METHOD FOR PRODUCING OLEFIN POLYMER AND OLEFIN POLYMER PRODUCED USING THE SAME

Abstract

The present invention relates to a method for producing an olefin polymer and an olefin polymer produced using the same. The method for producing an olefin polymer according to an embodiment of the present invention can adjust the processability of the olefin polymer produced using the same depending on the polymerization temperature.

Description

[Technical Field]

[0001] The present invention relates to a method for producing an olefin polymer and an olefin polymer produced using the same. Specifically, the present invention relates to a method for producing an olefin polymer in which processability can be adjusted depending on the polymerization temperature and an olefin polymer produced using the same. [Background technology]

[0002] Metallocene catalysts, one of the catalysts used to polymerize olefins, are compounds in which ligands such as cyclopentadienyl, indenyl, or cycloheptadienyl are coordinated to a transition metal or a transition metal halide, and have a sandwich structure as their basic structure.

[0003] In contrast to Ziegler-Natta catalysts, another catalyst used to polymerize olefins, in which 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, metallocene catalysts are known as single-site catalysts, in that all active sites have the same polymerization properties because they are a single compound with a uniform structure. Polymers polymerized with such metallocene catalysts have narrow molecular weight distributions, uniform comonomer distributions, and higher copolymerization activity than Ziegler-Natta catalysts.

[0004] Meanwhile, linear low-density polyethylene (LLDPE) is produced by copolymerizing ethylene and alpha-olefins at low pressure using a polymerization catalyst. It has a narrow molecular weight distribution, short chain branches (SCB) of a certain length, and generally no long chain branches (LCB). In addition to the properties of regular polyethylene, films made from linear low-density polyethylene have high breaking strength and elongation, as well as excellent tear strength and impact strength. As a result, they are widely used in stretch films and overlap films, where existing low-density polyethylene and high-density polyethylene are difficult to use.

[0005] However, linear low density polyethylene produced using a metallocene catalyst has poor processability due to its narrow molecular weight distribution, and films produced therefrom tend to have poor heat seal properties.

[0006] Therefore, there is a demand for a method for producing an olefin polymer that allows the processability to be adjusted as needed. Summary of the Invention [Problem to be solved by the invention]

[0007] An object of the present invention is to provide a method for producing an olefin polymer, which allows the processability to be adjusted depending on the polymerization temperature.

[0008] Another object of the present invention is to provide an olefin polymer produced by the above production method. [Means for solving the problem]

[0009] According to one embodiment of the present invention, there is provided a method for producing an olefin polymer by polymerizing an olefin monomer at a polymerization temperature of 70 to 90°C in the presence of a hybrid catalyst comprising at least one first transition metal compound represented by the following chemical formula 1 and at least one second transition metal compound selected from the group consisting of a compound represented by the following chemical formula 2 and a compound represented by the following chemical formula 3, wherein (1) the density of the olefin polymer is 0.915 to 0.935 g / cm 3 (2) Melt index (MI) measured at 190°C under a load of 2.16 kg 2.16 ) is 0.5 to 1.5 g / 10 min, and (3) the melt index (MI) measured at 190°C under a load of 21.6 kg 21.6 ) and melt index (MI) measured under a load of 2.16 kg. 2.16 The melt flow ratio (MFR) of the olefin polymer satisfies the following mathematical formula 1: [Mathematical formula 1] -0.4T+53.7 <MFR<-0.4T+55.7 [ka] [ka] [ka] In the mathematical formula, MFR is the melt index ratio, T is the polymerization temperature (°C), M1 and M2 are different from each other and each independently represent titanium (Ti), zirconium (Zr), or hafnium (Hf), and X is each independently represent 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, R1~R 10are each independently hydrogen, 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, substituted or unsubstituted C 1-20 Alkylidene, or substituted or unsubstituted C 1-20 Cyril, R1 to R 10 each independently represents a substituted or unsubstituted saturated or unsaturated C 4-20 A ring may be formed.

[0010] In an embodiment of the present invention, M1 and M2 are different from each other and each is zirconium or hafnium, and X is each halogen or C. 1-20 alkyl, and R to R 10 are hydrogen, substituted or unsubstituted C 1-20 Alkyl, substituted or unsubstituted C 1-20 Alkenyl, or substituted or unsubstituted C 6-20 It may also be aryl.

[0011] In a preferred embodiment of the present invention, M1 is hafnium, M2 is zirconium, and X may be chlorine or methyl.

[0012] In a preferred embodiment of the present invention, the first transition metal compound may be at least one of the transition metal compounds represented by the following chemical formulas 1-1 and 1-2, and the second transition metal compound may be at least one of the transition metal compounds represented by the following chemical formulas 2-1, 2-2, and 3-1. [ka] [ka] [ka] [ka] [ka]

[0013] In the above chemical formula, Me is a methyl group.

[0014] In an embodiment of the present invention, the molar ratio of the secondary transition metal compound to the first transition metal compound ranges from 100:1 to 1:100.

[0015] In an embodiment of the present invention, the catalyst may further comprise at least one promoter compound selected from the group consisting of compounds represented by the following Chemical Formula 4, compounds represented by the following Chemical Formula 5, and compounds represented by the following Chemical Formula 6: [ka] [ka] [Chemical formula 6] [LH] + [Z(A)4] - or [L] + [Z(A)4] - In the above Chemical Formula 4, n is an integer of 2 or more, and R a is a halogen atom, C 1-20 C substituted with hydrocarbon or halogen groups 1-20 is a hydrocarbon group, In the above Chemical Formula 5, D is aluminum (Al) or boron (B), and R b , R c and R d are each independently a halogen atom, C1-20 Hydrocarbon groups, halogen-substituted C 1-20 Hydrocarbon group or C 1-20 is an alkoxy group, In the formula 6, 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 C 6-20 an aryl group or a substituted or unsubstituted C 1-20 It is an alkyl group.

[0016] In an embodiment of the present invention, the catalyst may further comprise a support supporting the transition metal compound, the promoter compound, or both.

[0017] In a preferred embodiment of the present invention, the support may comprise at least one selected from the group consisting of silica, alumina, and magnesia.

[0018] Here, the total amount of the 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.

[0019] In a specific example of the present invention, the olefin polymer is a copolymer of an olefin monomer and an olefin comonomer. Specifically, the olefin monomer may be ethylene, and the olefin comonomer 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 olefin polymer is a linear low-density polyethylene in which the olefin monomer is ethylene and the olefin comonomer is 1-hexene.

[0020] In an embodiment of the present invention, the polymerization of the olefinic monomer may be carried out by gas phase polymerization, specifically, the polymerization of the olefinic monomer may be carried out in a gas phase fluidized bed reactor.

[0021] According to one embodiment of the present invention, a sintered body produced by the above-described production method has (1) a density of 0.915 to 0.935 g / cm 3 (2) Melt index (MI) measured at 190°C under a load of 2.16 kg 2.16 ) is 0.5 to 1.5 g / 10 min.

[0022] In a specific example of the present invention, the olefin polymer (1) has a viscosity of 0.915 to 0.925 g / cm 3 and (2) a melt index of 0.8 to 1.2 g / 10 min when measured at 190° C. under a load of 2.16 kg.

[0023] In an embodiment of the present invention, the olefin polymer may be produced such that a film having a thickness of 50 μm, when measured according to ASTM D1709, has a drop impact strength (unit: g) that satisfies the following mathematical formula 2: [Mathematical formula 2] -1.8T 2 +275T-9830<Drop impact strength<-1.8T 2 +275T-9730 In the above mathematical formula, T is the polymerization temperature (°C). [Effects of the Invention]

[0024] The method for producing an olefin polymer according to an embodiment of the present invention can adjust the processability of the olefin polymer depending on the polymerization temperature. [Brief explanation of the drawings]

[0025] [Figure 1] 1 is a graph showing the change in MFR depending on the polymerization temperature in a production method for an olefin polymer according to an embodiment of the present invention. [Figure 2]1 is a graph showing the change in drop impact strength depending on the polymerization temperature in a method for producing an olefin polymer according to an embodiment of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0026] The present invention will now be described in more detail.

[0027] Method for producing olefin polymer According to one embodiment of the present invention, there is provided a method for producing an olefin polymer by polymerizing an olefin monomer at a polymerization temperature of 70 to 90°C in the presence of a hybrid catalyst comprising at least one first transition metal compound represented by the following chemical formula 1 and at least one second transition metal compound selected from the group consisting of a compound represented by the following chemical formula 2 and a compound represented by the following chemical formula 3, wherein (1) the density of the olefin polymer is 0.915 to 0.935 g / cm 3 (2) Melt index (MI) measured at 190°C under a load of 2.16 kg 2.16 ) is 0.5 to 1.5 g / 10 min, and (3) the melt index (MI) measured at 190°C under a load of 21.6 kg 21.6 ) and melt index (MI) measured under a load of 2.16 kg. 2.16 The melt flow ratio (MFR) of the olefin polymer satisfies the following mathematical formula 1:

[0028] [Mathematical formula 1] -0.4T+53.7 <MFR<-0.4T+55.7

[0029] [ka]

[0030] [ka]

[0031] [ka]

[0032] In the above mathematical formula, MFR is the melt index ratio and T is the polymerization temperature (°C).

[0033] In Chemical Formulas 1 to 3, M1 and M2 are different from each other and each independently represent titanium (Ti), zirconium (Zr), or hafnium (Hf). Specifically, M1 and M2 may be different from each other and each independently represent zirconium or hafnium. Preferably, M1 may be hafnium, and M2 may be zirconium.

[0034] 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, X is a halogen or C 1-20 It may be alkyl. Preferably, X may be chlorine or methyl.

[0035] R1~R 10 are each independently hydrogen, 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, substituted or unsubstituted C 1-20Alkylidene, or substituted or unsubstituted C 1-20 silyl, where R to R 10 each independently represents a substituted or unsubstituted saturated or unsaturated C 4-20 Specifically, R to R 10 are hydrogen, substituted or unsubstituted C 1-20 Alkyl, substituted or unsubstituted C 1-20 Alkenyl, or substituted or unsubstituted C 6-20 It may also be aryl.

[0036] In an embodiment of the present invention, M1 and M2 are different from each other and each is zirconium or hafnium, and X is each halogen or C 1-20 alkyl, and R to R 10 are hydrogen, substituted or unsubstituted C 1-20 Alkyl, substituted or unsubstituted C 1-20 Alkenyl, or substituted or unsubstituted C 6-20 It may also be aryl.

[0037] In a preferred embodiment of the present invention, M1 is hafnium, M2 is zirconium, and X may be chlorine or methyl.

[0038] In a preferred embodiment of the present invention, the first transition metal compound may be at least one of the transition metal compounds represented by the following chemical formulas 1-1 and 1-2, and the second transition metal compound may be at least one of the transition metal compounds represented by the following chemical formulas 2-1, 2-2, and 3-1.

[0039] [ka]

[0040] [ka]

[0041] [ka]

[0042] [ka]

[0043] [ka]

[0044] In the above chemical formula, Me is a methyl group.

[0045] In a specific example of the present invention, the molar ratio of the second transition metal compound to the first transition metal compound is in the range of 100:1 to 1:100. Preferably, the molar ratio of the second transition metal compound to the first transition metal compound is in the range of 50:1 to 1:50. More preferably, the molar ratio of the second transition metal compound to the first transition metal compound is in the range of 10:1 to 1:10.

[0046] In an embodiment of the present invention, the catalyst may further comprise at least one promoter compound selected from the group consisting of compounds represented by the following Chemical Formula 4, compounds represented by the following Chemical Formula 5, and compounds represented by the following Chemical Formula 6:

[0047] [ka]

[0048] In the above Chemical Formula 4, n is an integer of 2 or more, and R a is a halogen atom, C 1-20 Hydrocarbon or halogen-substituted C 1-20 Specifically, R a may be methyl, ethyl, n-butyl or isobutyl.

[0049] [ka]

[0050] In the above Chemical Formula 5, D is aluminum (Al) or boron (B), and R b , R c and R d are each independently a halogen atom, C 1-20 Hydrocarbon groups, halogen-substituted C 1-20 Hydrocarbon group or C 1-20 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.

[0051] [Chemical formula 6] [LH] + [Z(A)4] - or [L] + [Z(A)4] -

[0052] In the formula 6, 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 C 6-20 an aryl group or a substituted or unsubstituted C 1-20 It is an alkyl group. Specifically, [LH] + may be a dimethylanilinium cation, [Z(A)4] - is [B(C6F5)4] - [L] + is [(C6H5)3C] + may be.

[0053] Specifically, examples of the compound represented by Chemical Formula 4 include methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, and butylaluminoxane, and methylaluminoxane is preferred, but is not limited thereto.

[0054] Examples of the compound represented by Chemical Formula 5 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.

[0055] Examples of the compound represented by Chemical Formula 6 include triethylammonium tetraphenylboron, tributylammonium tetraphenylboron, trimethylammonium tetraphenylboron, tripropylammonium tetraphenylboron, trimethylammonium tetra(p-tolyl)boron, trimethylammonium tetra(o,p-dimethylphenyl)boron, tributylammonium tetra(p-trifluoromethylphenyl)boron, trimethylammonium tetra(p-trifluoromethylphenyl)boron, tributylammonium tetrapentafluorophenylboron, N,N-diethylanilinium tetraphenylboron, N,N-diethylanilinium tetrapentafluorophenylboron, diethylammonium tetrapentafluorophenylboron, triphenylphosphonium tetraphenylboron, trimethylphosphonium tetraphenylboron, triethylammonium tetraphenylaluminum, tributylammonium tetraphenylaluminum, trimethylammonium tetraphenylaluminum, tripropylammonium tetra Examples of suitable aluminum compounds include phenylaluminum, trimethylammonium tetra(p-tolyl)aluminum, tripropylammonium tetra(p-tolyl)aluminum, triethylammonium tetra(o,p-dimethylphenyl)aluminum, tributylammonium tetra(p-trifluoromethylphenyl)aluminum, trimethylammonium tetra(p-trifluoromethylphenyl)aluminum, tributylammonium tetrapentafluorophenylaluminum, N,N-diethylanilinium tetraphenylaluminum, N,N-diethylanilinium tetrapentafluorophenylaluminum, diethylammonium tetrapentatetraphenylaluminum, triphenylphosphonium tetraphenylaluminum, trimethylphosphonium tetraphenylaluminum, tripropylammonium tetra(p-tolyl)boron, triethylammonium tetra(o,p-dimethylphenyl)boron, triphenylcarbonium tetra(p-trifluoromethylphenyl)boron, and triphenylcarbonium tetrapentafluorophenylboron.

[0056] In an embodiment of the present invention, the catalyst may further comprise a support supporting the transition metal compound, the co-catalyst compound, or both. Specifically, the support may support both the transition metal compound and the co-catalyst compound.

[0057] The support may include a material containing hydroxyl groups on its surface. Preferably, a material 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 NaO, KCO, BaSO, and Mg(NO)2. These may also contain carbon, zeolite, magnesium chloride, and the like. However, the support is not limited to these materials and may be any material capable of supporting a transition metal compound and a promoter compound.

[0058] 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.

[0059] The micropore volume of the support may be 0.1 to 10 cc / g, preferably 0.5 to 5 cc / g, and more preferably 1.0 to 3.0 cc / g.

[0060] 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.

[0061] In a preferred embodiment of the present invention, the support may be silica. Here, the silica may be dried at a temperature of 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, the amount of moisture will be too high, causing a reaction between the moisture on the surface and the promoter compound, and if the drying temperature is more than 900°C, the structure of the support may collapse.

[0062] The concentration of hydroxy groups 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 concentration of hydroxy groups is less than 0.1 mmole / g, the amount of the first promoter compound supported will be low, and if it exceeds 5 mmole / g, the catalyst component may become inactive.

[0063] The total amount of the transition metal compound supported on the support may be 0.001 to 1 mmole per 1 g of support. When the ratio of the transition metal compound to the support satisfies the above range, the supported catalyst exhibits appropriate activity, which is advantageous in terms of maintaining the activity of the catalyst and being economical.

[0064] 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 catalytic activity and economy.

[0065] One or more types of supports may be used. For example, both the transition metal compound and the co-catalyst compound may be supported on one support, or the transition metal compound and the co-catalyst compound may be supported on two or more supports, respectively. Alternatively, only one of the transition metal compound and the co-catalyst compound may be supported on a support.

[0066] As a method for supporting a transition metal compound and / or a cocatalyst compound that can be used in an olefin polymerization catalyst, a physical adsorption method or a chemical adsorption method can be used.

[0067] For example, the physical adsorption method may be a method in which a solution in which a transition metal compound is dissolved is brought into contact with a support and then dried; a method in which a solution in which a transition metal compound and a promoter compound are dissolved is brought into contact with a support and then dried; or a method in which a solution in which a transition metal compound is dissolved is brought into contact with a support and then dried to produce a support on which the transition metal compound is supported, and separately a solution in which a promoter compound is dissolved is brought into contact with a support and then dried to produce a support on which the promoter compound is supported, and then these are mixed together.

[0068] The chemical adsorption method may be a method in which a promoter compound is first supported on the surface of a support, and then a transition metal compound is supported on the promoter compound, or a method in which the catalyst compound is covalently bonded to a functional group on the surface of the support (for example, in the case of silica, a hydroxy group (—OH) on the surface of the silica).

[0069] In an embodiment of the present invention, the olefin polymer may be polymerized by a polymerization reaction such as, but not limited to, free radical, cationic, coordination, condensation, or addition.

[0070] In one 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, specifically, the polymerization of the olefin monomer may be carried out in a gas phase fluidized bed reactor.

[0071] When the olefin polymer is produced by a solution polymerization method or a slurry polymerization method, examples of the solvent 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.

[0072] olefin polymer According to an embodiment of the present invention, a sintered body produced by the above-described production method has a density of 0.915 to 0.935 g / cm 3 (2) Melt index (MI) measured at 190°C under a load of 2.16 kg 2.16 ) is 0.5 to 1.5 g / 10 min.

[0073] In a specific example of the present invention, the olefin polymer has a density of 0.915 to 0.935 g / cm 3 Preferably, the density of the olefin polymer is 0.915 to 0.925 g / cm 3 may be.

[0074] In an embodiment of the present invention, the olefin polymer has a melt index (MI) 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 may preferably be 0.8 to 1.2 g / 10 min.

[0075] In an embodiment of the present invention, the olefin-based polymer may be a homopolymer of an olefin-based monomer or a copolymer of an olefin-based monomer and a comonomer. Preferably, the olefin-based polymer is a copolymer of an olefin-based monomer and an olefin-based comonomer.

[0076] Here, the olefin monomer is C 2-20 Alpha-olefin (α-olefin), C 1-20 Diolefin, C 3-20 Cycloolefin and C 3-20 At least one selected from the group consisting of cyclodiolefins.

[0077] 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 above-exemplified olefin monomers, or a copolymer containing two or more of them.

[0078] In an exemplary embodiment, the olefin-based polymer is a copolymer of ethylene and C 3-20 The olefin polymer may be a copolymer in which an alpha-olefin is copolymerized, and preferably a linear low-density polyethylene in which the olefin monomer of the olefin polymer is ethylene and the olefin comonomer is 1-hexene.

[0079] 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.

[0080] In an embodiment of the present invention, the olefin polymer may have a drop impact strength (unit: g) of a film produced therefrom having a thickness of 50 μm, which satisfies the following mathematical formula 2 when measured according to ASTM D1709:

[0081] [Mathematical formula 2] -1.8T 2 +275T-9830<Drop impact strength<-1.8T 2 +275T-9730

[0082] In the above mathematical formula, T is the polymerization temperature (°C).

[0083] It is understood that the processability and molecular weight distribution of the olefin polymer according to the embodiment of the present invention can be adjusted depending on the polymerization temperature, and the drop impact strength of the film produced thereby can also be adjusted depending on the polymerization temperature.

[0084] In embodiments of the present invention, the olefin polymer film can be effectively used as a stretch film, an overwrap film, a lamination, a silage wrap, an agricultural film, and the like.

[0085] In the present invention, the method for forming a film from the olefin polymer according to the embodiment of the present invention is not particularly limited, and any forming 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.

[0086] Example Manufacturing example The transition metal compound of formula 1-2 (dimethylbis(n-propylcyclopentadienyl)hafnium dichloride) and the transition metal compound of formula 3-1 ((pentamethylcyclopentadienyl)(n-propylcyclopentadienyl)zirconium dichloride) were purchased from MCN and used without further purification.

[0087] Manufacturing Example 1 4.07 g of the transition metal compound of formula 1-2 and 1.68 g of the transition metal compound of formula 3-1 were added to 892 g of a 10% toluene solution of methylaluminoxane and stirred at room temperature for 1 hour. After the reaction was completed, the solution was added to 200 g of silica (XPO-2402), and then 1.5 L of toluene was added and stirred at 70°C for 2 hours. After the catalyst was completely supported, it was washed three times with 500 ml of toluene and dried overnight in a vacuum at 60°C to obtain 280 g of powdered supported catalyst.

[0088] Examples 1 to 3 Using a continuous gas-phase fluidized bed reactor, an ethylene / 1-hexene copolymer was produced in the presence of the supported catalyst obtained in Production Example 1. The ethylene partial pressure in the reactor was about 15 kg / cm. 2 and the polymerization temperature was maintained as shown in Table 1 below.

[0089] The polymerization conditions for the above examples are shown in Table 1 below.

[0090] [Table 1]

[0091] Comparative Examples 1 to 3 For comparison, Hanwha Solutions' linear low density polyethylene M1810HN was produced under the same polymerization conditions as in Examples 1 to 3.

[0092] Test Example The physical properties of the olefin polymers of the above examples were measured according to the following methods and standards, and the results are shown in Table 2 below and in Figures 1 and 2.

[0093] (1)density Measurement was carried out in accordance with ASTM D1505.

[0094] (2) Melt index and melt flow ratio (MFR) According to ASTM D1238, the melt index was measured at 190°C under a load of 21.6 kg and a load of 2.16 kg, and the ratio (MI 21.6 / MI 2.16 ) was sought.

[0095] (3) Drop impact strength Each resin in the examples and comparative examples was extruded into a 50 μm thick film using a 40 mm blown film extruder (40 mm Φ screw, 75 mm Φ die, 2 mm die gap) under the following extrusion conditions: C1 / C2 / C3 / A / D1 / D2 = 160 / 165 / 170 / 175 / 180 / 180 °C, screw speed 60 rpm, and blow-up ratio (BUR) 2.

[0096] The drop impact strength of the produced film was measured according to ASTM D1709(B) method, in which a 50 μm thick film was fixed and then a weight with a diameter of 38.10±0.13 mm was dropped from a height of 0.66±0.01 m.

[0097] [Table 2] [Industrial Applicability]

[0098] As can be seen from Table 2 and Figures 1 and 2, the process for producing an olefin polymer according to an embodiment of the present invention can adjust the processability of the olefin polymer produced therefrom depending on the polymerization temperature. Furthermore, the process for producing an olefin polymer according to an embodiment of the present invention can also adjust the drop impact strength of the final film depending on the polymerization temperature.

Claims

1. The method includes a step of polymerizing an olefin-based monomer at a polymerization temperature of 70 to 90°C in the presence of a hybrid catalyst supported on a carrier, the hybrid catalyst comprising at least one first transition metal compound represented by the following chemical formula 1 and at least one second transition metal compound selected from a compound represented by the following chemical formula 2 and a compound represented by the following chemical formula 3, to obtain an olefin-based polymer, wherein (1) the density of the olefin-based polymer is 0.915 to 0.935 g / cm ３ (2) Melt Index (MI) measured at 190°C under a load of 2.16 kg ２．１６ (3) a melt index (MI) measured at 190°C under a load of 21.6 kg; ２１．６ ) and melt index (MI) measured under a load of 2.16 kg. ２．１６ ) ratio (melt flow ratio, MFR) satisfies the following mathematical formula 1: the first transition metal compound is at least one of transition metal compounds represented by the following chemical formulas 1-1 and 1-2, and the second transition metal compound is at least one of transition metal compounds represented by the following chemical formulas 2-1, 2-2, and 3-1, the support comprises at least one selected from the group consisting of silica, alumina, and magnesia; The method for producing an olefin polymer, wherein the polymerization of the olefin monomer is carried out by gas phase polymerization. [Mathematical formula 1] -0.4T+53.7<MFR<-0.4T+55.7 【Chemical 1】 【Chemistry 2】 【Chemistry 3】 In the above mathematical formula, MFR is the melt index ratio, T is the polymerization temperature (°C), and in the above chemical formula, M １ and M ２ are different from each other and each independently represent 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, R １ ~R １０ are each independently hydrogen, 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, substituted or unsubstituted C １－２０ Alkylidene, or substituted or unsubstituted C １－２０ Cyril and R １ ~R １０ each independently represents a substituted or unsubstituted saturated or unsaturated C ４－２０ A ring may be formed. 【Chemistry 4】 【Chemistry 5】 【Chemistry 6】 【Chemistry 7】 【Chemistry 8】 In the above chemical formula, Me is a methyl group.

2. The method for producing an olefin polymer according to claim 1, wherein the molar ratio of the second transition metal compound to the first transition metal compound is in the range of 100:1 to 1:

100.

3. A method for producing an olefin-based polymer as described in claim 1, wherein the catalyst further contains at least one promoter compound selected from the group consisting of compounds represented by the following chemical formula 4, compounds represented by chemical formula 5, and compounds represented by chemical formula 6. 【Chemistry 9】 【Chemistry 10】 [Chemical formula 6] [L-H] ＋ [Z(A) ４ ] － or [L] ＋ [Z(A) ４ ] － In the above Chemical Formula 4, n is an integer of 2 or more, and R ａ is a halogen atom, C １－２０ C substituted with hydrocarbon group or halogen １－２０ is a hydrocarbon group, In the formula 5, D is aluminum (Al) or boron (B), and R ｂ , R ｃ and R ｄ are each independently a halogen atom, C １－２０ Hydrocarbon groups, halogen-substituted C １－２０ Hydrocarbon group or C １－２０ is an alkoxy group, In the formula 6, 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 C ６－２０ an aryl group or a substituted or unsubstituted C １－２０ It is an alkyl group.

4. The method for producing an olefin polymer according to claim 3, wherein the catalyst further comprises a carrier supporting the transition metal compound, the co-catalyst compound, or both.

5. A method for producing an olefin-based polymer as described in Claim 4, wherein the total amount of the 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.

6. A method for producing an olefin-based polymer as described in claim 1, wherein the olefin-based polymer is a copolymer of the olefin-based monomer and an olefin-based comonomer.

7. The method for producing an olefin polymer described in claim 6, wherein the olefin monomer is ethylene and the olefin comonomer 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.

8. A method for producing an olefin-based polymer as described in Claim 7, wherein the olefin-based polymer is a linear low-density polyethylene in which the olefin-based monomer is ethylene and the olefin-based comonomer is 1-hexene.

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