KR20170105407A - Hybride catalyst compositon, preparation method thereof, and manufactured polyolefin using the same - Google Patents

Abstract

The present invention relates to a hybrid catalyst composition containing a first transition metal compound represented by chemical formula 1 and a second transition metal compound represented by chemical formula 2, formed of different chemical formulas. The hybrid catalyst composition comprising the first and second transition metal compounds exhibits high catalytic activity and can produce polyolefin having processability and mechanical properties.

Description

TECHNICAL FIELD [0001] The present invention relates to a hybrid catalyst composition, a process for producing the same, and a polyolefin prepared by using the same. BACKGROUND ART < RTI ID = 0.0 >

The present invention relates to a novel hybrid catalyst composition, a process for preparing the hybrid catalyst composition, and a polyolefin prepared using the hybrid catalyst composition.

Polyolefin-based polymers are widely used in shopping bags, vinyl houses, fishing nets, tobacco wrappers, cotton bags, yogurt bottles, battery cases, automobile bumpers, interior materials, shoe soles and washing machines in real life. Conventionally, polyolefin-based polymers such as polyethylene, polypropylene and ethylene-alpha olefin copolymers and their copolymers have been prepared by heterogeneous catalysts comprising titanium compounds and alkylaluminum compounds. Recently, a metallocene catalyst, which is a homogeneous catalyst having extremely high catalytic activity, has been developed and a method for producing a polyolefin using a metallocene catalyst has been studied.

The metallocene catalyst is a compound in which a cyclopentadienyl ligand is coordinatively bonded to a sandwich structure around a transition metal (or a transition metal halogen), and has various molecular structures depending on the type of the ligand and the kind of the central metal. In general, the metallocene catalyst itself is not active as a polymerization catalyst and is used together with a promoter such as methylaluminoxane. The metallocene catalyst is activated as a cation by the action of a cocatalyst, and at the same time, the cocatalyst stabilizes unsaturated cationic active species as an anion that is not coordinated to the metallocene catalyst to form a catalyst system having activity for various olefin polymerization .

Metallocene catalysts have been reported in the 1950s, but their activity has been low and research has not been active. Professor Kaminsky of Germany in 1976 first reported using methyl aluminoxane as a cocatalyst to have high activity, and then research on metallocene catalysts was actively conducted. The advantage of the metallocene catalyst is that it has a narrow molecular weight distribution, is easy to copolymerize, has a uniform distribution of the comonomer, and can control the stereostructure of the polymer according to the symmetry of the catalyst since it has a uniform active site.

On the other hand, since the metallocene catalyst has a narrow molecular weight distribution of a polymer produced by a uniform active site, there is a problem that the polymer has excellent mechanical strength but low processability. In order to solve such problems, various methods such as changing the molecular structure of the polymer or broadening the molecular weight distribution have been proposed. U.S. Patent No. 5,272,236 improves the processability of a polymer by introducing a long chain branch (LCB) as a side chain to the main chain of the polymer, but the supported catalyst has a low activity in the case of the supported catalyst. U.S. Patent No. 5,914,289 discloses a method of controlling a high molecular weight and a molecular weight distribution by supporting different metallocene catalysts, respectively, but since the metallocene catalyst is separately carried, the production time and solvent consumption are increased, resulting in low production efficiency.

A metallocene catalyst (a heterogeneous metallocene catalyst) having different characteristics is developed to solve the problems caused by using the metallocene catalyst as a single catalyst and to develop a catalyst having improved activity and improved processability with ease A method of hybridization is proposed. U.S. Patent No. 4,935,474, U.S. Patent No. 6,828,394, U.S. Patent No. 6,894,128, U.S. Patent No. 10-1437509, U.S. Patent No. 6,841,631 disclose a method for producing a bimodal molecular weight distribution using catalysts having different reactivities to comonomers Lt; RTI ID = 0.0 > polyolefin < / RTI > Polyolefins having a molecular weight distribution prepared in this manner have improved processability, but have different molecular weight distributions, resulting in poor kneading properties. Therefore, there is a problem that it is difficult to obtain a product having uniform physical properties after processing and the mechanical strength is lowered.

In order to solve the problem of heterogeneous metallocene hybrid supported catalysts, methods using two nucleophilic metallocene catalysts having two active sites have been proposed. Korean Patent No. 2003-0012308 discloses a method of controlling the molecular weight distribution and molecular weight of a carrier using a double nuclear metallocene catalyst, but there is a problem of low activity.

Various methods have been proposed to overcome the problems of the metallocene catalyst, but most of them have been solved only for the linear low density polyolefin. However, even when a metallocene catalyst having excellent activity and processability in the preparation of a low-density polyolefin is used, the activity of the metallocene catalyst tends to decrease as the concentration of the comonomer decreases. Therefore, the catalyst used for producing the low- When the polyolefin is produced, the activity is low, which is uneconomical.

Particularly, in the gas phase process, activity is an important factor. Since the activity of the metallocene catalyst is low during the production of a high-density polyolefin using a gas phase process, a large amount of fine particles are generated in the gas phase reactor. That is, due to the low activity of the metallocene catalyst, a large amount of fine particles are formed in the gas phase reactor, thereby generating a large amount of static electricity, and the fine particles adhere to the reactor wall surface to impede heat transfer, thereby lowering the temperature during the polymerization reaction. Further, as the reaction progresses, the fine particles attached to the wall surface of the vapor phase reactor continue to increase, resulting in a problem that stable operation becomes difficult.

A catalyst having high activity for solving the above problems and for producing a high-density polyolefin having excellent mechanical strength and processability is continuously required, and improvement is required.

It is an object of the present invention to provide a novel hybrid catalyst composition and a process for its preparation.

It is another object of the present invention to provide a novel hybrid catalyst composition having excellent polymerization activity and being capable of controlling molecular weight and molecular weight distribution and having high activity.

Another object of the present invention is to provide a high-density polyolefin having excellent mechanical strength and processability by using the hybrid catalyst composition.

According to an aspect of the present invention for achieving the above object, the present invention includes a first transition metal compound represented by the following formula (1) and a second transition metal compound represented by the following formula (2).

[Chemical Formula 1]

In Formula 1, M1 is a Group 4 transition metal of the Periodic Table of the Elements, and X ₁ and X ₂ may be the same or different and each independently represents a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, An alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 40 carbon atoms, an arylalkyl group having 7 to 40 carbon atoms, an alkylamido group having 1 to 20 carbon atoms, an arylamido group having 6 to 20 carbon atoms , Or an alkylidene group having 1 to 20 carbon atoms, and R ₁ to R ₁₂ may be the same or different and each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted 2-carbon group having 2 to 20 carbon atoms A substituted or unsubstituted C1 to C20 alkenyl group, a substituted or unsubstituted C6 to C20 aryl group, a substituted or unsubstituted C7 to C40 alkylaryl group, a substituted or unsubstituted C7 to C40 arylalkyl group, Or an unsubstituted silyl having 1 to 20 carbon atoms, or they may be connected to each other to form a ring.

(2)

In Formula 2, M2 is a Group 4 transition metal of the Periodic Table of Elements, and X ₃ and X ₄ may be the same or different from each other and each independently represents a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, An alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 40 carbon atoms, an arylalkyl group having 7 to 40 carbon atoms, an alkylamido group having 1 to 20 carbon atoms, an arylamido group having 6 to 20 carbon atoms , Or an alkylidene group having 1 to 20 carbon atoms, and R ₁₃ to R ₁₈ may be the same or different and each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted 2-carbon group having 2 to 20 carbon atoms A substituted or unsubstituted C1 to C20 alkenyl group, a substituted or unsubstituted C6 to C20 aryl group, a substituted or unsubstituted C7 to C40 alkyl aryl group, a substituted or unsubstituted C7 to C40 arylalkyl group, R ₁₉ and R ₂₀ may be the same or different and are each independently a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms or a substituted or unsubstituted aryl group having 1 to 20 carbon atoms, , A substituted or unsubstituted C 2 -C 20 alkenyl group, a substituted or unsubstituted C 6 -C 20 aryl group, a substituted or unsubstituted C 7 -C 40 alkylaryl group, a substituted or unsubstituted C 7 -C 40 aryl group, R ₂₁ to R ₂₆ may be the same or different from each other and each independently represents a hydrogen atom, a substituted or unsubstituted arylalkyl group, or a substituted or unsubstituted arylsilyl group having 1 to 20 carbon atoms, A substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C6 to C20 aryl group, a substituted or unsubstituted C7 alkyl group A substituted or unsubstituted arylalkyl group having 7 to 40 carbon atoms, or a substituted or unsubstituted silyl group having 1 to 20 carbon atoms, or they may be connected to each other to form a ring.

The first transition metal compound has a structure in which a ligand is connected in an asymmetric structure to one side and the other side of the transition metal (M1), and the second transition metal compound is bonded to one side and the other side of the transition metal Or a structure in which a ligand is connected in a symmetrical structure. In addition, the second transition metal compound may have a structure in which a ligand connected to one side and the other side of the transition metal (M2) is connected by Si.

The hybrid catalyst composition may further include a cocatalyst comprising one or more of the following chemical formulas (3) to (6).

(3)

In the general formula (3), R ₂₇ is a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group substituted with a halogen atom having 1 to 20 carbon atoms, and a is an integer of 2 or more.

[Chemical Formula 4]

Z (R < ₂₈ >) ₃

In the formula (4), Z represents aluminum (Al) or boron (B), R ₂₈ represents a halogen atom, a hydrocarbon group of 1 to 20 carbon atoms, a hydrocarbon group substituted by halogen of 1 to 20 carbon atoms, Alkoxy group.

[Chemical Formula 5]

[LH] ⁺ [Z (B) ₄ ] ^-

[Chemical Formula 6]

[L] ⁺ [Z (B) ₄ ] ^-

Wherein L is a neutral or cationic Lewis acid, Z is a Group 13 element of the Periodic Table of the Elements, B is a substituted or unsubstituted C6-C20 aryl group or a substituted or unsubstituted C1- Lt; / RTI > In addition, the hybrid catalyst composition may further include the first and second transition metal compounds and a carrier that supports the co-catalyst. The weight ratio of the carrier to the total amount of the transition metal (M1, M2) in the first and second transition metal compounds may be from 1: 1 to 1: 1000, and preferably from 1: 100 to 1: 500. The carrier may have an average particle size (average particle diameter) of 10 to 250 탆, a volume of fine pores of 0.1 to 10 cc / g, and a specific surface area of 1 to 1000 m 2 / g. The hybrid catalyst composition can be used in the production of ethylene-alpha olefin copolymers.

According to another aspect of the present invention, there is provided a method for producing a polyolefin using monomers in the presence of the above-mentioned hybrid catalyst composition, wherein the density is 0.910 g / cm 3 to 0.960 g / cm 3, and the molecular weight distribution (Mw / Mn) 3 to 10, a melt index (I ₂ ) of 0.2 to 100 at 2.16 Kg, and a melt index ratio (MFIR: I ₂₁ / I ₂ ) of at least 25. The polyolefin may comprise an ethylene-alpha olefin copolymer having a HMI (High Molecular Index) of 3.5 or more to 10 or less. Further, the polyolefin may have a melt tension of 0.06 F, N or more at 190 캜.

As described above, according to the present invention, a novel hybrid catalyst composition and a method for producing the same can be provided.

In addition, the present invention can provide a novel hybrid catalyst composition which is excellent in activity in the production of a polymer and can control the molecular weight and molecular weight distribution of the polymer.

Also, according to the present invention, it is possible to provide a high-density polyolefin having excellent mechanical strength and processability by using the hybrid catalyst composition.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a graph showing GPC-FTIR analysis for confirming comonomer distribution for the copolymers prepared in Examples 13, 14, and 18; FIG.
FIG. 2 is a graph showing GPC-FTIR analysis for confirming the comonomer distribution for the copolymers prepared in Comparative Examples 5 and 8. FIG.
3 is a graph showing the melt tension of Example 11 and a commercial product.

Hereinafter, a hybrid catalyst composition according to a specific embodiment of the present invention, a method for producing the same, and a polyolefin prepared using the hybrid catalyst composition and a method for producing the same will be described.

In one aspect of the present invention, the hybrid catalyst composition may include a first transition metal compound represented by the following formula (1) and a second transition metal compound represented by the following formula (2).

 [Chemical Formula 1]

In the above Formula 1, M1 is a Group 4 transition metal of the Periodic Table of the Elements, and may be, for example, hafnium (Hf), zirconium (Zr), or titanium (Ti). X ₁ and X ₂ may be the same or different and each independently represents a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, the carbon number of 7 to 40 alkyl aryl group, having 7 to 40 of the arylalkyl group, having 1 to 20 alkyl amido, C 6 -C 20 aryl amido group, or a group having 1 to 20 carbon atoms of the alkylidene group, R ₁ to R ₁₂ may be the same or different and each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted group having 6 to 20 carbon atoms An aryl group, a substituted or unsubstituted alkylaryl group having 7 to 40 carbon atoms, a substituted or unsubstituted arylalkyl group having 7 to 40 carbon atoms, or a substituted or unsubstituted silyl having 1 to 20 carbon atoms, It may form a control loop. For example, two of R ₆ and R ₇ , R ₆ and R ₁₂ , R ₈ and R ₉ , R ₉ and R ₁₀ , or R ₁₀ and R _{11 may} be connected to each other to form an aliphatic ring or aromatic ring have.

In the present invention, the term "substituted" as used herein means an aryl group substituted with a substituent such as a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, . The above-mentioned "hydrocarbon group" means a linear, branched or cyclic saturated or unsaturated hydrocarbon group unless otherwise specified, and the alkyl group, alkenyl group, alkynyl group and the like may be linear, branched or cyclic.

The first transition metal compound has an asymmetric structure in which one side and the other side of the first transition metal compound are made of different ligands with the transition metal (M1) therebetween, and a non-bridge structure in which the ligands on one side and the other side are not connected to each other . The asymmetric and unstiffened structures may form a steric hindrance so that the comonomer is less accessible to the catalytic active site of the first transition metal compound, thereby reducing the incorporation of the comonomer.

In one embodiment of the present invention, the first transition metal compound represented by Formula 1 may be any one or more of the following structural formulas.

M is any one of hafnium (Hf), zirconium (Zr), and titanium (Ti), and Me is methyl.

The second transition metal compound may be represented by the following general formula (2).

(2)

In Formula 2, M2 is a Group 4 transition metal of the Periodic Table of the Elements, and X ₃ and X ₄ may be the same or different from each other and each independently represents a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, An alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 40 carbon atoms, an arylalkyl group having 7 to 40 carbon atoms, an alkylamido group having 1 to 20 carbon atoms, an arylamido group having 6 to 20 carbon atoms , Or an alkylidene group having 1 to 20 carbon atoms, and R ₁₃ to R ₁₈ may be the same or different and each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted 2-carbon group having 2 to 20 carbon atoms A substituted or unsubstituted C1 to C20 alkenyl group, a substituted or unsubstituted C6 to C20 aryl group, a substituted or unsubstituted C7 to C40 alkyl aryl group, a substituted or unsubstituted C7 to C40 arylalkyl group, R ₁₉ and R ₂₀ may be the same or different and are each independently a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms or a substituted or unsubstituted aryl group having 1 to 20 carbon atoms, , A substituted or unsubstituted C 2 -C 20 alkenyl group, a substituted or unsubstituted C 6 -C 20 aryl group, a substituted or unsubstituted C 7 -C 40 alkylaryl group, a substituted or unsubstituted C 7 -C 40 aryl group, R ₂₁ to R ₂₆ may be the same or different from each other and each independently represents a hydrogen atom, a substituted or unsubstituted arylalkyl group, or a substituted or unsubstituted arylsilyl group having 1 to 20 carbon atoms, A substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C6 to C20 aryl group, a substituted or unsubstituted C7 alkyl group A substituted or unsubstituted arylalkyl group having 7 to 40 carbon atoms, or a substituted or unsubstituted silyl group having 1 to 20 carbon atoms, or they may be connected to each other to form a ring. For example, the adjacent two of R ₁₅ and R ₁₆ , R ₁₆ and R ₁₇ , R ₁₇ and R ₁₈ , R ₂₃ and R ₂₄ , R ₂₄ and R ₂₅ , or R ₂₅ and R ₂₆ are connected to each other to form an aliphatic ring or An aromatic ring can be formed.

In the present invention, the term "substituted" as used herein means an aryl group substituted with a substituent such as a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, . In addition, the above-mentioned "hydrocarbon group" may be a linear, branched or cyclic hydrocarbon group, and may also mean a saturated or unsaturated hydrocarbon group, unless otherwise specified. For example, the alkyl group, alkenyl group, alkynyl group and the like may be linear, branched or cyclic.

The second transition metal compound may have a symmetrical structure with ligands on one side and the other side with the transition metal (M2) as a center, and the bridge between the one side and the other side ligand may be connected. The symmetric structure and the bridge structure function to increase the incorporation of comonomer into the second transition metal compound by forming a steric structure in which the comonomer can easily approach the catalytic active site of the second transition metal compound.

For example, the second transition metal compound represented by Formula 2 may be any one of the following structural formulas.

M is any one of hafnium (Hf), zirconium (Zr), and titanium (Ti), Me is a methyl group, and Ph is a phenyl group.

As described above, the hybrid catalyst composition according to an embodiment of the present invention may include first and second transition metal compounds, wherein the first transition metal compound (see Chemical Formula 1) has a non-bridge structure And an asymmetric structure, and the second transition metal compound (see Chemical Formula 2) may have a bridge structure and a symmetrical structure connected by Si.

When a polymer is synthesized using a monomer and a comonomer together, for example, the monomer may be ethylene (CH ₂ ═CH ₂ ) and the comonomer may be propylene, 1-butene, 1-pentene, Is selected from the group consisting of pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, It can be either. The ethylene monomer has a short chain linear structure and is small in size. The comonomer may have a branch or a chain structure longer than the monomer, and may be three-dimensionally larger than the monomer. Preferably, the monomer can be easily introduced into the first transition metal compound, and the comonomer can be easily introduced into the second transition metal compound.

The first transition metal compound may have a ligand of one side and the other side in a non-bridge structure so that the respective ligands may not be fixed to each other. Therefore, the position of each ligand is continuously changed, so that the space between the transition metal and the ligand is not constant but fluidly changed. In addition, the first transition metal compound may have an asymmetric structure. The electron cycling phenomenon in which electrons are transferred to the transition metal (central metal) differs in each ligand, and the bond length between the transition metal and the ligand is not constant.

As described above, in the first transition metal compound, the change in the position of the one side and the other side of the ligand and the change in the length of the bond between the center metal and the ligand is such that a path through which the active site of the first transition metal compound flows It can be changed without constant. The monomer may have a short chain linear structure and may easily flow into the active site without being affected by the steric hindrance in the passage through the active site of the first transition metal compound. However, the comonomer is greatly affected by steric hindrance, .

In the second transition metal compound, the ligands on one side and the other side are fixed in a leg structure by Si to form a constant space between the transition metal and the ligand. In addition, the second transition metal compound may have a symmetrical structure, and the bond length between the ligand and the transition metal provided on one side and the other side may be kept constant without changing. In the second transition metal compound, the fixed position of one side and the other ligand and the coupling length between the center metal and the ligand are fixed, so that the passage through the active site of the second transition metal compound can be made constant. The comonomer can be easily introduced into the active site of the second transition metal compound relative to the active site of the first transition metal compound due to the constant space provided by the second transition metal compound.

That is, the first transition metal compound has a structure in which a monomer is advantageous to approach, and the second transition metal compound has a structure in which a comonomer is relatively easy to approach. Preferably, the first transition metal compound has a high degree of incorporation of the monomer, and the second transition metal compound may have a high incorporation of the comonomer. The first transition metal compound has low incorporation of comonomer and can form a low molecular weight compound, thereby improving the processability of the polymer and exhibiting high activity even when a high-density polymer is produced.

In the second transition metal compound, Si connecting the one side and the other side ligand can protect the catalytic active site of the second transition metal compound to provide a catalytic active site that is stabilized relative to the first transition metal compound . Therefore, the second transition metal compound can form a high molecular weight compound by the stabilized catalytic active site. Since the second transition metal compound may exhibit high comonomer incorporation, the synthesized polymer may have high mechanical properties. Specifically, the second transition metal compound can form a high molecular weight material by incorporating a high comonomer and concentrate the distribution of the comonomer in the high molecular weight material. As described above, the polymer having a uniform distribution concentration of the comonomer in the high molecular weight material can form a large amount of a bundle molecule (Tie molecule), and can improve the impact strength, the bending strength, the environmental stress cracking property and the melt tension . On the other hand, when the polyolefin is produced using a catalyst composed only of the second transition metal compound, the catalytic activity site for the monomer is too low to form an uneconomical and high-molecular weight material, resulting in poor processability.

For example, since the first transition metal compound and the second transition metal compound are provided in different structures, the hybrid catalyst composition according to the present invention has excellent activity in the production of the polymer, and the molecular weight and the molecular weight It is easy to control the molecular weight distribution. In addition, since the hybrid catalyst composition can separately control the synthesis of monomers and comonomers by the first and second transition metal compounds, the polyolefin thus produced can have both excellent mechanical properties and processability.

For example, the hybrid catalyst composition according to the present invention can be produced by mixing and supporting a second transition metal compound having excellent reactivity with a comonomer and a first transition metal compound having low reactivity with the comonomer.

The hybrid catalyst composition according to the present invention may further comprise the first and second transition metal compounds and a cocatalyst comprising at least one of the following chemical formulas (3) to (6).

(3)

In the general formula (3), R ₂₇ is a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group substituted with a halogen atom having 1 to 20 carbon atoms, and a is an integer of 2 or more. For example, the compound represented by Formula 3 may include at least one of methyl aluminoxane, ethyl aluminoxane, isobutyl aluminoxane, and butyl aluminoxane.

[Chemical Formula 4]

Z (R < ₂₈ >) ₃

In the formula (4), Z represents aluminum (Al) or boron (B), R ₂₈ represents a halogen atom, a hydrocarbon group of 1 to 20 carbon atoms, a hydrocarbon group substituted by halogen of 1 to 20 carbon atoms, Alkoxy group. For example, the compound represented by the above-mentioned formula (4) includes trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, tripropyl aluminum, tributyl aluminum, dimethyl chloro aluminum, triisopropyl aluminum, But are not limited to, isopentyl aluminum, trihexyl aluminum, trioctyl aluminum, ethyl dimethyl aluminum, methyldiethyl aluminum, triphenyl aluminum, tri-p-tolyl aluminum, dimethyl aluminum methoxide, dimethyl aluminum ethoxide, trimethyl boron, Triisobutylboron, triisopropylboron, triisobutylboron, tripropylboron, tributylboron, and tripentafluorophenylboron.

[Chemical Formula 5]

[LH] ⁺ [Z (B) ₄ ] ^-

[Chemical Formula 6]

[L] ⁺ [Z (B) ₄ ] ^-

In the general formulas (5) and (6), L is a neutral or cationic Lewis acid and Z is a Group 13 element of the Periodic Table of the Elements, for example, boron (B), aluminum (Al), gallium (Ga) ≪ / RTI > B is a substituted or unsubstituted aryl group having 6 to 20 carbon atoms or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms.

For example, the compound represented by Formula 5 or Formula 6 is methyl di-octa tesil ammonium tetrakis (pentafluorophenyl) borate _{([HNMe (C1 8 H 37} ) 2] + [B (C 6 F 5) 4] - ), Trimethylammonium tetrakis (phenyl) borate, triethylammonium tetrakis (phenyl) borate, tripropylammonium tetrakis (phenyl) borate, tributylammonium tetrakis (O, p-dimethylphenyl) borate, trimethylammonium tetrakis (o, p-dimethylphenyl) borate, triethylammonium tetrakis (P-trifluoromethylphenyl) borate, tributylammonium tetrakis (ptrifluoromethylphenyl) borate, tributylammonium tetrakis (pentafluorophenyl) borate, diethylammonium tetrakis (Phenyl) borate, triphenylphosphonium tetrakis (phenyl) borate, trimethylphosphonium tetrakis (phenyl) borate, N, N-diethylanilinium tetrakis (Pentafluorophenyl) borate, N, N-diethylanilinium tetrakis (pentafluorophenyl) borate, triphenylcarbonium tetrakis (ptrifluoromethylphenyl) borate, triphenylcarbonium tetrakis (Pentafluorophenyl) borate, trimethylammonium tetrakis (phenyl) aluminate, triethylammonium tetrakis (phenyl) aluminate, tripropylammonium tetrakis (phenyl) aluminate, tributylammonium tetrakis , Trimethylammonium tetrakis (p-tolyl) aluminate, tripropylammonium tetrakis (p-tolyl) aluminate, triethylammonium tetrakis (o, Phenyl) aluminate, tributylammonium tetrakis (ptrifluoromethylphenyl) aluminate, trimethylammonium tetrakis (p-trifluoromethylphenyl) aluminate, tributylammonium tetrakis (pentafluorophenyl) N, N-diethylanilinium tetrakis (phenyl) aluminate, N, N-diethylanilinium tetrakis (phenyl) aluminate, N, N-diethylanilinium tetrakis (pentafluorophenyl) , Triphenylphosphonium tetrakis (phenyl) aluminate, trimethylphosphonium tetrakis (phenyl) aluminate, triethylammonium tetrakis (phenyl) aluminate, and diethylammonium tetrakis (pentafluorophenyl) And tributylammonium tetrakis (phenyl) aluminate.

In one embodiment of the present invention, the hybrid catalyst composition may further include a carrier, which may carry the cocatalyst together with the first and second transition metal compounds. For example, the carrier may include at least one of silica, alumina, titanium oxide, zeolite, zinc oxide starch, and synthetic polymer.

In the hybrid catalyst composition, the weight ratio of the first transition metal compound to the second transition metal compound is preferably 1: 100 to 100: 1. The weight ratio of the total amount of the transition metal (M1, M2) to the carrier contained in the first and second transition metal compounds may be 1: 1 to 1: 1000. Preferably, the weight ratio of the carrier to the total amount of the transition metal (M1, M2) in the first and second transition metal compounds is 1: 100 to 1: 500. If the weight ratio of the carrier to the total amount of the transition metal in the first and second transition metal compounds is lower than the above range, a part of the first and second transition metal compounds may not be supported in the carrier, When the content is too large, the portion of the carrier not supported with the first and second transition metal compounds increases to lower the catalytic activity per unit volume. When the carrier and the transition metal contained in the first and second transition metal compounds are included within the above-mentioned ranges, the hybrid catalyst composition can exhibit proper supported catalyst activity, and thus is advantageous in maintaining the activity and economy of the catalyst.

The weight ratio of the carrier to the cocatalyst of Formula 3 or Formula 4 is 1: 100 to 100: 1, and the weight ratio of the carrier to the cocatalyst of Formula 5 or 6 may be 1:20 to 20: 1. When the cocatalyst and the first and second transition metal compounds are included in the above-mentioned weight ratio, it is advantageous in maintaining the activity and economical efficiency of the catalyst.

In the hybrid catalyst composition according to the present invention, the carrier may use a porous material having a large surface area. The carrier has an average particle size of 10 to 250 μm, preferably an average particle size of 10 to 150 μm, more preferably 20 to 100 μm. The microporous 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 support is 1 to 1000 m 2 / g, preferably 100 to 800 m 2 / g, and more preferably 200 to 600 m 2 / g. For example, the carrier may have an average particle size of 10 to 250 탆, a volume of fine pores of 0.1 to 10 cc / g, and a specific surface area of 1 to 1000 m 2 / g. The carrier may support the first and second transition metal compounds and the cocatalyst in the pores provided in the carrier to fix the positions of the first and second transition metal compounds and the cocatalyst and improve the catalytic efficiency. When the average particle size of the carrier is less than 10 mu m, the size of the carrier may be too small to cause a large amount of loss in the process of modifying the carrier. When the average particle size of the carrier is more than 250 mu m, Since the metal compound and the cocatalyst are supported only on the surface side pores of the carrier and are not supported on the inside of the carrier, the portion of the carrier not supporting the first and second transition metal compounds and the cocatalyst is increased, . The volume of the fine pores of the support is preferably from 0.1 cc / g to 10 cc / g. When the volume of the fine pores is less than 0.1 cc / g, the pore size is too small, And the volume of the micropores is 10 cc / g, the first and second transition metal compounds and the cocatalyst are too large in size to support the first and second transition metals, It is difficult to efficiently fix the positions of the compound and the cocatalyst. The specific surface area of the support is preferably from 1 m 2 / g to 1000 m 2 / g, and when it is less than 1 m 2 / g, the surface area of the support is too small as compared with the pore size of the support, If the specific surface area of the support is more than 1000 m < 2 > / g, the efficiency with which the first and second transition metal compounds and cocatalyst are supported in the carrier may decrease, which may be a problem.

In another embodiment of the present invention, the hybrid catalyst composition comprises a step of activating the first and second transition metal compounds, a step of supporting the activated first and second transition metal compounds on the carrier, Can be produced by a method for producing a composition. At this time, the hybrid catalyst composition may further include a cocatalyst, and the cocatalyst may be supported on the carrier before the first and second transition metal compounds. In addition, the method for producing the hybrid catalyst composition may further comprise the step of activating the first and second transition metal compounds. The first and second transition metal compounds may be separately activated and then mixed, or may be activated after mixing together. Also, the first and second transition metal compounds may be mixed with the co-catalyst to be activated and supported on the support, and after the co-catalyst is supported in the support, the first and second transition metal compounds are supported .

Preferably, the mixed catalyst composition according to the embodiment of the present invention comprises a step of preparing a first transition metal compound and a second transition metal compound, mixing the first and second transition metal compounds with a cocatalyst to prepare a mixture Mixing the first and second transition metal compounds with the cocatalyst in a solvent in which the carrier is provided, and stirring the mixture in a solvent in a reactor.

The first and second transition metal compounds may be activated by mixing (or contacting) the cocatalyst. The mixing can be carried out in an inert gas atmosphere, typically nitrogen or argon, without a solvent, or in the presence of a hydrocarbon solvent. For example, the activation temperature of the first and second transition metal compounds may be 0 to 100 캜, preferably 10 to 30 캜. The hydrocarbon 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 ether solvent such as diethyl ether or tetrahydrofuran, Can be used. Preferably, the solvent is toluene, hexane. In addition, when the hybrid catalyst composition is prepared, the reaction temperature may be 0 to 100 ° C, preferably 25 to 70 ° C. The reaction time is, but is not limited to, 5 minutes to 24 hours.

The first and second transition metal compounds may be used in the state of being dissolved in the hydrocarbon solvent uniformly or in the form of a solid powder from which the solvent is removed, but the present invention is not limited thereto.

When the carrier is silica in the hybrid catalyst composition, it may be used as a solid powder after removing the solvent. At this time, the drying temperature of silica carrying the hybrid catalyst composition is 200 to 900 ° C, preferably 300 to 800 ° C, and more preferably 400 to 700 ° C. If the drying temperature of the silica is less than 200 ° C., the amount of water remaining in the silica is large, and the moisture on the surface of the silica reacts with the cocatalyst. If the temperature exceeds 900 ° C., the structure of the carrier may collapse. Also, the concentration of the hydroxyl group in the dried silica may be 0.1 to 5 mmol / g, preferably 0.7 to 4 mmol / g, more preferably 1.0 to 2 mmol / g. If the concentration of the hydroxy group is less than 0.5 mmol / g, the supported amount of the co-catalyst may be lowered, and if the concentration exceeds 5 mmol / g, the first and second transition metal compounds are inactivated.

The hybrid catalyst composition can be used for olefin polymerization, and the polyolefin polymer produced therefrom is excellent in processability, long-term pressure resistance, impact resistance, melt tension and ESCR characteristics, and has high molecular weight and broad molecular weight Can have a characteristic having a distribution.

In another aspect of the present invention, a method for producing a polyolefin may be used, and the method for preparing the polyolefin may employ a hybrid catalyst composition according to an embodiment of the present invention. The polyolefin may be prepared using monomers or comonomers in the presence of the hybrid catalyst composition. The polyolefin prepared has a density of 0.910 g / cm3 to 0.960 g / cm3 and a molecular weight distribution (Mw / Mn) of 3 to 10 , The melt index (I ₂ ) at 2.16 Kg is 0.2 to 100, and the melt index ratio (MFIR: I ₂₁ / I ₂ ) may be 25 or more.

The polyolefin preferably has a density of 0.910 g / cm3 to 0.960 g / cm3. When the density of the polyolefin is less than 0.910 g / cm 3, the degree of crystallinity of the polyolefin is low and the mechanical strength is low. When the density of the polyolefin is more than 0.960 g / cm 3, the solubility of the polyolefin is decreased and the workability is lowered. When the molecular weight distribution (Mw / Mn) of the polyolefin is less than 3, the polyolefin has a high strength, but the workability deteriorates too much. When the molecular weight distribution (Mw / Mn) of the polyolefin is more than 10 The workability is good, but the physical properties such as mechanical strength are deteriorated, which is a problem. Further, together in 2.16Kg of the polyolefin melt index (I ₂₎ is preferably from 0.2 to 100, there is a problem in the production of the polyolefin, the fluidity of the polyolefin decreases when the melt index (I ₂₎ of less than 0.2, The viscosity of the polyolefin is so high that the amount lost in the reactor is increased and high temperature and high pressure are required in the reaction, which increases the process ratio and becomes a problem. The Melt Flow Index Ratio (MFIR: I ₂₁ / I ₂ ) of the polyolefin is a measure for measuring the degree of flowability of the polyolefin. The melt index ratio (MFIR: I ₂₁ / I ₂ ) of the polyolefin If it is less than 25, the flowability of the polyolefin during injection molding is too low, which is a problem.

The process for preparing the polyolefin may comprise the step of contacting the at least one monomer, such as an olefin monomer, with the hybrid catalyst composition to produce a polyolefin homopolymer or polyolefin copolymer. The polyolefin production process (polymerization reaction) may be a liquid phase, a slurry phase, or a gas phase polymerization reaction. In addition, the reaction conditions in each polymerization reaction can be variously modified depending on the polymerization method (liquid phase polymerization, slurry phase polymerization, gas phase polymerization) and the desired polymerization result or the form of the polymer. When the polymerization reaction is carried out in a liquid phase or a slurry, the solvent or the olefin monomer itself may be used as a medium. For example, the solvent is selected from the group consisting of propane, butane, pentane, hexane, octane, decane, dodecane, cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, benzene, toluene, xylene, dichloromethane, chloroethane, dichloroethane, Chlorobenzene, and chlorobenzene. These solvents may be mixed at a certain ratio.

In the specific examples, examples of the monomer include ethylene, alpha -olefins, cyclic olefins, dienes, trienes, styrenes, and the like. The α-olefins include aliphatic olefins having 3 to 12 carbon atoms, for example, 3 to 8 carbon atoms. Specific examples thereof include propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 4,4-dimethyl-1-pentene, 4,4-diethyl- -Hexene, 3,4-dimethyl-1-hexene, and the like. The? -Olefins may be homopolymerized or two or more olefins may be alternating, random, or block copolymerized. The copolymerization of the? -Olefins may be carried out by copolymerizing ethylene and an? -Olefin having 3 to 12 carbon atoms, such as 3 to 8 carbon atoms (specifically, ethylene and propylene, ethylene and 1-butene, ethylene and 1-hexene, 4-methyl-1-pentene, ethylene and 1-octene), and copolymers of propylene and an C4-C8 or C4-C8? -Olefin (specifically, propylene and 1-butene, Methyl-1-pentene, propylene and 4-methyl-1-butene, propylene and 1-hexene, propylene and 1-octene). In the copolymerization of ethylene or propylene with another? -Olefin, the amount of the other? -Olefin may be 99 mol% or less of the total monomer, and usually 80 mol% or less in the case of the ethylene copolymer.

In the method for producing a polyolefin according to an embodiment of the present invention, the amount of the mixed catalyst composition to be used is not particularly limited. For example, in the polymerized reaction system, the first and second transition metals the central metal concentrations (M1, M2) of the compound 1x10 ^-5 to 9x10 ^- may be a ⁵ mol / l. The temperature and pressure of the polymerization reaction are not particularly limited as they may vary depending on the reactants, reaction conditions, etc., but the temperature may be 0 to 200 ° C, preferably 100 to 180 ° C in the case of liquid phase polymerization, And may be 0 to 120 캜, preferably 60 to 100 캜 in the case of phase or vapor phase polymerization. Further, the pressure may be 1 to 150 bar, preferably 30 to 90 bar, and more preferably 10 to 20 bar. The pressure may be by injection of an olefin monomer gas (e.g., ethylene gas).

In addition, the polymerization reaction may be carried out batchwise, semi-continuously or continuously. The batch, semi-continuous or continuous method may be used individually, or one or more of them may be combined, and may be performed, for example, in two or more steps having different reaction conditions. The molecular weight of the final polymer can be controlled by varying the temperature of the polymerization reaction or by injecting hydrogen into the reactor.

The polyolefin according to one embodiment of the present invention can be obtained from an ethylene homopolymer or an ethylene-alpha olefin copolymer using the hybrid catalyst composition and can have a single molecular weight distribution. In addition, when the polyolefin polymer is produced using the hybrid catalyst composition, the polyolefin polymer has a broad molecular weight distribution, and a polymer having a high concentration of comonomer in the high molecular weight compound can be prepared . The polyolefin polymer is excellent in impact strength, bending strength, resistance to stress cracking, and melt tension, and can be used in blow molding molded articles, injection molded articles, films, pipes, and extrusion molded articles.

Hereinafter, the configuration and operation of the present invention will be described in more detail with reference to embodiments of the present invention. It is to be understood, however, that the same is by way of illustration and example only and is not to be construed in a limiting sense.

The hybrid catalyst composition according to an embodiment of the present invention may include first and second transition metal compounds, wherein the first and second transition metal compounds may be prepared in the following manner.

Preparation of first and second transition metal compounds

Preparation Example 1: Preparation of first transition metal compound [Indenyl (cyclopentadienyl)] ZrCl ₂

Butyllithium (n-BuLi) hexane solution (17 ml, 0.043 mol) was dissolved in hexane (150 ml) 0.043 mol) was slowly dropped. Subsequently, the temperature was gradually raised to room temperature and then stirred at room temperature for 12 hours. The resulting white suspension was filtered with a glass filter to obtain a white solid compound, which was sufficiently dried to obtain an indium lithium salt (yield: 99%).

CpZrCl ₃ (2.24 g, 8.53 mmol) was slowly dissolved in ether (30 mL) and then cooled to -30 ° C. Indenyl lithium salt (1.05 g, 8.53 mmol) dissolved in ether (15 mL) was slowly added dropwise to the ether solution in which CpZrCl ₃ was dissolved and then stirred overnight to obtain [Indenyl (cyclopentadienyl)] ZrCl ₂ (yield 97%).

Preparation Example 2: Preparation of first transition metal compound [2-methyl benzindenyl (cyclopentadienyl)] ZrCl ₂

2-methylbenzeneinden (cyclopentadienyl)] ZrCl ₂ (yield: 95%) was obtained in the same manner as in Production Example 1 using 2-methylbenzeindene.

Preparation Example 3: Preparation of first transition metal compound [2-phenyl benzindenyl (tetramethylcyclopentadienyl)] ZrCl ₂

2-phenylbenzeneinden (tetramethylcyclopentadienyl)] ZrCl ₂ (yield: 93%) was obtained in the same manner as in Production Example 1 using 2-methylbenzeindene and tetramethylcyclopentadiene.

Preparation Example 4: Preparation of first transition metal compound [fluorenyl (cyclopentadienyl)] ZrCl ₂

Fluorenyl (cyclopentadienyl)] ZrCl ₂ (yield: 92%) was obtained in the same manner as in Production Example 1, using fluorene and cyclopentadiene.

Preparation Example 5: Preparation of a second transition metal compound Me ₂ Si (2-methyl-4,5-benzoindenyl) ₂ ZrCl ₂

Production Example 5-1: Preparation of a ligand compound

Butyllithium (n-BuLi) hexane solution (8.1 mL, 1.1 eq, 1.6 M in Hexane) was added to 30 ml of hexane at -30 ° C, and 2-methylbenzeindene (2.13 g, Slowly added. The temperature was then slowly raised to room temperature and then stirred for 12 hours. The resulting solid was filtered, washed with hexane and then dried under vacuum to yield a light gray solid compound.

To the light gray solid compound was added slowly a dispersion of SiMe ₂ Cl ₂ (520 mg, 1 eq) in 15 ml of ether, the temperature was slowly raised to room temperature and the mixture was stirred for 12 hours. The organic layer was extracted with a mixture of ether and water, dried and then washed with hexane to obtain (2-methylbenzeindenyl) ₂ SiMe ₂ (yield: 55%).

¹ H NMR (CDCl ₃ ):? = 8.15-7.42 (m, 14H), 4.00 (m, 2H), 2.37

Production Example 5-2: Preparation of second transition metal compound

Production Example 5-1 Compound (0.4 g, 1 eq) was added to 15 ml of THF and n-butyllithium hexane solution (1.32 ml, 2.2 eq, 1.6M in hexane) was added slowly at -30 캜. Subsequently, the temperature was gradually raised to room temperature and stirred for 12 hours to prepare a dilithium salt. ZrCl ₄ (435 mg, 1 eq) was slowly added to the dilithium salt slurry solution and stirred for 12 hours. The solvent was removed in vacuo and washed with THF and MC to give Me ₂ Si (2-methyl-4,5-benzoindenyl) ₂ ZrCl ₂ (yield: 37%).

¹ H NMR (CDCl ₃ ):? = 7.97-7.26 (m, 14H), 7.97-7.08 (m, 14H), 2.59 (s, 6H) (s, 3 H), 1.26 (s, 3 H)

Preparation Example 6: Preparation of a second transition metal compound Me ₂ Si {2-methyl-4- (1-naphthyl)} ₂ ZrCl ₂

Production Example 6-1: Preparation of a ligand compound

2-methyl-4-bromo indene (2 g, 1 eq), palladium-tetrakis (triphenylphosphine), Pd (PPh ₃ ) ₄ , (553mg, 0.05eq), 1- NaphB (OH) to _{2 (1-naphthalene boronic acid)} (2.14g, 1.3eq) THF, MeOH solution: (degassing) after removal of the gas into the (4 1, 40ml) K ₂ CO ₃ (2-methyl-4- (1-naphthyl) indene) was obtained by injecting aqueous solution (2.0M, 3.3eq) at room temperature and refluxing for 12 hours at 80 ° C. N-butyllithium hexane solution (7.8 mL, 1.1 eq, 1.6M in hexane) was added slowly at -30 ° C, and the temperature was gradually lowered to room temperature And the mixture was stirred for 12 hours. The resulting solid was filtered, washed with hexane and dried under vacuum to give 2-methyl-4- (1-naphthyl) indenyl lithium. 2-methyl-4- (1-naphthyl) indenyl lithium (1.88 g, 2 eq) To 13 mL of toluene, 3 mL of THF, was added SiMe ₂ Cl ₂ (462 mg, 1 eq) was added slowly at -30 ° C, and the temperature was gradually raised. The mixture was stirred at 55 ° C for 12 hours to obtain 1.97 g of dimethyl-bis {2-methyl- 4- (1-naphthyl) indenyl) 97%).

_{^{1 H NMR (CDCl 3):}} δ = 7.94-7.16 (m, 20H), 6.25 (m, 2H), 3.90 (m, 2H), 2.24-2.05 (m, 6H), -0.15 (m, 6H)

Production Example 6-2: Production of second transition metal compound

Dimethyl-bis {2-methyl- 4- (1-naphthyl) indenyl)} was prepared in the same manner as in Production Example 3-2 by using the _{silane Me 2 Si {2-methyl} -4- (1-naphthyl)} 2 ZrCl ₂ was obtained (yield: 94%).

_{^{1 H NMR (CDCl 3):}} δ = rac-G7: 7.92-7.14 (m, 20H), 7.92-7.00 (m, 20H), 6.13 (s, 2H), 6.51 (s, 2H), 2.34 (s, (S, 3H), 1.25 (s, 3H), 1.38 (s, 6H)

Preparation Example 7: Preparation of a second transition metal compound Me ₂ Si {2-methyl-4- (2-naphthyl)} ₂ ZrCl ₂

Production Example 7-1: Preparation of a ligand compound

(2-methyl-4- (2-naphthyl) indene) was prepared in the same manner as in Production Example 4-1 using 2-methyl-7- 2-naphthyl) indenyl)} silane (yield: 51%).

_{^{1 H NMR (CDCl 3):}} δ = 8.00-7.20 (m, 20H), 6.84 (m, 2H), 3.84 (m, 2H), 2.14 (m, 6H), -0.12 (m, 6H)

Production Example 7-2: Preparation of second transition metal compound

The yield of Me ₂ Si {2-methyl-4- (2-naphthyl)} ₂ ZrCl ₂ was obtained in the same manner as in Production Example 4-2 using the compound of Preparation Example 7-1.

¹ H NMR (CDCl ₃ ):? = 8.16-6.90 (m, 22H), 2.48 (s, 6H), 2.29 (s, , 3H)

Preparation Example 8: Preparation of second transition metal compound Me ₂ Si (2-methyl-4-phenyl indenyl) ₂ ZrCl ₂

Production Example 8-1: Preparation of a ligand compound

A mixture of 2-methyl-4-bromo indene (2 g, 1 eq) (7 g, 1 eq), dichloro (1,3-bis (diphenylphosphino) propane) , 3-bis (diphenylphosphino) propane ) nickel, Ni (dppp) Cl 2) to (363mg, 0.02eq) of PhMgBr 3.0M (13.3g, 1.05eq, in ether) at 0 ℃ put in ether (100mL) 1 sigan Lt; / RTI > The temperature was gradually raised to room temperature, and the mixture was refluxed and stirred at 50 DEG C for 12 hours. After completion of the reaction, the solution was immersed in an ice bath and then 1N HCl acid was added thereto to lower the pH to 4. The organic layer was extracted with a separatory funnel and then treated with MgSO ₄ to remove water. Filtered and the solvent was dried to obtain 2-methyl-4- (phenyl) indene (yield: 97%). Me ₂ Si (2-methyl-4-phenyl indenyl) ₂ was prepared in the same manner as in Production Example 4-1 using 2-methyl-4- (phenyl) indene.

_{^{1 H NMR (CDCl 3):}} δ = 7.56-7.14 (m, 16H), 6.80 (m, 2H), 3.80 (s, 2H), 2.25 (s, 3H), 2.17 (s, 3H), 0.18 (m , 6H).

Production Example 8-2: Preparation of second transition metal compound

It was prepared in _{Me 2 Si (2-methyl-} 4-phenylindene) in the same manner as in Production Example 4-2 by using a _{2 Me 2 Si (2-methyl} -4-phenyl indenyl) 2 ZrCl 2 ( yield: 90% ).

_{^{1 H NMR (CDCl 3):}} δ = 7.68-7.10 (m, 16H), 7.68-6.83 (m, 18H), 6.95 (s, 2H), 2.46 (s, 6H), 2.26 (s, 6H), 1.48 (s, 3H), 1.34 (s, 6H), 1.26 (s, 3H).

Using the first and second transition metal compounds prepared according to the above Preparation Examples, the hybrid catalyst compositions according to the embodiments of the present invention were prepared as follows.

Preparation of hybrid catalyst composition

Example 1

Since the first and second transition metal compounds and the co-catalyst methylaluminoxane (MAO) react with moisture or oxygen in the air to lose their activity, all experiments were carried out under nitrogen conditions using a glove box and a Schlenk technique . The reactor used for preparing the hybrid catalyst composition (for example, a 10L supported catalyst reactor) was washed, the foreign matter was removed, the reactor was closed at a temperature of 110 ° C for 3 hours or more, Respectively.

(MAO) solution (methylaluminoxane: 1188 g) as a cocatalyst was added to 2.862 g of the compound of Preparation Example 1, which is the first transition metal compound, and 3.469 g of the compound of Production Example 8-2, which is the second transition metal compound, And the mixture was stirred at room temperature for 1 hour to prepare a cocatalyst mixture with the first and second transition metal compounds.

300 g of silica (XPO2402) as a carrier was charged into a reactor, and then 900 mL of purified toluene was added to the reactor charged with the silica and stirred. After the stirring step for one hour was completed, the first and second transition metal compounds and the co-catalyst mixture solution were added while stirring the reactor. The reactor was heated to 60 ° C and stirred for 2 hours.

After the precipitation reaction, the supernatant was removed, washed with 1 L of toluene, and vacuum dried at 60 ° C for 12 hours.

Example 2

The procedure of Example 1 was repeated except that 2.389 g of the compound of Preparation Example 2 and 4.387 g of the compound of Preparation Example 8-2 were used.

Example 3

Except that 2.712 g of the compound of Preparation Example 3 and 3.046 g of the compound of Preparation Example 7-2 were used.

Example 4

The procedure of Example 1 was repeated except that 2.662 g of the compound of Preparation Example 4 and 3.712 g of the compound of Preparation Example 6-2 were used.

Example 5

The procedure of Example 1 was repeated except that 2.359 g of the compound of Preparation Example 1 and 4.357 g of the compound of Preparation Example 5-2 were used.

Example 6

The procedure of Example 1 was repeated except that 2.329 g of the compound of Preparation Example 4 and 4.357 g of the compound of Preparation Example 8-2 were used.

Example 7

The procedure of Example 1 was repeated except that 2.359 g of the compound of Preparation Example 1 and 4.057 g of the compound of Preparation Example 7-2 were used.

Example 8

The procedure of Example 1 was repeated except that 2.359 g of the compound of Preparation Example 2 and 4.157 g of the compound of Preparation Example 5-2 were used.

Example 9

The procedure of Example 1 was repeated except that 2.159 g of the compound of Preparation Example 2 and 3.357 g of the compound of Preparation Example 6-2 were used.

Example 10

The procedure of Example 1 was repeated except that 2.659 g of the compound of Preparation Example 3 and 4.557 g of the compound of Preparation Example 5-2 were used.

Comparative Example 1

The compound of Preparation Example 1 and (nBuCp) ₂ ZrCl ₂ To Was prepared in the same manner as in Example 1,

Comparative Example 2

(nBuCp) ₂ ZrCl ₂ and Production Example 8-2 Compound Was prepared in the same manner as in Example 1,

Comparative Example 3

The compound of Preparation 1 and Me ₂ Si (Me ₄ Cp) (NtBu) TiCl ₂ Was prepared in the same manner as in Example 1,

Comparative Example 4

Only 6.214 g of the compound of Preparation Example 8-2 Was prepared in the same manner as in Example 1,

The first and second transition metal compounds, cocatalyst and carrier used in Examples 1 to 10 and Comparative Examples 1 to 4 described above are shown in Table 1 (preparation of hybrid catalyst composition).

division The first transition metal compound The second transition metal compound Co-catalyst carrier Example 1 Production Example 1
([Indenyl (cyclopentadienyl)] ZrCl 2: 2.862g Preparation Example 8-2 Me ₂ Si (2-methyl-4-phenyl indenyl) ₂ ZrCl ₂ : 3.469 g Methyl aluminum oxalate: 1188 g 300 g of silica (XPO2402) Example 2 Preparation Example 2 [2-methyl benzeindenyl (cyclopentadienyl)] ZrCl ₂ : 2.389 g Preparation Example 8-2 Me ₂ Si (2-methyl-4-phenyl indenyl) ₂ ZrCl ₂ : 4.387 g Methyl aluminum oxalate: 1188 g 300 g of silica (XPO2402) Example 3 Preparation Example 3 [2-phenyl benzindenyl (tetramethylcyclopentadienyl)] ZrCl ₂ : 2.712 g Preparation Example 7-2 Me ₂ Si {2-methyl-4- (2-naphthyl)} ₂ ZrCl ₂ : 3.046 g Methyl aluminum oxalate: 1188 g 300 g of silica (XPO2402) Example 4 Preparation Example 4 [fluorenyl (cyclopentadienyl)] ZrCl ₂ : 2.662 g Production Example 6-2 Me ₂ Si {2-methyl-4- (1-naphthyl)} ₂ ZrCl ₂ : 3.712 g Methyl aluminum oxalate: 1188 g 300 g of silica (XPO2402) Example 5 Preparation Example 1 [Indenyl (cyclopentadienyl)] ZrCl ₂ : 2.359 g Production Example 5-2 Me ₂ Si (2-methyl-4,5-benzoindenyl) ₂ ZrCl ₂ : 4.357 g Methyl aluminum oxalate: 1188 g 300 g of silica (XPO2402) Example 6 Preparation Example 4 [fluorenyl (cyclopentadienyl)] ZrCl ₂ : 2.329 g Preparation Example 8-2 Me ₂ Si (2-methyl-4-phenyl indenyl) ₂ ZrCl ₂ : 4.357 g Methyl aluminum oxalate: 1188 g 300 g of silica (XPO2402) Example 7 Preparation Example 1 [Indenyl (cyclopentadienyl)] ZrCl ₂ : 2.359 g Preparation Example 7-2 Me ₂ Si {2-methyl-4- (2-naphthyl)} ₂ ZrCl ₂ : 4.057 g Methyl aluminum oxalate: 1188 g 300 g of silica (XPO2402) Example 8 Preparation Example 2 [2-methyl benzindenyl (cyclopentadienyl)] ZrCl ₂ : 2.359 g Production Example 5-2 Me ₂ Si (2-methyl-4,5-benzoindenyl) ₂ ZrCl ₂ : 4.157 g Methyl aluminum oxalate: 1188 g 300 g of silica (XPO2402) Example 9 Preparation Example 2 [2-methyl benzeindenyl (cyclopentadienyl)] ZrCl ₂ : 2.159 g Production Example 6-2 Me ₂ Si {2-methyl-4- (1-naphthyl)} ₂ ZrCl ₂ : 3.357 g Methyl aluminum oxalate: 1188 g 300 g of silica (XPO2402) Example 10 Preparation Example 3 [2-phenyl benzindenyl (tetramethylcyclopentadienyl)] ZrCl ₂ : 2.659 g Production Example 5-2 Me ₂ Si (2-methyl-4,5-benzoindenyl) ₂ ZrCl ₂ : 4.557 g Methyl aluminum oxalate: 1188 g 300 g of silica (XPO2402) Comparative Example 1 Production Example 1 [Indenyl (cyclopentadienyl)] ZrCl ₂ : 2.862 g (nBuCp) ₂ ZrCl ₂ : 3.469 g Methyl aluminum oxalate: 1188 g 300 g of silica (XPO2402) Comparative Example 2 (nBuCp) ₂ ZrCl _2: 2.862 g Preparation Example 8-2 Me ₂ Si (2-methyl-4-phenyl indenyl) ₂ ZrCl ₂ : 3.469 g Methyl aluminum oxalate: 1188 g 300 g of silica (XPO2402) Comparative Example 3 Production Example 1 [Indenyl (cyclopentadienyl)] ZrCl ₂ : 2.862 g Me ₂ Si (Me ₄ Cp) (NtBu) TiCl ₂ : 3.469 g Methyl aluminum oxalate: 1188 g 300 g of silica (XPO2402) Comparative Example 4 Preparation Example 8-2 Me ₂ Si (2-methyl-4-phenyl indenyl) ₂ ZrCl ₂ : 6.214 g Methyl aluminum oxalate: 1188 g 300 g of silica (XPO2402)

As shown in Table 1, the ethylene-alpha olefin copolymers, which are polyolefins, were prepared using the hybrid catalyst compositions according to Examples 1 to 10 and Comparative Examples 1 to 4, as shown in Table 2 and Table 2 below.

Manufacture of polyolefins

Example 11

As shown in Table 2, the hybrid catalyst composition obtained in Example 1 was fed into a fluidized bed gas process continuous polymerization reactor (reactor) to produce a polyolefin. Ethylene was used as the monomer, and 1-hexene was used as the comonomer. The ethylene pressure in the reactor was maintained at about 14 to 15 bar and the polymerization temperature was 80 to 90 ° C.

Examples 12 to 20

As shown in Table 2, the polyolefins of Examples 12 to 20 were prepared using the hybrid catalyst compositions of Examples 2 to 10, respectively. At this time, a polyolefin (ethylene-alpha olefin copolymer) was prepared in the same manner as in Example 11 except for the above-mentioned hybrid catalyst composition.

Comparative Examples 5 to 8

As shown in Table 2, the polyolefins of Comparative Examples 5 to 8 were prepared using the hybrid catalyst compositions of Comparative Examples 1 to 4, respectively. At this time, polyolefins were prepared in the same manner as in Example 11 except for the above-mentioned hybrid catalyst composition.

In the following Table 2 (polyolefin production), the hybrid catalyst compositions for Examples 11 to 20 and Comparative Examples 5 to 8 were mixed and the ethylene pressure, hydrogen / ethylene molar ratio and 1-hexene / ethylene Respectively. The ethylene was a monomer of a polyolefin and 1-hexene was used as a comonomer. The hydrogen was used as a chain transfer agent used to control the molecular weight of the polyolefin during the reaction.

division Hybrid catalyst composition Ethylene pressure (bar) Hydrogen / Ethylene mole ratio (%) 1-hexene / ethylene molar ratio (%) Example 11 Example 1 15.0 0.125 0.159 Example 12 Example 2 15.2 0.115 0.168 Example 13 Example 3 14.7 0.082 0.31 Example 14 Example 4 14.4 0.048 0.3 Example 15 Example 5 15.0 0.164 0.102 Example 16 Example 6 14.1 0.108 0.33 Example 17 Example 7 15.2 0.026 0.31 Example 18 Example 8 15.1 0.065 0.233 Example 19 Example 9 15.2 0.118 0.120 Example 20 Example 10 15.1 0.087 0.114 Comparative Example 5 Comparative Example 1 15.1 0.027 0.69 Comparative Example 6 Comparative Example 2 15.05 0.116 0.36 Comparative Example 7 Comparative Example 3 15.2 0.13 0.22 Comparative Example 8 Comparative Example 4 15.1 0.118 0.23

Method of measuring physical properties of polyolefin

(1) Density was measured according to ASTM D1505.

(2) The melt index (I ₂ , 2.16 kg) was an extrusion amount of 10 minutes at a load of 2.16 kg and measured according to ASTM D1238 at a measurement temperature of 190 ° C.

(3) The Melt Flow Index Ratio (MFIR) is the ratio of the flow index (I ₂₁ , 21.6 kg load) divided by the melt index (I ₂ , 2.16 kg load).

(4) Molecular weight and molecular weight distribution (PDI) were measured by gel permeation chromatography-FT-IR (GPC-FTIR).

(5) The impact strength was measured according to ASTM D256.

(6) Environmental Stress Cracking Resistance (ESCR) was measured by placing 10 samples in ASTM D1693 at 50 ° C in a 10% IGEPAL solution and then failing (cracking) in 5 samples. Were evaluated.

(7) Melt tension measurement was performed on Gottfert Rheotens attached to a Gottfert Rheotester 2000 capillary rheometer.

(8) High Molecular Index (HMI)

The ratio of the weight average molecular weight (Mw) to the Z average molecular weight (Mz) obtained by gel permeation chromatography is shown. The higher the value, the higher the number of high molecular weight components in the polymer.

(9) Broad Orthogonal Comonomer Distribution Index (BOCDI)

A short chain branch (SCB) distribution is a numerical value indicating the concentration of SCB in the polymer. BOCDI was obtained by referring to the method described in Korean Patent No. 10-2012-0038798.

The results of measuring the physical properties of Examples 11 to 20 and Comparative Examples 5 to 8 are shown in Table 3 (confirmation of physical properties of polyolefin).

division Catalytic activity (gPE / gCat) Melt Index
(I ₂ , 2.16 kg) Melt flow rate
(MFIR) BOCDI HMI
(High Molecular Index) density
(Density) Example 11 5000 2.6 43.0 0.69 4.7 0.9518 Example 12 5600 0.95 74.5 0.78 5.1 0.9523 Example 13 5800 0.31 64.0 0.81 5.6 0.9424 Example 14 5900 0.29 46.4 0.47 5.7 0.9403 Example 15 5100 2.5 44.0 0.58 4.5 0.9560 Example 16 6400 2.09 97.3 0.39 4.2 0.9237 Example 17 5400 0.76 35.0 0.51 5.0 0.9373 Example 18 5150 0.53 38.8 0.68 5.4 0.9433 Example 19 5050 3.65 47.5 0.37 4.0 0.9567 Example 20 4930 1.2 52.9 0.48 4.4 0.9536 Example
medium 5433 1.488 54.34 0.576 4.86 0.9457 Comparative Example 5 3800 0.83 16.7 -0.12 2.2 0.9361 Comparative Example 6 4500 0.75 21.2 -0.08 2.1 0.9406 Comparative Example 7 1500 0.70 18.0 -0.01 2.5 0.9423 Comparative Example 8 1600 1.09 22.3 -0.01 2.0 0.9337 Comparative Example
medium 2850 0.8425 19.55 -0.055 2.2 0.9382

FIG. 1 is a graph showing GPC-FTIR analysis for confirming comonomer distribution for the copolymers prepared in Examples 13, 14, and 18, FIG. 2 is a graph showing the results of analysis of the copolymers prepared in Comparative Examples 5 and 8, GPC-FTIR analysis to identify comonomer distribution.

Referring to FIGS. 1 and 2 and Tables 1 to 3, it was confirmed that the mixed catalyst composition according to an embodiment of the present invention shows higher catalytic activity than the comparative example.

In Fig. 1 and Fig. 2, the red color represents the distribution of the comonomer and the blue color represents the molecular weight distribution. In FIG. 1, it was confirmed that the comonomer was distributed widely in the polymer itself, and the mechanical properties were excellent. On the other hand, in FIG. 2, it was confirmed that a large number of comonomers were distributed in the low molecular weight polymer.

Since the average value of the catalytic activity used in Examples 11 to 20 was 5433 gPE / gCat, whereas the average value of the catalytic activity obtained in Comparative Examples 5 to 8 was 2850 gPE / gCat, It was confirmed that the catalytic activity was increased about twice or more.

The average value of the melt flow rate (melt index ratio, MFIR) in Examples 11 to 20 was 54.34, while the average value in Comparative Examples 5 to 8 was 19.55, and the mixed catalyst mixture according to the present invention was used It was confirmed that the prepared polyolefin was two times or more higher than that of Comparative Example. The melt flow rate is used as an index for confirming the fluidity of the polymer. The higher the molecular weight, the lower the melt flow rate. If the melt flow rate is higher, the flowability (workability) . That is, it was confirmed that the polyolefin prepared in accordance with the present invention is superior in workability to the polyolefin prepared according to the comparative example.

BOCDI is a numerical value indicating the distribution of short chain branching (SCB) in polyolefins. The positive value indicates the concentration of SCB in the polymer. It was confirmed that the polyolefins prepared according to the examples of the present invention all have a (+) value, while the polyolefins prepared according to the comparative examples all have a (-) value. That is, it was confirmed that the polyolefin prepared by using the hybrid catalyst composition according to the embodiment of the present invention has a large amount of comonomer in the high molecular weight compound.

HMI can greatly affect the mechanical properties and processability of polyolefins. When the HMI is at least 3.5, it means that a large amount of high molecular weight material is formed. When a large amount of the high molecular weight material is formed, the mechanical properties such as melt tension, environmental stress cracking resistance and impact strength of the polyolefin are improved. On the other hand, when the HMI is more than 10, there is a problem that the workability during processing is remarkably lowered and the appearance of the product becomes very poor. Therefore, the polyolefin according to the embodiment of the present invention is preferably an ethylene-alpha olefin copolymer having an HMI of not less than 3.5 and not more than 10. When the HMI of the polyolefin is less than 3.5, the stress cracking resistance and the melt tension are lowered, and when the HMI is more than 10, the workability is lowered.

Comparison of Example 7 polyolefins were produced using the mixed catalyst compositions according to Comparative Example 3, the mixed catalyst composition of the Comparative Example 3 Production Example 1 ([Indenyl (cyclopentadienyl)] ZrCl 2) and Me ₂ Si (Me ₄ Cp ) (NtBu) TiCl ₂ . That is, even when two kinds of transition metal compounds are used in combination, a compound having an asymmetric structure on both sides of the transition metal Ti, such as Production Example 1 and Me ₂ Si (Me ₄ Cp) (NtBu) TiCl ₂ , It was confirmed that the catalytic activity was low.

In the case of Comparative Example 6 having a structure different from that of the second transition metal compound (see Chemical Formula 2), the catalytic activity was relatively good, while the workability was poor, the high molecular weight was low, the comonomer was concentrated in the low molecular weight, It was confirmed that the tensile strength and the stress crack resistance were low. Therefore, in the case of Comparative Example 6, commercial use is not easy.

Table 4 below shows the results of comparing the polyolefins according to the embodiments of the present invention with commercially available HDPE and confirming their properties. It was confirmed that the polyolefin according to the embodiment of the present invention is superior in both workability and mechanical properties to HDPE which is commercially available. It was confirmed that both the melt index (I ₂ ) and the melt flow rate (MFIR), which are measures of workability, are superior to those of the polyolefin according to the embodiment of the present invention.

This indicates that the polyolefin according to the embodiment of the present invention contains a large amount of a high molecular weight material as an ethylene-alpha olefin copolymer and has excellent resistance to stress cracking and impact strength. Since a large amount of comonomers are distributed in the high molecular weight material, (I ₂ ) and melt flow rate (MFIR).

Table 4 shows that the olefin copolymer of the present invention of the present invention has excellent processability and excellent mechanical properties as compared with conventional commercially available HDPE. It can be confirmed that the processability of the olefin copolymer of the present invention is excellent through the melt index (I ₂ ) and the melt index ratio (MFIR) which are the indexes representing the workability. It was confirmed that the olefin copolymer of the present invention contains a large amount of high molecular weight and exhibits excellent resistance to stress cracking and impact strength. Also, FIG. 3 confirms that a high molecular weight comonomer is widely distributed and a high molecular weight is present, and thus an excellent melt tension is exhibited.

3 is a graph showing the melt tension of Example 11 and a commercial product. Commercially available products include products A (HDPE C910C, density 0.945 g / cm ³ , (HDPE ME2500, density 0.950 g / cm ³ , melt index 2.0 g / 10 min), product B (HDPE 7303, density 0.956 g / cm ³ , melt index 2.0 g / 10 min) Respectively. Referring to Table 4 and FIG. 3, the polyolefin according to an embodiment of the present invention has an impact strength measured according to ASTM D256 of 20 kJ / m < 2 > or more and 190 DEG C The melt tension was 0.06 F, N or more.

Referring to FIG. 3, it can be seen that Example 11 according to the present invention has larger values of F and N than commercial products A, B and C. The values of F and N mean that the melt tension is increased as the value is increased, which means that the processing conditions are widened and the workability is excellent even under various conditions. That is, the polyolefin according to an embodiment of the present invention has F and N values that are superior to commercial products generally used in the art, and thus the polyolefin can be processed under various conditions, so that it can be easily applied to various fields There is an advantage.

division Melt Index
(I ₂ , 2.16 kg) Melt flow rate
(MFIR) density
(Density)
(g / cm3) ESCR (h) Impact strength
(kJ / m 2) HMI
(High Molecular Index) Example 11 2.6 43 0.9518 17 22 4.7 Example 15 2.5 44 0.9560 16 20 4.5 A product 2.4 29 0.9556 11 17.5 3.4 B products 2.1 37 0.9523 14 14 2.7 C products 2.1 29 0.9538 12 19 2.2

As described above, the hybrid catalyst composition according to the embodiment of the present invention can produce a polyolefin resin having an excellent activity in the production of a high-density polyolefin and an excellent workability because of its wide molecular weight distribution. The polyolefin prepared using the hybrid catalyst composition has a high comonomer content in a high molecular weight material and a low content of a comonomer in a low molecular weight material, so that the impact strength, flexural strength, ESCR, melt tension, Has an excellent single molecular weight distribution. Further, the polyolefin according to the embodiment of the present invention has a small molecular weight distribution and a low extrusion load during processing, and the extrusion amount is large, so that the productivity is excellent.

The polyolefin according to the embodiment of the present invention can be usefully used for manufacturing a pipe having excellent pressure resistance characteristics, a bottle cap having excellent processing characteristics, a container, and the like.

Claims (11)

1. An ethylene-alpha olefin copolymer produced by polymerization of an olefin monomer in the presence of a hybrid catalyst composition comprising a first transition metal compound represented by the following formula (1) and a second transition metal compound represented by the following formula (2)
1) a density of 0.910 g / cm3 to 0.960 g / cm3,
2) Molecular weight distribution (Mw / Mn) is 3 to 10,
3) an ethylene-alpha olefin copolymer having a melt index (I ₂ ) of from 0.2 to 100 at 2.16 Kg and a melt index ratio (MFIR: I ₂₁ / I ₂ )
[Chemical Formula 1]

In Formula 1,
M1 is a Group 4 transition metal of the Periodic Table of the Elements,
X ₁ and X ₂ are both a halogen atom,
R ₁ to R _{6, which} may be the same or different from each other, are each independently a hydrogen atom or an unsubstituted alkyl group having 1 to 20 carbon atoms,
R ₆ to R ₁₂ may be the same or different and are each independently a hydrogen atom, an unsubstituted alkyl group having 1 to 20 carbon atoms, or an unsubstituted aryl group having 6 to 20 carbon atoms, or they may be connected to each other to form an aromatic ring You can,
(2)

The compound of formula (2)

, ≪ / RTI >
Wherein M is any one of hafnium (Hf), zirconium (Zr), and titanium (Ti), Me is a methyl group, and Ph is a phenyl group. The method according to claim 1,
Wherein the first transition metal compound represented by Formula 1 is at least one of the following structural formulas:

M is any one of hafnium (Hf), zirconium (Zr), and titanium (Ti), and Me is methyl. The method according to claim 1,
Wherein the second transition metal compound is a structure in which a ligand connected to one side and the other side of the transition metal (M2) is connected by Si. The method according to claim 1,
Wherein the mixed catalyst composition further comprises a cocatalyst comprising one or more of the following Chemical Formulas (3) to (6):
(3)

In Formula 3,
R ₂₇ is a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group substituted with halogen having 1 to 20 carbon atoms,
a is an integer of 2 or more.
[Chemical Formula 4]
Z (R < ₂₈ >) ₃
In Formula 4,
Z is aluminum (Al) or boron (B)
R ₂₈ is a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group substituted with a halogen having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms.
[Chemical Formula 5]
[LH] ⁺ [Z (B) ₄ ] ^-
[Chemical Formula 6]
[L] ⁺ [Z (B) ₄ ] ^-
In the above formulas (5) and (6)
L is a neutral or cationic Lewis acid,
Z is a Group 13 element of the Periodic Table of the Elements,
B is a substituted or unsubstituted aryl group having 6 to 20 carbon atoms or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms. 5. The method of claim 4,
Wherein the mixed catalyst composition further comprises a carrier that supports the first and second transition metal compounds and the cocatalyst. 6. The method of claim 5,
Wherein the weight ratio of the carrier to the total amount of the transition metals (M1, M2) in the first and second transition metal compounds in the hybrid catalyst composition is 1: 100 to 1: 1000. 6. The method of claim 5,
In the mixed catalyst composition, the weight ratio of the carrier to the cocatalyst of the formula (3) or (4) is 1: 100 to 100: 1, and the weight ratio of the carrier to the cocatalyst of the formula (5) ≪ / RTI > ethylene-alpha olefin copolymer. 6. The method of claim 5,
Wherein the carrier has an average particle size of 10 to 250 탆, a volume of fine pores of 0.1 to 10 cc / g, and a specific surface area of 1 to 1000 m 2 / g. The method according to claim 1,
Wherein the alpha olefin monomer is at least one compound selected from the group consisting of ethylene, propylene, 1-butene, 1-hexene, 1-octene and 1-decene. The method according to claim 1,
And an HMI (High Molecular Index) of 3.5 or more to 10 or less. The method according to claim 1,
Wherein the impact strength measured according to ASTM D256 is 20 kJ / m < ² > or more.

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