KR20190074798A - Supported hybrid metallocene catalyst and method for preparing of polyolefin using the same - Google Patents

Abstract

The present invention relates to a novel hybrid supported metallocene catalyst and a method for manufacturing a polyolefin using the same. The hybrid supported metallocene catalyst according to the present invention can be used in manufacturing the polyolefin and can manufacture the polyolefin having excellent processability and mechanical properties.

Description

TECHNICAL FIELD [0001] The present invention relates to a mixed supported metallocene catalyst and a process for producing a polyolefin using the same. BACKGROUND ART [0002]

The present invention relates to a novel hybrid supported metallocene catalyst and a process for producing a polyolefin using the same.

Olefin polymerization catalyst systems can be classified into Ziegler-Natta and metallocene catalyst systems, both of which have been developed for their respective characteristics. The Ziegler-Natta catalyst has been widely applied to conventional commercial processes since the invention of the 50's. However, since the Ziegler-Natta catalyst is a multi-site catalyst containing a plurality of active sites, the molecular weight distribution of the polymer is broad, There is a problem that the desired physical properties can not be secured.

On the other hand, the metallocene catalyst is composed of a combination of a main catalyst mainly composed of a transition metal compound and a cocatalyst, which is an organometallic compound mainly composed of aluminum. Such metallocene catalysts are homogeneous complex catalysts that are single site catalysts. Therefore, it is possible to obtain a polymer having a narrow molecular weight distribution and a uniform composition distribution of the comonomer, and it is possible to change the stereoregularity of the polymer, the copolymerization characteristics, the molecular weight, the degree of crystallinity and the like according to the modification of the ligand structure and the polymerization conditions of the catalyst .

Among these, an anisometallocene catalyst is an organometallic catalyst containing two ligands connected to each other by a bridge group, in which the rotation of the ligand is prevented by the bridge group and the activity and structure of the metal center are determined.

In particular, in the polymerization of polypropylene, the ansa-metallocene catalyst has advantages advantageous in the production of polymers with low xylene solubles content (e.g., less than 1% by weight). However, the metallocene catalyst for propylene polymerization is difficult to carry and difficult to carry in the process of being carried on a carrier, and thus, a process problem such as fouling frequently occurs.

Also, in general, the metallocene supported catalyst is characterized by producing a polymer having a narrow molecular weight distribution. However, when the molecular weight distribution is too narrow, it is disadvantageous from the viewpoint of processability. On the other hand, when the molecular weight distribution is too wide, there is a tendency in terms of physical strength, so it is important to prepare a polymer having proper balance of properties in terms of workability and strength.

In this background, there is a constant demand for a catalyst capable of producing a better polyolefin having a balance between physical properties and processability, and further improvement is required.

The present invention provides a hybrid supported metallocene catalyst capable of producing a polyolefin having excellent processability and improved mechanical properties, and a process for producing a polyolefin using the same.

According to one embodiment of the present invention,

A first metallocene compound represented by Formula 1 below; A second metallocene compound represented by Formula 2 below; A cocatalyst compound; And a carrier.

[Chemical Formula 1]

In Formula 1,

X is the same or different halogen,

R ₁ is C _6-20 aryl substituted with C _2-20 alkoxyalkyl,

R _2, R ₃ and R ₄ are each independently hydrogen, halogen, C _1-20 alkyl, C _2-20 alkenyl, C _1-20 ether, C _1-20 alkoxy, C _6-20 aryl, C _{7- 20} alkylaryl, or _C7-20 arylalkyl,

A is carbon, silicon or germanium,

R ₅ and R ₆ are each independently C _1-20 alkyl,

(2)

In Formula 2,

X 'are the same or different halogen,

R ₇ is C _6-20 aryl substituted with C _1-20 alkyl,

R _8, R ₉ and R ₁₀ are each independently hydrogen, halogen, C _1-20 alkyl, C _2-20 alkenyl, C _1-20 ether, C _1-20 alkoxy, C _6-20 aryl, C _{7- 20} alkylaryl, or _C7-20 arylalkyl,

A 'is carbon, silicon or germanium,

R ₁₁ and R ₁₂ is one of the C _2-20 alkoxyalkyl, and the other is C _1-20 alkyl.

According to another embodiment of the present invention, there is provided a process for producing a polyolefin comprising polymerizing an olefin monomer in the presence of the hybrid supported metallocene catalyst.

The hybrid supported metallocene catalyst according to the present invention is capable of controlling the molecular weight distribution in order to balance an appropriate balance between physical properties and processability. The product obtained therefrom is a polyolefin which can maintain processability while having excellent physical properties, . The polyolefin prepared using the hybrid supported metallocene catalyst is excellent in workability and mechanical properties and has a low xylene solubilized content, and can be usefully used for various injection products and fibers.

The terminology used herein is for the purpose of describing exemplary embodiments only and is not intended to limit the invention. The singular expressions include plural expressions unless the context clearly dictates otherwise. In this specification, the terms "comprises", "comprising", or "having" are used to designate the presence of stated features, steps, components, or combinations thereof, and are not intended to preclude the presence of one or more other features, Components, or combinations thereof, as a matter of convenience, without departing from the spirit and scope of the invention.

The invention is capable of various modifications and may take various forms, which illustrate specific embodiments and are described in detail below. It should be understood, however, that the invention is not intended to be limited to the particular forms disclosed, but is intended to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention.

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

The hybrid supported metallocene catalyst according to the present invention comprises: a first metallocene compound represented by the following general formula (1); A second metallocene compound represented by Formula 2 below; A cocatalyst compound; And a carrier.

[Chemical Formula 1]

In Formula 1,

X is the same or different halogen,

R ₁ is C _6-20 aryl substituted with C _2-20 alkoxyalkyl,

R _2, R ₃ and R ₄ are each independently hydrogen, halogen, C _1-20 alkyl, C _2-20 alkenyl, C _1-20 ether, C _1-20 alkoxy, C _6-20 aryl, C _{7- 20} alkylaryl, or _C7-20 arylalkyl,

A is carbon, silicon or germanium,

R ₅ and R ₆ are each independently C _1-20 alkyl,

(2)

In Formula 2,

X 'are the same or different halogen,

R ₇ is C _6-20 aryl substituted with C _1-20 alkyl,

R _8, R ₉ and R ₁₀ are each independently hydrogen, halogen, C _1-20 alkyl, C _2-20 alkenyl, C _1-20 ether, C _1-20 alkoxy, C _6-20 aryl, C _{7- 20} alkylaryl, or _C7-20 arylalkyl,

A 'is carbon, silicon or germanium,

R ₁₁ and R ₁₂ is one of the C _2-20 alkoxyalkyl, and the other is C _1-20 alkyl.

In the metallocene compounds according to the present invention, the substituents of the above formulas (1) and (2) will be described in more detail as follows.

The halogen may be fluorine (F), chlorine (Cl), bromine (Br) or iodine (I).

C _1-20 alkyl can be linear, branched or cyclic alkyl. Specifically, C _1-20 alkyl is C _1-20 straight chain alkyl, C _1-10 straight chain alkyl, C _1-5 straight chain alkyl, C _3-20 branched chain or cyclic alkyl, C _3-15 branched chain or cyclic Alkyl, or C _3-10 branched chain or cyclic alkyl. More specifically, C _1-20 alkyl may be methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert-butyl, n-pentyl, isopentyl or cyclohexyl.

C _2-20 alkenyl may be straight-chain, branched or cyclic alkenyl. Specifically, C _2-20 alkenyl C _2-20 straight chain alkenyl, C _2-10 linear alkenyl, C _2-5 straight chain alkenyl, C _{3- 20} branched alkenyl, C _3-15 branched Al C _3-10 branched chain alkenyl, C _5-20 cyclic alkenyl, or C _5-10 cyclic alkenyl. More specifically, C _2-20 alkenyl may be ethenyl, propenyl, butenyl, pentenyl or cyclohexenyl, and the like.

C _6-20 aryl can mean monocyclic, bicyclic or tricyclic aromatic hydrocarbons. Specifically, C _6-20 aryl may be phenyl, naphthyl or anthracenyl.

C _7-20 alkylaryl may mean a substituent wherein at least one hydrogen of the aryl is substituted by an alkyl. Specifically, C _7-20 alkylaryl may be methylphenyl, ethylphenyl, n-propylphenyl, iso-propylphenyl, n-butylphenyl, iso-butylphenyl, tert-butylphenyl or cyclohexylphenyl.

C _7-20 arylalkyl can mean a substituent wherein at least one of the hydrogens of the alkyl is replaced by an aryl. Specifically, _C7-20 arylalkyl may be benzyl, phenylpropyl or phenylhexyl.

C _1-20 alkoxy can be linear, branched or cyclic alkoxy. Specific examples of the C _1-20 alkoxy include, but are not limited to, methoxy, ethoxy, n-butoxy, tert-butoxy, phenyloxy, cyclohexyloxy and the like.

C _2-20 alkoxyalkyl may mean a substituent wherein at least one of the hydrogens of the alkyl is substituted by alkoxy. Specifically, C _2-20 alkoxyalkyl is exemplified by methoxymethyl, ethoxymethyl, methoxyethyl, ethoxyethyl, butoxymethyl, butoxyethyl, butoxypropyl, butoxybutyl, butoxyheptyl, butoxy Hexyl, and the like, but are not limited thereto.

In the mixed supported metallocene catalyst according to the present invention, R ₁ in the above formula (1) may be phenyl substituted with C _2-20 alkoxyalkyl, more preferably R ₁ may be tertbutoxymethylphenyl, But is not limited thereto.

Formula 1 of R ₂ to R ₄ may be each independently hydrogen, methyl, ethyl, propyl, isopropyl, n- butyl, tert- butyl, pentyl, hexyl, heptyl, octyl, or phenyl, R _2, R ₃ and R ₄ are more preferably hydrogen, but are not limited thereto.

R ₅ to R ₆ in Formula 1 may each independently be methyl, ethyl, propyl, isopropyl, n-butyl or tert-butyl, and more preferably R ₅ to R ₆ are methyl. It is not.

X in the above formula (1) are the same as or different from each other, and each independently is chlorine (Cl), but is not limited thereto.

It is more preferable that A in the formula (1) is silicon, but it is not limited thereto.

Specifically, the first metallocene compound represented by Formula 1 may be represented by Formula 1-1.

 [Formula 1-1]

The first metallocene compound represented by Formula 1 includes two indenyl derivatives having the same structure symmetrically. Since the two indenyl derivatives are connected to each other by a bridge group, And can exhibit high polymerization activity even when carried on a carrier.

Further, since the substituent (R ₁ ) having bulky properties is substituted with a functional group capable of acting as a Lewis base as an oxygen-donor at the carbon position 5 of each indenyl derivative , To inhibit the formation of meso form by imparting steric hindrance. In addition, it is possible to impart the stability of the supported catalyst during the preparation of the supported catalyst, and the polyolefin produced using the supported catalyst can form excellent morphology. Accordingly, when the first metallocene compound represented by Formula 1 is supported on a carrier and used as a catalyst in the production of polyolefin, a polyolefin having high activity and excellent morphology and excellent processability and mechanical properties can be produced.

In the mixed supported metallocene catalyst according to the present invention, R ₇ in Formula 2 may be phenyl substituted with C _1-20 alkoxyalkyl, more preferably R ₇ may be t-butylphenyl, But is not limited thereto.

R ₈ to R ₁₀ of said formula (II) may be each independently hydrogen, methyl, ethyl, propyl, isopropyl, n- butyl, tert- butyl, pentyl, hexyl, heptyl, octyl, or phenyl, R ₈ to R ₁₀ is more preferably hydrogen, but it is not limited thereto.

R ₁₁ and R ₁₂ in the general formula (2) are each independently different from each other such as methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, n- butoxyhexyl, or tert-butoxyhexyl, one of R ₁₁ and R ₁₂ is methyl, and the other one is more preferably tert-butoxyhexyl, but is limited thereto It is not.

X 'in the above formula (2) are the same or different from each other and each independently is chlorine (Cl), but it is not limited thereto.

In the above formula (2), A 'is more preferably silicon, but is not limited thereto.

Specifically, the second metallocene compound of Formula 2 may be represented by the following Formula 2-1.

 [Formula 2-1]

The second metallocene compound represented by the general formula (2) includes asymmetrically two indenyl derivatives having different structures. Since the two indenyl derivatives are connected by a bridge group, And can exhibit high polymerization activity even when carried on a carrier.

In addition, since a bulky group such as C _6-20 aryl (R ₇ ) substituted with C _1-20 alkyl is substituted for the carbon atom position 5 of each indenyl derivative, a steric hindrance is imparted Thereby inhibiting the formation of the meso form.

In addition, a methyl group and an isopropyl group substituent are introduced at the 2-carbon position of each indenyl derivative, and a bridge group connecting the two indenyl ligands is connected to an Lewis acid as an oxygen- And a structure containing a functional group capable of acting as a base. When a second metallocene compound having such a specific structure is loaded on a carrier together with the first metallocene compound and activated by an appropriate method to be used as a catalyst in the olefin polymerization reaction, it exhibits high activity and excellent morphology, A polyolefin having excellent mechanical properties can be produced.

The metallocene compounds represented by the above-described formulas (1) and (2) can be prepared according to a known synthesis method of an organic compound, and detailed production methods are described in the following examples.

The hybrid supported metallocene catalysts according to the present invention may contain at least one of the first metallocene compounds represented by Formula 1 and at least one second metallocene compound selected from the compounds represented by Formula 2 Together with a co-catalyst compound.

As described above, the first metallocene compound represented by the formula (1) of the hybrid supported metallocene catalyst contributes to the production of polypropylene having a relatively high molecular weight portion due to a broad molecular weight distribution, 2 metallocene compounds can contribute to polypropylene production with a low molecular weight fraction due to a relatively narrow molecular weight distribution.

According to one embodiment of the present invention, the hybrid supported metallocene catalyst is prepared by reacting the first metallocene compound represented by Formula 1 and the second metallocene compound represented by Formula 2 at a molar ratio of 10: 1 to 1: 2 Or in a molar ratio of 5: 1 to 1: 1, but is not limited thereto. When the first and second metallocene compounds are contained at the above-mentioned molar ratio, they exhibit appropriate catalytic activity and may be more advantageous in achieving balanced physical properties of the polyolefin.

Therefore, the polyolefin produced by using the mixed supported metallocene catalyst containing different metallocene compounds including the metallocene compounds of the above formulas (1) and (2) has a good balance of processability and mechanical properties, Lt; / RTI >

In the mixed supported metallocene catalyst according to the present invention, the co-catalyst to be supported on the support for activating the metallocene compound is an organometallic compound containing a Group 13 metal, And is not particularly limited as long as it can be used in polymerization.

Specifically, the promoter compound may include at least one of the promoter compounds represented by the following formulas (3) to (6).

(3)

_{- [Al (R 13) -O} ] n -

In Formula 3,

R ₁₃ may be the same or different from each other, and each independently halogen; Hydrocarbons having 1 to 20 carbon atoms; Or a hydrocarbon having 1 to 20 carbon atoms substituted with halogen;

n is an integer of 2 or more;

[Chemical Formula 4]

D (R _{14) 3}

In Formula 4,

R ₁₄ may be the same or different from each other, and each independently halogen; Hydrocarbons having 1 to 20 carbon atoms; Or a hydrocarbon having 1 to 20 carbon atoms substituted with halogen;

D is aluminum or boron;

[Chemical Formula 5]

[LH] ⁺ [ZA ₄ ] ^- or [L] ⁺ [ZA ₄ ] ^-

In Formula 5,

L is a neutral or cationic Lewis acid; H is a hydrogen atom; Z is a Group 13 element; A may be the same as or different from each other, and independently at least one hydrogen atom is an aryl group having 6 to 20 carbon atoms or an alkyl group having 1 to 20 carbon atoms substituted or unsubstituted with halogen, hydrocarbon having 1 to 20 carbon atoms, alkoxy or phenoxy .

Examples of the compound represented by the general formula (3) include methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, butylaluminoxane and the like. A more preferred compound is methylaluminoxane.

Examples of the compound represented by Formula 4 include trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, dimethylchloroaluminum, triisopropylaluminum, tri-s-butylaluminum, tricyclopentylaluminum , Tripentyl aluminum, triisopentyl aluminum, trihexyl aluminum, trioctyl aluminum, ethyl dimethyl aluminum, methyldiethyl aluminum, triphenyl aluminum, tri-p-tolyl aluminum, dimethyl aluminum methoxide, dimethyl aluminum ethoxide, Boron, triethylboron, triisobutylboron, tripropylboron, tributylboron and the like, and more preferred compounds are selected from trimethylaluminum, triethylaluminum and triisobutylaluminum.

Examples of the compound represented by Formula 5 include triethylammonium tetraphenylboron, tributylammonium tetraphenylboron, trimethylammonium tetraphenylboron, tripropylammonium tetraphenylboron, trimethylammonium tetra (p-tolyl) Boron, trimethylammoniumtetra (o, p-dimethylphenyl) boron, tributylammoniumtetra (ptrifluoromethylphenyl) boron, trimethylammoniumtetra (ptrifluoromethylphenyl) boron, tributylammoniumtetra N, N-diethylanilinium tetraphenylboron, N, N-diethylanilinium tetrapentafluorophenylboron, diethylammonium tetrapentafluorophenylboron, triphenylphosphonium Tetraphenylboron, trimethylphosphonium tetraphenylboron, triethylammonium tetraphenyl aluminum, tributylammonium tetraphenyl aluminum, trimethylammonium tetraphenyl aluminum (P-tolyl) aluminum, triethylammoniumtetra (o, p-dimethylphenyl) aluminum, tributylammonium tributylammonium (P-trifluoromethylphenyl) aluminum, trimethylammonium tetra (p-trifluoromethylphenyl) aluminum, tributylammonium tetrapentafluorophenyl aluminum, N, N-diethylanilinium tetraphenyl aluminum, N , N-diethylanilinium tetrapentafluorophenyl aluminum, diethylammonium tetrapentatetraphenyl aluminum, triphenylphosphonium tetraphenyl aluminum, trimethylphosphonium tetraphenyl aluminum, tripropylammonium tetra (p-tolyl) Boron, triethylammoniumtetra (o, p-dimethylphenyl) boron, tributylammoniumtetra (p -trifluoromethylphenyl) boron, triphenylcarboniumtetra (p- Phenyl) boron and the like, triphenylamine car I phenylboronic as Titanium tetra-penta flow.

In the mixed supported metallocene catalyst according to the present invention, the mass ratio of the transition metal to the support of the first and second metallocene compounds is preferably 1: 1 to 1: 1,000. When the carrier and the metallocene compound are contained at the above mass ratio, they exhibit appropriate supported catalyst activity, which may be advantageous in terms of maintaining the activity of the catalyst and economical efficiency.

In addition, the mass ratio of the promoter compound to the support is preferably 1:20 to 20: 1, and the mass ratio of the promotor compound to the support is preferably 1:10 to 100: 1.

In the hybrid supported metallocene catalyst according to the present invention, a carrier containing a hydroxy group on the surface thereof can be used as the carrier, and preferably, a hydroxy group and a siloxane group having high reactivity, You can use your carrier.

Silica-alumina, silica-magnesia, and the like, which are usually dried at high temperature, and which are usually made of oxides such as Na ₂ O, K ₂ CO ₃ , BaSO ₄ , and Mg (NO ₃ ) ₂ , Sulfate, and nitrate components.

The drying temperature of the carrier is preferably 100 to 800 ° C. When the drying temperature of the carrier is less than 100 ° C., the moisture is too much to react with the cocatalyst on the surface. When the temperature exceeds 800 ° C., the pores on the surface of the carrier are combined to reduce the surface area. And only the siloxane group is left, and the reaction site with the co-catalyst is reduced, which is not preferable.

The amount of hydroxyl groups on the surface of the support is preferably 0.1 to 10 mmol / g, more preferably 0.2 to 5 mmol / g. The amount of the hydroxyl group on the surface of the carrier can be controlled by the preparation method and conditions of the carrier or by drying conditions such as temperature, time, vacuum or spray drying.

If the amount of the hydroxyl group is less than 0.1 mmol / g, the number of sites of reaction with the co-catalyst is small. If the amount is more than 10 mmol / g, the hydroxyl group may be present in the water other than the hydroxyl group present on the surface of the carrier particle. not.

The hybrid supported metallocene catalyst according to the present invention is characterized in that it comprises a step of supporting a promoter compound on a support, supporting the first metallocene compound on the support, and supporting the second metallocene compound on the support . ≪ / RTI > In the method for preparing the hybrid supported metallocene catalyst, the order of the step of supporting the first and second metallocene compounds may be changed as necessary. That is, a first metallocene compound is first supported on a carrier, and then a second metallocene compound is further supported to prepare a hybrid supported metallocene catalyst, or a second metallocene compound is first supported on a carrier , The first metallocene compound may be supported thereon. Alternatively, the first and second metallocene compounds may be simultaneously introduced and carried.

According to another aspect of the present invention, there is provided a process for producing a polyolefin comprising polymerizing an olefin monomer in the presence of the hybrid supported metallocene catalyst.

In the process for producing a polyolefin according to the present invention, specific examples of the olefinic monomer include ethylene, propylene, 1-butene, 1-pentene, 4-methyl- , 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-eicosene and the like.

More preferably, the polyolefin is homopolypropylene or random polypropylene, but is not limited thereto.

The polymerization reaction can be homopolymerized with one olefin monomer or copolymerized with two or more monomers using one continuous slurry polymerization reactor, a loop slurry reactor, a gas phase reactor or a solution reactor.

The mixed supported metallocene catalyst may be an aliphatic hydrocarbon solvent having 5 to 12 carbon atoms such as pentane, hexane, heptane, nonane, decane and isomers thereof and aromatic hydrocarbon solvents such as toluene and benzene, dichloromethane, A hydrocarbon solvent substituted with the same chlorine atom, or the like. The solvent used here is preferably used by removing a small amount of water or air acting as a catalyst poison by treating with a small amount of alkylaluminum, and it is also possible to use a further cocatalyst.

With the hybrid supported metallocene catalyst of the present invention, the polymerization temperature may be from about 25 to about 500 캜, preferably from about 25 to about 200 캜, more preferably from about 50 to about 150 캜. Further, the polymerization pressure is from about 1 to about 100kgf / cm ^2, preferably from about 1 to about 70kgf / cm ^2, more preferably from about 5 to about 50kgf / cm ^2.

The polyolefin according to the present invention can be obtained by homopolymerization of propylene or copolymerization of ethylene and propylene using the hybrid supported metallocene compound as a catalyst.

The hybrid supported metallocene catalyst of the present invention exhibits excellent activity, and the polyolefin produced using the hybrid supported metallocene catalyst of the present invention has excellent mechanical properties such as strength and processability.

For example, the polyolefins prepared by the process of the present invention exhibit narrow molecular weight distribution (Mw / Mn, PDI) characteristics of from about 2.5 to about 4.5, preferably from about 2.5 to about 3.5 and exhibit tensile strength, Mechanical strength such as flexural modulus and flexural strength can be improved.

At the same time, good workability can be exhibited despite a relatively narrow molecular weight distribution.

Accordingly, the polyolefin produced by the production method of the present invention can be used in various applications requiring such physical properties, and in particular, can be preferably used as an injection molded article requiring excellent strength and processability.

Hereinafter, preferred embodiments of the present invention will be described in order to facilitate understanding of the present invention. However, the following examples are provided only for the purpose of easier understanding of the present invention, and the present invention is not limited thereto.

<Examples>

&Lt; Synthesis Example of Metallocene Compound >

Synthetic example  One

1-1> Preparation of 1-bromo-4- (tert-butoxymethyl) benzene

H ₂ SO ₄ (1.47 mL) and anhydrous MgSO ₄ (12.9 g, 107 mmol) were added to CH ₂ Cl ₂ (80 mL) and the mixture was stirred at room temperature for 15 minutes. To another flask, 4-bromobenzyl alcohol (5.0 g, 26.7 mmol) and t- butanol (12.8 mL, 134 mmol) were dissolved in CH ₂ Cl ₂ (30 mL) and then added to the above mixture. The mixture was stirred overnight at room temperature and then sat. NaHCO ₃ was added. After removal of water by anhydrous MgSO ₄ and concentrated under reduced pressure, and the resulting solution a white column chromatography (E / H = 1/20 ) 1-bromo-4- , to obtain (tert -butoxymethyl) benzene (5.9 g , 90%) &Lt; / RTI &gt; as a solid.

_{^{1 H NMR (500MHz, CDCl 3}} , 7.24ppm): 1.28 (9H, s), 4.39 (2H, s), 7.22 (2H, d), 7.44 (2H, d)

1-2> 7- (4- ( tert- Butoxymethyl) phenyl) -2-methyl- 1H- indene Synthesis

1-Bromo-4- ( tert- butoxymethyl) benzene (4.52 g, 18.6 mmol) was dissolved in anhydrous THF (20 mL) under Ar. The temperature was lowered to -78 ° C and n- BuLi (2.5 M in hexane, 8.2 mL) was added, followed by stirring at room temperature for 30 minutes. The temperature was again lowered to -78 ° C, trimethyl borate (6.2 mL, 55.6 mmol) was added, and the mixture was stirred at room temperature overnight. Sat. NH ₄ Cl was added and extracted with MTBE. Anhydrous MgSO ₄ was added and the water was removed by filtration. The solution was concentrated under reduced pressure and the following reaction was carried out without further purification.

Above and the resulting compound 7-bromo-2-methyl- 1 H -indene (3.87 g, 18.6 mmol), Na 2 CO 3 toluene of (5.91 g, 55.8 mmol) ( 40 mL), H 2 O (20 mL), EtOH (20 mL) and stirred. The above solution of Pd (PPh ₃₎ into a ₄ (1.07 g, 0.93 mmol) was stirred overnight at 90 ℃. After the reaction was completed, MTBE and water were added and the organic layer was separated. After removal of water by anhydrous MgSO ₄ and concentrated under reduced pressure, and the resulting solution was purified by column chromatography (E / H = 1/30 ) 7- (4- (tert -butoxymethyl) phenyl) -2-methyl-1 H -indene (2.9 g, 53%).

_{^{1 H NMR (500MHz, CDCl 3}} , 7.24ppm): 1.33 (9H, s), 2.14 (3H, s), 3.36 (2H, s), 4.50 (2H, s), 6.53 (1H, s), 7.11- 7.45 (7 H, m)

1-3> bis (4- (4- ( tert -butoxymethyl) phenyl) -2-methyl-1 H -inden-1-yl) Preparation of dimethylsilane

7- (4- (tert -butoxymethyl) phenyl ) -2-methyl-1 H -indene (2.88 g, 9.85 mmol) and CuCN (44 mg, 0.49 mmol) to toluene (18 mL) and THF (2 mL under Ar ). The solution was cooled to -30 ° C and n-BuLi (2.5 M in hexane, 4.1 mL) was slowly added. After stirring at this temperature for about 20 minutes, the temperature was raised to room temperature and then stirred for 2.5 hours. To this solution was added dimethyldichlorosilane (0.59 mL, 4.89 mmol) and stirred overnight at room temperature. After the reaction was completed, MTBE and water were added and the organic layer was separated. After removal of the water and concentrate the obtained organic layer with anhydrous MgSO ₄ and purified by column chromatography (hexane) bis (4- (4- (tert -butoxymethyl) phenyl) -2-methyl-1 H -inden-1-yl) dimethylsilane (2.95 g, 93%) as a white solid.

_{^{1 H NMR (500MHz, CDCl 3}} , 7.24ppm): -0.20 (6H, s), 1.35 (18H, s), 2.19 (3H, s), 2.25 (3H, s), 3.81 (2H, s), 4.53 (4H, s), 6.81 (2H, s), 7.18-7.52 (14H, m)

1-4> dimethylsilanyl-bis (4- ( 4- (tert -butoxymethyl) phenyl) -2-methyl-1 H -inden-1-yl) zirconium dichloride Preparation of

bis (4- (4- (tert -butoxymethyl ) phenyl) -2-methyl-1 H -inden-1-yl) dimethylsilane (2.0 g, 3.12 mmol) placed in a 50 mL Schlenk flask under Ar diethyl ether (20 mL ) Was injected and dissolved. The temperature was lowered to -78 ° C and n-BuLi (2.5 M in hexane, 2.7 mL) was added, followed by stirring at room temperature for 2 hours. The solvent was vacuum distilled under vacuum, and ZrCl ₄ (THF) ₂ (1.18 g, 3.12 mmol) was added in a globe box and the temperature was lowered to -78 ° C. Diethyl ether (20 mL) was added to the mixture, the temperature was raised to room temperature, and the mixture was stirred overnight. The solvent was distilled off under reduced pressure and dissolved in CH ₂ Cl ₂ to remove the solid. The solution was concentrated under reduced pressure and the resulting solid was washed with toluene, CH ₂ Cl ₂ racemic rich of a yellow solid dimethylsilanyl-bis (4- (4- ( tert -butoxymethyl) phenyl) -2-methyl-1 H -inden-1 -yl) zirconium dichloride (260 mg, 10%, r / m ~ 16/1).

_{^{1 H NMR (500MHz, CDCl 3}} , 7.24ppm): 1.28 (18H, s), 1.33 (6H, s), 2.24 (6H, s), 4.46 (4H, s), 6.93 (2H, s), 7.08- 7.65 (14H, m)

Synthesis Example 2

2-methyl-1H-inden-1-yl) (methyl) (2-isopropyl- Preparation of 4- (4- (t-butyl) phenyl) -1H-inden-1-yl)

20 g (76.222 mmol) of 2-methyl-4- (4- (t-butyl) phenyl) indene was dissolved in 640 mL of a mixed solvent (Hex / MTBE = 15/1), n- 33.5 mL of a solution (2.5 M in hexane) was slowly added dropwise. Thereafter, the obtained reaction mixture was stirred at room temperature for one day, and 19.7 g (72.411 mmol) of the (6-t-butoxyhexyl) dichloromethylsilane prepared in Synthesis Example 1 was added to hexane 80.5 mL of the dissolved solution was slowly added, and the resulting reaction mixture was stirred at room temperature for one day. Thereafter, the reaction mixture was distilled under reduced pressure to remove the solvent, redispersed in hexane, and filtered under reduced pressure. Then, the filtered solution was dried to obtain monosilane.

22.1 g (76.222 mmol) of 2-isopropyl-4- (4- (t-butyl) phenyl) indene and 136.5 mg (1.525 mmol) of CuCN were dissolved in 200 mL of diethyl ether, , 33.5 mL of n-butyllithium solution (2.5 M in hexane) was slowly added dropwise to the solution. Thereafter, the obtained reaction mixture was stirred at room temperature for one day, and the monosilane prepared in the reaction mixture was dissolved in 180 mL of diethyl ether and then added. Thereafter, the obtained reaction mixture was stirred at room temperature for one day, then organic matter was extracted with water and MTBE, and distilled under reduced pressure. The product was then purified by column chromatography to give the final ligand in a yield of 67%.

2-methyl-1H-inden-1-yl) (methyl) (2-isopropyl- Preparation of 4- (4- (t-butyl) phenyl) -1H-inden-1-yl) silane zirconium dichloride

(Methyl) (2-isopropyl-4H-indol-3-yl) 1.00 g (1.331 mmol) of (4- (t-butyl) phenyl) -1H-inden-1-yl) silane was dissolved in 33 mL of diethyl ether, M in hexane) was slowly added dropwise. Thereafter, the obtained reaction mixture was stirred at room temperature for about 4 hours, and then bis (N, N'-diphenyl-1,3-propanediamido) dichlorosilicon bis (tetrahydrofuran) [Zr 706 mg (1.331 mmol) of ₅ H ₆ NCH ₂ CH ₂ CH ₂ NC ₅ H ₆ ) Cl ₂ (C ₄ H ₅ O) ₂ ] was dissolved in 33 mL of diethyl ether and the mixture was stirred at room temperature for one day. Thereafter, the red reaction solution was cooled to -20 deg. C, 4 equivalents of a 1 M HCl ether solution was slowly added dropwise to the cooled solution, and the resulting solution was further stirred at room temperature for 1 hour. After filtration and vacuum drying, the obtained solid was dissolved in pentane, and crystals were precipitated for 48 hours. After filtration under reduced pressure, the solid was dried to obtain an orange-colored transition metal compound in a yield of 8% (rac only).

¹ H NMR (500 MHz, CDCl ₃ , 7.26 ppm): 1.05 (3H, d), 1.09 (3H, d), 1.20 (1H, s), 2.27-2.31 (1H, m), 3.37 (2H, t), 6.48 12H, m)

Synthesis Example 3

3-1> Preparation of (6-t-butoxyhexyl) dichloromethylsilane

100 ml of a solution of t-butoxyhexyl magnesium chloride (about 0.14 mol, ether) was added dropwise to 100 ml of a trichloromethylsilane solution (about 0.21 mol, hexane) at -100 ° C for 3 hours, Lt; / RTI &gt;

After separating the transparent organic layer from the mixed solution, the separated transparent organic layer was vacuum dried to remove excess trichloromethylsilane. Thus, a transparent liquid (6-t-butoxyhexyl) dichloromethylsilane was obtained (yield: 84%).

^{1 H NMR (500 MHz, CDCl} 3, 7.24 ppm): 0.76 (3H, s), 1.11 (2H, t), 1.18 (9H, s), 1.32 ~ 1.55 (8H, m), 3.33 (2H, t)

3-2 Preparation of (6-t-butoxyhexyl) (methyl) -bis (2-methyl-4-phenylindenyl) silane

15.4 mL of n-butyllithium solution (2.5 M in hexane) was slowly added dropwise to 77 mL of 2-methyl-4-phenylindene toluene / THF = 10/1 solution (34.9 mmol) at 0 ° C, Followed by stirring at room temperature for one day. Then, 5 g of (6-t-butoxyhexyl) dichloromethylsilane prepared previously was added dropwise to the mixed solution at -78 ° C, and the mixture was stirred for about 10 minutes and then at 80 ° C for 1 hour. Then, the organic layer was separated by adding water, and the silica column was purified and vacuum dried to obtain a sticky yellow oil in a yield of 78% (racemic: meso = 1: 1)

¹ H NMR (500 MHz, CDCl ₃ , 7.24 ppm): 0.10 (3H, s), 0.98 (2H, t), 1.25 (9H, s), 1.36-1.50 , 2.26 (6H, s), 3.34 (2H, t), 3.81 (2H, s), 6.87 7.53 (4 H, t), 7.61 (4 H, d)

3-3 Preparation of [(6-t-butoxyhexylmethylsilane-diyl) -bis (2-methyl-4-phenylindenyl)] zirconium dichloride

To a solution of the above-prepared (6-t-butoxyhexyl) (methyl) bis (2-methyl-4-phenyl) indenylsilane ether / hexane = 1/1 solution (3.37 mmol) in n-butyl lithium M in hexane) was slowly added dropwise at -78 ° C, stirred at room temperature for about 2 hours, and vacuum dried. Then, the salt was washed with hexane, followed by filtration and vacuum drying to obtain a yellow solid. The ligand salt synthesized in a glove box and bis (N, N'-diphenyl-1,3-propanediamido) dichlorozirconium bis (tetrahydrofuran) [Zr (C ₅ H ₆ NCH ₂ CH ₂ CH ₂ NC ₅ H ₆ ) Cl ₂ (C ₄ H ₈ O) ₂ ] was weighed in a Schlenk flask, ether was slowly added dropwise at -78 ° C., And stirred for one day. Thereafter, the red reaction solution was separated by filtration, 4 equivalents of an HCl ether solution (1M) was slowly added dropwise at -78 ° C, and the mixture was stirred at room temperature for 3 hours. It was then filtered and dried in vacuo to give a transition metal compound of orange solid component in a yield of 85% (racemic: meso = 10: 1).

^{1 H NMR (500 MHz, C} 6 D 6, 7.24 ppm): 1.19 (9H, s), 1.32 (3H, s), 1.48 ~ 1.86 (10H, m), 2.25 (6H, s), 3.37 (2H, d), 7.67 (2H, d), 7.63 (2H, d), 6.95

&Lt; Preparation Example of Supported Catalyst >

Production Example 1

Silica (10 g, Sylopol 2410) was placed in a 500 mL high-pressure glass reactor under Ar, and 10 wt% MAO toluene solution (90 mmol) was slowly added at room temperature and stirred at 95 ° C for 18 hours. After completion of the reaction, the reaction mixture was allowed to cool to room temperature and allowed to stand for 15 minutes to decant the solvent using a cannula. Toluene (80 mL) was added, stirred for 1 minute, and allowed to stand for 20 minutes to decant the solvent using a cannula.

The metallocene compound (0.9 mmol) of Synthesis Example 1 and the metallocene compound (0.3 mmol) of Synthesis Example 2 were dissolved in toluene (40 mL), respectively, and then transferred to the above reactor using a cannula and washed with 60 mL of toluene . After stirring at 75 ° C for 5 hours, the mixture was cooled to room temperature and allowed to stand for 15 minutes to decant the solvent using a cannula. Toluene (80 mL) was added, stirred for 10 minutes, and allowed to stand for 10 minutes to decant the solvent using a cannula twice. In the same manner, hexane (80 mL) was added, stirred for 10 minutes, and allowed to stand for 20 minutes. The solvent was decanted with a cannula and dried at room temperature under vacuum for 4 hours. And further dried under vacuum at 45 캜 for 4 hours to obtain SiO ₂ of the metallocene compound-carrying compounds of Synthesis Examples 1 and ₂ Thereby obtaining a supported catalyst.

Production Example 2

Silica (10 g, Sylopol 2410) was placed in a 500 mL high-pressure glass reactor under Ar, and 10 wt% MAO toluene solution (90 mmol) was slowly added at room temperature and stirred at 95 ° C for 18 hours. After completion of the reaction, the reaction mixture was allowed to cool to room temperature and allowed to stand for 15 minutes to decant the solvent using a cannula. Toluene (80 mL) was added, stirred for 1 minute, and allowed to stand for 20 minutes to decant the solvent using a cannula.

The metallocene compound (0.8 mmol) of Synthesis Example 1 and the metallocene compound (0.4 mmol) of Synthesis Example 2 were dissolved in toluene (40 mL), respectively, and then transferred to the above reactor using a cannula and washed with 60 mL of toluene . After stirring at 75 ° C for 5 hours, the mixture was cooled to room temperature and allowed to stand for 15 minutes to decant the solvent using a cannula. Toluene (80 mL) was added, stirred for 10 minutes, and allowed to stand for 10 minutes to decant the solvent using a cannula twice. In the same manner, hexane (80 mL) was added, stirred for 10 minutes, and allowed to stand for 20 minutes. The solvent was decanted with a cannula and dried at room temperature under vacuum for 4 hours. And further dried under vacuum at 45 캜 for 4 hours to obtain SiO ₂ of the metallocene compound-carrying compounds of Synthesis Examples 1 and ₂ Thereby obtaining a supported catalyst.

Comparative Preparation Example 1

Silica (10 g, Sylopol 2410) was placed in a 500 mL high-pressure glass reactor under Ar, and 10 wt% MAO toluene solution (90 mmol) was slowly added at room temperature and stirred at 95 ° C for 18 hours. After completion of the reaction, the reaction mixture was allowed to cool to room temperature and allowed to stand for 15 minutes to decant the solvent using a cannula. Toluene (80 mL) was added, stirred for 1 minute, and allowed to stand for 20 minutes to decant the solvent using a cannula.

The metallocene compound (1 mmol) of Synthesis Example 1 was dissolved in toluene (60 mL), transferred to the above reactor using a cannula, and washed with 60 mL of toluene. After stirring at 75 ° C for 5 hours, the mixture was cooled to room temperature and allowed to stand for 15 minutes to decant the solvent using a cannula. Toluene (80 mL) was added, stirred for 10 minutes, and allowed to stand for 10 minutes to decant the solvent using a cannula twice. In the same manner, hexane (80 mL) was added, stirred for 10 minutes, and allowed to stand for 20 minutes. The solvent was decanted with a cannula and dried at room temperature under vacuum for 4 hours. The further dried under vacuum at 45 ℃ to 4 hours, a supported metallocene compound to the metal of Synthesis Example 1 SiO ₂ Thereby obtaining a supported catalyst.

Comparative Production Example 2

The metallocene compound of Synthesis Example 3 was supported by the same method as in Comparative Preparation Example 1 except that the metallocene compound of Synthesis Example 3 was used instead of the metallocene compound of Synthesis Example 1 in Comparative Production Example 1 SiO ₂ To thereby prepare a supported catalyst.

&Lt; Example of olefin polymerization >

Example 1

The 2L stainless steel reactor was vacuum dried at 80 deg. C and then cooled. Then, 1.5 mmol of triethylaluminum was added at room temperature, 900 g of propylene was introduced, and then 522 ppm of hydrogen gas was introduced. After stirring for 10 minutes, 40 mg of the supported metallocene catalyst obtained in Preparation Example 1 and 20 mL of n-hexane mixed slurry solution were introduced into the reactor under a nitrogen pressure. After the temperature of the reactor was elevated to 70 캜, polymerization was carried out for 1 hour. After completion of the reaction, the unreacted propylene was removed by bending, and then a polypropylene powder was obtained.

Example 2

In the same manner as in Example 1 except that 40 mg of the supported metallocene catalyst obtained in Production Example 2 was used instead of the supported metallocene catalyst of Production Example 1 and hydrogen gas was introduced at 530 ppm, Respectively.

Comparative Example 1

In the same manner as in Example 1 except that 80 mg of the supported metallocene catalyst obtained in Comparative Preparation Example 1 was used instead of the supported metallocene catalyst of Production Example 1 and hydrogen gas was introduced at 550 ppm, Polymerization was carried out.

Comparative Example 2

The same procedure as in Example 1 was repeated except that 200 mg of the supported metallocene catalyst obtained in Comparative Preparation Example 2 was used in place of the supported metallocene catalyst of Production Example 1 and 587 ppm of hydrogen gas was added thereto, Polymerization was carried out.

<Experimental Example>

Property evaluation of polyolefin

The properties of the propylene polymer obtained in Examples 1 to 2 and Comparative Examples 1 to 2 and an injection product using the propylene polymer were evaluated in the following manner and are shown in Table 1.

1) Bulk density: ASTM 1505

2) Melt Index (MI, 2.16 kg): measured at 190 DEG C according to ASTM 1238.

3) Molecular weight, molecular weight distribution: Number-average molecular weight, weight-average molecular weight and Z-average molecular weight were measured using Gel Permeation Chromatography-FT-IR (GPC-FTIR) at a measuring temperature of 160 ° C. The molecular weight distribution is represented by the ratio of the weight average molecular weight to the number average molecular weight.

4) Melting point (Tm): The melting point of the polypropylene was measured using a differential scanning calorimeter (DSC, DSC 2920, manufacturer: TA instrument) according to ASTM D3418. Specifically, the polymer was heated to 220 ° C., and the temperature was maintained for 5 minutes. After the temperature was further lowered to 20 ° C., the temperature was increased again. The temperature rising rate and the falling rate were adjusted to 10 ° C./min

5) Tensile strength at yield: Measured according to ASTM D 638. At this time, the test speed was 500 mm / min, and the average value was measured 10 times per one specimen.

6) Flexural Modulus and Flexural Strength: The flexural modulus was measured according to ASTM D 790.

7) Spiral Flow: Measured according to ASTM D 3123. The processing conditions are as follows:

- Injection machine: Engel e-Victory 120 (120 tons)

- Mold: Spiral Flow 1.0T

- Injection temperature: 230 ℃

8) Xylene-soluble powder (XS): Xylene was added to the polypropylene, and the mixture was heated at 135 ° C for 1 hour, cooled for 30 minutes, and then pretreated. The sample was pretreated with OmliSec (Viscotek FIPA equipment) at a flow rate of 1 ml / min and the peak area of the refractive index was calculated.

    Example 1     Example 2    Comparative Example 1    Comparative Example 2 catalyst Production Example 1 Production Example 2 Comparative Preparation Example 1 Comparative Production Example 2 activation
(g / gCat · hr) 9500 10500 4000 1500 H ₂ input
(ppm) 522 530 550 587 MI _2.16
(g / 10 min) 144 150 146 151 Tm (占 폚) 149.5 150.1 146.1 152.0 Weight average molecular weight
(g / mol) 68,700 68,600 67,100 71,100 Molecular weight distribution (PDI) 3.1 3.2 5.2 2.3 Bulk density
(g / cm ³⁾ 0.41 0.42 0.40 0.31 Xs (%) 0.6 0.5 0.9 0.8 Tensile Strength at Yield
(kg / cm ² ) 355 356 345 350 Flexural Modulus
(kg / cm ² ) 16,728 16,770 16,120 16,841 Flexural Strength
(kg / cm ² ) 518 520 509 512 Spiral Flow
(cm) 57.1 ± 1 58.1 ± 1 61.1 ± 1 48.1 ± 1

Referring to Table 1, the polyolefin prepared using the hybrid supported catalyst of the present invention exhibited good physical properties and mechanical properties, and thus exhibited harmonized physical properties. In particular, it shows excellent mechanical properties as compared with Comparative Example 1, and as compared with Comparative Example 2, the workability measured by spiral flow is improved, and it is confirmed that the opposite properties that can not be solved in the prior art can be achieved at the same time.

Claims (14)

A first metallocene compound represented by Formula 1 below;
A second metallocene compound represented by Formula 2 below;
A cocatalyst compound; And
Composite supported metallocene catalyst comprising a carrier:
[Chemical Formula 1]

In Formula 1,
X is the same or different halogen,
R ₁ is C _6-20 aryl substituted with C _2-20 alkoxyalkyl,
R _2, R ₃ and R ₄ are each independently hydrogen, halogen, C _1-20 alkyl, C _2-20 alkenyl, C _1-20 ether, C _1-20 alkoxy, C _6-20 aryl, C _{7- 20} alkylaryl, or _C7-20 arylalkyl,
A is carbon, silicon or germanium,
R ₅ and R ₆ are each independently C _1-20 alkyl,
(2)

In Formula 2,
X 'are the same or different halogen,
R ₇ is C _6-20 aryl substituted with C _1-20 alkyl,
R _8, R ₉ and R ₁₀ are each independently hydrogen, halogen, C _1-20 alkyl, C _2-20 alkenyl, C _1-20 ether, C _1-20 alkoxy, C _6-20 aryl, C _{7- 20} alkylaryl, or _C7-20 arylalkyl,
A 'is carbon, silicon or germanium,
R ₁₁ and R ₁₂ is one of the C _2-20 alkoxyalkyl, and the other is C _1-20 alkyl.
The method according to claim 1,
Wherein R ₁ in Formula 1 is phenyl substituted with C _2-20 alkoxyalkyl.
The method according to claim 1,
Wherein R ₂ , R _3, and R ₄ in Formula 1 are hydrogen.
The method according to claim 1,
Wherein the first metallocene compound represented by Formula 1 is represented by Formula 1-1:
[Formula 1-1]

The method according to claim 1,
Wherein R &lt; ₇ &gt; in the above formula (2) is phenyl substituted by _C1-20 alkoxyalkyl.
The method according to claim 1,
Wherein R ₈ to R ₁₀ in Formula 2 are hydrogen.
The method according to claim 1,
Wherein one of R &lt; ₁₁ &gt; and R &lt; ₁₂ &gt; in the above formula (2) is methyl and the other is tert-butoxyhexyl.
The method according to claim 1,
Wherein the second metallocene compound of Formula 2 is represented by the following Formula 2-1:
[Formula 2-1]

The method according to claim 1,
Wherein the first metallocene compound represented by Formula 1 and the second metallocene compound represented by Formula 2 are present in a molar ratio of 10: 1 to 1: 2.
The method according to claim 1,
Wherein the co-catalyst compound is a mixed supported metallocene catalyst comprising at least one compound represented by the following general formula (3), (4) or (5)
(3)
_{- [Al (R 13) -O} ] n -
In Formula 3,
R ₁₃ may be the same or different from each other, and each independently halogen; Hydrocarbons having 1 to 20 carbon atoms; Or a hydrocarbon having 1 to 20 carbon atoms substituted with halogen;
n is an integer of 2 or more;
[Chemical Formula 4]
D (R _{14) 3}
In Formula 4,
R ₁₄ may be the same or different from each other, and each independently halogen; Hydrocarbons having 1 to 20 carbon atoms; Or a hydrocarbon having 1 to 20 carbon atoms substituted with halogen;
D is aluminum or boron;
[Chemical Formula 5]
[LH] ⁺ [ZA ₄ ] ^- or [L] ⁺ [ZA ₄ ] ^-
In Formula 5,
L is a neutral or cationic Lewis acid; H is a hydrogen atom; Z is a Group 13 element; A may be the same as or different from each other, and independently at least one hydrogen atom is an aryl group having 6 to 20 carbon atoms or an alkyl group having 1 to 20 carbon atoms substituted or unsubstituted with halogen, hydrocarbon having 1 to 20 carbon atoms, alkoxy or phenoxy .
10. A process for producing a polyolefin comprising polymerizing an olefin monomer in the presence of a hybrid supported metallocene catalyst according to any one of claims 1 to 10.
12. The method of claim 11,
The olefin-based monomer may be at least one selected from the group consisting of ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, , 1-tetradecene, 1-hexadecene, and 1-eicosene.
12. The method of claim 11,
Wherein the polyolefin is homopolypropylene or random polypropylene.
12. The method of claim 11,
Wherein the polyolefin has a molecular weight distribution (PDI) of 2.5 to 4.5.