KR102285143B1 - Process for preparing a catalyst for polymerizing an olefin - Google Patents

Abstract

The present invention relates to a method for preparing a catalyst for olefin polymerization. Specifically, the present invention relates to a method for preparing a metallocene-supported catalyst capable of producing a polyolefin in which gel formation is suppressed by controlling the pore structure of the carrier. The method for preparing a metallocene-supported catalyst according to an embodiment of the present invention suppresses the formation of macromolecular polyolefins by controlling the pore structure of the support, thereby producing polyolefins with minimized gel formation.

Description

Method for producing a catalyst for olefin polymerization {PROCESS FOR PREPARING A CATALYST FOR POLYMERIZING AN OLEFIN}

The present invention relates to a method for preparing a catalyst for olefin polymerization. Specifically, the present invention relates to a method for preparing a metallocene-supported catalyst capable of producing a polyolefin in which gel formation is suppressed by controlling the pore structure of the carrier.

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

In contrast to the Ziegler-Natta catalyst, which is another catalyst used to polymerize olefins, the active site metal component is dispersed on an inactive solid surface and the properties of the active site are not uniform, the metallocene catalyst has a uniform structure. Because it is a compound with The polymer polymerized with such a metallocene catalyst has a narrow molecular weight distribution and a uniform distribution of comonomers.

Polyethylene produced by a metallocene catalyst has a short chain branch (SCB) of a constant length, and generally does not have a long chain branch (LCB). However, when the polymer is produced at the active site in the pores of the catalyst, the polyethylene may have long-chain branches or macromolecules may be generated depending on the pore shape, structure, and type of catalyst.

On the other hand, when the polyolefin resin is melted and processed, there may be a component that does not completely melt, such an insoluble mass is called a gel. When such a gel is present in the polyolefin resin, it is undesirable because the film prepared from the resin may deteriorate the transparency or quality of the product appearance.

Usually, a gel can result from a catalyst. In addition, during the production and processing of resins, gels (foreign gels) may be generated by foreign substances, and due to incomplete extrusion, differences in molecular weight/density, etc. between resins, or insufficient dispersion of resins, gels (non-dispersed or non-uniform gels) may be created. Alternatively, a gel (oxidized or carbonized gel) may be produced by oxidizing the resin by staying for a long time in the extruder, and a macromolecule may be created in a reactor or extruder by a physicochemical cross-linking reaction to produce a gel (cross-linked gel). .

As mentioned above, depending on the catalyst, macromolecules are generated from molecules having long-chain branching at the active sites in the pores, and physical cross-linking occurs during extrusion, which may cause gel formation.

It is an object of the present invention to provide a method for preparing a metallocene-supported catalyst capable of preparing polyolefins in which gel formation is suppressed by controlling the pore structure of the carrier.

According to one embodiment of the present invention for achieving this object, (1a) adding a cocatalyst compound to one or more transition metal compounds; or (1b) adding a promoter compound to the carrier; and (2) supporting a transition metal compound on a carrier, comprising means for adjusting the pore volume of the supported catalyst to satisfy Relational Equation 1 below, a method for preparing a supported metallocene catalyst for olefin polymerization is provided .

[Relational Expression 1]

Here, the transition metal compound may be a mixture of a first transition metal compound represented by Formula 1 below and a second transition metal compound represented by Formula 2 below.

[Formula 1]

[Formula 2]

In Formulas 1 and 2, M1 and M2 are each independently a Group 4 transition metal of the Periodic Table of the Elements;

X ₁ to X ₄ are each independently a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, alkylaryl having 7 to 40 carbon atoms a group, an arylalkyl group having 7 to 40 carbon atoms, an alkylamido group having 1 to 20 carbon atoms, an arylamido group having 6 to 20 carbon atoms, or an alkylidene group having 1 to 20 carbon atoms;

R ₁ to R ₁₀ are each independently a hydrogen atom, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C6-C20 aryl group, 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 linked to each other to form a ring;

The _{cyclopentadiene to which R 1} to R ₅ is bonded and the cyclopentadiene to which R ₆ to R ₁₀ are bonded may have the same structure or different structures, and since each cyclopentadiene is not connected, the compound having a non-bridged structure to form,

R ₁₁ to R ₁₆ are each independently a hydrogen atom, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C6-C20 aryl group, 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 linked to each other to form a ring;

R ₁₇ and R ₁₈ are each independently a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C6-C20 aryl group, substituted or unsubstituted a cyclic alkylaryl group having 7 to 40 carbon atoms or a substituted or unsubstituted arylalkyl group having 7 to 40 carbon atoms, which may be linked to each other to form a ring;

R ₁₉ to R ₂₂ are each independently a hydrogen atom, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C6-C20 aryl group, 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 linked to each other to form a ring;

Indene bonded to R ₁₁ to R _{16 and cyclopentadiene bonded to R 19} to R ₂₂ have different structures, and indene and cyclopentadiene are bonded with silicon (Si) to form a bridge structure.

More preferably, the first transition metal compound is [indenyl (cyclopentadienyl)] zirconium dichloride, [4-methylindenyl (cyclopentadienyl)] zirconium dichloride, [indenyl (tetramethylcyclopenta dienyl)]zirconium dichloride, [2-methylindenyl (tetramethylcyclopentadienyl)]zirconium dichloride, [2-methylbenzoindenyl (cyclopentadienyl)]zirconium dichloride and [4,5- and at least one selected from the group consisting of benzoindenyl (tetramethylcyclopentadienyl)]zirconium dichloride.

The second 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) It includes at least one selected from the group consisting of zirconium dichloride.

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

[Formula 1a]

[Formula 2a]

In Formulas 1a and 2a, Me is a methyl group, and Ph is a phenyl group.

In this case, the first transition metal compound and the second transition metal compound may be included in a weight ratio of 20:1 to 1:20.

Preferably, the cocatalyst compound may include at least one selected from the group consisting of a compound represented by Formula 3 below, 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 having 1 to 20 carbon atoms, or a hydrocarbon group having 1 to 20 carbon atoms substituted with a halogen,

In Formula 4, D is aluminum (Al) or boron (B), 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 C 1 to 20 carbon atom a hydrocarbon group or an alkoxy group having 1 to 20 carbon atoms,

In the above formula (5), L is a neutral or cationic Lewis base, [LH] ⁺ and [L] ⁺ are a Bronsted acid, Z is a group 13 element, A is each independently a substituted or unsubstituted carbon number of 6 It is an aryl group of ~20 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, ethylaluminoxane, isobutylaluminoxane and butylaluminoxane.

In addition, the compound represented by Formula 4 is trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, dimethylchloroaluminum, triisopropylaluminum, tri- s -butylaluminum, tricyclopentylaluminum, Tripentyl aluminum, triisopentyl aluminum, trihexyl aluminum, trioctyl aluminum, ethyl dimethyl aluminum, methyldiethyl aluminum, triphenyl aluminum, tri- p -tolyl aluminum, dimethyl aluminum methoxide, dimethyl aluminum ethoxide, trimethyl boron , at least one selected from the group consisting of triethyl boron, triisobutyl boron, tripropyl boron and tributyl boron.

In addition, the compound represented by the above formula (5) is triethylammonium tetraphenyl boron, tributyl ammonium tetraphenyl boron, trimethyl ammonium tetraphenyl boron, tripropyl ammonium tetraphenyl boron, trimethyl ammonium tetra ( p -tolyl) Boron, trimethylammonium tetra( o , p -dimethylphenyl)boron, tributylammonium tetra( p -trifluoromethylphenyl)boron, trimethylammonium tetra( p -trifluoromethylphenyl)boron, tributylammonium tetra Pentafluorophenyl boron, N,N-diethylanilinium tetraphenylboron, N,N-diethylaniliniumtetrapentafluorophenylboron, diethylammonium tetrapentafluorophenylboron, triphenylphosphonium Tetraphenylboron, trimethylphosphoniumtetraphenylboron, triethylammonium tetraphenylaluminum, tributylammonium tetraphenylaluminum, trimethylammonium tetraphenylaluminum, tripropylammoniumtetraphenylaluminum, trimethylammonium tetra( p -tolyl) ) Aluminum, tripropylammonium tetra( p -tolyl)aluminum, triethylammoniumtetra( o , p -dimethylphenyl)aluminum, tributylammonium tetra( p -trifluoromethylphenyl)aluminum, trimethylammonium tetra( p -trifluoromethylphenyl)aluminum, tributylammonium tetrapentafluorophenylaluminum, N,N-diethylaniliniumtetraphenylaluminum, N,N-diethylaniliniumtetrapentafluorophenylaluminum, di Ethylammonium tetrapentatetraphenylaluminum, triphenylphosphoniumtetraphenylaluminum, trimethylphosphoniumtetraphenylaluminum, tripropylammoniumtetra( p -tolyl)boron, triethylammoniumtetra( o , p -dimethylphenyl)boron , tributylammonium tetra( p -trifluoromethylphenyl)boron, triphenylcarboniumtetra( p -trifluoromethylphenyl)boron and triphenylcarboniumtetrapentafluorophenylboron selected from the group consisting of at least one

Preferably, the carrier may include at least one selected from the group consisting of silica, alumina and magnesia.

More preferably, the first transition metal compound, the second transition metal compound, and the promoter compound may be supported on a single type of carrier. Specifically, the first transition metal compound, the second transition metal compound, and the promoter compound may be supported on silica.

At this time, the total amount of the first transition metal compound and the second transition metal compound supported on the support may be 0.5 to 3.0 wt% based on the total weight of the catalyst after loading, and the amount of the promoter compound supported on the support is the total amount of the catalyst after loading. It may be 20-30% by weight based on the weight.

In the method for preparing a supported metallocene catalyst for olefin polymerization according to an embodiment of the present invention, the means for controlling the pore volume of the supported catalyst is (a) adjusting the content of the cocatalyst in step (1a) or (1b) How to; (b) a method of adjusting the total amount, content ratio, or both of the transition metal compound in step (1a); and (c) adding an additive before or after step (1a) or before or after step (1b).

Preferably, the additive may include at least one selected from the group consisting of aluminum stearate, sodium stearate, calcium stearate, zinc stearate, aluminum tristearate, aluminum acetate and zinc acetate.

In this case, the additive may be added in an amount of 0.001 wt% or more and less than 20 wt% based on the total weight of the supported catalyst.

The method for preparing a metallocene-supported catalyst according to an embodiment of the present invention suppresses the formation of macromolecular polyolefins by controlling the pore structure of the support, thereby producing polyolefins with minimized gel formation.

1 is a photograph of a gel that appears during polyolefin extrusion.

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

A method for preparing a supported metallocene catalyst for olefin polymerization according to an embodiment of the present invention comprises the steps of (1a) adding a promoter compound to one or more transition metal compounds; or (1b) adding a promoter compound to the carrier; and (2) supporting the transition metal compound on the carrier, including means for controlling the pore volume of the supported catalyst to satisfy the following relational expression (1).

[Relational Expression 1]

In the above step (1a), a cocatalyst compound is added to one or more transition metal compounds.

Here, the transition metal compound may include at least one of a first transition metal compound represented by Formula 1 below and a second transition metal compound represented by Formula 2 below. Preferably, the transition metal compound may be a mixture of a first transition metal compound represented by Formula 1 below and a second transition metal compound represented by Formula 2 below.

[Formula 1]

[Formula 2]

In Formulas 1 and 2, M1 and M2 are each independently a Group 4 transition metal 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 X ₄ are each independently a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, alkylaryl having 7 to 40 carbon atoms group, an arylalkyl group having 7 to 40 carbon atoms, an alkylamido group having 1 to 20 carbon atoms, an arylamido group having 6 to 20 carbon atoms, or an alkylidene group having 1 to 20 carbon atoms. Specifically, X ₁ to X ₄ may each independently be a halogen, more specifically chlorine (Cl).

R ₁ to R ₁₀ are each independently a hydrogen atom, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C6-C20 aryl group, A substituted or unsubstituted C7-40 alkylaryl group, or a substituted or unsubstituted C7-40 arylalkyl group, may be connected to each other to form a ring.

In addition, _{the cyclopentadiene to which R 1} to R ₅ is bonded and the cyclopentadiene to which R ₆ to R ₁₀ are bonded may have the same structure or different structures, and since each cyclopentadiene is not connected, a non-bridged structure compounds can be formed.

R ₁₁ to R ₁₆ are each independently a hydrogen atom, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C6-C20 aryl group, A substituted or unsubstituted C7-40 alkylaryl group, or a substituted or unsubstituted C7-40 arylalkyl group, may be connected to each other to form a ring.

R ₁₇ and R ₁₈ are each independently a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C6-C20 aryl group, substituted or unsubstituted A cyclic alkylaryl group having 7 to 40 carbon atoms or a substituted or unsubstituted arylalkyl group having 7 to 40 carbon atoms may be connected to each other to form a ring.

R ₁₉ to R ₂₂ are each independently a hydrogen atom, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C6-C20 aryl group, A substituted or unsubstituted C7-40 alkylaryl group, or a substituted or unsubstituted C7-40 arylalkyl group, may be connected to each other to form a ring.

In addition, indene bonded to _{R 11} to R _{16 and cyclopentadiene bonded to R 19} to R ₂₂ have different structures, and indene and cyclopentadiene are bonded to silicon (Si) to form a bridge structure. can

Preferably, the first transition metal compound is [indenyl(cyclopentadienyl)]zirconium dichloride, [4-methylindenyl(cyclopentadienyl)]zirconium dichloride, [indenyl(tetramethylcyclopentadie) nyl)]zirconium dichloride, [2-methylindenyl (tetramethylcyclopentadienyl)]zirconium dichloride, [2-methylbenzoindenyl (cyclopentadienyl)]zirconium dichloride and [4,5-benzo Indenyl (tetramethylcyclopentadienyl)] may include at least one selected from the group consisting of zirconium dichloride.

The second 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) It may include at least one selected from the group consisting of zirconium dichloride.

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

[Formula 1a]

[Formula 2a]

In Formulas 1a and 2a, Me is a methyl group, and Ph is a phenyl group.

The catalyst for olefin polymerization according to an embodiment of the present invention may include the above first transition metal compound and the second transition metal compound in a weight ratio of 20:1 to 1:20. Preferably, the catalyst for olefin polymerization may include the first transition metal compound and the second transition metal compound in a weight ratio of 10:1 to 1:10. More preferably, the catalyst for olefin polymerization may include the first transition metal compound and the 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, an appropriate supported catalyst activity may be exhibited, which may be advantageous in terms of maintaining the activity of the catalyst and economic feasibility. In addition, the olefin-based polymer prepared in the presence of a catalyst for olefin polymerization satisfying the above range exhibits excellent processability, and a film prepared therefrom may exhibit excellent mechanical and optical properties.

Meanwhile, the cocatalyst compound of the above step (1a) may include at least one of a compound represented by Formula 3, a compound represented by Formula 4, and a compound represented by Formula 5 below.

[Formula 3]

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

[Formula 4]

In Formula 4, D is aluminum (Al) or boron (B), 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 C 1 to 20 carbon atom It is a hydrocarbon group or a C1-C20 alkoxy group. 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 a Bronsted acid, Z is a group 13 element, A is each independently a substituted or unsubstituted carbon number of 6 It is an aryl group of ~20 or a substituted or unsubstituted alkyl group of 1~20 carbon atoms. Specifically, [LH] ⁺ may be a dimethylanilinium cation, [Z(A) ₄ ] ^- may be [B(C ₆ F ₅ ) ₄ ] ^- , [L] ⁺ may be [(C ₆ H) ₅ ) ₃ C] ⁺ .

Examples of the compound represented by the above formula (3) include methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, butylaluminoxane, and the like, and methylaluminoxane is preferable, but is not limited thereto.

Examples of the compound represented by the above formula (4) include trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, dimethylchloroaluminum, triisopropylaluminum, tri- s -butylaluminum, tricyclopentylaluminum , tripentyl aluminum, triisopentyl aluminum, trihexyl aluminum, trioctyl aluminum, ethyl dimethyl aluminum, methyldiethyl aluminum, triphenyl aluminum, tri- p -tolyl aluminum, dimethyl aluminum methoxide, dimethyl aluminum ethoxide, trimethyl boron, triethylboron, triisobutylboron, tripropylboron, tributylboron, and the like, and trimethylaluminum, triethylaluminum and triisobutylaluminum are preferred, but are not limited thereto.

Examples of the compound represented by the above formula (5) 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 tetra Pentafluorophenyl boron, N,N-diethylanilinium tetraphenylboron, N,N-diethylaniliniumtetrapentafluorophenylboron, diethylammonium tetrapentafluorophenylboron, triphenylphosphonium Tetraphenylboron, trimethylphosphoniumtetraphenylboron, triethylammonium tetraphenylaluminum, tributylammonium tetraphenylaluminum, trimethylammonium tetraphenylaluminum, tripropylammoniumtetraphenylaluminum, trimethylammonium tetra( p -tolyl) ) Aluminum, tripropylammonium tetra( p -tolyl)aluminum, triethylammoniumtetra( o , p -dimethylphenyl)aluminum, tributylammonium tetra( p -trifluoromethylphenyl)aluminum, trimethylammonium tetra( p -trifluoromethylphenyl)aluminum, tributylammonium tetrapentafluorophenylaluminum, N,N-diethylaniliniumtetraphenylaluminum, N,N-diethylaniliniumtetrapentafluorophenylaluminum, di Ethylammonium tetrapentatetraphenylaluminum, triphenylphosphoniumtetraphenylaluminum, trimethylphosphoniumtetraphenylaluminum, tripropylammoniumtetra( p -tolyl)boron, triethylammoniumtetra( o , p -dimethylphenyl)boron , tributylammonium tetra( p -trifluoromethylphenyl)boron, triphenylcarboniumtetra( p -trifluoromethylphenyl)boron, and triphenylcarboniumtetrapentafluorophenyl boron.

The process of adding a promoter compound to one or more transition metal compounds in step (1a) may be performed in the presence of a solvent. At this time, the solvent is an aliphatic hydrocarbon solvent such as hexane and pentane, an aromatic hydrocarbon solvent such as toluene and benzene, a hydrocarbon solvent substituted with a chlorine atom such as dichloromethane, diethyl ether, an ether solvent such as tetrahydrofuran (THF), It may be most organic solvents such as acetone and ethyl acetate, preferably toluene or hexane, but is not particularly limited thereto.

The process of adding the promoter compound to the one or more transition metal compounds in step (1a) may be carried out at a temperature of 0 to 100 °C, preferably at a temperature of 10 to 30 °C.

In addition, it is preferable to sufficiently stir the cocatalyst compound for 5 minutes to 24 hours, preferably 30 minutes to 3 hours after adding the promoter compound to the one or more transition metal compounds in step (1a).

In the above step (1b), a cocatalyst compound is added to the carrier.

Here, the carrier may include a material containing a hydroxyl group on the surface, preferably dried to remove moisture on the surface, a material having a high reactivity hydroxyl group and siloxane group 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, silica-magnesia, and the like may be used as the carrier, and these are typically oxides such _{as Na 2} O, K ₂ CO ₃ , BaSO ₄ , and Mg(NO ₃ ) _{2 .} , carbonate, sulfate, and nitrate components. They may also contain carbon, zeolites, magnesium chloride, and the like. However, the carrier is not limited thereto, and is not particularly limited as long as it can support the first and second transition metal compounds and the promoter compound.

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 20 to 100 μm.

The micropore volume of the carrier may be 0.1-10 cc/g, preferably 0.5-5 cc/g, and more preferably 1.0-3.0 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 silica drying temperature may be 200 ~ 900 ℃. 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, the surface moisture and the cocatalyst react, and if it exceeds 900 ℃, the structure of the carrier may be collapsed.

The concentration of hydroxyl groups in the dried silica may be 0.1-5 mmole/g, preferably 0.7-4 mmole/g, and more preferably 1.0-2 mmole/g. When the concentration of the hydroxyl group is less than 0.1 mmole/g, the supported amount of the cocatalyst is lowered, and when it exceeds 5 mmole/g, a problem in that the catalyst component is deactivated may occur.

The process of adding the promoter compound to the carrier in step (1b) may be performed in the presence of a solvent. At this time, the solvent is substantially the same as described in step (1a) above.

The process of adding the promoter compound to the carrier in step (1b) may be carried out at a temperature of 0 to 100 °C, preferably at a temperature of 10 to 50 °C.

In addition, it is preferable to sufficiently stir the promoter compound for 5 minutes to 24 hours, preferably 30 minutes to 3 hours after adding the promoter compound to the carrier in step (1b).

In the above step (2), the transition metal compound is supported on a carrier.

Specifically, by contacting the transition metal compound activated by the addition of the promoter compound to the transition metal compound in step (1a) with the carrier, or by contacting the transition metal compound with the carrier on which the promoter compound is supported in step (1b), the transition A metal compound may be supported on a carrier.

The process of supporting the transition metal compound on the carrier in step (2) may be performed in the presence of a solvent. At this time, the solvent is substantially the same as described in step (1a) above.

The process of supporting the transition metal compound on the carrier in step (2) may be carried out at a temperature of 0 to 100 °C, preferably at a temperature of room temperature to 90 °C.

In addition, the process of supporting the transition metal compound on the carrier in (2) may be performed by sufficiently stirring the mixture of the transition metal compound and the carrier for 5 minutes to 24 hours, preferably 30 minutes to 3 hours.

Preferably, the first transition metal compound, the second transition metal compound, and the promoter compound may be supported on a single type of carrier. Specifically, the first transition metal compound, the second transition metal compound, and the promoter compound may be supported on silica.

At this time, the total amount of the first transition metal compound and the second transition metal compound supported on the support may be 0.5 to 3.0 wt% based on the total weight of the catalyst after loading, and the amount of the promoter compound supported on the support is the total amount of the catalyst after loading. It may be 20-30% by weight based on the weight.

The method for preparing a supported metallocene catalyst for olefin polymerization according to an embodiment of the present invention may further include (3) washing the supported catalyst with a solvent and drying the supported catalyst.

Specifically, after the loading of the transition metal compound is completed, the supported catalyst is precipitated by allowing it to stand for 3 minutes to 3 hours. Then, the supported catalyst is separated by removing the supernatant, washed with a solvent, and dried at a temperature of room temperature to 80° C. for 6 to 48 hours to obtain a supported catalyst. Here, the solvent is substantially the same as described in step (1a) above.

The method for preparing a supported metallocene catalyst for olefin polymerization according to an embodiment of the present invention includes means for adjusting the pore volume of the supported catalyst to satisfy Relational Equation 1 below.

[Relational Expression 1]

Preferably, the ratio of the pore volume of the supported catalyst after adjustment to the pore volume of the supported catalyst before adjustment has a value of 0.8 to 0.95.

In the method for preparing a supported metallocene catalyst for olefin polymerization according to an embodiment of the present invention, the means for controlling the pore volume of the supported catalyst is (a) adjusting the content of the cocatalyst in step (1a) or (1b) How to; (b) a method of adjusting the total amount, content ratio, or both of the transition metal compound in step (1a); and (c) adding an additive before or after step (1a) or before or after step (1b).

Preferably, the additive may include at least one selected from methyl carboxylates such as aluminum stearate, sodium stearate, calcium stearate, zinc stearate, aluminum tristearate, aluminum acetate, zinc acetate. More preferably, the additive is aluminum stearate.

In addition, the metallocene catalyst system for olefin polymerization may further include an inert carrier on which a metallocene compound, a metal salt, and an antistatic agent are supported.

In this case, the additive may be added in an amount of 0.001 wt% or more and less than 20 wt% based on the total weight of the supported catalyst. Preferably, the additive may be added in an amount of 0.001 to 15% by weight, 0.001 to 10% by weight, or 0.001 to 5% by weight based on the total weight of the supported catalyst.

The metallocene catalyst system of the present invention including one or more of the additives described above minimizes static electricity generated by friction between polymer particles or friction between polymer particles and the inner wall of the reactor during the production of polyolefin through gas phase polymerization or slurry polymerization. However, it is possible to stably maintain the intrinsic activity of the catalyst. This is presumed to be because the metallocene catalyst system forms the particle size and bulk density of the polymer present in the reactor in a range where static electricity generation due to friction can be minimized.

The additive may be used without any particular limitation in a conventional addition method in the technical field to which the present invention pertains. In general, the additive may be used as a catalyst composition in a solution state uniformly dissolved in a hydrocarbon solvent or the like or may be used in a solid powder state from which the solvent is removed, but is not particularly limited thereto. At this time, as the solvent, an aliphatic hydrocarbon solvent such as hexane and pentane, an aromatic hydrocarbon solvent such as toluene and benzene, a hydrocarbon solvent substituted with a chlorine atom such as dichloromethane, diethyl ether, ether-based solvent such as tertrahydrofuran (THF) It may be most organic solvents such as solvent, acetone, ethyl acetate, etc., preferably toluene or hexane, but is not particularly limited thereto.

On the other hand, an olefin-based polymer can be provided by polymerizing an olefin-based monomer in the presence of a catalyst prepared by the method for preparing a metallocene-supported catalyst for olefin polymerization of an embodiment of the present invention.

Here, the olefin-based polymer may be a homopolymer of an olefin-based monomer or a copolymer of an olefin-based monomer and a comonomer.

Olefin-based monomers include an alpha-olefin having 2 to 20 carbon atoms, a diolefin having 1 to 20 carbon atoms, a cycloolefin having 3 to 20 carbon atoms, and a cyclodiolefin having 3 to 20 carbon atoms. ) at least one selected from the group consisting of.

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

In an exemplary embodiment, the olefin-based polymer may be a copolymer in which ethylene and an alpha-olefin having 3 to 20 carbon atoms are copolymerized, preferably a copolymer in which ethylene and 1-hexene are copolymerized, but is not limited thereto.

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

The olefin-based polymer according to an embodiment of the present invention may be polymerized by, for example, a polymerization reaction such as free radical, cationic, coordination, condensation, and addition. However, it is not limited thereto.

In a preferred embodiment, the olefin-based polymer may be prepared by a gas phase polymerization method, a solution polymerization method, or a slurry polymerization method. When the olefin-based polymer is prepared by solution polymerization or slurry polymerization, examples of the solvent that can be used include aliphatic hydrocarbon solvents having 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 is not limited thereto.

In addition, a film may be provided by molding the olefin-based polymer prepared according to an embodiment of the present invention.

The method for producing a film according to an embodiment of the present invention is not particularly limited, and methods known in the art to which the present invention pertains may be used. For example, the heat-shrinkable polypropylene film may be manufactured by processing the olefin-based polymer according to an embodiment of the present invention by a conventional method such as blown film molding, extrusion molding, or casting molding. Among them, blown film molding is most preferable.

The film prepared as described above may contain the olefin-based polymer of the present invention, thereby inhibiting the production of gel.

Specifically, in the film according to an embodiment of the present invention, the total number of gels may be reduced by 50% or more, 60% or more, or 70% or more compared to a supported metallocene catalyst for olefin polymerization in which the pore volume is not controlled. . In the film according to an embodiment of the present invention, the total number of gels is preferably reduced by 80% or more, more preferably by 90% or more compared to the metallocene-supported catalyst for olefin polymerization in which the pore volume is not controlled.

In addition, the film according to an embodiment of the present invention reduces the number of fine gels having a size of 400 μm or less by 60% or more, 70% or more, or 80% or more compared to a metallocene-supported catalyst for olefin polymerization whose pore volume is not controlled. it may have been In the film according to an embodiment of the present invention, the total number of gels is preferably reduced by 90% or more, more preferably by 95% or more compared to the metallocene-supported catalyst for olefin polymerization in which the pore volume is not controlled.

As such, the film according to an embodiment of the present invention has excellent transparency and appearance, since the number of fine gels having a size of 400 μm or less as well as the total number of gels is significantly reduced.

Example

Hereinafter, the present invention will be described in more detail through Examples and Comparative Examples. However, the following examples are only for illustrating the present invention, and the scope of the present invention is not limited thereto.

manufacturing example One: [Indenyl (cyclopentadienyl)] Synthesis of zirconium dichloride (first transition metal compound)

Indene (5 g, 0.043 mole) was dissolved in hexane (150 ml) in a dry box, thoroughly mixed, and cooled to -30°C. Then, a 2.5 M n-butyllithium (n-BuLi) hexane solution (17 ml, 0.043 mole) was slowly added to the hexane solution, and the mixture was stirred at room temperature for 12 hours. The white suspension was filtered through a glass filter to obtain a white solid, which was sufficiently dried to obtain 5.2 g (yield: 99%) of indene lithium salt.

(Cyclopentadienyl)zirconium trichloride (CpZrCl ₃ ) (2.24 g, 8.53 mmole) was slowly dissolved in ether (30 mL) in a glove box, and then cooled to -30°C. An indene lithium salt (1.05 g, 8.53 mmole) dissolved in ether (15 mL) was slowly added to the ether solution, followed by stirring for 24 hours.

Ether was removed from the resulting yellow suspension under reduced pressure in vacuo, followed by extraction with methylene chloride (50 mL). After passing through Celite to remove lithium chloride (LiCl) and drying, as a purified first metallocene compound [indenyl (cyclopentadienyl)] zirconium dichloride 2.82 g (yield: 97%) got it

manufacturing example 2: rac - Dimethylsilylbis(2-methyl-4-phenylindenyl) Synthesis of zirconium dichloride (second transition metal compound)

Step A: 2- methyl -7-phenyl-1H- indene synthesis

7-Bromo-2-methyl-1H-indene (7 g, 1 equiv) and [1,3-bis(diphenylphosphino)propane]nickel(II) chloride (363 mg, 0.02 equiv) were mixed with ether (100 ㎖), and 3.0 M phenyl magnesium bromide ether solution (8.23 g, 1.05 equiv) was added at 0° C. for 1 hour, and then the temperature was gradually increased and the mixture was stirred under reflux at 50° C. for 12 hours.

After completion of the reaction, the solution was immersed in an ice bath, and the pH was lowered to 4 by adding 1 N hydrochloric acid. After extracting the organic layer, it _{was treated with magnesium sulfate (MgSO 4} ) to remove water and the solvent was dried to obtain 6.68 g (yield: 97%) of 2-methyl-7-phenyl-1H-indene as a white solid.

Step B: of dimethylbis(2-methyl-4-phenylindenyl)silane synthesis

2-Methyl-7-phenyl-1H-indene (2.14 g, 1 equiv) was dissolved in hexane (50 ml), and a 1.6 M n-butyllithium (n-BuLi) hexane solution (7.8 ml, 1.2 equiv) was added to -30 After adding slowly at ℃, the temperature was gradually raised to room temperature and stirred for 12 hours. The resulting solid was filtered, washed with hexane and dried under vacuum. 20 ml of toluene and 5 ml of tetrahydrofuran (THF) were added to the resulting 2-methyl-4 phenylindenyl lithium (1.5 g, 2 equivalents), and dimethyldichlorosilane (456 mg, 1 equivalent) was slowly added at -30°C. After the addition, the temperature was raised slowly and stirred at 80° C. for 2 hours.

After completion of the reaction, the solvent was removed, the organic layer was extracted using a mixed solution of ether and water, and the water was removed by treatment with magnesium sulfate. 1.3 g (yield: 80%) of dimethylbis(2-methyl-4-phenylindenyl)silane was obtained by column chromatography. At this time, a mixed solution having a volume ratio of hexane and methylene chloride of 20:1 was used as the mobile phase.

Step C: rac - Dimethylsilylbis(2-methyl-4-phenylindenyl)zirconium dichloride synthesis

To a solution of dimethylbis(2-methyl-4-phenylindenyl)silane (1.4 g, 1 equiv.) in ether (20 ml), a 1.6 M n-butyllithium hexane solution (4 ml, 2.1 equiv) was added at -30°C. After slowly adding the mixture, the temperature was gradually raised to room temperature and stirred for 12 hours. After drying the solvent, the resulting solid was washed with hexane and dried under vacuum to obtain a dilithium salt. Zirconium chloride (ZrCl ₄ ) (484 mg, 1 equiv) was slowly added to a solution of dilithium salt (1 g, 2 equiv) and ether (100 mL) at -30 °C, and the temperature was slowly raised and stirred for 4 hours.

After completion of the reaction, the solvent was removed and rac-dimethylsilylbis(2-methyl-4-phenylindenyl)zirconium dichloride 130 mg (yield: 10%) was obtained through recrystallization using methylene chloride as a recrystallization solvent.

comparative example One

1.796 g of the first transition metal compound of Preparation Example 1 and 4.946 g of the second transition metal compound of Preparation Example 2 were mixed with 1,117.4 g of a 10 wt% toluene solution of methylaluminum oxane (MAO) in a glove box (Al/Zr = 150 ) and stirred at room temperature for 1 hour. Meanwhile, 281.52 g of silica (XP2402) was added to the reactor, and 1,000 ml of purified toluene was added and mixed. Thereafter, the transition metal compound solution was injected into the silica slurry and stirred in an oil bath at 75° C. for 3 hours. After the support was completed and the solid/liquid was sufficiently separated, the supernatant was removed. The supported catalyst was washed three times using toluene and dried in a vacuum at 60° C. for 30 minutes to obtain 355 g of a hybrid supported catalyst in the form of a free-flowing powder.

Example One

395 g of a supported hybrid catalyst was obtained in the same manner as in Comparative Example 1, except that 1.933 g of the first transition metal compound, 5.327 g of the second transition metal compound of Preparation Example 2, and 1,203.35 g of a toluene solution of methylaluminumoxane were used.

Example 2

After removing the supernatant, the obtained supported catalyst was mixed with 6.00 g of aluminum stearate and 500 ml of toluene, and 350 g of a hybrid supported catalyst was obtained in the same manner as in Comparative Example 1, except that the mixture was stirred at room temperature for 1 hour.

Example 3

360 g of a supported hybrid catalyst was obtained in the same manner as in Example 2, except that the first transition metal compound and the second transition metal compound were mixed with a toluene solution of methylaluminum oxane and dried, and then mixed with 8.80 g of aluminum stearate.

Example 4

1.511 g of the first transition metal compound and 5.153 g of the second transition metal compound were used, and the first transition metal compound and the second transition metal compound were mixed with 8.8 g of aluminum stearate before mixing with a toluene solution of methylaluminum oxane. Except for that, 360 g of a supported hybrid catalyst was obtained in the same manner as in Comparative Example 1.

comparative example 2

360 g of a supported hybrid catalyst was obtained in the same manner as in Comparative Example 1, except that 2.158 g of the first transition metal compound, 3.963 g of the second transition metal compound, and 1,074.42 g of a toluene solution of methylaluminum oxane were used.

comparative example 3

After removing the supernatant, the obtained supported catalyst was mixed with 80.0 g of aluminum stearate and 1,000 ml of toluene, and 400 g of a hybrid supported catalyst was obtained in the same manner as in Comparative Example 1, except that the mixture was stirred at room temperature for 1 hour.

The catalyst preparation conditions of Comparative Examples 1 to 3 and Examples 1 to 4 are summarized in Table 1 below.

MAO Al content
(weight%) Molar ratio of transition metal compound Al/Zr Additive powder addition (wt%)* Additive solution addition (wt%)* Comparative Example 1 13.0 4:6 150 0 0 Example 1 14.0 4:6 150 0 0 Example 2 12.5 4:6 150 0 1.5 Example 3 12.5 4:6 150 2.22 1.5 Example 4 12.5 3.5:6.5 150 2.22 0 Comparative Example 2 12.5 5:5 150 0 0 Comparative Example 3 12.5 4:6 150 0 20

* Based on additive content

Experimental example

The pore volume of each hybrid supported catalyst obtained in Comparative Examples 1 to 3 and Examples 1 to 4 was measured using gas adsorption analysis. Specifically, the pore volume was measured using a specific surface area analyzer (ASAP2420) that measures the surface area, pore volume, and pore size of mesoporous/microporous materials using physical adsorption of nitrogen gas. , the pore size was calculated through the BJH desorption method. In Examples and Comparative Examples of the present invention, pretreatment was performed by a desorption drying method at room temperature for 4 hours, and desorption proceeded while lowering the temperature to -195.85° C., and the temperature was raised to room temperature and adsorption was measured.

In addition, the ratio of the pore volume (after treatment) of the supported hybrid catalysts of Examples 1 to 4 and Comparative Examples 2 to 3 to the pore volume (before treatment) of the supported hybrid catalyst of Comparative Example 1 was calculated. The results are shown in Table 2.

Thereafter, using a fluidized bed gas phase reactor, 50 mg of each of the hybrid supported catalysts obtained in Comparative Examples 1 to 3 and Examples 1 to 4 and 0.5 ml of 1M triisobutyl aluminum (TIBAL) as a scavenger were used in the presence of ethylene and 1- Hexene was copolymerized for 1 hour. The temperature in the reactor was maintained at about 80° C., and the polymerization degree of the ethylene/1-hexene copolymer prepared by adding hydrogen in addition to ethylene and 1-hexene was controlled. At this time, the pressure of ethylene was 14 kgf/cm 2 and the amount of 1-hexene was 15 cc. Table 2 shows the catalyst activity during polymerization.

Then, an ethylene/1-hexene copolymer was extruded at a screw speed of 80 rpm in an extruder having a 40 mm diameter screw, a 75 mm diameter die and a 2 mm die gap, and a cast film with a width of 41 mm and a 2.0 m2 area was formed. Thus, a film having a thickness of 60 µm was obtained.

The total number of gels and the number of fine gels having a size of 400 μm or less in each film having a size of 2.0 m 2 thus obtained were visually measured. The results are shown in Table 2.

pore volume
(㎤/g) Ratio of pore volumes before and after treatment catalytic activity
(gPE/gCat-hr) total number of gels number of microgels Reduction of gel (%) whole gel fine gel Comparative Example 1 0.880002 - 5,160 1,485,619 158,204 - - Example 1 0.764019 0.86 8,714 265,275 15,690 82 90 Example 2 0.834345 0.95 6,086 41,444 1,067 97 99 Example 3 0.826506 0.93 5,343 35,703 809 98 99 Example 4 0.740240 0.84 6,567 1,278,526 67,013 90 98 Comparative Example 2 0.890300 0.98 5,167 149,150 2,484 14 58 Comparative Example 3 - - Measurable - - - -

As can be seen from Table 2, the olefin-based polymer produced in the presence of the supported hybrid catalyst prepared in Examples of the present invention was compared to the olefin-based polymer produced in the presence of the supported hybrid catalyst prepared in Comparative Example 1. The number was reduced by more than 80%, and the number of microgels was reduced by more than 90%.

Therefore, the hybrid supported catalyst prepared according to the preparation method of the embodiment of the present invention can provide an olefin-based film excellent in transparency and appearance by significantly inhibiting the generation of gel, and the film is a stretch film, an overlap film, a lamie, It can be effectively used as silage wrap, agricultural film, and the like.

Claims (16)

(1a) adding a cocatalyst compound to one or more transition metal compounds; or (1b) adding a promoter compound to the carrier; And (2) a method for preparing a supported metallocene catalyst for olefin polymerization, comprising the step of supporting the transition metal compound on a carrier, comprising means for adjusting the pore volume of the supported catalyst to satisfy Relation 1 below,
The transition metal compound is a mixture of a first transition metal compound represented by Formula 1 below and a second transition metal compound represented by Formula 2 below,
The means for controlling the pore volume of the supported catalyst comprises (a) a method of controlling the content of the cocatalyst in step (1a) or step (1b); (b) a method of adjusting the total amount, content ratio, or both of the transition metal compound in step (1a); and (c) adding an additive before or after step (1a) or before or after step (1b) comprising at least one selected from the group consisting of,
Preparation of a supported metallocene catalyst for olefin polymerization, wherein the additive comprises at least one selected from the group consisting of aluminum stearate, sodium stearate, calcium stearate, zinc stearate, aluminum tristearate, aluminum acetate and zinc acetate method:
[Relational Expression 1]

[Formula 1]

[Formula 2]

In Formulas 1 and 2, M1 and M2 are each independently a Group 4 transition metal of the Periodic Table of the Elements;
X ₁ to X ₄ are each independently a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, alkylaryl having 7 to 40 carbon atoms group, an arylalkyl group having 7 to 40 carbon atoms, an alkylamido group having 1 to 20 carbon atoms, or an arylamido group having 6 to 20 carbon atoms;
R ₁ to R ₁₀ are each independently a hydrogen atom, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C6-C20 aryl group, 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 linked to each other to form a ring;
The _{cyclopentadiene to which R 1} to R ₅ is bonded and the cyclopentadiene to which R ₆ to R ₁₀ are bonded may have the same structure or different structures, and since each cyclopentadiene is not connected, the compound having a non-bridged structure to form,
R ₁₁ to R ₁₆ are each independently a hydrogen atom, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C6-C20 aryl group, 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 linked to each other to form a ring;
R ₁₇ and R ₁₈ are each independently a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C6-C20 aryl group, substituted or unsubstituted a cyclic alkylaryl group having 7 to 40 carbon atoms or a substituted or unsubstituted arylalkyl group having 7 to 40 carbon atoms, which may be linked to each other to form a ring;
R ₁₉ to R ₂₂ are each independently a hydrogen atom, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C6-C20 aryl group, 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 linked to each other to form a ring;
Indene bonded to R ₁₁ to R _{16 and cyclopentadiene bonded to R 19} to R ₂₂ are bonded to silicon (Si) to form a bridge structure. delete 2. The method of claim 1, wherein the first transition metal compound is [indenyl (cyclopentadienyl)] zirconium dichloride, [4-methylindenyl (cyclopentadienyl)] zirconium dichloride, [indenyl (tetramethylcyclo Pentadienyl)]zirconium dichloride, [2-methylindenyl (tetramethylcyclopentadienyl)]zirconium dichloride, [2-methylbenzoindenyl (cyclopentadienyl)]zirconium dichloride and [4,5 -benzoindenyl(tetramethylcyclopentadienyl)]zirconium dichloride;
The second 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) A method for producing a supported metallocene catalyst for olefin polymerization comprising at least one selected from the group consisting of zirconium dichloride. According to claim 1, wherein the first transition metal compound is [indenyl (cyclopentadienyl)] zirconium dichloride represented by the following formula (1a), the second transition metal compound is rac-dimethylsilylbis represented by the following formula (2a) (2-methyl-4-phenylindenyl) zirconium dichloride olefin polymerization method for preparing a supported metallocene catalyst:
[Formula 1a]

[Formula 2a]

In Formulas 1a and 2a, Me is a methyl group, and Ph is a phenyl group. The method of claim 1, wherein the first transition metal compound and the second transition metal compound are contained in a weight ratio of 20:1 to 1:20. According to claim 1, wherein the cocatalyst compound is at least one metallocene supported catalyst for olefin polymerization selected from the group consisting of a compound represented by the following formula (3), a compound represented by the following formula (4), and a compound represented by the following formula (5) Manufacturing method:
[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 C _1-20 hydrocarbon group, or a C _1-20 hydrocarbon group substituted with a 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 halogen-substituted C _1-20 hydrocarbon group. Or a C _1-20 alkoxy group,
In the above formula (5), L is a neutral or cationic Lewis base, [LH] ⁺ and [L] ⁺ are a Bronsted acid, Z is a group 13 element, A is each independently substituted or unsubstituted C _{6 It is a -20} aryl group or a substituted or unsubstituted C _1-20 alkyl group. The method according to claim 6, wherein the compound represented by Formula 3 is at least one selected from the group consisting of methylaluminoxane, ethylaluminoxane, isobutylaluminoxane and butylaluminoxane. . 7. The compound according to claim 6, wherein the compound represented by Formula 4 is trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, dimethylchloroaluminum, triisopropylaluminum, tri- s -butylaluminum, tri Cyclopentyl aluminum, tripentyl aluminum, triisopentyl aluminum, trihexyl aluminum, trioctyl aluminum, ethyl dimethyl aluminum, methyldiethyl aluminum, triphenyl aluminum, tri- p -tolyl aluminum, dimethyl aluminum methoxide, dimethyl aluminum ethoxy A method for preparing a supported metallocene catalyst for olefin polymerization, which is at least one selected from the group consisting of seed, trimethylboron, triethylboron, triisobutylboron, tripropylboron, and tributylboron. 7. The method according to claim 6, wherein the compound represented by Formula 5 is triethylammonium tetraphenylboron, tributylammonium tetraphenylboron, trimethylammonium tetraphenylboron, tripropylammonium tetraphenylboron, or trimethylammonium tetra( p). -Tolyl) boron, trimethylammonium tetra( o , p -dimethylphenyl) boron, tributylammonium tetra( p -trifluoromethylphenyl) boron, trimethylammonium tetra( p -trifluoromethylphenyl) boron, tributyl Ammonium tetrapentafluorophenyl boron, N,N-diethylanilinium tetraphenylboron, N,N-diethylaniliniumtetrapentafluorophenylboron, diethylammonium tetrapentafluorophenylboron, tri Phenylphosphonium tetraphenyl boron, trimethyl phosphonium tetraphenyl boron, triethyl ammonium tetraphenyl aluminum, tributyl ammonium tetraphenyl aluminum, trimethyl ammonium tetraphenyl aluminum, tripropyl ammonium tetraphenyl aluminum, trimethyl ammonium tetra ( p -tolyl)aluminum, tripropylammonium tetra( p -tolyl)aluminum, triethylammonium tetra( o , p -dimethylphenyl)aluminum, tributylammonium tetra( p -trifluoromethylphenyl)aluminum, trimethylammonium Umtetra( p -trifluoromethylphenyl)aluminum, tributylammonium tetrapentafluorophenylaluminum, N,N-diethylaniliniumtetraphenylaluminum, N,N-diethylaniliniumtetrapentafluorophenyl Aluminum, diethylammonium tetrapentatetraphenylaluminum, triphenylphosphoniumtetraphenylaluminum, trimethylphosphoniumtetraphenylaluminum, tripropylammonium tetra( p -tolyl)boron, triethylammoniumtetra( o , p -dimethyl Group consisting of phenyl) boron, tributylammonium tetra( p -trifluoromethylphenyl)boron, triphenylcarboniumtetra( p -trifluoromethylphenyl)boron and triphenylcarboniumtetrapentafluorophenylboron A method for producing at least one supported metallocene catalyst for olefin polymerization, which is selected from The method of claim 1, wherein the carrier comprises at least one selected from the group consisting of silica, alumina and magnesia. The method according to claim 10, wherein the first transition metal compound, the second transition metal compound, and the promoter compound are supported on a single type of carrier. The method of claim 11, wherein the first transition metal compound, the second transition metal compound, and the promoter compound are supported on silica. The method according to claim 11, wherein the total amount of the first transition metal compound and the second transition metal compound supported on the carrier is 0.5 to 3.0 wt% based on the total weight of the catalyst after being supported, and the amount of the promoter compound supported on the carrier is supported. A method for preparing a metallocene-supported catalyst for olefin polymerization in an amount of 20 to 30% by weight based on the total weight of the post catalyst. delete delete The method for preparing a supported metallocene catalyst for olefin polymerization according to claim 1, wherein the additive is added in an amount of 0.001 wt% or more and less than 20 wt% based on the total weight of the supported catalyst.

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