KR20210128041A - Mixed Catalytic Composition, Catalyst Comprising the Same, and Processes for Preparing the Same - Google Patents

Abstract

The present invention relates to a hybrid catalyst composition comprising a heterogeneous transition metal compound, a catalyst for olefin polymerization comprising the same, and a preparation method therefor. More specifically, the present invention relates to a hybrid catalyst composition comprising two or more transition metal compounds having asymmetric non-bridged bis(cyclopentadienyl) groups, each of which has a different center metal, a catalyst for olefin polymerization comprising the same, and a preparation method for the hybrid catalyst composition and the catalyst.

Description

Mixed Catalytic Composition, Catalyst Comprising the Same, and Processes for Preparing the Same

The present invention relates to a hybrid catalyst composition comprising a heterogeneous transition metal compound, a catalyst for olefin polymerization comprising the same, and a method for preparing the same. Specifically, the present invention relates to a hybrid catalyst composition comprising a heterogeneous transition metal compound having a non-bridged asymmetric biscyclopentadienyl (bisCp) group in which the central metal is different, and olefin polymerization comprising the same It relates to a catalyst for use and a method for preparing the hybrid catalyst composition and catalyst.

Polyolefin-based polymers are widely used in real life as materials for shopping bags, plastic houses, fishing nets, cigarette wrappers, ramen bags, yogurt bottles, battery cases, automobile bumpers, interior materials, shoe soles, washing machines, and the like.

Conventionally, polyolefin-based polymers such as polyethylene, polypropylene, and ethylene-alpha olefin copolymers and copolymers thereof have been prepared using a heterogeneous catalyst such as a Ziegler-Natta catalyst composed of a titanium compound and an alkyl aluminum compound.

Recently, a method for preparing polyolefin using a metallocene catalyst, which is a homogeneous catalyst with very high catalytic activity, has been studied. The metallocene catalyst is a compound in which ligands such as cyclopentadienyl, indenyl, and cycloheptadienyl are coordinated to a transition metal or transition metal halide compound, and has a sandwich structure in a basic form. . In this case, it has various molecular structures according to the type of ligand and the type of the central metal.

In a heterogeneous Ziegler-Natta catalyst, the metal component as the active site is dispersed on an inactive solid surface and the properties of the active site are not uniform, whereas the metallocene catalyst is a compound having a certain structure. Therefore, it is known as a single-site catalyst with all active sites having the same polymerization properties.

In general, since a metallocene catalyst has no activity as a polymerization catalyst by itself, it is used together with a cocatalyst such as methyl aluminoxane. The metallocene catalyst is activated as a cation by the action of the co-catalyst, and at the same time, the co-catalyst is an anion that is not coordinated with the metallocene catalyst and stabilizes the unsaturated cationic active species to form a catalyst system having activity in various olefin polymerizations.

Such a metallocene catalyst is easy to copolymerize and can control the three-dimensional structure of the polymer according to the symmetry of the catalyst, and the polymer prepared therefrom has a narrow molecular weight distribution and uniform distribution of comonomers.

On the other hand, the polymer prepared by the metallocene catalyst has a problem in that the mechanical strength is excellent but the processability is low due to a narrow molecular weight distribution. In order to solve this problem, various methods such as changing the molecular structure of the polymer or widening the molecular weight distribution have been proposed. For example, in U.S. Patent No. 5,272,236, a catalyst for introducing a long chain branch (LCB) as a side branch to the main chain of the polymer is used to improve the processability of the polymer, but in the case of a supported catalyst, there is a problem of low activity. do.

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

Meanwhile, in Korean Patent No. 1797890, a heterogeneous mixture of a first transition metal compound including a cyclopentadienyl group not connected by a bridge and an indenyl group and a second transition metal compound including a substituted bisindenyl group connected by a silyl bridge Metallocene catalysts are disclosed.

In general, such a hybrid catalyst is prepared by preparing each transition metal compound and then mixing it in a constant ratio and supporting it.

U.S. Patent No. 5,272,236 U.S. Patent No. 4,935,474 U.S. Patent No. 6,828,394 U.S. Patent No. 6,894,128 Korean Patent No. 1437509 U.S. Patent No. 6,841,631 Korean Patent No. 1797890

An object of the present invention is a hybrid catalyst composition comprising a heterogeneous transition metal compound having a non-bridged asymmetric biscyclopentadienyl (bisCp) group in which the central metal is different, and olefin polymerization including the same to provide a catalyst.

Another object of the present invention is to provide a method for preparing a hybrid catalyst composition and a catalyst for olefin polymerization comprising the same by adjusting the precursor ratio of the transition metal compound.

According to one embodiment for achieving the object of the present invention, there is provided a hybrid catalyst composition comprising a transition metal compound represented by Formulas 1 and 2 below.

[Formula 1]

[Formula 2]

In the above formulas 1 and 2, M ₁ and M ₂ are different and each independently titanium (Ti), zirconium (Zr) or hafnium (Hf),

each X is independently halogen, C _1-20 alkyl, C _2-20 alkenyl, C _2-20 alkynyl, C _6-20 aryl, C _1-20 alkyl C _6-20 aryl, C _6-20 aryl C _1-20 alkyl, C _1-20 alkylamido, C _6-20 arylamido or C _1-20 alkylidene;

R ₁ to R ₅ and R ₆ to R ₁₀ are each independently hydrogen, substituted or unsubstituted C _1-20 alkyl, substituted or unsubstituted C _2-20 alkenyl, substituted or unsubstituted C _6-20 aryl, substituted or unsubstituted C _{1 -20} alkyl C _6-20 aryl, substituted or unsubstituted C _6-20 aryl C _1-20 alkyl, substituted or unsubstituted C _1-20 heteroalkyl, substituted or unsubstituted C _3-20 heteroaryl, substituted or unsubstituted C _1-20 alkylamido, substituted or unsubstituted C _6-20 arylamido, substituted or unsubstituted C _1-20 alkylidene, or substituted or unsubstituted C _1-20 silyl;

R ₁ to R ₅ and R ₆ to R ₁₀ may be each independently connected to adjacent groups to form a substituted or unsubstituted saturated or unsaturated C _4-20 ring.

Preferably, the molar ratio of the compound represented by Formula 1 to the compound represented by Formula 2 above may be in the range of 50:1 to 1:50.

Specifically, in the above formulas 1 and 2, M ₁ and M ₂ are different from each other and each is zirconium or hafnium, X is halogen or substituted or unsubstituted C _1-20 alkyl, R ₁ to R ₅ and R ₆ to R ₁₀ may each be hydrogen, substituted or unsubstituted C _1-20 alkyl, substituted or unsubstituted C _1-20 alkenyl, or substituted or unsubstituted C _6-20 aryl.

Preferably, the transition metal compound represented by Formula 1 above is at least one of the transition metal compounds represented by Formulas 1-1 to 1-18 below, and the transition metal compound represented by Formula 2 is selected from Formulas 2-1 to 1-18 below. At least one of the transition metal compounds represented by 2-18.

[Formula 1-1] [Formula 1-2] [Formula 1-3]

[Formula 1-4] [Formula 1-5] [Formula 1-6]

[Formula 1-7] [Formula 1-8] [Formula 1-9]

[Formula 1-10] [Formula 1-11] [Formula 1-12]

[Formula 1-13] [Formula 1-14] [Formula 1-15]

[Formula 1-16] [Formula 1-17] [Formula 1-18]

[Formula 2-1] [Formula 2-2] [Formula 2-3]

[Formula 2-4] [Formula 2-5] [Formula 2-6]

[Formula 2-7] [Formula 2-8] [Formula 2-9]

[Formula 2-10] [Formula 2-11] [Formula 2-12]

[Formula 2-13] [Formula 2-14] [Formula 2-15]

[Formula 2-16] [Formula 2-17] [Formula 2-18]

According to one embodiment of the present invention, (1) dissolving any one of the compound represented by the following formula (3) and the compound represented by the following formula (4) in a solvent; (2) adding a compound represented by the following formula (5) and a compound represented by the following formula (6) to the solution obtained in step (1), followed by reacting with stirring; (3) to the reaction mixture obtained in step (2), after adding another one of the compound represented by the following formula (3) and the compound represented by the following formula (4), followed by reacting under stirring, represented by the above formulas 1 and 2 A method for preparing a hybrid catalyst composition comprising a transition metal compound is provided.

[Formula 3]

[Formula 4]

[Formula 5]

M ₁ X ₄

[Formula 6]

M ₂ X ₄

In Formulas 3 to 6 above, M ₁ , M ₂ , X, R ₁ to R ₅ and R ₆ to R ₁₀ are the same as described in the hybrid catalyst composition comprising a heterogeneous transition metal compound above.

Preferably, the compound represented by Formula 3 above is at least one of the compounds represented by Formulas 3-1 to 3-6 below, and the compound represented by Formula 4 is represented by Formulas 4-1 to 4-7 below. at least one of the compounds.

[Formula 3-1] [Formula 3-2] [Formula 3-3]

[Formula 3-4] [Formula 3-5] [Formula 3-6]

[Formula 4-1] [Formula 4-2] [Formula 4-3]

[Formula 4-4] [Formula 4-5] [Formula 4-6]

[Formula 4-7]

Here, the solvent may include at least one selected from the group consisting of hexane, pentane, toluene, benzene, dichloromethane, diethyl ether, tetrahydrofuran, acetone, and ethyl acetate.

Preferably, the compound represented by the above formula (5) and the compound represented by the above formula (6) are different from each other and each ZrCl ₄ or HfCl ₄ .

Here, the molar ratio of the compound represented by Formula 5 to the compound represented by Formula 6 above may be in the range of 50:1 to 1:50.

Preferably, in the above step (2), the reaction temperature is 0° C. to 120° C., and the reaction time is 1 to 72 hours.

In addition, in the above step (3), the reaction temperature is 0 °C to 120 °C, and the reaction time is 1 to 72 hours.

Preferably, the compound represented by the above formula (3) may be used in step (1), and the compound represented by the above formula (4) may be used in step (3).

Preferably, the molar ratio of the compound represented by Formula 3 to the compound represented by Formula 4 above may be in the range of 50:1 to 1:50.

The method for preparing a hybrid catalyst composition according to an embodiment of the present invention may further include (3') drying the hybrid catalyst composition in step (3).

In addition, the method for preparing a hybrid catalyst composition according to an embodiment of the present invention comprises (3") dissolving the dry hybrid catalyst composition obtained in step (3') in a solvent and then removing unreacted substances and/or impurities with a filter. Additional steps may be included.

Here, the solvent may include at least one selected from the group consisting of hexane, pentane, toluene, benzene, dichloromethane, diethyl ether, tetrahydrofuran, acetone, and ethyl acetate.

According to one embodiment for achieving another object of the present invention, a hybrid catalyst composition comprising a transition metal compound represented by Formulas 1 and 2 above; and a catalyst for olefin polymerization comprising a cocatalyst compound.

Here, the cocatalyst compound may be at least one selected from the group consisting of a compound represented by the following Chemical Formula 7, a compound represented by Chemical Formula 8, and a compound represented by Chemical Formula 9.

[Formula 7]

[Formula 8]

[Formula 9]

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

In the above formula (7), 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 Chemical Formula 8, 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 (9), 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.

Specifically, the compound represented by Chemical Formula 7 is at least one selected from the group consisting of methylaluminoxane, ethylaluminoxane, isobutylaluminoxane and butylaluminoxane.

In addition, the compound represented by Formula 8 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 (9) is 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 Tetraphenyl boron, trimethylphosphonium tetraphenyl boron, triethylammonium 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, 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 rephenylcarboniumtetrapentafluorophenylboron selected from the group consisting of at least one

Preferably, the catalyst for olefin polymerization further includes a carrier supporting the hybrid catalyst composition. Specifically, the carrier may support both the hybrid catalyst composition and the cocatalyst compound.

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

Here, the total amount of the hybrid transition metal compound supported on the carrier is 0.001 to 1 mmole based on 1 g of the carrier, and the amount of the cocatalyst compound supported on the carrier is 2 to 15 mmole based on 1 g of the carrier.

According to another embodiment of the present invention, (1) dissolving any one of the compound represented by the above formula (3) and the compound represented by the above formula (4) in a solvent; (2) adding the compound represented by the above formula (5) and the compound represented by the above formula (6) to the solution obtained in step (1), followed by reacting with stirring; (3) to the reaction mixture obtained in step (2), the other one of the compound represented by the above formula (3) and the compound represented by the above formula (4) is added and reacted under stirring, and the transition metal compound represented by the above formulas (1) and (2) obtaining a hybrid catalyst composition comprising; (4) There is provided a method for preparing a catalyst for olefin polymerization comprising the step of supporting the hybrid catalyst composition obtained in step (3), the cocatalyst compound, or both on a carrier.

The hybrid catalyst composition comprising a heterogeneous transition metal compound and the catalyst for olefin polymerization comprising the same according to an embodiment of the present invention can prepare polyolefins having excellent processability and mechanical properties according to the content of the transition metal compound.

In addition, a hybrid catalyst composition comprising a heterogeneous transition metal compound and a method for preparing a catalyst for olefin polymerization comprising the same include a catalyst for polyolefin polymerization having excellent processability and mechanical properties by precisely controlling the ratio of the mixed transition metal compound. can be provided easily.

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

Hybrid catalyst composition comprising heterogeneous transition metal compounds

According to one embodiment of the present invention, there is provided a hybrid catalyst composition comprising a transition metal compound represented by Formulas 1 and 2 below.

[Formula 1]

[Formula 2]

In Formulas 1 and 2, M ₁ and M ₂ are different from each other and are titanium (Ti), zirconium (Zr), or hafnium (Hf). Specifically, M ₁ and M ₂ may be different from each other and may be zirconium or hafnium.

each X is independently halogen, C _1-20 alkyl, C _2-20 alkenyl, C _2-20 alkynyl, C _6-20 aryl, C _1-20 alkyl C _6-20 aryl, C _6-20 aryl C _1-20 alkyl, C _1-20 alkylamido, C _6-20 arylamido or C _1-20 alkylidene. Specifically, each X may be halogen or substituted or unsubstituted C _1-20 alkyl. More specifically, each X may be chlorine.

R ₁ to R ₅ and R ₆ to R ₁₀ are each independently hydrogen, substituted or unsubstituted C _1-20 alkyl, substituted or unsubstituted C _2-20 alkenyl, substituted or unsubstituted C _6-20 aryl, substituted or unsubstituted C _{1 -20} alkyl C _6-20 aryl, substituted or unsubstituted C _6-20 aryl C _1-20 alkyl, substituted or unsubstituted C _1-20 heteroalkyl, substituted or unsubstituted C _3-20 heteroaryl, substituted or unsubstituted C _1-20 alkylamido, substituted or unsubstituted C _6-20 arylamido, substituted or unsubstituted C _1-20 alkylidene, or substituted or unsubstituted C _1-20 silyl. where R ₁ to R ₅ and R ₆ to R ₁₀ may be each independently connected to adjacent groups to form a substituted or unsubstituted saturated or unsaturated C _4-20 ring. Specifically, R ₁ to R ₅ and R ₆ to R ₁₀ may each be hydrogen, substituted or unsubstituted C _1-20 alkyl, substituted or unsubstituted C _1-20 alkenyl, or substituted or unsubstituted C _6-20 aryl.

In a preferred embodiment of the present invention, the molar ratio of the compound represented by Formula 1 to the compound represented by Formula 2 above may be in the range of 50:1 to 1:50. Preferably, the molar ratio of these two compounds is from 10:1 to 1:10. More preferably, the molar ratio of these two compounds is 3:1 to 1:3.

In a preferred embodiment of the present invention, in the above formulas 1 and 2, M ₁ and M ₂ are different from each other and are zirconium or hafnium, X is halogen or substituted or unsubstituted C _1-20 alkyl, R ₁ to R ₅ and R ₆ to R ₁₀ may each be hydrogen, substituted or unsubstituted C _1-20 alkyl, substituted or unsubstituted C _1-20 alkenyl, or substituted or unsubstituted C _6-20 aryl.

In a more preferred embodiment of the present invention, the transition metal compound represented by Formula 1 above is at least one of the transition metal compounds represented by Formulas 1-1 to 1-18 below, and the transition metal compound represented by Formula 2 above is It may be at least one of the transition metal compounds represented by Formulas 2-1 to 2-18 below.

[Formula 1-1] [Formula 1-2] [Formula 1-3]

[Formula 1-4] [Formula 1-5] [Formula 1-6]

[Formula 1-7] [Formula 1-8] [Formula 1-9]

[Formula 1-10] [Formula 1-11] [Formula 1-12]

[Formula 1-13] [Formula 1-14] [Formula 1-15]

[Formula 1-16] [Formula 1-17] [Formula 1-18]

[Formula 2-1] [Formula 2-2] [Formula 2-3]

[Formula 2-4] [Formula 2-5] [Formula 2-6]

[Formula 2-7] [Formula 2-8] [Formula 2-9]

[Formula 2-10] [Formula 2-11] [Formula 2-12]

[Formula 2-13] [Formula 2-14] [Formula 2-15]

[Formula 2-16] [Formula 2-17] [Formula 2-18]

Method for preparing hybrid catalyst composition

According to one embodiment of the present invention, (1) dissolving any one of the compound represented by the following formula (3) and the compound represented by the following formula (4) in a solvent; (2) adding a compound represented by the following formula (5) and a compound represented by the following formula (6) to the solution obtained in step (1), followed by reacting with stirring; (3) to the reaction mixture obtained in step (2), after adding another one of the compound represented by the following formula (3) and the compound represented by the following formula (4), followed by reacting under stirring, represented by the above formulas 1 and 2 A method for preparing a hybrid catalyst composition comprising a transition metal compound is provided.

[Formula 3]

[Formula 4]

[Formula 5]

M ₁ X ₄

[Formula 6]

M ₂ X ₄

In Formulas 3 to 6 above, M ₁ , M ₂ , X, R ₁ to R ₅ and R ₆ to R ₁₀ are the same as described in the hybrid catalyst composition comprising a heterogeneous transition metal compound above.

Step (1)

Specifically, in the above step (1), any one of the compound represented by Formula 3 and the compound represented by Formula 4 above is dissolved in a solvent.

Preferably, the compound represented by Formula 3 is at least one of the compounds represented by Formulas 3-1 to 3-6 below, and the compound represented by Formula 4 is represented by Formulas 4-1 to 4-7 below. It may be at least one of the compounds.

[Formula 3-1] [Formula 3-2] [Formula 3-3]

[Formula 3-4] [Formula 3-5] [Formula 3-6]

[Formula 4-1] [Formula 4-2] [Formula 4-3]

[Formula 4-4] [Formula 4-5] [Formula 4-6]

[Formula 4-7]

Here, 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, an etheric solvent such as diethyl ether and tetrahydrofuran, acetone and ethyl It may include at least one selected from the group consisting of acetate. Preferably, the above solvent may be toluene, but is not particularly limited thereto.

When any one of the compound represented by the above formula (3) and the compound represented by the above formula (4) is dissolved in a solvent, the temperature and the dissolution time are not particularly limited. For example, at a temperature of -78°C to 80°C, preferably at a temperature of -40°C to 60°C, more preferably at a temperature of room temperature, any of the compound represented by Formula 3 and the compound represented by Formula 4 One can be added to the solvent and stirred to dissolve it for 10 minutes to 17 hours, preferably 20 minutes to 10 hours, more preferably about 1 hour.

Step (2)

In step (2), the compound represented by the above formula (5) and the compound represented by the above formula (6) are added to the solution obtained in step (1), and then reacted under stirring.

Preferably, the compound represented by the above formula (5) and the compound represented by the above formula (6) are different from each other and each ZrCl ₄ or HfCl ₄ .

Here, the molar ratio of the compound represented by Formula 5 to the compound represented by Formula 6 above may be in the range of 50:1 to 1:50. Preferably, the molar ratio of these two compounds is 5:1 to 1:5. More preferably, the molar ratio of these two compounds is 3:1 to 1:3.

The temperature at the time of adding the compound represented by the formula (5) and the compound represented by the formula (6) is preferably in the range of -78°C to 30°C. More preferably, the temperature at which the compound represented by Formula 5 and the compound represented by Formula 6 are added may be -40°C to 10°C. Most preferably, the temperature at which the compound represented by Formula 6 is added may be -30°C.

After adding the compound represented by the formula (5) and the compound represented by the formula (6), the temperature is gradually raised to a range of 0°C to 120°C, more preferably 25°C to 80°C, and most preferably about 60°C. The reaction is carried out under stirring for 1 to 72 hours, preferably 5 to 48 hours, more preferably about 24 hours.

Step (3)

In the above step (3), the other one of the compound represented by the following formula (3) and the compound represented by the following formula (4) is added to the reaction mixture obtained in the step (2), and then reacted under stirring.

When the other one of the compound represented by Formula 3 and the compound represented by Formula 4 is added, the temperature is preferably in the range of -78°C to 30°C. More preferably, the temperature when the other one of the compound represented by Formula 3 and the compound represented by Formula 4 is added may be -40°C to 10°C. Most preferably, the temperature at which the other one of the compound represented by Formula 3 and the compound represented by Formula 4 is added may be -30°C.

After adding the other one of the compound represented by the above formula (3) and the compound represented by the above formula (4), the temperature is in the range of 0°C to 120°C, more preferably in the range of 0°C to 60°C, most preferably at room temperature. The reaction is carried out under stirring for 1 to 72 hours, preferably 3 to 24 hours, more preferably about 7 hours.

In the preparation method according to a preferred embodiment of the present invention, the compound represented by the above formula (3) may be used in step (1), and the compound represented by the above formula (4) may be used in step (3).

In addition, the molar ratio of the compound represented by Formula 3 to the compound represented by Formula 4 above may be in the range of 50:1 to 1:50. Preferably, the molar ratio of these two compounds is from 10:1 to 1:10. More preferably, the molar ratio of these two compounds is 3:1 to 1:3.

The method for preparing a hybrid catalyst composition according to an embodiment of the present invention may further include (3') drying the hybrid catalyst composition obtained in step (3). Here, the drying conditions of the composition are not particularly limited, but may be carried out in a temperature range of 25°C to 80°C, more preferably in a temperature range of 25°C to 50°C, and most preferably at a temperature of about 25°C.

In addition, the method for preparing a hybrid catalyst composition according to another embodiment of the present invention comprises (3") dissolving the dry hybrid catalyst composition obtained in step (3') in a solvent and then removing unreacted substances and/or impurities with a filter. It may further comprise a step, wherein the solvent may be substantially the same as the solvent used in the above step (1). Preferably, dichloromethane may be used, but is not limited thereto. / or a filter for removing impurities is not particularly limited, but it is preferable to use a Celite filter.

Catalyst for Olefin Polymerization

According to another embodiment of the present invention, a hybrid catalyst composition comprising a transition metal compound represented by Formulas 1 and 2 below; and a catalyst for olefin polymerization comprising a cocatalyst compound.

[Formula 1]

[Formula 2]

In Formulas 1 and 2 above, M ₁ , M ₂ , X, R ₁ to R ₅ and R ₆ to R ₁₀ are the same as described in the hybrid catalyst composition comprising a heterogeneous transition metal compound above.

In a preferred embodiment of the present invention, the molar ratio of the compound represented by Formula 1 to the compound represented by Formula 2 above may be in the range of 50:1 to 1:50. Preferably, the molar ratio of these two compounds is from 10:1 to 1:10. More preferably, the molar ratio of these two compounds is 3:1 to 1:3.

In a preferred embodiment of the present invention, in Formulas 1 and 2, M ₁ and M ₂ are different from each other and each is zirconium or hafnium, X is halogen or substituted or unsubstituted C _1-20 alkyl, R ₁ to R ₅ and R ₆ to R ₁₀ may each be hydrogen, substituted or unsubstituted C _1-20 alkyl, substituted or unsubstituted C _1-20 alkenyl, or substituted or unsubstituted C _6-20 aryl.

In a more preferred embodiment of the present invention, the transition metal compound represented by Formula 1 above is at least one of the transition metal compounds represented by Formulas 1-1 to 1-18 below, and the transition metal compound represented by Formula 2 above is It may be at least one of the transition metal compounds represented by Formulas 2-1 to 2-18 below.

[Formula 1-1] [Formula 1-2] [Formula 1-3]

[Formula 1-4] [Formula 1-5] [Formula 1-6]

[Formula 1-7] [Formula 1-8] [Formula 1-9]

[Formula 1-10] [Formula 1-11] [Formula 1-12]

[Formula 1-13] [Formula 1-14] [Formula 1-15]

[Formula 1-16] [Formula 1-17] [Formula 1-18]

[Formula 2-1] [Formula 2-2] [Formula 2-3]

[Formula 2-4] [Formula 2-5] [Formula 2-6]

[Formula 2-7] [Formula 2-8] [Formula 2-9]

[Formula 2-10] [Formula 2-11] [Formula 2-12]

[Formula 2-13] [Formula 2-14] [Formula 2-15]

[Formula 2-16] [Formula 2-17] [Formula 2-18]

Meanwhile, the promoter compound may include at least one of a compound represented by the following Chemical Formula 7, a compound represented by Chemical Formula 8, and a compound represented by Chemical Formula 9.

[Formula 7]

In Formula 7, n is an integer of 2 or more, and R _a may be a halogen atom, a C _1-20 hydrocarbon, or a halogen-substituted C _1-20 hydrocarbon. Specifically, R _a may be methyl, ethyl, n -butyl or isobutyl.

[Formula 8]

In Chemical Formula 8, 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. 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 9]

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

In the above formula (9), 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. 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] ⁺ .

Specifically, examples of the compound represented by Chemical Formula 7 include methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, butylaluminoxane, and the like, and methylaluminoxane is preferred, but is not limited thereto.

Examples of the compound represented by the above formula (8) 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 (9) 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 Tetraphenyl boron, trimethylphosphonium tetraphenyl boron, triethylammonium 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, 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 rephenylcarboniumtetrapentafluorophenylboron.

In a preferred embodiment of the present invention, the catalyst for olefin polymerization may further include a carrier supporting the hybrid catalyst composition. Specifically, the carrier may support both the hybrid catalyst composition and the cocatalyst compound.

In this case, the carrier may include a material containing a hydroxyl group on the surface, and preferably a material having a high reactivity hydroxyl group and a siloxane group, which is 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, 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 transition metal compound 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 room temperature ~ 900 ℃. The drying temperature may be preferably from room temperature to 800°C, more preferably from room temperature to 700°C. When the drying temperature is lower than room temperature, there is too much moisture, so that the surface moisture and the cocatalyst react, and when it exceeds 900° C., the structure of the carrier may collapse.

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 total amount of the hybrid transition metal compound supported on the carrier may be 0.001 to 1 mmole based on 1 g of the carrier. When the ratio of the hybrid transition metal compound and the carrier satisfies the above range, an appropriate supported catalyst activity is exhibited, which is advantageous in terms of maintaining the activity of the catalyst and economic feasibility.

The amount of the promoter compound supported on the carrier may be 2 to 15 mmole based on 1 g of the carrier. When the ratio of the promoter compound and the carrier satisfies the above range, it is advantageous in terms of maintaining the activity of the catalyst and economic feasibility.

One type or two or more types of carriers may be used. For example, both the hybrid catalyst composition and the promoter compound may be supported on one type of support, or the hybrid catalyst composition and the promoter compound may be supported on two or more types of support, respectively. In addition, only one of the hybrid catalyst composition and the cocatalyst compound may be supported on the carrier.

Method for preparing catalyst for olefin polymerization

According to another embodiment of the present invention, (1) dissolving any one of the compound represented by the above formula (3) and the compound represented by the above formula (4) in a solvent; (2) adding the compound represented by the above formula (5) and the compound represented by the above formula (6) to the solution obtained in step (1), followed by reacting with stirring; (3) to the reaction mixture obtained in step (2), the other one of the compound represented by the above formula (3) and the compound represented by the above formula (4) is added and reacted under stirring, and the transition metal compound represented by the above formulas (1) and (2) obtaining a hybrid catalyst composition comprising; (4) There is provided a method for preparing a catalyst for olefin polymerization comprising the step of supporting the hybrid catalyst composition obtained in step (3), the cocatalyst compound, or both on a carrier.

[Formula 1]

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

M ₁ X ₄

[Formula 6]

M ₂ X ₄

In Formulas 1 to 6 above, M ₁ , M ₂ , X, R ₁ to R ₅ and R ₆ to R ₁₀ are the same as described in the hybrid catalyst composition comprising a heterogeneous transition metal compound above.

Specific details of steps (1) to (3) are substantially the same as steps (1) to (3) of the method for preparing the hybrid catalyst composition.

The method for preparing a catalyst for olefin polymerization according to another embodiment of the present invention may further include (3') drying the composition obtained in step (3). In this case, the specific content of the step (3') is substantially the same as the step (3') of the method for preparing the hybrid catalyst composition.

In addition, the method for preparing a catalyst for olefin polymerization according to another embodiment of the present invention comprises the steps of (3") dissolving the dry composition obtained in step (3') above in a solvent and then removing unreacted substances and/or impurities with a filter. In this case, the specific details of the above step (3") are substantially the same as the step (3") of the above method for preparing the hybrid catalyst composition.

Step (4)

In the above step (4), the hybrid catalyst composition, the cocatalyst compound, or both are supported on a carrier.

As a method for supporting the hybrid catalyst composition and/or the cocatalyst compound, a physical adsorption method or a chemical adsorption method may be used.

For example, the physical adsorption method is a method of drying a solution in which the hybrid catalyst composition is dissolved in contact with a carrier and then drying, a method in which a solution in which the hybrid catalyst composition and a cocatalyst compound are dissolved is contacted with a carrier and then drying, or a hybrid catalyst composition The dissolved solution is brought into contact with the carrier and dried to prepare a carrier on which the hybrid catalyst composition is supported. Separately, a solution in which the cocatalyst compound is dissolved is contacted with the carrier and dried to prepare a carrier on which the cocatalyst compound is supported. After that, it may be a method of mixing them.

The chemical adsorption method is a method in which a promoter compound is first supported on the surface of a carrier, and then a hybrid catalyst composition is supported on the promoter compound, or a functional group on the surface of the support (for example, in the case of silica, a hydroxyl group on the silica surface (-OH) )) and a method of covalently bonding a hybrid transition metal compound and the like.

Here, the solvent used for supporting the hybrid catalyst composition and/or the cocatalyst compound is not particularly limited. For example, the solvent may be 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 etheric solvent such as diethyl ether or tetrahydrofuran, acetone And it may include at least one selected from the group consisting of ethyl acetate.

In a preferred embodiment, the process of supporting the hybrid catalyst composition and/or the cocatalyst compound on the carrier in step (4) above may be performed 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 hybrid catalyst composition and/or the promoter compound on the carrier in step (4) is performed by reacting the hybrid catalyst composition and/or the mixture of the promoter compound and the carrier for 1 minute to 24 hours, preferably 5 minutes to 15 minutes. It can be carried out by sufficiently stirring for a period of time.

polymerization of olefins

An olefin-based polymer may be prepared by polymerizing an olefin-based monomer in the presence of a catalyst for olefin polymerization according to 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.

The olefinic monomer is composed of C _2-20 alpha-olefin, C _1-20 diolefin, C _3-20 cycloolefin and C _3-20 cyclodiolefin. at least one selected from the group.

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 of ethylene and C _3-20 alpha-olefin, preferably a copolymer of ethylene and 1-hexene, 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 a solution polymerization method or a slurry polymerization method, examples of the solvent that can be used include C _5-12 aliphatic hydrocarbon solvents 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.

Example

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

Example One

164 mg (1.16 mmole, 4.8 eq.) of lithium pentamethylcyclopentadienide of Formula 3-1 above was dissolved in 20 ml of toluene at room temperature. While stirring this slowly, at -30°C, zirconium chloride (ZrCl ₄ ) 56 mg (0.24 mmole, 1.0 eq.) and hafnium chloride (HfCl ₄ ) 232 mg (0.72 mmole, 3.0 eq.) were slowly added so as not to generate heat. Then, the mixture was stirred at 60° C. for 24 hours. Lower the temperature to -30 ℃, lithium n of Formula 4-1 above, the reaction mixture - (. 0.96 mmole, 4.0 eq ) the profile cyclopenta Deanna Id (lithium n -propylcyclopentadienide) 110 ㎎ was added slowly. This was reacted by stirring at room temperature for 7 hours. After removing lithium chloride (LiCl) with a Celite filter, the product was dried to obtain the compound of Formula 1-1 ((pentamethylcyclopentadienyl) ( n -propylcyclopentadienyl) zirconium dichloride) and the compound of Formula 2-1 ((pentamethylcyclopentadienyl) ( n 294 mg (yield: 65%) of a mixture of -propylcyclopentadienyl) hafnium dichloride) was obtained.

^The structure of the hybrid (1:3) transition metal compound of the compound of Formula 1-1 was confirmed by 1 H NMR.

¹ H-NMR (CDCl ₃ , 300 MHz) 6.03-6.01 (m, 2H), 5.96-5.92 (m, 8H), 5.89-5.87 (m, 6H), 2.65-2.58 (m, 8H), 2.07 (s) , 45H), 2.02 (s, 15H), 1.60-1.53 (m, 8H), 0.95-0.89 (m, 12H).

Example 2

160 mg (1.12 mmole, 2.4 eq.) of lithium pentamethylcyclopentadienide of Formula 3-1 above was dissolved in 20 ml of toluene at room temperature. With slow stirring, 109 mg (0.47 mmole, 1.0 eq.) of zirconium chloride and 150 mg (0.47 mmole, 1.0 eq.) of hafnium chloride were slowly added so that no heat was generated at -30° C., and then at 60° C. for 24 hours. stirred. After the temperature was lowered to -30°C, 107 mg (0.94 mmole, 2.0 eq.) of lithium n-propylcyclopentadienide of Formula 4-1 above was slowly added to the reaction mixture. This was reacted by stirring at room temperature for 7 hours. After removing lithium chloride (LiCl) through a Celite filter, the product was dried to obtain 324 mg (yield: 77%) of a mixture of the compound of Formula 1-1 and the compound of Formula 2-1.

^The structure of the hybrid (1:1) transition metal compound of the compound of Formula 1-1 was confirmed by 1 H NMR.

¹ H-NMR (CDCl ₃ , 300 MHz) 6.03-6.01 (m, 2H), 5.96-5.92 (m, 4H), 5.89-5.87 (m, 2H), 2.65-2.58 (m, 4H), 2.07 (s) , 15H), 2.02 (s, 15H), 1.60-1.53 (m, 4H), 0.95-0.89 (m, 6H).

Example 3

164 mg (1.16 mmole, 4.8 eq.) of lithium pentamethylcyclopentadienide of Formula 3-1 above was dissolved in 20 ml of toluene at room temperature. With slow stirring, 168 mg (0.72 mmole, 3.0 eq.) of zirconium chloride and 77 mg (0.24 mmole, 3.0 eq.) of hafnium chloride were slowly added at -30°C so that no heat was generated, and then at 60°C for 24 hours. stirred. After the temperature was lowered to -30°C, 110 mg (0.96 mmole, 4.0 eq.) of lithium n-propylcyclopentadienide of Formula 4-1 above was slowly added to the reaction mixture. This was reacted by stirring at room temperature for 7 hours. After removing lithium chloride (LiCl) with a Celite filter, the product was dried to obtain 325 mg (yield: 79%) of a mixture of the compound of Formula 1-1 and the compound of Formula 2-1.

^The structure of the hybrid (3:1) transition metal compound of the compound of Formula 1-1 was confirmed by 1 H NMR.

¹ H-NMR (CDCl ₃ , 300 MHz) 6.03-6.01 (m, 6H), 5.96-5.92 (m, 8H), 5.89-5.87 (m, 2H), 2.65-2.58 (m, 8H), 2.07 (s) , 15H), 2.02 (s, 45H), 1.60-1.53 (m, 8H), 0.95-0.89 (m, 12H).

The composition ratios of the reactants and products of the above examples are shown in Table 1 below.

Example reactant (eq.) product (molar ratio) transference number(%) chemical formula
3-1 chemical formula
5-1 chemical formula
6-1 chemical formula
4-1 chemical formula
1-1 chemical formula
2-1 One 4.8 1.0 3.0 4.0 One 3 65 2 2.4 1.0 1.0 2.0 One One 77 3 4.8 3.0 1.0 4.0 3 One 79

The hybrid catalyst composition comprising a heterogeneous transition metal compound and the catalyst for olefin polymerization comprising the same according to an embodiment of the present invention can prepare various polyolefins having excellent processability and mechanical properties depending on the content of the corresponding transition metal compound.

In addition, the hybrid catalyst composition and the method for preparing a catalyst for olefin polymerization including the same can easily provide a catalyst for polyolefin polymerization having excellent processability and mechanical properties by precisely controlling the ratio of the hybrid transition metal compound.

Claims (25)

A hybrid catalyst composition comprising a transition metal compound represented by Formulas 1 and 2 below:
[Formula 1]

[Formula 2]

In Formulas 1 to 3, M ₁ and M ₂ are different and each independently titanium (Ti), zirconium (Zr) or hafnium (Hf),
each X is independently halogen, C _1-20 alkyl, C _2-20 alkenyl, C _2-20 alkynyl, C _6-20 aryl, C _1-20 alkyl C _6-20 aryl, C _6-20 aryl C _1-20 alkyl, C _1-20 alkylamido, C _6-20 arylamido or C _1-20 alkylidene;
R ₁ to R ₅ and R ₆ to R ₁₀ are each independently hydrogen, substituted or unsubstituted C _1-20 alkyl, substituted or unsubstituted C _2-20 alkenyl, substituted or unsubstituted C _6-20 aryl, substituted or unsubstituted C _{1 -20} alkyl C _6-20 aryl, substituted or unsubstituted C _6-20 aryl C _1-20 alkyl, substituted or unsubstituted C _1-20 heteroalkyl, substituted or unsubstituted C _3-20 heteroaryl, substituted or unsubstituted C _1-20 alkylamido, substituted or unsubstituted C _6-20 arylamido, substituted or unsubstituted C _1-20 alkylidene, or substituted or unsubstituted C _1-20 silyl;
R ₁ to R ₅ and R ₆ to R ₁₀ may be each independently connected to adjacent groups to form a substituted or unsubstituted saturated or unsaturated C _4-20 ring. The hybrid catalyst composition of claim 1, wherein the molar ratio of the compound represented by Formula 1 to the compound represented by Formula 2 is in the range of 50:1 to 1:50. The method according to claim 1, wherein M ₁ and M ₂ are different from each other and each is zirconium or hafnium, X is each halogen or substituted or unsubstituted C _1-20 alkyl, and R ₁ to R ₅ and R ₆ to R ₁₀ are each hydrogen, substituted or unsubstituted C _1-20 alkyl, substituted or unsubstituted C _1-20 alkenyl, or substituted or unsubstituted C _6-20 aryl. The method according to claim 1, wherein the transition metal compound represented by Formula 1 is at least one of the transition metal compounds represented by Formulas 1-1 to 1-18, and the transition metal compound represented by Formula 2 is represented by Formula 2- At least one of the transition metal compounds represented by 1 to 2-18, a hybrid catalyst composition:
[Formula 1-1] [Formula 1-2] [Formula 1-3]

[Formula 1-4] [Formula 1-5] [Formula 1-6]

[Formula 1-7] [Formula 1-8] [Formula 1-9]

[Formula 1-10] [Formula 1-11] [Formula 1-12]

[Formula 1-13] [Formula 1-14] [Formula 1-15]

[Formula 1-16] [Formula 1-17] [Formula 1-18]

[Formula 2-1] [Formula 2-2] [Formula 2-3]

[Formula 2-4] [Formula 2-5] [Formula 2-6]

[Formula 2-7] [Formula 2-8] [Formula 2-9]

[Formula 2-10] [Formula 2-11] [Formula 2-12]

[Formula 2-13] [Formula 2-14] [Formula 2-15]

[Formula 2-16] [Formula 2-17] [Formula 2-18]

. (1) dissolving any one of the compound represented by the following formula (3) and the compound represented by the following formula (4) in a solvent; (2) adding a compound represented by the following formula (5) and a compound represented by the following formula (6) to the solution obtained in step (1), followed by reacting with stirring; (3) to the reaction mixture obtained in step (2), adding another one of the compound represented by the following formula (3) and the compound represented by the following formula (4), followed by reacting under stirring, represented by the following formulas 1 and 2 Method for preparing a hybrid catalyst composition comprising a transition metal compound to be:
[Formula 1]

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]
M ₁ X ₄
[Formula 6]
M ₂ X ₄
In Formulas 1 to 6 above, M ₁ , M ₂ , X, R ₁ to R ₅ and R ₆ to R ₁₀ are as defined in claim 1. The method according to claim 5, wherein the compound represented by Formula 3 is at least one of the compounds represented by Formulas 3-1 to 3-6, and the compound represented by Formula 4 is represented by Formulas 4-1 to 4-7 below. At least one of the indicated compounds, a method for preparing a hybrid catalyst composition:
[Formula 3-1] [Formula 3-2] [Formula 3-3]

[Formula 3-4] [Formula 3-5] [Formula 3-6]

[Formula 4-1] [Formula 4-2] [Formula 4-3]

[Formula 4-4] [Formula 4-5] [Formula 4-6]

[Formula 4-7]

. The method according to claim 5, wherein the solvent comprises at least one selected from the group consisting of hexane, pentane, toluene, benzene, dichloromethane, diethyl ether, tetrahydrofuran, acetone and ethyl acetate. Preparation of a hybrid catalyst composition Way. The method of claim 5, wherein the compound represented by Formula 5 and the compound represented by Formula 6 are different from each other and each is ZrCl ₄ or HfCl ₄ , the method for preparing a hybrid catalyst composition. The method of claim 5, wherein the molar ratio of the compound represented by Formula 5 to the compound represented by Formula 6 is in the range of 50:1 to 1:50. The method of claim 5, wherein the reaction temperature in step (2) is 0° C. to 120° C., and the reaction time is 1 to 72 hours. The method of claim 5, wherein the reaction temperature in step (3) is 0° C. to 120° C., and the reaction time is 1 to 72 hours. The method according to claim 5, wherein the compound represented by Formula 3 is used in step (1), and the compound represented by Formula 4 is used in step (3). The method of claim 5, wherein the molar ratio of the compound represented by Formula 3 to the compound represented by Formula 4 is in the range of 50:1 to 1:50. The method of claim 5, further comprising (3') drying the hybrid catalyst composition obtained in step (3). 15. The method of claim 14, (3") further comprising the step of dissolving the dry hybrid catalyst composition obtained in step (3') in a solvent and then removing unreacted substances and/or impurities with a filter. manufacturing method. 16. The method according to claim 15, wherein the solvent comprises at least one selected from the group consisting of hexane, pentane, toluene, benzene, dichloromethane, diethyl ether, tetrahydrofuran, acetone and ethyl acetate. Preparation of a hybrid catalyst composition Way. The hybrid catalyst composition of any one of claims 1 to 4; and a catalyst for olefin polymerization comprising a cocatalyst compound. The catalyst for olefin polymerization according to claim 17, wherein the cocatalyst compound is at least one selected from the group consisting of a compound represented by the following Chemical Formula 7, a compound represented by Chemical Formula 8, and a compound represented by Chemical Formula 9:
[Formula 7]

[Formula 8]

[Formula 9]
[LH] ⁺ [Z(A) ₄ ] ^- or [L] ⁺ [Z(A) ₄ ] ^-
In the above formula (7), 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 Chemical Formula 8, 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 (9), 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 catalyst for olefin polymerization according to claim 18, wherein the compound represented by Chemical Formula 7 is at least one selected from the group consisting of methylaluminoxane, ethylaluminoxane, isobutylaluminoxane and butylaluminoxane. 19. The method according to claim 18, wherein the compound represented by Formula 8 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 Seed, trimethyl boron, triethyl boron, triisobutyl boron, tripropyl boron and at least one selected from the group consisting of tributyl boron olefin polymerization catalyst. 19. The method according to claim 18, wherein the compound represented by Formula 9 is triethylammonium tetraphenyl boron, tributyl ammonium tetraphenyl boron, trimethyl ammonium tetraphenyl boron, tripropyl ammonium tetraphenyl boron, or trimethyl ammonium 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 The group consisting of phenyl) boron, tributylammonium tetra( p -trifluoromethylphenyl)boron, triphenylcarboniumtetra( p -trifluoromethylphenyl)boron and rephenylcarboniumtetrapentafluorophenylboron At least one catalyst for olefin polymerization selected from. The catalyst for olefin polymerization according to claim 17, further comprising a carrier supporting the hybrid catalyst composition, the cocatalyst compound, or both. The catalyst for olefin polymerization according to claim 22, wherein the carrier comprises at least one selected from the group consisting of silica, alumina and magnesia. The method according to claim 22, wherein the total amount of the hybrid transition metal compound supported on the carrier is 0.001 to 1 mmole based on 1 g of the carrier, and the amount of the promoter compound supported on the carrier is 2 to 15 mmole based on 1 g of the carrier. Catalysts for olefin polymerization. (1) dissolving any one of the compound represented by Formula 3 and the compound represented by Formula 4 above in a solvent; (2) adding the compound represented by the above formula (5) and the compound represented by the above formula (6) to the solution obtained in step (1), followed by reacting with stirring; (3) to the reaction mixture obtained in step (2), the other one of the compound represented by the above formula (3) and the compound represented by the above formula (4) is added and reacted under stirring, and the transition metal compound represented by the above formulas (1) and (2) obtaining a hybrid catalyst composition comprising; (4) A method for preparing a catalyst for olefin polymerization comprising the step of supporting the hybrid catalyst composition obtained in step (3), the cocatalyst compound, or both on a carrier:
[Formula 1]

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]
M ₁ X ₄
[Formula 6]
M ₂ X ₄
In Formulas 1 to 6 above, M ₁ , M ₂ , X, R ₁ to R ₅ and R ₆ to R ₁₀ are as defined in claim 1.