KR102619077B1 - Process for Preparing a Polyolefin - Google Patents

Abstract

The present invention relates to a method for producing olefinic polymers. Specifically, the present invention relates to a method for producing an olefin-based polymer that adjusts the physical properties of the olefin polymer through a method of supporting heterogeneous transition metal compounds. The method for producing an olefin polymer according to an embodiment of the present invention can control the physical properties of the olefin polymer through a method of supporting a heterogeneous transition metal compound.

Description

Method for producing olefinic polymer {Process for Preparing a Polyolefin}

The present invention relates to a method for producing olefinic polymers. Specifically, the present invention relates to a method for producing an olefin-based polymer that can control the physical properties of the olefin polymer through a method of supporting heterogeneous transition metal compounds.

A metallocene catalyst, one of the catalysts used to polymerize olefins, is a transition metal or transition metal halogen compound coordinated with a ligand such as cyclopentadienyl, indenyl, or cycloheptadienyl. As a combined compound, it has a sandwich structure in its basic form.

While the Ziegler-Natta catalyst, which is another catalyst used to polymerize olefins, has non-uniform active site properties because the metal component as the active site is dispersed on the inert solid surface, the metallocene catalyst has a constant structure. Since it is a single compound with , it is known as a single-site catalyst in which all active sites have the same polymerization characteristics. Polymers polymerized with such metallocene catalysts have narrow molecular weight distribution and uniform comonomer distribution.

Generally, metallocene catalysts are not active as polymerization catalysts by themselves, so they are used together with cocatalysts such as methylaluminoxane. By the action of the co-catalyst, the metallocene catalyst is activated to positive ions, and at the same time, the co-catalyst stabilizes the unsaturated cationic active species as an anion that is not coordinated to the metallocene catalyst, forming a catalyst system active in various olefin polymerizations.

These metallocene catalysts are easy to copolymerize and can control the three-dimensional structure of the polymer depending on the symmetry of the catalyst, and the polymers prepared from them have the advantage of narrow molecular weight distribution and uniform distribution of comonomers.

On the other hand, polymers prepared using metallocene catalysts have excellent mechanical strength due to narrow molecular weight distribution, but have the problem of low processability. To solve this problem, various methods have been proposed, such as changing the molecular structure of the polymer or broadening the molecular weight distribution. For example, in US Patent No. 5,272,236, the processability of the polymer was improved by using a catalyst that introduces a long chain branch (LCB) as a side branch into the main chain of the polymer, but there is a problem of low activity in the case of supported catalysts. do.

In order to solve these problems of single metallocene catalysts and to develop catalysts that have excellent activity and improved processability more easily, a method of supporting a mixture of metallocene catalysts (heterogeneous metallocene catalysts) with different characteristics has been adopted. presented. For example, in U.S. Patent No. 4,935,474, U.S. Patent No. 6,828,394, U.S. Patent No. 6,894,128, Republic of Korea Patent No. 1437509, and U.S. Patent No. 6,841,631, catalysts with different reactivity to comonomers are used to form bimodal catalysts. A method for producing a polyolefin having a molecular weight distribution is disclosed. Polyolefins with a heterogeneous molecular weight distribution prepared in this way have improved processability, but have lower homogeneity due to having different molecular weight distributions. Therefore, there is a problem that it is difficult to obtain a product with uniform physical properties after processing and the mechanical strength is reduced.

However, even in the case of polymerizing olefinic monomers using a metallocene catalyst using heterogeneous transition metal compounds, a method for producing olefinic polymers, especially linear low-density polyethylene, with various physical properties in a simple manner is still required. It is becoming.

US Patent No. 5,272,236 US Patent No. 4,935,474 US Patent No. 6,828,394 US Patent No. 6,894,128 Republic of Korea Patent No. 1437509 US Patent No. 6,841,631

The purpose of the present invention is to provide a method for producing an olefin-based polymer that can control the physical properties of the olefin polymer through a method of supporting heterogeneous transition metal compounds.

According to one embodiment of the present invention to achieve this object, (1) one of the first transition metal compound represented by Formula 1 below and the second transition metal compound represented by Formula 2 below as a first cocatalyst compound Obtaining an intermediate supported catalyst by mixing with and then contacting with a carrier; (2) contacting the other of the first transition metal compound and the second transition metal compound alone or together with the second cocatalyst compound with the intermediate supported catalyst obtained in step (1) to obtain a hybrid metallocene supported catalyst; and (3) polymerizing an olefinic monomer in the presence of the hybrid metallocene supported catalyst obtained in step (2), comprising: a first transition metal compound, a second transition metal compound, 1 By changing at least one of the supporting order and usage amount of the cocatalyst compound and the second cocatalyst compound, the melt index, melt rate ratio (MFR), weight average molecular weight (Mw), molecular weight distribution (PDI), and density of the olefin polymer are changed. A method for producing an olefin-based polymer that adjusts at least one physical property selected from the group is provided.

[Formula 1]

[Formula 2]

In the above formulas 1 and 2, M1 and M2 are each independently a transition metal of group 4 of the periodic table of elements;

_{X 1} to group, an arylalkyl group with 7 to 40 carbon atoms, an alkylamido group with 1 to 20 carbon atoms, or an arylamido group with 6 to 20 carbon atoms;

R ₁ to R ₆ and R ₉ to R ₁₄ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, or a substituted or unsubstituted carbon number 6 It is an aryl group of ~20 carbon atoms, a substituted or unsubstituted alkylaryl group of 7 to 40 carbon atoms, or a substituted or unsubstituted arylalkyl group of 7 to 40 carbon atoms, and may be connected to each other to form a ring;

R ₇ and R ₈ are each independently a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, substituted or unsubstituted It is a ringed alkylaryl group with 7 to 40 carbon atoms or a substituted or unsubstituted arylalkyl group with 7 to 40 carbon atoms, and can be connected to each other to form a ring;

The indene bonded to R ₁ to R ₆ and the indene bonded to R ₉ to R ₁₄ may have the same or different structures, and the indene bonded to R ₁ to R ₆ and the indene bonded to R ₉ to R ₁₄ may be They form a bridge structure where Si is connected to each other;

R ₁₅ to R ₂₆ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group with 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group with 2 to 20 carbon atoms, a substituted or unsubstituted aryl group with 6 to 20 carbon atoms, A substituted or unsubstituted alkylaryl group having 7 to 40 carbon atoms, or a substituted or unsubstituted arylalkyl group having 7 to 40 carbon atoms, which may be connected to each other to form a ring;

The cyclopentadiene bonded to R ₁₅ to R ₁₉ and the indene bonded to R ₂₀ to R ₂₆ are asymmetric structures with different structures, and the cyclopentadiene bonded to R ₁₅ to R ₁₉ and the indene bonded to R ₂₀ to R ₂₆ The indenes forming a non-bridged structure are not connected to each other.

Preferably, the first transition metal compound is rac-dimethylsilylbis(2-methyl-4-phenylindenyl)zirconium dichloride, dimethylsilyl{tetramethylcyclopentadienyl}{2-methyl-4-(4- t-butylphenyl)indenyl}zirconium dichloride, dimethylsilyl(tetramethylcyclopentadienyl)(2-methyl-4-phenylindenyl)zirconium dichloride and dimethylsilyl(tetramethylcyclopentadienyl)(4- and at least one selected from the group consisting of phenylindenyl)zirconium dichloride.

In addition, the second transition metal compound is [indenyl (cyclopentadienyl)] zirconium dichloride, [4-methylindenyl (cyclopentadienyl)] zirconium dichloride, [indenyl (tetramethylcyclopentadienyl) ]zirconium dichloride, [2-methylindenyl(tetramethylcyclopentadienyl)]zirconium dichloride, [2-methylbenzoindenyl(cyclopentadienyl)]zirconium dichloride and [4,5-benzoindenyl (Tetramethylcyclopentadienyl)] and at least one selected from the group consisting of zirconium dichloride.

More preferably, the first transition metal compound is rac-dimethylsilylbis(2-methyl-4-phenylindenyl)zirconium dichloride represented by Formula 1a below, and the second transition metal compound is represented by Formula 2a below [Indenyl (cyclopentadienyl)] may be zirconium dichloride.

[Formula 1a]

[Formula 2a]

In Formula 1a above, Me is a methyl group and Ph is a phenyl group.

Meanwhile, the first cocatalyst compound and the second cocatalyst compound may each include at least one selected from the group consisting of a compound represented by Formula 3, a compound represented by Formula 4, and a compound represented by Formula 5 below. .

[Formula 3]

[Formula 4]

[Formula 5]

[LH] ⁺ [Z(A) ₄ ] ^- or [L] ⁺ [Z(A) ₄ ] ^-

In the above formula (3), n is an integer of 2 or more, R _a is a halogen atom, a hydrocarbon group with 1 to 20 carbon atoms, or a hydrocarbon group with 1 to 20 carbon atoms substituted with halogen,

In the above formula 4, 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, or a halogen-substituted hydrocarbon group having 1 to 20 carbon atoms. It is a hydrocarbon group or an alkoxy group with 1 to 20 carbon atoms,

In the above formula 5, L is a neutral or cationic Lewis base, [LH] ⁺ and [L] ⁺ are Bronsted acids, Z is a group 13 element, and A is each independently substituted or unsubstituted carbon number 6 It is an aryl group of ~20 carbon atoms or a substituted or unsubstituted alkyl group of 1-20 carbon atoms.

Specifically, the compound represented by Formula 3 above is at least one selected from the group consisting of methylaluminoxane, ethyl aluminoxane, isobutyl aluminoxane, and butyl aluminoxane.

In addition, the compound represented by Formula 4 is trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, tripropyl aluminum, tributyl aluminum, dimethylchloroaluminum, triisopropyl aluminum, tri- s -butyl aluminum, tricyclopentyl aluminum, Tripentyl aluminum, triisopentyl aluminum, trihexyl aluminum, trioctyl aluminum, ethyldimethyl aluminum, methyldiethyl aluminum, triphenyl aluminum, tri- p -tolyl aluminum, dimethyl aluminum methoxide, dimethyl aluminum ethoxide, trimethyl boron. , triethyl boron, triisobutyl boron, tripropyl boron, and tributyl boron.

In addition, the compound represented by the above formula 5 is triethylammonium tetraphenyl borate, tributylammonium tetraphenyl borate, trimethylammonium tetraphenyl borate, tripropylammonium tetraphenyl borate, trimethylammonium tetra ( p -tolyl) Borate, trimethylammonium tetra ( o , p -dimethylphenyl)borate, tributylammonium tetra ( p -trifluoromethylphenyl)borate, trimethylammonium tetra ( p -trifluoromethylphenyl)borate, tributylammonium tetra Pentafluorophenyl borate, N,N-diethylanilinium tetraphenylborate, N,N-diethylanilinium tetrapentafluorophenylborate, diethylammonium tetrapentafluorophenylborate, triphenylphosphonium Tetraphenylborate, Trimethylphosphonium Tetraphenylborate, Triethylammonium Tetraphenyl Aluminate, Tributylammonium Tetraphenyl Aluminate, Trimethylammonium Tetraphenyl Aluminate, Tripropylammonium Tetraphenyl Aluminate, 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 tetrapentafluorophenyl aluminate, N,N-diethylaniliniumtetraphenylaluminate, N,N-diethyl Anilinium tetrapentafluorophenyl aluminate, diethylammonium tetrapentatetetraphenyl aluminate, triphenylphosphonium tetraphenylaluminate, trimethylphosphonium tetraphenylaluminate, tripropylammonium tetra( p -tolyl)borate , triethylammonium tetra ( o , p -dimethylphenyl)borate, triphenylcarbonium tetra ( p -trifluoromethylphenyl)borate and triphenylcarboniumtetrapentafluorophenylborate. There is at least one.

In a specific embodiment of the present invention, in step (2), the other of the first transition metal compound and the second transition metal compound may be contacted with the intermediate supported catalyst obtained in step (1) together with the second cocatalyst compound. .

Preferably, the first co-catalyst compound and the second co-catalyst compound are the same. More preferably, the first co-catalyst compound and the second co-catalyst compound are methylaluminoxane.

In a specific embodiment of the present invention, a first transition metal compound is used in step (1) and a second transition metal compound is used in step (2).

In a specific embodiment of the present invention, the carrier may include at least one selected from the group consisting of silica, alumina, and magnesia.

Preferably, the first transition metal compound, the second transition metal compound, the first cocatalyst compound, and the second cocatalyst compound may be supported on silica.

At this time, the total amount of the first and second transition metal compounds supported on the carrier is 0.001 to 1 mmole based on 1 g of the carrier, and the total amount of the cocatalyst compound supported on the carrier is 2 to 1 mmole based on 1 g of the carrier. It may be 15 mmole.

In a specific embodiment of the present invention, the first transition metal compound and the second transition metal compound may be used in a weight ratio of 20:1 to 1:20.

The method (2') for producing an olefin-based polymer according to an embodiment of the present invention may further include washing the hybrid metallocene supported catalyst obtained in step (2) above with a solvent and drying it.

In a specific embodiment of the present invention, the olefinic polymer is a homopolymer of an olefinic monomer or a copolymer of an olefinic monomer and an olefinic comonomer. Specifically, the olefinic monomer is ethylene, and the olefinic comonomer is propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1 -One or more selected from the group consisting of undecene, 1-dodecene, 1-tetradecene, and 1-hexadecene. Preferably, the olefinic polymer is a linear low density polyethylene wherein the olefinic monomer is ethylene and the olefinic comonomer is 1-hexene.

According to another embodiment of the present invention, an olefin-based polymer produced by the above olefin-based polymer production method is provided.

The method for producing an olefin polymer according to an embodiment of the present invention can control the physical properties of the olefin polymer through a method of supporting a heterogeneous transition metal compound.

Hereinafter, the present invention will be described in more detail.

The method for producing an olefin-based polymer according to an embodiment of the present invention is (1) mixing one of the first transition metal compound represented by Formula 1 below and the second transition metal compound represented by Formula 2 below as a first cocatalyst compound. Obtaining an intermediate supported catalyst by mixing with and then contacting with a carrier; (2) contacting the other of the first transition metal compound and the second transition metal compound alone or together with the second cocatalyst compound with the intermediate supported catalyst obtained in step (1) to obtain a hybrid metallocene supported catalyst; and (3) polymerizing the olefin-based monomer in the presence of the hybrid metallocene supported catalyst obtained in step (2).

Step (1)

In step (1) above, either the first transition metal compound represented by Formula 1 below or the second transition metal compound represented by Formula 2 below is mixed with the first cocatalyst compound and then contacted with a carrier to form an intermediate supported catalyst. get

Here, the first transition metal compound is represented by Formula 1 below, and the second transition metal compound is represented by Formula 2 below.

[Formula 1]

[Formula 2]

In the above formulas 1 and 2, M1 and M2 are each independently transition metals of group 4 of the periodic table of elements. Specifically, M1 and M2 may each independently be titanium (Ti), zirconium (Zr), or hafnium (Hf), and more specifically, zirconium (Zr).

_{X 1} to It is an alkylaryl group, an arylalkyl group with 7 to 40 carbon atoms, an alkylamido group with 1 to 20 carbon atoms, or an arylamido group with 6 to 20 carbon atoms. Specifically, X ₁ to X ₄ may each independently be a halogen, and more specifically, may be chlorine (Cl).

R ₁ to R ₆ , R ₉ to R ₁₄ and R ₁₅ to R ₂₆ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, or a substituted or an unsubstituted aryl group having 6 to 20 carbon atoms, a substituted or unsubstituted alkylaryl group having 7 to 40 carbon atoms, or a substituted or unsubstituted arylalkyl group having 7 to 40 carbon atoms, and may be connected to each other to form a ring. .

R ₇ and R ₈ are each independently a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, substituted or unsubstituted It is a ringed alkylaryl group with 7 to 40 carbon atoms or a substituted or unsubstituted arylalkyl group with 7 to 40 carbon atoms, and can be connected to each other to form a ring.

At this time, the indene bonded to R ₁ to R ₆ and the indene bonded to R ₉ to R ₁₄ may have the same or different structures, and the indene bonded to R ₁ to R ₆ and the indene bonded to R ₉ to R ₁₄ Indene forms a bridge structure where Si is connected to each other.

The cyclopentadiene bonded to R ₁₅ to R ₁₉ and the indene bonded to R ₂₀ to R ₂₆ are asymmetric structures with different structures, and the cyclopentadiene bonded to R ₁₅ to R ₁₉ and the indene bonded to R ₂₀ to R ₂₆ The indenes forming a non-bridged structure are not connected to each other.

Preferably, the first transition metal compound is rac-dimethylsilylbis(2-methyl-4-phenylindenyl)zirconium dichloride, dimethylsilyl{tetramethylcyclopentadienyl}{2-methyl-4-(4- t-butylphenyl)indenyl}zirconium dichloride, dimethylsilyl(tetramethylcyclopentadienyl)(2-methyl-4-phenylindenyl)zirconium dichloride and dimethylsilyl(tetramethylcyclopentadienyl)(4- It may include at least one selected from the group consisting of phenylindenyl)zirconium dichloride.

In addition, the second transition metal compound is [indenyl (cyclopentadienyl)] zirconium dichloride, [4-methylindenyl (cyclopentadienyl)] zirconium dichloride, [indenyl (tetramethylcyclopentadienyl) ]zirconium dichloride, [2-methylindenyl(tetramethylcyclopentadienyl)]zirconium dichloride, [2-methylbenzoindenyl(cyclopentadienyl)]zirconium dichloride and [4,5-benzoindenyl (Tetramethylcyclopentadienyl)] may contain at least one selected from the group consisting of zirconium dichloride.

More preferably, the first transition metal compound is rac-dimethylsilylbis(2-methyl-4-phenylindenyl)zirconium dichloride represented by Formula 1a below, and the second transition metal compound is represented by Formula 2a below [Indenyl (cyclopentadienyl)] may be zirconium dichloride.

[Formula 1a]

[Formula 2a]

In Formula 1a above, Me is a methyl group and Ph is a phenyl group.

Meanwhile, the first cocatalyst compound may include one or more of the compound represented by Formula 3, the compound represented by Formula 4, and the compound represented by Formula 5 below.

[Formula 3]

In Formula 3 above, n is an integer of 2 or more, and R _a may be a halogen atom, a hydrocarbon with 1 to 20 carbon atoms, or a hydrocarbon with 1 to 20 carbon atoms substituted with halogen. Specifically, R _a may be methyl, ethyl, n -butyl, or isobutyl.

[Formula 4]

In the above formula 4, 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, or a halogen-substituted hydrocarbon group having 1 to 20 carbon atoms. It is a hydrocarbon group or an alkoxy group with 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 are Each may be pentafluorophenyl.

[Formula 5]

[LH] ⁺ [Z(A) ₄ ] ^- or [L] ⁺ [Z(A) ₄ ] ^-

In the above formula 5, L is a neutral or cationic Lewis base, [LH] ⁺ and [L] ⁺ are Bronsted acids, Z is a group 13 element, and A is each independently substituted or unsubstituted carbon number 6 It is an aryl group with ~20 carbon atoms or a substituted or unsubstituted alkyl group with 1 to 20 carbon atoms. Specifically, [LH] ⁺ may be a dimethylanilinium cation, [Z(A) ₄ ] ^- may be [B(C ₆ F ₅ ) ₄ ] ^- , and [L] ⁺ may be [(C ₆ H ₅ ) ₃ C] ⁺ may be.

Examples of the compound represented by the above formula (3) include methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, and butylaluminoxane, and methylaluminoxane is preferred, but is not limited to these.

Examples of compounds represented by the above formula 4 include trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, tripropyl aluminum, tributyl aluminum, dimethylchloroaluminum, triisopropyl aluminum, tri- s -butyl aluminum, and tricyclopentyl aluminum. , tripentyl aluminum, triisopentyl aluminum, trihexyl aluminum, trioctyl aluminum, ethyldimethyl aluminum, methyldiethyl aluminum, triphenyl aluminum, tri- p -tolyl aluminum, dimethyl aluminum methoxide, dimethyl aluminum ethoxide, trimethyl Examples include boron, triethyl boron, triisobutyl boron, tripropyl boron, and tributyl boron, and trimethyl aluminum, triethyl aluminum, and triisobutyl aluminum are preferred, but are not limited to these.

Examples of compounds represented by the above formula 5 include triethylammonium tetraphenyl borate, tributylammonium tetraphenyl borate, trimethylammonium tetraphenyl borate, tripropylammonium tetraphenyl borate, and trimethylammonium tetra ( p -tolyl). Borate, trimethylammonium tetra ( o , p -dimethylphenyl)borate, tributylammonium tetra ( p -trifluoromethylphenyl)borate, trimethylammonium tetra ( p -trifluoromethylphenyl)borate, tributylammonium tetra Pentafluorophenyl borate, N,N-diethylanilinium tetraphenylborate, N,N-diethylanilinium tetrapentafluorophenylborate, diethylammonium tetrapentafluorophenylborate, triphenylphosphonium Tetraphenylborate, trimethylphosphonium tetraphenylborate, triethylammonium tetraphenyl aluminum, tributylammonium tetraphenyl aluminum, trimethylammonium tetraphenyl aluminum, tripropylammonium tetraphenyl aluminum, 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 tetrapentafluorophenyl aluminum, N,N-diethylanilinium tetraphenylaluminum, N,N-diethylaniliniumtetrapentafluorophenyl aluminum, di Ethylammonium tetrapentatetetraphenyl aluminum, triphenylphosphonium tetraphenylaluminum, trimethylphosphonium tetraphenylaluminum, tripropylammonium tetra( p -tolyl)borate, triethylammonium tetra( o , p -dimethylphenyl)borate , triphenylcarbonium tetra( p -trifluoromethylphenyl)borate, triphenylcarboniumtetrapentafluorophenylborate, etc.

In step (1), the process of mixing either the first transition metal compound or the second transition metal compound with the first cocatalyst compound may be performed in the presence of a solvent. At this time, the solvent is an aliphatic hydrocarbon solvent such as hexane or pentane, an aromatic hydrocarbon solvent such as toluene or benzene, a hydrocarbon solvent substituted with a chlorine atom such as dichloromethane, an ether-based solvent such as diethyl ether or tetrahydrofuran, acetone, or ethyl. It may be most organic solvents such as acetate, and preferably toluene or hexane, but is not particularly limited thereto.

In step (1), the process of mixing any one of the first transition metal compound and the second transition metal compound with the first cocatalyst compound is performed at a temperature of 0 to 100 ° C., preferably 10 to 80 ° C. You can.

Additionally, in step (1), either the first transition metal compound or the second transition metal compound is mixed with the first cocatalyst compound and then sufficiently stirred for 5 minutes to 24 hours, preferably 30 minutes to 3 hours. It is desirable to do so.

In step (1), a mixture of any one of the first transition metal compound and the second transition metal compound and the first cocatalyst compound may be supported on the carrier by contacting the carrier. As a result, an intermediate supported catalyst is obtained.

Here, the carrier may include a material containing a hydroxy group on the surface, and preferably a material having highly reactive hydroxy and siloxane groups that has been dried to remove moisture from the surface may be used. For example, the carrier may include at least one selected from the group consisting of silica, alumina, and magnesia. Specifically, silica dried at high temperature, silica-alumina, and silica-magnesia can be used as carriers, and they are usually oxides such as Na ₂ O, K ₂ CO ₃ , BaSO ₄ , and Mg(NO ₃ ) ₂ , may contain carbonate, sulfate, and nitrate components. Additionally, they may contain carbon, zeolite, magnesium chloride, etc. However, the carrier is not particularly limited to these.

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

The micropore volume of the carrier 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.

The specific surface area of the carrier may be 1 to 1,000 m2/g, preferably 100 to 800 m2/g, and more preferably 200 to 600 m2/g.

In a preferred embodiment, when the carrier 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℃, there is too much moisture and the moisture on the surface reacts with the co-catalyst compound, and if it exceeds 900℃, the structure of the carrier may collapse.

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 the hydroxy group is less than 0.1 mmole/g, the amount of co-catalyst compound supported is low, and if it exceeds 5 mmole/g, the problem of deactivation of the catalyst component may occur.

In step (1), the process of contacting a mixture of any one of the first transition metal compound and the second transition metal compound and the first cocatalyst compound with a carrier may be performed in the presence of a solvent. At this time, the specific details of the solvent are substantially the same as described above.

In step (1), the process of contacting the mixture of any one of the first transition metal compound and the second transition metal compound and the first cocatalyst compound with the carrier is carried out at a temperature of 0 to 100 ° C., preferably 10 to 80 ° C. It can be performed at any temperature.

Additionally, in step (1), the mixture of any one of the first transition metal compound and the second transition metal compound and the first cocatalyst compound is contacted with the carrier for 5 minutes to 24 hours, preferably 30 minutes to 3 hours. It is desirable to sufficiently stir it during this time.

Step (2)

In step (2) above, the other one of the first transition metal compound and the second transition metal compound, alone or together with the second cocatalyst compound, is brought into contact with the intermediate supported catalyst obtained in step (1) to form a hybrid metallocene supported catalyst. get

Preferably, in step (2), the other of the first transition metal compound and the second transition metal compound may be contacted with the intermediate supported catalyst obtained in step (1) together with the second cocatalyst compound.

In this case, the second cocatalyst compound may include one or more of the compound represented by Formula 3, the compound represented by Formula 4, and the compound represented by Formula 5. The specific details of the compounds represented by Formulas 3, 4, and 5 are substantially the same as those described in step (1) above.

In step (2), when the other of the first transition metal compound and the second transition metal compound is contacted with the intermediate supported catalyst obtained in step (1) together with the second cocatalyst compound, the order of contact is not important. Accordingly, the other of the first transition metal compound and the second transition metal compound and the second cocatalyst compound may be brought into contact with the intermediate supported catalyst obtained in step (1) in this order, in reverse order, or simultaneously.

In step (2), the process of contacting the other of the first transition metal compound and the second transition metal compound alone or together with the second cocatalyst compound with the intermediate supported catalyst obtained in step (1) is carried out in the presence of a solvent. It can be. At this time, the specific details of the solvent are substantially the same as described in step (1) above.

In step (2), the process of contacting the other of the first transition metal compound and the second transition metal compound alone or together with the second cocatalyst compound with the intermediate supported catalyst obtained in step (1) is carried out at a temperature of 0 to 100°C. It may be carried out at a temperature, preferably between 10 and 80°C.

Additionally, in step (2), the other of the first transition metal compound and the second transition metal compound is brought into contact with the intermediate supported catalyst obtained in step (1) alone or together with the second cocatalyst compound for 5 minutes. It is desirable to sufficiently stir it for 24 hours, preferably 30 minutes to 3 hours.

In specific embodiments of the present invention, the first co-catalyst compound and the second co-catalyst compound may be the same or different from each other. In a preferred embodiment, the first co-catalyst compound and the second co-catalyst compound may be the same. Specifically, the first co-catalyst compound and the second co-catalyst compound may be methylaluminoxane.

In a specific embodiment of the present invention, a first transition metal compound may be used in step (1) and a second transition metal compound may be used in step (2).

In a specific embodiment of the present invention, the first transition metal compound, the second transition metal compound, and the first cocatalyst compound may be supported on a single type of carrier. Specifically, the first transition metal compound, the second transition metal compound, and the first cocatalyst compound may be supported on silica.

Additionally, when a second cocatalyst compound is used, the first transition metal compound, the second transition metal compound, the first cocatalyst compound, and the second cocatalyst compound may be supported on a single type of carrier. Specifically, the first transition metal compound, the second transition metal compound, the first cocatalyst compound, and the second cocatalyst compound may be supported on silica.

At this time, the total amount of the first and second transition metal compounds supported on the carrier is 0.001 to 1 mmole based on 1 g of the carrier, and the total amount of the cocatalyst compound supported on the carrier is 2 to 1 mmole based on 1 g of the carrier. It may be 15 mmole.

The hybrid metallocene supported catalyst for olefin polymerization according to an embodiment of the present invention may include the first transition metal compound and the second transition metal compound in a weight ratio of 20:1 to 1:20. Preferably, the hybrid metallocene supported catalyst for olefin polymerization may include a first transition metal compound and a second transition metal compound in a weight ratio of 10:1 to 1:10. More preferably, the hybrid metallocene supported catalyst for olefin polymerization may include a first transition metal compound and a second transition metal compound in a weight ratio of 6:4 to 4:6. When the content ratio of the first transition metal compound and the second transition metal compound is within the above range, appropriate supported catalyst activity may be exhibited, which may be advantageous in terms of maintaining the activity of the catalyst and economic efficiency. In addition, olefin-based polymers produced in the presence of an olefin polymerization catalyst that satisfies the above range exhibit excellent processability, and films produced therefrom can exhibit excellent mechanical and optical properties.

Step (2')

The method for producing an olefin-based polymer according to an embodiment of the present invention may further include washing the hybrid metallocene supported catalyst obtained in step (2) with a solvent and drying it.

Specifically, the hybrid metallocene supported catalyst obtained in step (2) is allowed to stand for 3 minutes to 3 hours to precipitate the supported catalyst. Next, the supernatant is removed to separate the supported catalyst, washed with a solvent, and dried at a temperature of room temperature to 80°C for 6 to 48 hours to obtain the supported catalyst. Here, the solvent is substantially the same as described in step (1) above.

Step (3)

In step (3) above, olefin-based monomers are polymerized in the presence of the hybrid metallocene supported catalyst obtained in step (2).

The olefinic polymer obtained in step (3) may be a homopolymer of an olefinic monomer or a copolymer of an olefinic monomer and a comonomer.

Olefinic monomers include alpha-olefins with 2 to 20 carbon atoms, diolefins with 1 to 20 carbon atoms, cycloolefins with 3 to 20 carbon atoms, and cyclodiolefins with 3 to 20 carbon atoms. ) is at least one selected from the group consisting of.

For example, olefinic monomers include ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-undecene, -It may be dodecene, 1-tetradecene, or 1-hexadecene, and the olefin-based polymer may be a homopolymer containing only one type of the olefin-based monomer exemplified above, or a copolymer containing two or more types.

In a specific embodiment of the present invention, the olefin-based polymer may be a copolymer of ethylene and an alpha-olefin having 3 to 20 carbon atoms, and a copolymer of ethylene and 1-hexene is preferred, but is limited to these. That is not the case.

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

In a specific embodiment of the present invention, the olefin-based polymer may be polymerized, for example, by polymerization reactions such as free radical, cationic, coordination, condensation, addition, etc. However, it is not limited to these.

In specific embodiments of the present invention, the olefin-based polymer may be produced by gas phase polymerization, solution polymerization, or slurry polymerization. When the olefin-based polymer is produced by solution polymerization or slurry polymerization, examples of solvents that can be used include aliphatic hydrocarbon solvents with 5 to 12 carbon atoms such as pentane, hexane, heptane, nonane, decane, and isomers thereof; Aromatic hydrocarbon solvents such as toluene and benzene; Hydrocarbon solvents substituted with chlorine atoms, such as dichloromethane and chlorobenzene; and mixtures thereof, but are not limited thereto.

In the method for producing an olefin-based polymer according to an embodiment of the present invention, at least one of the loading order and usage amount of the first transition metal compound, the second transition metal compound, the first cocatalyst compound, and the second cocatalyst compound is changed. At least one physical property of the olefin polymer can be adjusted.

Specifically, by changing at least one of the loading order and usage amount of the first transition metal compound, the second transition metal compound, the first cocatalyst compound, and the second cocatalyst compound, the melt flow ratio and melt flow ratio of the olefin polymer are changed. ; MFR), weight average molecular weight (Mw), molecular weight distribution (PDI), and density can be adjusted.

In a specific embodiment of the present invention, the melt index ratio of the olefin polymer ( At least one of MFR), molecular weight distribution (PDI), and density can be adjusted.

According to another embodiment of the present invention, an olefin-based polymer produced by the above olefin-based polymer production method is provided.

Example

Hereinafter, the present invention will be described in more detail through examples and comparative examples. However, the examples below are only for illustrating the present invention, and the scope of the present invention is not limited to these only.

As a heterogeneous transition metal compound, the transition metal compound of formula 1a purchased from sPCI was used without additional purification, and the transition metal compound of formula 2a purchased from MCN was used without additional purification. As the first and second cocatalyst compounds, methylaluminoxane (MAO, 10% by weight toluene solution) was purchased from Lake Materials and used without further purification.

All examples and comparative examples were conducted under a nitrogen atmosphere while blocking contact between air and water. In the polymerization reaction, ethylene (C2), 1-hexene (1-C6), hexane (C6), hydrogen (H ₂ ), and nitrogen (N ₂ ) were all used after passing through a purification device.

Example One

50 mg of the transition metal compound (M1) of Chemical Formula 1a and 2.26 g of methylaluminoxane (MAO1) were added to a round glass reactor in a glove box (Al/M = 150), and stirred for 1 hour. Separately, 3.0 g of silica (SP2402, Grace Davison) was mixed with toluene (30 ml). The mixed solution (M1+MAO1) obtained above was injected into this silica slurry and stirred at 75°C for 1 hour (step (1)).

18 mg of the transition metal compound (M2) of Formula 2a and 9.03 g of methylaluminoxane (MAO2) were added to a round glass reactor in a glove box (Al/M = 150), and stirred for 1 hour. This mixed solution (M2+MAO2) was injected into the silica slurry mixed solution (M1+MAO1) obtained in step 1 and stirred at 75°C for 1 hour (step (2)).

The hybrid metallocene supported catalyst obtained in step 2 was washed three times with toluene (10 ml), the supernatant was removed, and dried in vacuum at room temperature for 30 minutes to obtain 3.7 g of pink powder.

Example 2

3.6 g of a hybrid metallocene supported catalyst was obtained in the same manner as in Example 1, except that the amount of MAO1 in step (1) was changed to 6.77 g and the amount of MAO2 in step (2) was changed to 4.51 g.

Example 3

In step (1), the amount of MAO1 was changed to 11.28 g, and in step (2), 3.7 g of a hybrid metallocene supported catalyst was obtained in the same manner as in Example 1, except that 10 g of toluene was used instead of MAO2.

Example 4

Hybrid metallocene was supported in the same manner as in Example 1, except that in step (1), the amount of MAO1 was changed to 13.54 g and the amount of silica was changed to 2.78 g, and in step (2), 10 g of toluene was used instead of MAO2. 3.1 g of catalyst was obtained.

Example 5

Example except that in step (1), the amount of MAO1 was changed to 11.23 g and the amount of M1 was changed to 41 mg, and in step (2), the amount of M2 was changed to 15 mg, and 10 g of toluene was used instead of MAO2. 3.3 g of a hybrid metallocene supported catalyst was obtained in the same manner as in 1.

Example 6

In step (1), the amount of MAO1 was changed to 10.03 g and the amount of M1 was changed to 41 mg, and in step (2), 10 g of toluene was used instead of MAO2. Hybrid metallocene was supported in the same manner as Example 1. 3.2 g of catalyst was obtained.

Comparative example One

Add 50 mg of the transition metal compound (M1) of the formula 1a, 18 mg of the transition metal compound (M2) of the formula 2a, and 11.28 g of methylaluminoxane (MAO) into a round glass reactor in the glove box (Al/M = 150). , and stirred for 1 hour. Separately, 3.0 g of silica (SP2402, Grace Davison) was mixed with toluene (30 ml). The mixed solution (M1+M2+MAO) obtained above was injected into this silica slurry and stirred at 75°C for 2 hours.

The obtained hybrid metallocene supported catalyst was washed three times with toluene (10 ml), the supernatant was removed, and dried at room temperature in vacuum for 30 minutes to obtain 3.5 g of pink powder.

Test example

An olefin-based polymer was prepared using each of the hybrid metallocene supported catalysts prepared in Examples 1 to 6 and Comparative Example 1 using a 2-liter autoclave reactor. 1 liter of hexane was added to the reactor, and 0.6 ml of 1M triisobutyl aluminum (TiBAL) was added as a scavenger. The amount of 1-hexene shown in Table 1 below was added to the reactor, and then 50 mg of a hybrid metallocene supported catalyst was added to the reactor.

While the polymerization reaction was in progress, the partial pressure of ethylene was maintained at 14 kgf/cm2 and hydrogen gas was added in the amount shown in Table 1 below. At this time, polymerization was performed for 1 hour while maintaining the reaction temperature at about 80°C. After drying the obtained olefin polymer at room temperature, its physical properties were measured using the method below. Specific polymerization conditions are shown in Table 1 below, and the physical property measurement results of the olefin-based polymer are shown in Table 2 below.

(1) Melt index and melt flow ratio (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 obtained.

(2) Molecular weight (Mw) and molecular weight distribution (PDI)

It was measured using gel permeation chromatography-FTIR (GPC-FTIR).

(3) Density

Measurements were made according to ASTM D1505.

catalyst
(mg) hydrogen
(cc/min) 1-hexene
(㎖) polymer yield
(g) catalytic activity
(gPE/gCat-hr) Example 1 50 5 5 221 4,420 Example 2 50 5 5 107 2,140 Example 3 50 5 5 200 4,000 Example 4-1 50 5 5 203 4,060 Example 4-2 50 20 0 103.5 2,070 Example 5-1 50 5 5 161 3,220 Example 5-2 50 15 0 143 2,860 Example 6-1 50 15 5 151 3,020 Example 6-2 50 15 0 144 2,880 Comparative Example 1-1 50 5 5 198 3,960 Comparative Example 1-2 50 10 5 126 3,520 Comparative Example 1-3 50 20 5 131 2,620

MI _2.16
(g/10 minutes) MFR Mw
(g/mole) PDI density
(g/cc) Example 1 0.23 83.6 107,062 5.6 0.9475 Example 2 0.19 150.6 194,187 3.2 0.9443 Example 3 0.13 90.0 142,472 6.8 0.9455 Example 4-1 0.006 520.0 146,272 9.2 0.9420 Example 4-2 0.13 147.2 151,648 13.8 0.9482 Example 5-1 2.06 117.3 109,017 18.0 0.9580 Example 5-2 2.95 84.4 246,283 43.9 0.9705 Example 6-1 5.4 84.5 73,082 12.1 0.9570 Example 6-2 4.5 70.2 83,060 28.0 0.9625 Comparative Example 1-1 0.29 71.7 128,614 4.0 0.9480 Comparative Example 1-2 5.6 69.8 100,758 5.7 0.9516 Comparative Example 1-3 30.8 66.7 94,543 11.8 0.9530

As can be seen from Tables 1 and 2, the method for producing an olefin-based polymer according to an embodiment of the present invention involves the supporting order of the first transition metal compound, the second transition metal compound, the first cocatalyst compound, and the second cocatalyst compound. By changing at least one of and the amount used, at least one of the melt index, melt rate ratio (MFR), weight average molecular weight (Mw), molecular weight distribution (PDI), and density of the olefin polymer can be adjusted.

Claims (19)

(1) mixing either a first transition metal compound represented by Formula 1 below or a second transition metal compound represented by Formula 2 below with a first cocatalyst compound and then contacting the carrier with a carrier to obtain an intermediate supported catalyst; (2) contacting the other of the first transition metal compound and the second transition metal compound alone or together with the second cocatalyst compound with the intermediate supported catalyst obtained in step (1) to obtain a hybrid metallocene supported catalyst; and (3) polymerizing the olefinic monomer in the presence of the hybrid metallocene supported catalyst obtained in step (2),
A first transition metal compound is used in step (1), a second transition metal compound is used in step (2), the first cocatalyst compound and the second cocatalyst compound are the same,
A group consisting of the melt index, melt rate ratio (MFR), weight average molecular weight (Mw), molecular weight distribution (PDI), and density of the olefin polymer by changing at least one of the amounts of the first cocatalyst compound and the second cocatalyst compound. Method for producing an olefin-based polymer that adjusts at least one physical property selected from:
[Formula 1]

[Formula 2]

In the above formulas 1 and 2, M1 and M2 are each independently a transition metal of group 4 of the periodic table of elements;
_{X 1} to group, an arylalkyl group with 7 to 40 carbon atoms, an alkylamido group with 1 to 20 carbon atoms, or an arylamido group with 6 to 20 carbon atoms;
R ₁ to R ₆ and R ₉ to R ₁₄ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, or a substituted or unsubstituted carbon number 6 It is an aryl group of ~20 carbon atoms, a substituted or unsubstituted alkylaryl group of 7 to 40 carbon atoms, or a substituted or unsubstituted arylalkyl group of 7 to 40 carbon atoms, and may be connected to each other to form a ring;
R ₇ and R ₈ are each independently a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, substituted or unsubstituted It is a ringed alkylaryl group with 7 to 40 carbon atoms or a substituted or unsubstituted arylalkyl group with 7 to 40 carbon atoms, and can be connected to each other to form a ring;
The indene bonded to R ₁ to R ₆ and the indene bonded to R ₉ to R ₁₄ may have the same or different structures, and the indene bonded to R ₁ to R ₆ and the indene bonded to R ₉ to R ₁₄ may be It forms a bridge structure where Si is connected to each other;
R ₁₅ to R ₂₆ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group with 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group with 2 to 20 carbon atoms, a substituted or unsubstituted aryl group with 6 to 20 carbon atoms, A substituted or unsubstituted alkylaryl group having 7 to 40 carbon atoms, or a substituted or unsubstituted arylalkyl group having 7 to 40 carbon atoms, which may be connected to each other to form a ring;
The cyclopentadiene bonded to R ₁₅ to R ₁₉ and the indene bonded to R ₂₀ to R ₂₆ are asymmetric structures with different structures, and the cyclopentadiene bonded to R ₁₅ to R ₁₉ and the indene bonded to R ₂₀ to R ₂₆ The indenes form a non-bridged structure that is not connected to each other,
The first transition metal compound is rac-dimethylsilylbis(2-methyl-4-phenylindenyl)zirconium dichloride, dimethylsilyl{tetramethylcyclopentadienyl}{2-methyl-4-(4-t-butylphenyl) )indenyl}zirconium dichloride, dimethylsilyl(tetramethylcyclopentadienyl)(2-methyl-4-phenylindenyl)zirconium dichloride and dimethylsilyl(tetramethylcyclopentadienyl)(4-phenylindenyl) Contains at least one selected from the group consisting of zirconium dichloride;
The second transition metal compound is [indenyl(cyclopentadienyl)]zirconium dichloride, [4-methylindenyl(cyclopentadienyl)]zirconium dichloride, and [indenyl(tetramethylcyclopentadienyl)]zirconium. dichloride, [2-methylindenyl(tetramethylcyclopentadienyl)]zirconium dichloride, [2-methylbenzoindenyl(cyclopentadienyl)]zirconium dichloride, and [4,5-benzoindenyl(tetramethylbenzoindenyl)]zirconium dichloride. methylcyclopentadienyl)] and at least one selected from the group consisting of zirconium dichloride. delete The method of claim 1, wherein the first transition metal compound is rac-dimethylsilylbis(2-methyl-4-phenylindenyl)zirconium dichloride represented by Formula 1a below, and the second transition metal compound is represented by Formula 2a below Method for producing an olefinic polymer that is [indenyl (cyclopentadienyl)] zirconium dichloride:
[Formula 1a]

[Formula 2a]

In Formula 1a above, Me is a methyl group and Ph is a phenyl group. The method of claim 1, wherein the cocatalyst compound is at least one selected from the group consisting of a compound represented by Formula 3 below, a compound represented by Formula 4 below, and a compound represented by Formula 5 below:
[Formula 3]

[Formula 4]

[Formula 5]
[LH] ⁺ [Z(A) ₄ ] ^- or [L] ⁺ [Z(A) ₄ ] ^-
In Formula 3 above, n is an integer of 2 or more, R _a is a halogen atom, a C _1-20 hydrocarbon group, or a C _1-20 hydrocarbon group substituted with halogen,
In Formula 4 above, D is aluminum (Al) or boron (B), and R _b , R _c and R _d are each independently a halogen atom, a C _1-20 hydrocarbon group, or a C _1-20 hydrocarbon group substituted with halogen. or C _1-20 alkoxy group,
In Formula 5 above, L is a neutral or cationic Lewis base, [LH] ⁺ and [L] ⁺ are Bronsted acids, Z is a Group 13 element, and A is each independently a substituted or unsubstituted C _{6 -20} It is an aryl group or a substituted or unsubstituted C _1-20 alkyl group. The method of claim 4, wherein the compound represented by Formula 3 is at least one selected from the group consisting of methylaluminoxane, ethyl aluminoxane, isobutyl aluminoxane, and butyl aluminoxane. The method of claim 4, wherein the compound represented by Formula 4 is trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, tripropyl aluminum, tributyl aluminum, dimethylchloroaluminum, triisopropyl aluminum, tri- s -butyl aluminum, tri- Cyclopentyl aluminum, tripentyl aluminum, triisopentyl aluminum, trihexyl aluminum, trioctyl aluminum, ethyldimethyl aluminum, methyldiethyl aluminum, triphenyl aluminum, tri- p -tolyl aluminum, dimethyl aluminum methoxide, dimethyl aluminum ethoxide. A method for producing at least one olefinic polymer selected from the group consisting of seed, trimethyl boron, triethyl boron, triisobutyl boron, tripropyl boron, and tributyl boron. The method of claim 4, wherein the compound represented by Formula 5 is triethylammonium tetraphenyl borate, tributylammonium tetraphenyl borate, trimethylammonium tetraphenyl borate, tripropylammonium tetraphenyl borate, trimethylammonium tetra( p -Tolyl)borate, trimethylammonium tetra( o , p -dimethylphenyl)borate, tributylammonium tetra( p -trifluoromethylphenyl)borate, trimethylammonium tetra( p -trifluoromethylphenyl)borate, tributyl Ammonium Tetrapentafluorophenyl Borate, N,N-Diethylanilinium Tetraphenylborate, N,N-Diethylanilinium Tetrapentafluorophenyl Borate, Diethylammonium Tetrapentafluorophenyl Borate, Tri Phenylphosphonium tetraphenyl borate, trimethylphosphonium tetraphenyl borate, triethylammonium tetraphenylaluminate, tributylammonium tetraphenylaluminate, trimethylammonium tetraphenylaluminate, tripropylammonium tetraphenylaluminate, trimethyl Ammonium tetra ( p -tolyl) aluminate, tripropylammonium tetra ( p -tolyl) aluminate, triethylammonium tetra ( o , p -dimethylphenyl) aluminate, tributylammonium tetra ( p -trifluoride) Romethylphenyl) aluminate, trimethylammonium tetra( p -trifluoromethylphenyl)aluminate, tributylammonium tetrapentafluorophenyl aluminate, N,N-diethylanilinium tetraphenyl aluminate, N,N -Diethylanilinium tetrapentafluorophenyl aluminate, diethylammonium tetrapentatetetraphenyl aluminate, triphenylphosphonium tetraphenylaluminate, trimethylphosphonium tetraphenylaluminate, tripropylammonium tetra ( p - Tolyl) borate, triethylammonium tetra ( o , p -dimethylphenyl) borate, triphenyl carbonium tetra ( p -trifluoromethylphenyl) borate, and triphenyl carbonium tetrapentafluorophenyl borate. A method for producing at least one olefin-based polymer selected from. The method of claim 1, wherein in step (2), the other of the first transition metal compound and the second transition metal compound is in contact with the intermediate supported catalyst obtained in step (1) together with the second cocatalyst compound. method. The method for producing an olefin-based polymer according to claim 8, wherein the first cocatalyst compound and the second cocatalyst compound are methylaluminoxane. delete The method of claim 1, wherein the carrier includes at least one selected from the group consisting of silica, alumina, and magnesia. The method of claim 11, wherein the first transition metal compound, the second transition metal compound, the first cocatalyst compound, and the second cocatalyst compound are supported on silica. The method of claim 12, wherein the total amount of the first transition metal compound and the second transition metal compound supported on the carrier is 0.001 to 1 mmole based on 1 g of the carrier, and the total amount of the cocatalyst compound supported on the carrier is 1 g of the carrier. Method for producing olefin-based polymers of 2 to 15 mmole as a standard. The method of claim 1, wherein the first transition metal compound and the second transition metal compound are used in a weight ratio of 20:1 to 1:20. The method of claim 1, further comprising (2') washing the hybrid metallocene supported catalyst obtained in step (2) with a solvent and drying it. The method of claim 1, wherein the olefinic polymer obtained in step (3) is a homopolymer of an olefinic monomer or a copolymer of an olefinic monomer and an olefinic comonomer. The method of claim 16, wherein the olefinic monomer is ethylene, and the olefinic comonomer is propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1- A method for producing at least one olefin-based polymer selected from the group consisting of decene, 1-undecene, 1-dodecene, 1-tetradecene, and 1-hexadecene. The method of claim 17, wherein the olefinic polymer is a linear low density polyethylene in which the olefinic monomer is ethylene and the olefinic comonomer is 1-hexene. delete