support carrying the hybrid transition metal compound, the cocatalyst compound, or both.

[0073] The support may include a substance containing hydroxyl groups on its surface. Preferably, a substance having highly reactive hydroxyl groups and siloxane groups that has been dried to remove moisture from its surface can be used. For example, the support may include at least one selected from the group consisting of silica, alumina, and magnesia. Specifically, silica, silica-alumina, and silica-magnesia dried at high temperatures can be used as the support. These typically contain oxides, carbonates, sulfates, and nitrates such as Na2O, K2CO3, BaSO4, and Mg(NO3)2. They may also contain carbon, zeolite, magnesium chloride, etc. However, the support is not particularly limited to these.

[0074] The carrier may have an average particle size of 10 to 250 μm, preferably an average particle size of 10 to 150 μm, and more preferably an average particle size of 20 to 100 μm.

[0075] The micropore volume of the carrier may be 0.1 to 10 ml / g, preferably 0.5 to 5 ml / g, and more preferably 1.0 to 3.0 ml / g.

[0076] The specific surface area of ​​the carrier is 1 to 1,000 m 2 / g, preferably 100 to 800m 2 / g, more preferably 200 to 600m 2 / g.

[0077] In a preferred embodiment, when the support is silica, the drying temperature for the silica may be 200 to 900° C. The drying temperature may be preferably 300 to 800° C., more preferably 400 to 700° C. If the drying temperature is less than 200° C., there will be too much moisture on the surface, causing a reaction between the moisture and the first promoter compound, and if the drying temperature exceeds 900° C., the structure of the support may collapse.

[0078] The hydroxyl group concentration in the dried silica may be 0.1 to 5 mmole / g, preferably 0.7 to 4 mmole / g, and more preferably 1.0 to 2 mmole / g. If the hydroxyl group concentration is less than 0.1 mmole / g, the amount of the co-catalyst supported will be low, and if it exceeds 5 mmole / g, the catalyst component may become inactive.

[0079] The total amount of the mixed transition metal compound supported on the support may be 0.001 to 1 mmole per gram of support. When the ratio of the mixed transition metal compound to the support satisfies the above range, the supported catalyst exhibits appropriate activity, which is advantageous in terms of maintaining the catalyst activity and economy.

[0080] The total amount of promoter compounds supported on the carrier may be 2 to 15 mmole per gram of carrier. If the ratio of promoter compounds to carrier satisfies the above range, it is advantageous in terms of maintaining catalyst activity and economy.

[0081] One or more types of supports may be used. For example, both the mixed transition metal compound and the co-catalyst compound may be supported on one support, or two or more types of supports may each support the mixed transition metal compound and the co-catalyst compound. Alternatively, only one of the mixed transition metal compound and the co-catalyst compound may be supported on a support.

[0082] In an embodiment of the present invention, the olefin polymer may be a homopolymer of an olefin monomer or a copolymer of an olefin monomer and a comonomer. Preferably, the olefin polymer is a copolymer of an olefin monomer and an olefin comonomer.

[0083] Here, the olefin monomer is C2-C 20 Alpha-olefin (α-olefin), C 3-20 Diolefin, C 3-20 Cycloolefin and C 4-20 At least one selected from the group consisting of cyclodiolefins.

[0084] For example, the 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, or 1-hexadecene, and the olefin polymer may be a homopolymer containing only one of the olefin monomers exemplified above, or a copolymer containing two or more of them.

[0085] In an exemplary embodiment, the olefin-based polymer is a copolymer of ethylene and C 3-20 The olefin-based polymer may be a copolymer in which an alpha-olefin is copolymerized. Preferably, the olefin-based polymer may be a linear low-density polyethylene in which the olefin-based monomer is ethylene and the olefin-based comonomer is 1-hexene.

[0086] In this case, the ethylene content is preferably 55 to 99.9% by weight, more preferably 90 to 99.9% by weight, and the alpha-olefin comonomer content is preferably 0.1 to 45% by weight, more preferably 0.1 to 10% by weight.

[0087] In an embodiment of the present invention, the olefin polymer may be produced by a gas phase polymerization method, a solution polymerization method, a slurry polymerization method, etc. Preferably, the polymerization of the olefin monomer may be carried out by a gas phase polymerization method, more specifically, the polymerization of the olefin monomer may be carried out in a gas phase fluidized bed reactor.

[0088] When olefin polymers are produced by solution polymerization or slurry polymerization, examples of solvents that can be used include C olefins such as pentane, hexane, heptane, nonane, decane, and their isomers. 5-12 Examples of suitable solvents include, but are not limited to, aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents such as toluene and benzene, hydrocarbon solvents substituted with chlorine atoms such as dichloromethane and chlorobenzene, and mixtures thereof.

[0089] The olefin polymer produced by the method for producing an olefin polymer according to the embodiment of the present invention has a density of 0.930 to 0.970 g / cm 3 and the melt index (I) measured at 190°C under a load of 2.16 kg 2.16 ) is 0.1~2.0g / 10min, the weight average molecular weight is 100,000~150,000g / mol, and melt fracture or shark skin phenomenon occurs when measured with a capillary rheometer. The shear rate is defined by the following mathematical formula 1. -1 That's all.

[0090]

number

[0091] In the above mathematical formula:

number

[0092] olefin polymer According to one embodiment of the present invention, an olefin polymer having a density of 0.930 to 0.970 g / cm is produced by the above-mentioned method for producing an olefin polymer. 3 and the melt index (I) measured at 190°C under a load of 2.16 kg 2.16 ) is 0.1 to 2.0 g / 10 min, the weight average molecular weight is 100,000 to 150,000 g / mol, and when measured with a capillary rheometer, melt fracture or shark skin phenomenon occurs. -1 The above olefin polymer is provided.

[0093] The olefin polymer according to the embodiment of the present invention has a density of 0.930 to 0.970 g / cm 3 Preferably, the density of the olefin polymer is 0.930 to 0.965 g / cm 3 , more preferably 0.935 to 0.960 g / cm 3 may be.

[0094] The olefin polymer according to the embodiment of the present invention has a melt index (I ) measured at 190° C. under a load of 2.16 kg. 2.16 The melt index of the olefin polymer measured at 190°C under a load of 2.16 kg is preferably 0.1 to 2.0 g / 10 min, more preferably 0.2 to 1.5 g / 10 min.

[0095] The olefin polymer according to the embodiment of the present invention has a weight average molecular weight of 100,000 to 150,000 g / mol, preferably 100,000 to 145,000 g / mol, more preferably 100,000 to 140,000 g / mol.

[0096] In an embodiment of the present invention, the olefin polymer has a melt index (I ) measured at 190° C. under a load of 21.6 kg. 21.6 ) and the melt index (I 2.16 The melt flow ratio (MFR) of the olefin polymer may be 30 to 200. Preferably, the MFR of the olefin polymer may be 30 to 150, more preferably 40 to 135.

[0097] The olefin polymer according to an embodiment of the present invention exhibits melt fracture or shark skin phenomenon when measured using a capillary rheometer, and is defined by the following mathematical formula 1 at a shear rate of 1,500 sec -1 Preferably, the shear rate at which melt fracture or shark skin occurs is 1,750 sec -1 More than 2,000 seconds, preferably -1 It may be more than that.

[0098]

number

[0099] In the above mathematical formula:

number

[0100] Melt fracture or sharkskin is a common name for the phenomenon in which irregular irregularities or shark scales appear on the surface of a polymer during extrusion, or the surface loses its luster. The higher the shear rate at which such melt fracture or sharkskin occurs, the better the processability of the polymer.

[0101] The olefin polymer according to an embodiment of the present invention may have a bimodal or multimodal molecular weight distribution as measured by gel permeation chromatography (GPC).

[0102] Specifically, in a GPC graph of an olefin polymer according to an embodiment of the present invention, a point where the slope of the tangent line changes from a positive value to a negative value is defined as a "peak," and a point where the slope of the tangent line changes from a negative value to a positive value is defined as a "valley." The olefin polymer according to an embodiment of the present invention may exhibit a bimodal or multimodal molecular weight distribution having two or more peaks.

[0103] In an embodiment of the present invention, when the olefin polymer is shown on a Van Gurp-Palmen graph, an inflection point may exist.

[0104] The presence or absence of long chain branches in an ethylene polymer can be determined by the presence or absence of an inflection point in a Van Gurp-Palmen graph measured using a rheometer or by the tendency for the graph to diverge as the complex modulus (G*) decreases. The Van Gurp-Palmen graph shows that the phase angle (y-axis) diverges as the complex modulus (x-axis) decreases, and the graph has an inflection point as the complex modulus value increases. These graph characteristics indicate that the ethylene polymer contains a large amount of long chain branches.

[0105] As will be described later, the olefin polymer film produced from the olefin polymer according to the embodiment of the present invention exhibits suppressed gel formation. Therefore, it can be confirmed that the presence of an inflection point on the Van Gurp-Palmen graph of the olefin polymer according to the embodiment of the present invention is due to the presence of long chain branches, and as a result, it can be understood that the olefin polymer according to the embodiment of the present invention exhibits excellent high-speed processability.

[0106] In a specific example of the present invention, when the olefin polymer is blown into a film having a thickness of 30 to 60 μm, the gel index, which is defined as the number of gels having a size of 0.05 mm or more present in an arbitrary 5 cm × 5 cm film area, may be 1 or less.

[0107] Olefin polymer film According to one embodiment of the present invention, there is provided an olefin polymer film produced by molding the above-mentioned olefin polymer. The olefin polymer film according to this embodiment of the present invention has a gel index of 1 or less, which is defined as the number of gels of 0.05 mm or more in size present in any 5 cm x 5 cm film area, when the olefin polymer is molded into a film of 30 to 60 μm in thickness by film blow molding.

[0108] The method for producing the olefin polymer film according to the embodiment of the present invention is not particularly limited, and any method known in the art to which the present invention pertains can be used. For example, the olefin polymer can be processed by a conventional method such as film blowing, extrusion, or casting to produce an olefin polymer film. Among these, film blowing is most preferred.

[0109] Example The present invention will be described in more detail below with reference to examples and comparative examples. However, the following examples are for the purpose of illustrating the present invention, and the scope of the present invention is not limited to these examples.

[0110] Manufacturing Example 1 26 mg of the transition metal compound of formula 2-1, 58 mg of the transition metal compound of formula 2-2, and 22 mg of the transition metal compound of formula 5-1 were mixed with 16 g of a 10 wt% methylaluminoxane (MAO) toluene solution (Al / Zr = 150) in a glove box and stirred at room temperature for 1 hour. Meanwhile, 4 g of silica (XP2402) was added to a reactor, and 30 ml of purified toluene was added and mixed. The above transition metal compound solution was poured into the resulting silica slurry and stirred in an oil bath at 75 °C for 3 hours. After the loading was complete and the solid / liquid phases were fully separated, the supernatant was removed. The supported catalyst was washed three times with toluene and dried in a vacuum at 60 °C for 10 hours to obtain 3.8 g of a free-flowing powdery hybrid supported catalyst.

[0111] Manufacturing Example 2 3.8 g of a free-flowing powdery hybrid supported catalyst was obtained in the same manner as in Production Example 1, except that 38 mg of the transition metal compound of Chemical Formula 2-1, 46 mg of the transition metal compound of Chemical Formula 2-2, and 22 mg of the transition metal compound of Chemical Formula 5-1 were used.

[0112] Manufacturing Example 3 3.8 g of a free-flowing powdery hybrid supported catalyst was obtained in the same manner as in Production Example 1, except that 12 mg of the transition metal compound of Chemical Formula 2-1, 58 mg of the transition metal compound of Chemical Formula 2-2, and 28 mg of the transition metal compound of Chemical Formula 1-4 were used.

[0113] Production Example 4 3.8 g of a free-flowing powdery hybrid supported catalyst was obtained in the same manner as in Production Example 1, except that 13 mg of the transition metal compound of Chemical Formula 2-1, 80 mg of the transition metal compound of Chemical Formula 2-2, and 18 mg of the transition metal compound of Chemical Formula 1-1 were used.

[0114] Manufacturing Example 5 3.8 g of a free-flowing powdery hybrid supported catalyst was obtained in the same manner as in Production Example 1, except that 26 mg of the transition metal compound of Chemical Formula 2-1, 114 mg of the transition metal compound of Chemical Formula 3-1, and 58 mg of the transition metal compound of Chemical Formula 1-4 were used.

[0115] Manufacturing Example 6 3.8 g of a free-flowing powdery hybrid supported catalyst was obtained in the same manner as in Production Example 1, except that 12 mg of the transition metal compound of Chemical Formula 2-1, 54 mg of the transition metal compound of Chemical Formula 3-1, and 28 mg of the transition metal compound of Chemical Formula 1-1 were used.

[0116] Manufacturing Example 7 3.8 g of a free-flowing powdery hybrid supported catalyst was obtained in the same manner as in Production Example 1, except that 22 mg of the transition metal compound of Chemical Formula 2-1, 44 mg of the transition metal compound of Chemical Formula 2-3, and 28 mg of the transition metal compound of Chemical Formula 1-1 were used.

[0117] Manufacturing Example 8 0.8 g of the transition metal compound of formula 2-1, 3.8 g of the transition metal compound of formula 2-2, and 1.9 g of the transition metal compound of formula 5-1 were mixed with 1.1 kg of a 10 wt% toluene solution of methylaluminoxane (MAO) (Al / Zr = 150) in a glove box and stirred at room temperature for 1 hour. Meanwhile, 250 g of silica (XP2402) was added to a reactor, and 30 ml of purified toluene was added and mixed. The resulting silica slurry was then poured into the transition metal compound solution and stirred in an oil bath at 75°C for 3 hours. After the loading was complete and the solid / liquid phases were fully separated, the supernatant was removed. The supported catalyst was washed three times with toluene and dried in a vacuum at 60°C for 10 hours to obtain 230 g of a free-flowing powdery hybrid supported catalyst.

[0118] Manufacturing Example 9 230 g of a free-flowing powdery hybrid supported catalyst was obtained in the same manner as in Production Example 8, except that 0.8 g of the transition metal compound of Chemical Formula 2-1, 5 g of the transition metal compound of Chemical Formula 2-2, and 1.2 g of the transition metal compound of Chemical Formula 1-1 were used.

[0119] Manufacturing Example 10 225 g of a free-flowing powdery hybrid supported catalyst was obtained in the same manner as in Production Example 8, except that 0.8 g of the transition metal compound of Chemical Formula 2-1, 3.8 g of the transition metal compound of Chemical Formula 2-2, and 1.8 g of the transition metal compound of Chemical Formula 1-4 were used.

[0120] Examples 1 to 2 and Comparative Examples 1 to 5 Using 10 to 100 mg of each of the supported catalysts obtained in Preparation Examples 1 to 7, ethylene and 1-hexene were copolymerized in a fluidized bed gas-phase reactor in the presence of 0.6 ml of 1 M triisobutylaluminum (TIBAL) as a scavenger. The temperature inside the reactor was maintained at 80°C, and the ethylene pressure was 14 kgf / cm. 2 The amount of 1-hexene was 100 ml, and the total amount of hydrogen charged was 1,300 ml. The polymerization conditions are shown in Table 1 below.

[0121] [Table 1]

[0122] Example 3 and Comparative Examples 6 to 7 Using each of the supported catalysts obtained in Preparation Examples 8 to 10, ethylene and 1-hexene were copolymerized in a pilot-scale continuous fluidized-bed gas-phase reactor. The polymerization conditions are shown in Table 2 below.

[0123] [Table 2]

[0124] Experimental example The physical properties of the olefin polymers obtained in the examples and comparative examples were measured as follows. The measurement results are shown in Tables 3 and 4. For comparison, Hanwha Solutions' high-speed processable product 8380 was used as Control Example 1.

[0125] (1) Melt index and melt flow rate (MFR) According to ASTM D 1238, the melt index was measured at 190°C with a load of 21.6 kg and a load of 2.16 kg, and the ratio (MI 21.6 / MI 2.16 ) was sought.

[0126] (2) Density Measurement was carried out in accordance with ASTM D1505.

[0127] (3) Gel permeation chromatography A GPC-FTIR (GPC-FTIR) spectrometer (Model GPC-6, manufactured by Polymer Char) was used. Measurements were performed at 160°C using trichlorobenzene as the solvent.

[0128] (4) Processability Measurements were performed using a Gottfert RG25 capillary rheometer. Measurement conditions were a circular hole, length 20 mm, effective length 20 mm, diameter / width 2, height 0 mm, run angle 180°, piston diameter 15 mm, and capillary diameter 2 mm at 230°C. Measurements were performed based on the shear rate at which sharkskin and melt fracture occurred, and the shear rate was calculated using Equation 1 above.

[0129] run (5) Gel index A film having a thickness of 55 μm was produced at 190° C. using a Colliun blown film molding machine, and the number of gels having a size of 0.05 mm or more present within a 5 cm×5 cm film area was counted.

[0130] -0: 10 or less in total -1: Total over 10 to 30 -2: Total over 30 to 50 -3: Total over 50 to 100 -4: Total over 100 to 200 -5: Total over 200 (film molding was difficult)

[0131] (6) Van Gurp-Palmen graph The dynamic frequency sweep was performed using an advanced rheometric expansion system (ARES). Measurements were performed at 190°C using 25 mm parallel plates in the form of disks. The Van Gurp-Palmen graph shows the complex modulus (G, dyne / cm) on the x-axis. 2 ), and the Y-axis indicates the phase difference (phase angle, d(delta)).

[0132] [Table 3]

[0133] [Table 4]

[0134] As can be seen from Tables 1 and 2, the formation of gels was suppressed in the films produced from the olefin polymers of Examples 1 and 2, which are within the scope of the present invention. In contrast, the number of gels increased in the films produced from the olefin polymers of Comparative Examples 1 to 5.

[0135] On the other hand, as can be seen from Tables 3 and 4 above, the olefin polymer of Example 3, which falls within the scope of the present invention, suppressed gel formation and exhibited extremely high shear rates, indicating high-speed processability. The olefin polymer of Example 3 was similar to the commercial product (Control Example 1) in terms of gel level, but exhibited far superior high-speed processability. On the other hand, in Comparative Example 6, the number of gels increased significantly, making it impossible to measure the shear rate. In Comparative Example 7, the shear rate was excellent, but the number of gels increased compared to Example 3.

[0136] 1, the olefin polymer of Example 3 showed an inflection point in the Van Gurp-Palmen graph, unlike Comparative Examples 6 and 7 and Control Example 1. This indicates that the olefin polymer of Example 3 had long chain branches and that gel formation due to entanglement of these long chain branches was suppressed.

Claims

1. (a) at least one first transition metal compound selected from transition metal compounds represented by the following chemical formulas 1 to 4; (b) at least one second transition metal compound selected from transition metal compounds represented by the following chemical formula 5; and (c) a step of polymerizing ethylene and at least one alpha-olefin in the presence of a mixed metallocene catalyst containing a co-catalyst compound to obtain an olefin polymer, wherein the density of the olefin polymer is 0.930 to 0.970 g / cm ３ and the melt index (I) measured at 190°C under a load of 2.16 kg ２．１６ ) is 0.1 to 2.0 g / 10 min, the weight average molecular weight is 100,000 to 150,000 g / mol, and when measured with a capillary rheometer, melt fracture or shark skin phenomenon occurs, defined by the following mathematical formula 1, and the shear rate is 1,500 sec －１ The above is the method for producing an olefin polymer. [Equation 1] 【number】 In the above mathematical formula: [Equation 2] is the apparent shear rate (sec －１ ) and V is the volumetric flow (mm ３ / sec), R is the radius of the circular hole capillary (mm), In the above chemical formula, l1 and m1 are each independently an integer of 0 to 5; l2, l3, l4 and m2 each independently represent an integer of 0 to 4; m3 and m4 each independently represent an integer of 0 to 2, p is the oxidation state of M and is +3, +4 or +5; q is the formal charge of the YZL ligand and is 0, −1, −2, or −3; M is independently titanium (Ti), zirconium (Zr), or hafnium (Hf); X is independently a halogen, C １－２０ Alkyl, C ２－２０ Alkenyl, C ２－２０ Alkynyl, C ６－２０ Aryl, C １－２０ Alkyl C ６－２０ Aryl, C ６－２０ Aryl C １－２０ Alkyl, C １－２０ Alkylamide or C ６－２０ is an aryl amide, Each Q is independently carbon (C), silicon (Si), germanium (Ge), or tin (Sn); Q' is an anionic leaving group, and each Q' is independently hydrogen, substituted or unsubstituted C １－４０ Hydrocarbon group, substituted or unsubstituted C １－４０ a heterohydrocarbon group, a heteroatom, or a halogen; Q″ is a substituted or unsubstituted C ２－４ is an alkylene group, L is nitrogen; Y is nitrogen or phosphorus; Z is nitrogen or phosphorus; R １ ~R ４ , R ７ , R ８ , R １８ , R １９ are each independently substituted or unsubstituted C １－２０ Alkyl, substituted or unsubstituted C ２－２０ Alkenyl, substituted or unsubstituted C ６－２０ Aryl, substituted or unsubstituted C １－２０ Alkyl C ６－２０ Aryl, substituted or unsubstituted C ６－２０ Aryl C １－２０ Alkyl, substituted or unsubstituted C １－２０ Heteroalkyl, substituted or unsubstituted C ３－２０ Heteroaryl, substituted or unsubstituted C １－２０ Alkylamide, substituted or unsubstituted C ６－２０ Arylamide, or substituted or unsubstituted C １－２０ silyl, each of which independently connects adjacent groups to form a substituted or unsubstituted saturated or unsaturated C ４－２０ may or may not form a ring, R ５ , R ６ , R ９ and R １０ are each independently substituted or unsubstituted C １－２０ Alkyl, substituted or unsubstituted C １－２０ Alkenyl, substituted or unsubstituted C ６－２０ Aryl, substituted or unsubstituted C １－２０ Alkyl C ６－２０ Aryl, substituted or unsubstituted C ６－２０ Aryl C １－２０ Alkyl, substituted or unsubstituted C １－２０ Heteroalkyl, substituted or unsubstituted C ３－２０ Heteroaryl, substituted or unsubstituted C １－２０ Alkylamide, substituted or unsubstituted C ６－２０ Arylamide, or substituted or unsubstituted C １－２０ Cyril, but R ５ and R ６ , R ９ and R １０ are each independently linked to each other to form a substituted or unsubstituted saturated or unsaturated C ２－２０ may or may not form a ring, R １１ and R １２ are each independently C １－２０ a hydrocarbon group or a heteroatom-containing group, where the heteroatom is silicon, germanium, tin, lead, or phosphorus, or R １１ and R １２ may be linked together, R １３ is absent or hydrogen, C １－２０ alkyl, halogen or heteroatom-containing group; R １４ and R １５ are each independently an alkyl group, an aryl group, a substituted aryl group, a cyclic alkyl group, a substituted cyclic alkyl group, or a polycyclic ring system; R １６ and R １７ may each independently be absent, a hydrogen, an alkyl group, a halogen, a heteroatom, a hydrocarbon group, or a heteroatom-containing group.

2. 2. The method for producing an olefin polymer according to claim 1, wherein the molar ratio of the first transition metal compound to the second transition metal compound is in the range of 10:1 to 1:

10.

3. The method for producing an olefin polymer according to claim 1, wherein the transition metal compound of Chemical Formula 1 is at least one of transition metal compounds represented by the following Chemical Formulas 1-1 to 1-4, the transition metal compound of Chemical Formula 2 is at least one of transition metal compounds represented by the following Chemical Formulas 2-1 to 2-3, the transition metal compound of Chemical Formula 3 is a transition metal compound represented by the following Chemical Formula 3-1, and the transition metal compound of Chemical Formula 4 is a transition metal compound represented by the following Chemical Formula 4-1. 【Chemistry 2】 In the above chemical formula, n-Bu is n-butyl, t-Bu is t-butyl, and Ph is phenyl.

4. The method for producing an olefin polymer according to claim 1, wherein the transition metal compound of Chemical Formula 5 is a transition metal compound represented by the following Chemical Formula 5-1: 【Transformation 3】

5. The method for producing an olefin polymer according to claim 1, wherein the co-catalyst compound comprises at least one selected from the group consisting of compounds represented by the following chemical formula 6, compounds represented by the following chemical formula 7, and compounds represented by the following chemical formula 8: 【Chemistry 4】 [Chemical formula 8] [L-H] ＋ [Z(A) ４ ] － or [L] ＋ [Z(A) ４ ] － In the above chemical formula 6, n is an integer of 2 or more, and R ａ represents a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group having 1 to 20 carbon atoms substituted with a halogen atom, In the above formula 7, D is aluminum (Al) or boron (B), and R ｂ , R ｃ and R ｄ are each independently a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen-substituted hydrocarbon group having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms, In the above formula 8, L is a neutral or cationic Lewis base, [L-H] ＋ and [L] ＋ is a Bronsted acid, Z is a Group 13 element, and each A is independently a substituted or unsubstituted aryl group having 6 to 20 carbon atoms or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms.

6. 6. The method for producing an olefin polymer according to claim 5, wherein the compound represented by Chemical Formula 6 is at least one selected from the group consisting of methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, and butylaluminoxane.

7. 6. The method for producing an olefin polymer according to claim 5, wherein the compound represented by Chemical Formula 7 is at least one selected from the group consisting of 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, and tributylboron.

8. The compound represented by Chemical Formula 8 includes triethylammonium tetraphenylborate, tributylammonium tetraphenylborate, trimethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, trimethylammonium tetra(p-tolyl)borate, trimethylammonium tetra(o,p-dimethylphenyl)borate, tributylammonium tetra(p-trifluoromethylphenyl)borate, trimethylammonium tetra(p-trifluoromethylphenyl)borate, tributylammonium tetrapentafluorophenylborate, N,N-diethylanilinium tetraphenylborate, N,N-diethylanilinium tetrapentafluorophenylborate, diethylammonium tetrapentafluorophenylborate, triphenylphosphonium tetraphenylborate, trimethylphosphonium tetraphenylborate, triethylammonium tetraphenylaluminate, and tributylammonium tetraphenylborate. Aluminate, trimethylammonium tetraphenylaluminate, tripropylammonium tetraphenylaluminate, trimethylammonium tetra(p-tolyl)aluminate, tripropylammonium tetra(p-tolyl)aluminate, triethylammonium tetra(o,p-dimethylphenyl)aluminate, tributylammonium tetra(p-trifluoromethylphenyl)aluminate, trimethylammonium tetra(p-trifluoromethylphenyl)aluminate, tributylammonium tetrapentafluorophenylaluminate, N,N-diethylanilinium tetraphenylaluminate, N,N-diethylanilinium tetrapentafluorophenylaluminate, diethylammonium tetrapentatetraphenylaluminate, triphenylphosphonium tetraphenylaluminate, trimethylphosphonium tetraphenylaluminate, tripropylammonium tetra(p-tolyl)borate, triethylammonium tetra(o,The method for producing an olefin polymer according to claim 5, wherein the olefin is at least one selected from the group consisting of triphenylcarbonium tetra(p-dimethylphenyl)borate, triphenylcarbonium tetra(p-trifluoromethylphenyl)borate, and triphenylcarbonium tetrapentafluorophenylborate.

9. 2. The method for producing an olefin polymer according to claim 1, wherein the mixed metallocene catalyst further comprises a support supporting the mixed transition metal compound, the cocatalyst compound, or both.

10. The method for producing an olefin polymer according to claim 9, wherein the support comprises at least one selected from the group consisting of silica, alumina, and magnesia.

11. The method for producing an olefin polymer according to claim 9, wherein the total amount of the mixed transition metal compounds supported on the support is 0.001 to 1 mmole per 1 g of the support, and the total amount of the co-catalyst compounds supported on the support is 2 to 15 mmole per 1 g of the support.

12. The method for producing an olefin polymer according to claim 1, wherein the alpha-olefin is at least one selected from the group consisting of propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, and 1-hexadecene.

13. The method for producing an olefin polymer according to claim 12, wherein the alpha-olefin is 1-hexene.

14. 2. The method for producing an olefin polymer according to claim 1, wherein the polymerization of ethylene and at least one alpha-olefin is carried out by gas phase polymerization.

15. The process for producing an olefin polymer according to claim 14, wherein the polymerization of ethylene and at least one alpha-olefin is carried out in a gas-phase fluidized bed reactor.

16. An olefin polymer produced by the method for producing an olefin polymer according to any one of claims 1 to 15, having a density of 0.930 to 0.970 g / cm ３ and the melt index (I) measured at 190°C under a load of 2.16 kg ２．１６ ) is 0.1 to 2.0 g / 10 min, the weight average molecular weight is 100,000 to 150,000 g / mol, and when measured with a capillary rheometer, melt fracture or shark skin phenomenon occurs, defined by the following mathematical formula 1, and the shear rate is 1,500 sec －１ The olefin polymer is as described above. [Equation 3] In the above mathematical formula: [Equation 4] V, R are as defined in claim 1.

17. Melt index (I) measured at 190°C under a load of 21.6 kg ２１．６ ) and the melt index (I) measured under a load of 2.16 kg ２．１６ 17. The olefin polymer according to claim 16, wherein the melt flow ratio (MFR) is 30 to 200.

18. The olefin-based polymer according to claim 16, wherein an inflection point exists when the olefin-based polymer is plotted on a Van Gurp-Palmen graph.

19. The olefin polymer according to claim 16, wherein, when the olefin polymer is blown into a film having a thickness of 30 to 60 μm, the gel index, defined as the number of gels having a size of 0.05 mm or more present in an arbitrary 5 cm × 5 cm film area, is 1 or less.

20. The olefin polymer according to claim 16, wherein the olefin polymer film is produced by molding the olefin polymer, and when the olefin polymer is blown into a film having a thickness of 30 to 60 μm, the gel index, defined as the number of gels having a size of 0.05 mm or more present in an arbitrary 5 cm × 5 cm film area, is 1 or less.

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