KR102579801B1 - 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 containing heterogeneous transition metal compounds, a catalyst for olefin polymerization containing the same, and a method for producing the same. Specifically, the present invention relates to a hybrid catalyst composition comprising two or more transition metal compounds having non-bridged, asymmetric biscyclopentadienyl groups with different center metals, and a catalyst composition comprising the same for olefin polymerization. It relates to catalysts and corresponding hybrid catalyst compositions and methods of preparing the catalysts.

Description

Mixed catalyst composition, catalyst containing the same, and method for preparing the same {Mixed Catalytic Composition, Catalyst Comprising the Same, and Processes for Preparing the Same}

The present invention relates to a hybrid catalyst composition containing heterogeneous transition metal compounds, a catalyst for olefin polymerization containing the same, and a method for producing the same. Specifically, the present invention relates to a hybrid catalyst composition comprising heterogeneous transition metal compounds having non-bridged asymmetric biscyclopentadienyl (bisCp) groups with different center metals, and olefin polymerization comprising the same. It relates to a catalyst for use and a corresponding hybrid catalyst composition and method for producing the catalyst.

Polyolefin polymers are used in a variety of ways in everyday life, such as shopping bags, greenhouses, fishing nets, cigarette wrappers, ramen bags, yogurt bottles, battery cases, car bumpers, interior materials, shoe soles, and washing machines.

Conventionally, polyolefin-based polymers such as polyethylene, polypropylene, and ethylene-alphaolefin copolymers and their copolymers have been manufactured using heterogeneous catalysts such as Ziegler-Natta catalysts composed of titanium compounds and alkyl aluminum compounds.

Recently, methods for producing polyolefins using metallocene catalysts, which are homogeneous catalysts with very high catalytic activity, are being studied. Metallocene catalysts are compounds in which a transition metal or transition metal halogen compound is coordinated with a ligand such as cyclopentadienyl, indenyl, or cycloheptadienyl, and have a basic sandwich structure. . At this time, it has various molecular structures depending on the form of the ligand and the type of central metal.

While the Ziegler-Natta catalyst, which is a heterogeneous catalyst, has non-uniform active site properties because the metal component, which is the active site, is dispersed on the inert solid surface, the metallocene catalyst is a single compound with a certain structure. Therefore, it is known as a single-site catalyst in which all active sites have the same polymerization characteristics.

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

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

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

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

Meanwhile, in Korean Patent No. 1797890, a heterogeneous mixture of a first transition metal compound containing a cyclopentadienyl group and an indenyl group not connected by a bridge and a second transition metal compound containing a substituted bisindenyl group connected by a silyl bridge is used. A metallocene catalyst is disclosed.

Generally, such hybrid catalysts are manufactured by preparing each transition metal compound and then mixing them at a certain ratio and supporting them.

US Patent No. 5,272,236 US Patent No. 4,935,474 US Patent No. 6,828,394 US Patent No. 6,894,128 Republic of Korea Patent No. 1437509 US Patent No. 6,841,631 Republic of Korea Patent No. 1797890

The object of the present invention is to provide a hybrid catalyst composition comprising heterogeneous transition metal compounds having non-bridged asymmetric biscyclopentadienyl (bisCp) groups with different center metals, and a catalyst composition comprising the same for olefin polymerization. It provides 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 containing the same by controlling the precursor ratio of the transition metal compound.

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

[Formula 1]

[Formula 2]

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

_{Each of _ _ _ _ _ 1-20} alkyl, C _1-20 alkylamido, or C _6-20 arylamido,

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, or substituted or unsubstituted C _1-20 silyl,

R ₁ to R ₅ and R ₆ to R ₁₀ may each independently be 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 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 are _zirconium or _hafnium , respectively, to R ₅ and R ₆ to R ₁₀ may each be hydrogen, substituted or unsubstituted C _1-20 alkyl, substituted or unsubstituted C _2-20 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, and the transition metal compound represented by Formula 2 is one of Formulas 2-1 to 1-18 below. It is 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 either a compound represented by Formula 3 below or a compound represented by Formula 4 below in a solvent; (2) adding a compound represented by Formula 5 below and a compound represented by Formula 6 below to the solution obtained in step (1) and reacting with stirring; (3) Adding the other one of the compound represented by Formula 3 below and the compound represented by Formula 4 below to the reaction mixture obtained in step (2) and then reacting with stirring, represented by Formulas 1 and 2 above. A method for producing a hybrid catalyst composition containing a transition metal compound is provided.

[Formula 3]

[Formula 4]

[Formula 5]

_{M 1}

[Formula 6]

_{M 2}

In Formulas 3 to 6 above, M ₁ , M ₂ , X, R ₁ to R ₅ and R ₆ to R ₁₀ are as described above in the section on hybrid catalyst compositions containing heterogeneous transition metal compounds.

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 Formula 5 above and the compound represented by Formula 6 above are different from each other and each contains ZrCl ₄ or HfCl ₄ .

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

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

Additionally, in step (3) above, 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 may be in the range of 50:1 to 1:50.

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

In addition, the method for producing a hybrid catalyst composition according to an embodiment of the present invention includes dissolving the dry hybrid catalyst composition obtained in step (3') in a solvent and then removing unreacted products and/or impurities through 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; A catalyst for olefin polymerization comprising a cocatalyst compound is provided.

Here, the cocatalyst compound may be one or more selected from the group consisting of a compound represented by Formula 7, a compound represented by Formula 8, and a compound represented by Formula 9 below.

[Formula 7]

[Formula 8]

[Formula 9]

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

In Formula 7 above, n is an integer of 2 or more, R _a is a halogen atom, a C _1-20 hydrocarbon group, or a C _1-20 hydrocarbon group substituted with halogen,

In Formula 8 above, D is aluminum (Al) or boron (B), and R _b , R _c and R _d are each independently a halogen atom, a C _1-20 hydrocarbon group, or a C _1-20 hydrocarbon group substituted with halogen. or C _1-20 alkoxy group,

In Formula 9 above, L is a neutral or cationic Lewis base, [LH] ⁺ and [L] ⁺ are Bronsted acids, Z is a Group 13 element, and A is each independently a substituted or unsubstituted C _{6 -20} It is an aryl group or a substituted or unsubstituted C _1-20 alkyl group.

Specifically, the compound represented by Formula 7 above is at least one selected from the group consisting of methylaluminoxane, ethyl aluminoxane, isobutyl aluminoxane, and butyl aluminoxane.

In addition, the compound represented by Formula 8 is trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, tripropyl aluminum, tributyl aluminum, dimethylchloroaluminum, triisopropyl aluminum, tri- s -butyl aluminum, tricyclopentyl aluminum, Tripentyl aluminum, triisopentyl aluminum, trihexyl aluminum, trioctyl aluminum, ethyldimethyl aluminum, methyldiethyl aluminum, triphenyl aluminum, tri- p -tolyl aluminum, dimethyl aluminum methoxide, dimethyl aluminum ethoxide, trimethyl boron. , triethyl boron, triisobutyl boron, tripropyl boron, and tributyl boron.

In addition, the compound represented by the above formula 9 is triethylammonium tetraphenyl boron, tributylammonium tetraphenyl boron, trimethyl ammonium tetraphenyl boron, tripropylammonium tetraphenyl boron, and trimethylammonium tetra ( p -tolyl). Boron, trimethylammonium tetra ( o , p -dimethylphenyl) boron, tributylammonium tetra ( p -trifluoromethylphenyl) boron, trimethylammonium tetra ( p -trifluoromethylphenyl) boron, tributylammonium tetra Pentafluorophenylboron, N,N-diethylanilinium tetraphenylboron, N,N-diethylanilinium tetrapentafluorophenylboron, diethylammonium tetrapentafluorophenylboron, triphenylphosphonium Tetraphenylboron, trimethylphosphonium tetraphenylboron, triethylammonium tetraphenylaluminum, tributylammonium tetraphenylaluminum, trimethylammoniumtetraphenylaluminum, tripropylammoniumtetraphenylaluminum, trimethylammonium tetra( p -tolyl ) Aluminum, tripropylammonium tetra ( p -tolyl) aluminum, triethylammonium tetra ( o , p -dimethylphenyl) aluminum, tributylammonium tetra ( p -trifluoromethylphenyl) aluminum, trimethylammonium tetra ( p -trifluoromethylphenyl) aluminum, tributylammonium tetrapentafluorophenyl aluminum, N,N-diethylanilinium tetraphenylaluminum, N,N-diethylaniliniumtetrapentafluorophenyl aluminum, di Ethylammonium tetrapentatetetraphenyl aluminum, triphenylphosphonium tetraphenylaluminum, trimethylphosphonium tetraphenylaluminum, tripropylammonium tetra( p -tolyl)boron, triethylammonium tetra( o , p -dimethylphenyl)boron , tributylammonium tetra ( p -trifluoromethylphenyl) boron, triphenylcarbonium tetra ( p -trifluoromethylphenyl) boron and triphenylcarbonium tetrapentafluorophenyl boron. There is 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 stomach carrier may include at least one selected from the group consisting of silica, alumina, and magnesia.

Here, the total amount of the mixed 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 Formula 3 and the compound represented by Formula 4 in a solvent; (2) adding the compound represented by Formula 5 and the compound represented by Formula 6 to the solution obtained in step (1) and reacting with stirring; (3) Add the other one of the compound represented by Formula 3 and the compound represented by Formula 4 to the reaction mixture obtained in step (2) and react with stirring to produce transition metal compounds represented by Formulas 1 and 2. Obtaining a hybrid catalyst composition comprising; (4) A method for producing a catalyst for olefin polymerization is provided, which includes the step of supporting the hybrid catalyst composition obtained in step (3), the cocatalyst compound, or both on a carrier.

The hybrid catalyst composition containing heterogeneous transition metal compounds according to an embodiment of the present invention and the catalyst for olefin polymerization containing the same can produce polyolefins with excellent processability and mechanical properties depending on the content of the transition metal compound.

In addition, a hybrid catalyst composition containing heterogeneous transition metal compounds and a method for producing a catalyst for olefin polymerization containing the same are prepared by precisely controlling the ratio of the hybrid transition metal compounds, thereby producing a catalyst for polyolefin polymerization with excellent processability and mechanical properties. It can be easily provided.

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

Hybrid catalyst composition containing heterogeneous transition metal compounds

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

[Formula 1]

[Formula 2]

In Formulas 1 and 2 above, 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 of _ _ _ _ _ 1-20} alkyl, C _1-20 alkylamido, or C _6-20 arylamido. 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, or substituted or unsubstituted C _1-20 silyl. Here, R ₁ to R ₅ and R ₆ to R ₁₀ may each independently be 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 _2-20 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 may be in the range of 50:1 to 1:50. Preferably, the molar ratio of these two compounds is 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 each halogen or substituted or unsubstituted C _1-20 alkyl, and 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 _2-20 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 either a compound represented by Formula 3 below or a compound represented by Formula 4 below in a solvent; (2) adding a compound represented by Formula 5 below and a compound represented by Formula 6 below to the solution obtained in step (1) and reacting with stirring; (3) Adding the other one of the compound represented by Formula 3 below and the compound represented by Formula 4 below to the reaction mixture obtained in step (2) and then reacting with stirring, represented by Formulas 1 and 2 above. A method for producing a hybrid catalyst composition containing a transition metal compound is provided.

[Formula 3]

[Formula 4]

[Formula 5]

_{M 1}

[Formula 6]

_{M 2}

In Formulas 3 to 6 above, M ₁ , M ₂ , X, R ₁ to R ₅ and R ₆ to R ₁₀ are as described above in the section on hybrid catalyst compositions containing heterogeneous transition metal compounds.

Step (1)

Specifically, in step (1), either the compound represented by Formula 3 or the compound represented by Formula 4 is dissolved in a solvent.

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 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 or pentane, an aromatic hydrocarbon solvent such as toluene or benzene, a hydrocarbon solvent substituted with a chlorine atom such as dichloromethane, an ether-based solvent such as diethyl ether or tetrahydrofuran, acetone, and ethyl. It may contain at least one member selected from the group consisting of acetate. Preferably, the above solvent may be toluene, but is not particularly limited thereto.

When dissolving either the compound represented by Formula 3 above or the compound represented by Formula 4 above in a solvent, the temperature and dissolution time are not particularly limited. For example, at a temperature of -78°C to 80°C, preferably -40°C to 60°C, more preferably at room temperature, any of the compounds represented by Formula 3 and the compound represented by Formula 4 above One can be dissolved by adding it to the solvent and stirring 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 Formula 5 and the compound represented by Formula 6 are added to the solution obtained in Step (1) and then reacted with stirring.

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

Here, the molar ratio of the compound represented by Formula 5 to the compound represented by Formula 6 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 when adding the compound represented by Formula 5 and the compound represented by Formula 6 is preferably in the range of -78°C to 30°C. More preferably, the temperature when adding the compound represented by Formula 5 and the compound represented by Formula 6 may be -40°C to 10°C. Most preferably, the temperature when adding the compound represented by Formula 5 and the compound represented by Formula 6 may be -30°C.

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

Step (3)

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

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

After adding the other one of the compound represented by Formula 3 and the compound represented by Formula 4 above, 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. and reacted with stirring for 1 to 72 hours, preferably 3 to 24 hours, more preferably about 7 hours.

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

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

The method for producing 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) above. Here, the drying conditions of the composition are not particularly limited, but can be carried out at a temperature in the temperature range of 25°C to 80°C, more preferably in the temperature range of 25°C to 50°C, and most preferably at about 25°C.

In addition, the method for producing a hybrid catalyst composition according to another embodiment of the present invention includes dissolving the dry hybrid catalyst composition obtained in step (3') in a solvent and then removing unreacted products and/or impurities through a filter. It may further include a step. Here, the solvent may be substantially the same as the solvent used in step (1) above. Preferably, dichloromethane may be used, but is not limited to this. Unreacted products and /Although the filter for removing impurities is not particularly limited, 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; A catalyst for olefin polymerization comprising a cocatalyst compound is provided.

[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 as described above in the section on hybrid catalyst compositions containing heterogeneous transition metal compounds.

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 may be in the range of 50:1 to 1:50. Preferably, the molar ratio of these two compounds is 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 above, M ₁ and M ₂ are different from each other and are each 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 may each be hydrogen, substituted or unsubstituted C _1-20 alkyl, substituted or unsubstituted C _2-20 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 cocatalyst compound may include one or more of the compound represented by Formula 7, the compound represented by Formula 8, and the compound represented by Formula 9 below.

[Formula 7]

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

[Formula 8]

In Formula 8 above, D is aluminum (Al) or boron (B), and R _b , R _c and R _d are each independently a halogen atom, a C _1-20 hydrocarbon group, or a C _1-20 hydrocarbon group substituted with halogen. Or it is 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 Formula 9 above, L is a neutral or cationic Lewis base, [LH] ⁺ and [L] ⁺ are Bronsted acids, Z is a Group 13 element, and A is each independently a substituted or unsubstituted C _{6 -20} It is an aryl group or a substituted or unsubstituted C _1-20 alkyl group. Specifically, [LH] ⁺ may be a dimethylanilinium cation, [Z(A) ₄ ] ^- may be [B(C ₆ F ₅ ) ₄ ] ^- , and [L] ⁺ may be [(C ₆ H ₅ ) ₃ C] ⁺ may be.

Specifically, examples of the compound represented by Formula 7 include methylaluminoxane, ethyl aluminoxane, isobutyl aluminoxane, and butylaluminoxane, and methylaluminoxane is preferred, but is not limited thereto.

Examples of compounds represented by the above formula 8 include trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, tripropyl aluminum, tributyl aluminum, dimethylchloroaluminum, triisopropyl aluminum, tri- s -butyl aluminum, and tricyclopentyl aluminum. , tripentyl aluminum, triisopentyl aluminum, trihexyl aluminum, trioctyl aluminum, ethyldimethyl aluminum, methyldiethyl aluminum, triphenyl aluminum, tri- p -tolyl aluminum, dimethyl aluminum methoxide, dimethyl aluminum ethoxide, trimethyl Examples include boron, triethyl boron, triisobutyl boron, tripropyl boron, and tributyl boron, and trimethyl aluminum, triethyl aluminum, and triisobutyl aluminum are preferred, but are not limited to these.

Examples of compounds represented by the above formula (9) include triethylammonium tetraphenylboron, tributylammonium tetraphenylboron, trimethylammonium tetraphenylboron, tripropylammonium tetraphenylboron, and trimethylammonium tetra ( p -tolyl). Boron, trimethylammonium tetra ( o , p -dimethylphenyl) boron, tributylammonium tetra ( p -trifluoromethylphenyl) boron, trimethylammonium tetra ( p -trifluoromethylphenyl) boron, tributylammonium tetra Pentafluorophenylboron, N,N-diethylanilinium tetraphenylboron, N,N-diethylanilinium tetrapentafluorophenylboron, diethylammonium tetrapentafluorophenylboron, triphenylphosphonium Tetraphenylboron, trimethylphosphonium tetraphenylboron, triethylammonium tetraphenylaluminum, tributylammonium tetraphenylaluminum, trimethylammoniumtetraphenylaluminum, tripropylammoniumtetraphenylaluminum, trimethylammonium tetra( p -tolyl ) Aluminum, tripropylammonium tetra ( p -tolyl) aluminum, triethylammonium tetra ( o , p -dimethylphenyl) aluminum, tributylammonium tetra ( p -trifluoromethylphenyl) aluminum, trimethylammonium tetra ( p -trifluoromethylphenyl) aluminum, tributylammonium tetrapentafluorophenyl aluminum, N,N-diethylanilinium tetraphenylaluminum, N,N-diethylaniliniumtetrapentafluorophenyl aluminum, di Ethylammonium tetrapentatetetraphenyl aluminum, triphenylphosphonium tetraphenylaluminum, trimethylphosphonium tetraphenylaluminum, tripropylammonium tetra( p -tolyl)boron, triethylammonium tetra( o , p -dimethylphenyl)boron , tributylammonium tetra ( p -trifluoromethylphenyl) boron, triphenyl carbonium tetra ( p -trifluoromethylphenyl) boron, triphenyl carbonium tetrapentafluorophenyl boron, etc.

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.

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

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

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

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

In a preferred embodiment, when the carrier is silica, the drying temperature for the silica may be from room temperature to 900°C. The drying temperature may be preferably room temperature to 800°C, more preferably room temperature to 700°C. If the drying temperature is lower than room temperature, there is too much moisture and the moisture on the surface reacts with the cocatalyst, and if it exceeds 900°C, the structure of the carrier may collapse.

The concentration of hydroxy groups in the dried silica may be 0.1 to 5 mmole/g, preferably 0.7 to 4 mmole/g, and more preferably 1.0 to 2 mmole/g. If the concentration of the hydroxy group is less than 0.1 mmole/g, the amount of cocatalyst supported is low, and if it exceeds 5 mmole/g, the problem of deactivation of the catalyst component 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 mixed transition metal compound and the carrier satisfies the above range, appropriate supported catalyst activity is exhibited, which is advantageous in terms of maintaining the activity of the catalyst and economic efficiency.

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

One or two or more types of carriers may be used. For example, both the hybrid catalyst composition and the co-catalyst compound may be supported on one type of carrier, or the hybrid catalyst composition and the co-catalyst compound may each be supported on two or more types of carriers. Additionally, only one of the hybrid catalyst composition and the cocatalyst compound may be supported on the carrier.

Method for producing catalyst for olefin polymerization

According to another embodiment of the present invention, (1) dissolving any one of the compound represented by Formula 3 and the compound represented by Formula 4 in a solvent; (2) adding the compound represented by Formula 5 and the compound represented by Formula 6 to the solution obtained in step (1) and reacting with stirring; (3) Add the other one of the compound represented by Formula 3 and the compound represented by Formula 4 to the reaction mixture obtained in step (2) and react with stirring to produce transition metal compounds represented by Formulas 1 and 2. Obtaining a hybrid catalyst composition comprising; (4) A method for producing a catalyst for olefin polymerization is provided, which includes 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}

[Formula 6]

_{M 2}

In Formulas 1 to 6 above, M ₁ , M ₂ , X, R ₁ to R ₅ and R ₆ to R ₁₀ are as described above in the section on hybrid catalyst compositions containing heterogeneous transition metal compounds.

The specific details of steps (1) to (3) above are substantially the same as steps (1) to (3) of the method for producing the hybrid catalyst composition.

The method for producing a catalyst for olefin polymerization according to another embodiment of the present invention may further include (3') drying the composition obtained in step (3) above. At this time, the specific details of step (3') above are substantially the same as step (3') of the method for producing the hybrid catalyst composition.

In addition, the method for producing a catalyst for olefin polymerization according to another embodiment of the present invention includes the step (3") of dissolving the dry composition obtained in step (3') in a solvent and then removing unreacted products and/or impurities through a filter. It may further include. At this time, the specific details of step (3") above are substantially the same as step (3") of the method for producing the above hybrid catalyst composition.

Step (4)

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

As a method of supporting the hybrid catalyst composition and/or co-catalyst 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 a hybrid catalyst composition is dissolved after contacting it with a carrier, a method of contacting a solution in which a hybrid catalyst composition and a co-catalyst compound are dissolved and then drying the solution, or a method of drying a solution in which a hybrid catalyst composition and co-catalyst compound are dissolved. This dissolved solution is brought into contact with a carrier and then dried to prepare a carrier on which the hybrid catalyst composition is supported. Separately, the solution in which the co-catalyst compound is dissolved is brought into contact with the carrier and then dried to prepare a carrier on which the co-catalyst compound is supported. After doing so, it may be a method of mixing them.

The chemical adsorption method is a method of first supporting a co-catalyst compound on the surface of a carrier and then supporting a hybrid catalyst composition on the co-catalyst compound, or by supporting a functional group on the surface of the carrier (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.

Here, the solvent used to support the hybrid catalyst composition and/or co-catalyst compound is not particularly limited. For example, solvents include aliphatic hydrocarbon solvents such as hexane and pentane, aromatic hydrocarbon solvents such as toluene and benzene, hydrocarbon solvents substituted with chlorine atoms such as dichloromethane, diethyl ether, ether solvents such as tetrahydrofuran, and acetone. and ethyl acetate.

In a preferred embodiment, the process of supporting the hybrid catalyst composition and/or co-catalyst 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 co-catalyst compound on the carrier in step (4) is performed by allowing the mixture of the hybrid catalyst composition and/or co-catalyst compound and the carrier to be maintained for 1 minute to 24 hours, preferably 5 minutes to 15 minutes. This can be done by sufficiently stirring for a period of time.

Polymerization of Olefins

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

In an exemplary embodiment, the olefin-based polymer may be a copolymer of ethylene and C _3-20 alpha-olefin, and a copolymer of ethylene and 1-hexene is preferred, but is not limited thereto.

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

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

As a preferred embodiment, the olefin-based polymer may be produced by gas phase polymerization, solution polymerization, or slurry polymerization. When the olefin-based polymer is produced by a solution polymerization method or a slurry polymerization method, examples of solvents 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 are not limited thereto.

Example

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

Example One

164 mg (1.16 mmole, 4.8 eq.) of lithium pentamethylcyclopentadienide of the above formula 3-1 was dissolved in 20 ml of toluene at room temperature. While slowly stirring this, 56 mg (0.24 mmole, 1.0 eq.) of zirconium chloride (ZrCl ₄ ) and 232 mg (0.72 mmole, 3.0 eq.) of zirconium chloride (HfCl ₄ ) were added slowly at -30°C to prevent heat generation. Then, it was stirred at 60°C for 24 hours. After lowering the temperature to -30°C, 110 mg (0.96 mmole, 4.0 eq.) of lithium n -propylcyclopentadienide of Chemical Formula 4-1 was slowly added to the reaction mixture. This was stirred at room temperature for 7 hours to react. After removing lithium chloride (LiCl) with a Celite filter, the product was dried to produce a compound of Formula 1-1 ((pentamethylcyclopentadienyl)( n -propylcyclopentadienyl) zirconium dichloride) and a compound of Formula 2-1 ((pentamethylcyclopentadienyl)( n 294 mg (yield: 65%) of a mixture of -propylcyclopentadienyl) hafnium dichloride was obtained.

The hybrid (1:3) transition metal compound structure of the compound of Formula 1-1 above 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 the above formula 3-1 was dissolved in 20 ml of toluene at room temperature. While slowly stirring this, 109 mg (0.47 mmole, 1.0 eq.) of zirconium chloride and 150 mg (0.47 mmole, 1.0 eq.) of zirconium chloride were added slowly to prevent heat generation at -30°C, and then stirred at 60°C for 24 hours. It was stirred. After lowering the temperature to -30°C, 107 mg (0.94 mmole, 2.0 eq.) of lithium n -propylcyclopentadienide of Chemical Formula 4-1 above was slowly added to the reaction mixture. This was stirred at room temperature for 7 hours to react. After removing lithium chloride (LiCl) using 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 hybrid (1:1) transition metal compound structure of the compound of Formula 1-1 above 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 the above formula 3-1 was dissolved in 20 ml of toluene at room temperature. While slowly stirring this, 168 mg (0.72 mmole, 3.0 eq.) of zirconium chloride and 77 mg (0.24 mmole, 3.0 eq.) of zirconium chloride were added slowly to prevent heat generation at -30°C, and then stirred at 60°C for 24 hours. It was stirred. After lowering the temperature to -30°C, 110 mg (0.96 mmole, 4.0 eq.) of lithium n -propylcyclopentadienide of Chemical Formula 4-1 above was slowly added to the reaction mixture. This was stirred at room temperature for 7 hours to react. After removing lithium chloride (LiCl) using 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 hybrid (3:1) transition metal compound structure of the compound of Formula 1-1 was confirmed by ^1H 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 in 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 containing heterogeneous transition metal compounds according to an embodiment of the present invention and the catalyst for olefin polymerization containing the same can produce various polyolefins with excellent processability and mechanical properties depending on the content of the transition metal compound.

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

Claims (25)

Hybrid catalyst composition comprising heterogeneous transition metal compounds having an asymmetric structure and 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 from each other and each independently titanium (Ti), zirconium (Zr), or hafnium (Hf),
_{Each of _ _ _ _ _ 1-20} alkyl, C _1-20 alkylamido, or C _6-20 arylamido,
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, or substituted or unsubstituted C _1-20 silyl,
R ₁ to R ₅ and R ₆ to R ₁₀ may each independently be connected to adjacent groups to form a substituted or unsubstituted, saturated or unsaturated C _4-20 ring. The hybrid catalyst composition according to 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 of claim 1, wherein M ₁ and M ₂ are different from each other and are each zirconium or hafnium, X is each halogen or C _1-20 alkyl, and R ₁ to R ₅ and R ₆ to R ₁₀ is each hydrogen, substituted or unsubstituted C _1-20 alkyl, substituted or unsubstituted C _2-20 alkenyl, or substituted or unsubstituted C _6-20 aryl. The method of 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- Hybrid catalyst composition, which is at least one of the transition metal compounds represented by 1 to 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]
. (1) dissolving either a compound represented by Formula 3 below or a compound represented by Formula 4 below in a solvent; (2) adding a compound represented by Formula 5 below and a compound represented by Formula 6 below to the solution obtained in step (1) and reacting with stirring; (3) Adding the other one of the compound represented by Formula 3 and the compound represented by Formula 4 below to the reaction mixture obtained in step (2) and then reacting with stirring, represented by Formulas 1 and 2 below. Method for producing a hybrid catalyst composition comprising a heterogeneous transition metal compound having an asymmetric structure:
[Formula 1]

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]
_{M 1}
[Formula 6]
_{M 2}
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 clause 1. The method of claim 5, wherein 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. Method for preparing a hybrid catalyst composition, which is at least one of the indicated 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]
. The preparation of a hybrid catalyst composition according to claim 5, wherein the solvent includes at least one selected from the group consisting of hexane, pentane, toluene, benzene, dichloromethane, diethyl ether, tetrahydrofuran, acetone, and ethyl acetate. method. 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 are ZrCl ₄ or HfCl ₄ . 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 in step (2), the reaction temperature is 0°C to 120°C and the reaction time is 1 to 72 hours. The method of claim 5, wherein in step (3), the reaction temperature is 0°C to 120°C and the reaction time is 1 to 72 hours. The method of claim 5, wherein the compound represented by the above formula (3) is used in step (1), and the compound represented by the above 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) above. The method of claim 14, wherein (3") further comprises the step of dissolving the dry hybrid catalyst composition obtained in step (3') in a solvent and then removing unreacted products and/or impurities through a filter. Manufacturing method. 16. Preparation of a hybrid catalyst composition according to claim 15, wherein the solvent includes at least one selected from the group consisting of hexane, pentane, toluene, benzene, dichloromethane, diethyl ether, tetrahydrofuran, acetone, and ethyl acetate. method. 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 Formula 7, a compound represented by Formula 8, and a compound represented by Formula 9:
[Formula 7]

[Formula 8]

[Formula 9]
[LH] ⁺ [Z(A) ₄ ] ^- or [L] ⁺ [Z(A) ₄ ] ^-
In Formula 7 above, n is an integer of 2 or more, R _a is a halogen atom, a C _1-20 hydrocarbon group, or a C _1-20 hydrocarbon group substituted with halogen,
In Formula 8 above, D is aluminum (Al) or boron (B), and R _b , R _c and R _d are each independently a halogen atom, a C _1-20 hydrocarbon group, or a C _1-20 hydrocarbon group substituted with halogen. or C _1-20 alkoxy group,
In Formula 9 above, L is a neutral or cationic Lewis base, [LH] ⁺ and [L] ⁺ are Bronsted acids, Z is a Group 13 element, and A is each independently a substituted or unsubstituted C _{6 -20} It is an aryl group or a substituted or unsubstituted C _1-20 alkyl group. The catalyst for olefin polymerization according to claim 18, wherein the compound represented by Formula 7 is at least one selected from the group consisting of methylaluminoxane, ethyl aluminoxane, isobutyl aluminoxane, and butylaluminoxane. The method of claim 18, wherein the compound represented by Formula 8 is trimethyl aluminum, triethylaluminum, triisobutyl aluminum, tripropyl aluminum, tributyl aluminum, dimethylchloroaluminum, triisopropyl aluminum, tri-s-butyl aluminum, tri- s -butyl aluminum. Cyclopentyl aluminum, tripentyl aluminum, triisopentyl aluminum, trihexyl aluminum, trioctyl aluminum, ethyldimethyl aluminum, methyldiethyl aluminum, triphenyl aluminum, tri- p -tolyl aluminum, dimethyl aluminum methoxide, dimethyl aluminum ethoxide. A catalyst for olefin polymerization that is at least one selected from the group consisting of seeds, trimethyl boron, triethyl boron, triisobutyl boron, tripropyl boron, and tributyl boron. The method of claim 18, wherein the compound represented by 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, tributyl Ammonium Tetrapentafluorophenylboron, N,N-Diethylanilinium Tetraphenylboron, N,N-Diethylanilinium Tetrapentafluorophenylboron, Diethylammonium Tetrapentafluorophenylboron, Tri Phenylphosphonium tetraphenyl boron, trimethyl phosphonium tetraphenyl boron, triethylammonium tetraphenylaluminum, tributylammonium tetraphenylaluminum, trimethylammonium tetraphenylaluminum, tripropylammonium tetraphenylaluminum, trimethylammonium 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 tetrapentafluorophenyl aluminum, N,N-diethylanilinium tetraphenyl aluminum, N,N-diethylanilinium tetrapentafluorophenyl Aluminum, diethylammonium tetrapentatetetraphenyl aluminum, triphenylphosphonium tetraphenylaluminum, trimethylphosphonium tetraphenylaluminum, tripropylammonium tetra( p -tolyl)boron, triethylammonium tetra( o , p -dimethyl A catalyst for olefin polymerization that is at least one selected from the group consisting of phenyl) boron, triphenylcarbonium tetra ( p -trifluoromethylphenyl) boron, and triphenylcarbonium tetrapentafluorophenyl boron. 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 includes at least one selected from the group consisting of silica, alumina, and magnesia. The method of 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 cocatalyst compound supported on the carrier is 2 to 15 mmole based on 1 g of the carrier. Catalyst for olefin polymerization. (1) dissolving either a compound represented by Formula 3 below or a compound represented by Formula 4 below in a solvent; (2) adding a compound represented by Formula 5 below and a compound represented by Formula 6 below to the solution obtained in step (1) and reacting with stirring; (3) Add the other one of the compound represented by Formula 3 and the compound represented by Formula 4 below to the reaction mixture obtained in step (2) and react with stirring to obtain an asymmetric structure represented by Formulas 1 and 2 below. Obtaining a hybrid catalyst composition containing a heterogeneous transition metal compound having a; (4) Method for producing 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}
[Formula 6]
_{M 2}
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 clause 1.