KR102023168B1

KR102023168B1 - Metallocene compounds, catalyst compositions comprising the same, and method for preparing olefin polymers using the same

Info

Publication number: KR102023168B1
Application number: KR1020150101899A
Authority: KR
Inventors: 이시정; 김석환; 박하나; 도상록; 박종우
Original assignee: 주식회사 엘지화학
Priority date: 2015-07-17
Filing date: 2015-07-17
Publication date: 2019-09-19
Also published as: KR20170009595A

Abstract

The present invention is a metallocene compound having a novel structure which can not only show high reactivity in the olefin polymerization but also easily control the properties of the internal structure, mechanical properties, etc. of the olefin polymer to be synthesized, a catalyst composition comprising the same, and A method for producing an olefin polymer using the catalyst composition.

Description

METALLOCENE COMPOUNDS, CATALYST COMPOSITIONS COMPRISING THE SAME, AND METHOD FOR PREPARING OLEFIN POLYMERS USING THE SAME}

The present invention relates to a metallocene compound having a novel activity and capable of controlling the microstructure of an olefinic polymer, a catalyst composition comprising the same, and a method for preparing an olefin polymer using the same.

Ziegler-Natta catalysts of titanium or vanadium compounds have been widely used in the commercial production process of conventional polyolefins. The Ziegler-Natta catalysts have high activity, but because they are multi-active catalysts, the molecular weight distribution of the resulting polymers is wide and comonomers are used. There is a limit in securing the desired physical properties because the composition distribution is not uniform.

Accordingly, recently, metallocene catalysts in which a ligand including a cyclopentadiene functional group and a transition metal such as titanium, zirconium, and hafnium have been developed have been widely used. Metallocene compounds are generally used by activation with aluminoxanes, boranes, borates or other activators. For example, a metallocene compound having a ligand including a cyclopentadienyl group and two sigma chloride ligands uses aluminoxane as an activator. These metallocene catalysts are single active site catalysts with one type of active site, and have a narrow molecular weight distribution of the produced polymer and can greatly control the molecular weight, stereoregularity, crystallinity, and especially the reactivity of the comonomer, depending on the structure of the catalyst and the ligand. There is an advantage. However, the polyolefin polymerized with a metallocene catalyst has a low melting point and a narrow molecular weight distribution, so when applied to some products, there is a problem in that it is difficult to apply in the field such as productivity decreases significantly due to the extruded load. A lot of efforts have been made to adjust.

In particular, in order to solve the problems of the metallocene catalyst described above, a number of metallocene compounds in which a ligand compound including a hetero atom is coordinated have been introduced. Specific examples of the metallocene compound containing such a hetero atom include an azaferrocene compound having a cyclopentadienyl group containing a nitrogen atom, and a functional group such as a dialkylamine connected to a cyclopentadienyl group as an additional chain. The metallocene compound of the structure, or the titanium (lV) metallocene compound into which the alkylamine functional group of the ring form like piperidine was introduce | transduced, etc. are mentioned.

However, among all these attempts, only a few metallocene catalysts are actually used in commercial plants, and have a higher activity and ansa-metallocene compounds that can control the microstructure of the olefinic polymer. There is still a need for research.

The present invention is to provide a metallocene compound with a novel structure that can control the microstructure of the olefin polymer while having high activity.

In addition, the present invention is to provide a catalyst composition comprising the metallocene compound.

In addition, the present invention is to provide a method for producing an olefin polymer using the catalyst composition.

The present invention provides a metallocene compound represented by the following formula (1).

The present invention also provides a catalyst composition comprising the metallocene compound.

In addition, the present invention provides a method for preparing an olefin polymer using the catalyst composition.

Hereinafter, a metallocene compound, a catalyst composition, and a method for preparing an olefin polymer using the same according to specific embodiments of the present invention will be described in detail.

According to one embodiment of the invention, a metallocene compound represented by the following Formula 1 may be provided.

[Formula 1]

In Chemical Formula 1,

R ₁ to R ₁₁ are each independently hydrogen, an alkyl group of 1 to 10 carbon atoms, an alkenyl group of 2 to 10 carbon atoms, an alkynyl group of 2 to 10 carbon atoms, an alkoxy group of 1 to 20 carbon atoms, or an aryl group of 6 to 20 carbon atoms , A cycloalkyl group having 3 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, and an arylalkyl group having 7 to 20 carbon atoms,

R ₁₂ is an alkyl group having 1 to 20 carbon atoms substituted with alkoxy having 1 to 20 carbon atoms,

R ₁₃ is hydrogen, an alkyl group having 1 to 10 carbon atoms, or an alkenyl group having 2 to 20 carbon atoms,

A is silicon or carbon,

Each X is independently halogen or an alkyl group having 1 to 20 carbon atoms.

The present inventors can easily control the electronic / stereoscopic environment around the transition metal due to the inherent chemical structure of the metallocene compound of Chemical Formula 1, and facilitate the characteristics such as microstructure, mechanical properties, etc. of the polyolefin to be synthesized. It was confirmed through the experiment that it can be adjusted.

The metallocene compound of Formula 1 has a symmetrical crosslinked structure in which two indenene groups are connected to a silicon or carbon bridge, and in particular, a functional group such as an alkyl group or an alkoxy group is introduced at a specific position of the indenene group. In addition, the metallocene compound may exhibit high activity during olefin polymerization, and in particular, a polyolefin having a high melting point and a low fine content may be prepared.

In particular, the metallocene compound of the embodiment has a bulky group of phenyl bonded to a specific position of the indacene group, thereby enhancing the electron donating effect and increasing the electron density around the metal. ) Can be increased, thus exhibiting high activity in olefin polymerization.

In addition, the metallocene compound includes an alkyl group having 1 to 20 carbon atoms substituted with alkoxy having 1 to 20 carbon atoms in a bridge group connecting an indacene group, thereby supporting a supported yield of the metallocene compound. It can increase the activity of the catalyst.

Hereinafter, the substituents defined in Chemical Formula 1 will be described in detail.

The alkyl group having 1 to 20 carbon atoms may include a linear or branched alkyl group, and the alkenyl group and alkynyl group having 2 to 20 carbon atoms may include a straight or branched alkenyl group and an alkynyl group, respectively.

The aryl group is preferably an aromatic ring having 6 to 20 carbon atoms, and specifically, phenyl, naphthyl, anthracenyl, pyridyl, dimethylanilinyl, anisolyl, and the like, but is not limited thereto.

The alkylaryl group refers to an aryl group having one or more linear or branched alkyl groups of 1 to 20 carbon atoms introduced therein, and the arylalkyl group refers to a straight or branched alkyl group having one or more aryl groups of 6 to 20 carbon atoms introduced thereto.

And a halogen group means fluorine (F), chlorine (Cl), bromine (Br), and iodine (I).

In the metallocene compound of the above embodiment, R ₂ , R ₃ and R ₄ may each independently be hydrogen or an alkyl group having 1 to 10 carbon atoms, preferably hydrogen, methyl or tert-butyl.

In addition, R ₁₀ may be an alkyl group having 1 to 10 carbon atoms, preferably methyl.

And, it is preferable that R ₁₂ is tert-butoxy-hexyl, and it is preferable that A is silicon.

On the other hand, preferred examples of the metallocene compound represented by Formula 1 include, but are not limited to, a compound represented by one of the following structural formulas:

,

,

The compound represented by Chemical Formula 1 may be synthesized in the same manner as in Scheme 1, but is not limited thereto. Method for producing a compound represented by the formula (1) will be described in more detail in Examples to be described later.

Scheme 1

In Scheme 1, the definitions of R ₁ to R ₁₃ and A are the same as those defined in Chemical Formula 1, and X is a halogen or an alkyl group having 1 to 20 carbon atoms.

In addition, according to another embodiment of the present invention, a catalyst composition for olefin polymerization including a metallocene compound represented by Formula 1 and a promoter may be provided.

The cocatalyst is not particularly limited since it may be used in the art to which the present invention pertains. Preferably, alkylaluminoxane may be used, and silica, silica-alumina, and organoaluminum compounds may be further included. In the case of using such a promoter, X bonded to the metal element of the compound represented by Chemical Formula 1 may be used as a catalyst in a form substituted with an alkyl group such as C _1-20 alkyl.

And, the catalyst composition is a metallocene compound represented by Formula 1; And promoters; In addition, the solvent may further include.

As the solvent, a solvent known to be usable in the catalyst composition for olefin polymerization can be used without particular limitation, and examples thereof include aliphatic hydrocarbon solvents such as pentane, hexane, heptane, nonane, decane, and isomers thereof; Aromatic hydrocarbon solvents such as toluene, xylene, benzene; Or a hydrocarbon solvent substituted with a chlorine atom such as dichloromethane or chlorobenzene. The content of the solvent in the catalyst composition can be appropriately adjusted according to the characteristics of the catalyst composition used and the conditions of the production process of the olefin polymer to be applied.

The olefin polymerization catalyst may be a catalyst supported on a carrier. The carrier is not particularly limited, since a conventional one can be used in the art to which the present invention pertains. Preferably, one or more carriers selected from the group consisting of silica, silica-alumina, and silica-magnesia may be used.

On the other hand, when supported on a carrier such as silica, since the silica carrier and the functional group of the compound represented by Chemical Formula 1 are supported by chemical bonding, there are almost no catalysts liberated from the surface in the olefin polymerization process. During manufacture, there may be less fouling phenomenon in which the reactor walls or polymer particles are entangled with each other.

Such carriers may be preferably silica dried at high temperature, silica-alumina and the like, and these are usually oxides, carbonates, sulfates, such as Na ₂ O, K ₂ CO ₃ , BaSO ₄ , Mg (NO ₃ ) ₂ , Nitrate components may be contained.

In addition, according to another embodiment of the invention, there may be provided a method for producing a polyolefin comprising the step of polymerizing the olefin monomer in the presence of the catalyst composition.

As described above, the metallocene compound of Formula 1 can easily control the electronic / three-dimensional environment around the metal, it is possible to easily control the properties, such as internal structure, mechanical properties of the polyolefin to be synthesized.

The polymerization reaction of the olefin monomer can be used without limitation, a polymerization process known to be used in the polymerization reaction of the olefin monomer, such as a continuous solution polymerization process, bulk polymerization process, suspension polymerization process slurry polymerization process or emulsion polymerization process.

Examples of the olefin monomer polymerizable using the metallocene compounds and the cocatalyst include ethylene, alpha-olefin, cyclic olefin, and the like, and a diene olefin monomer or a triene olefin monomer having two or more double bonds. And the like can also be polymerized. Specific examples of the monomers include ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dode Sen, 1-tetradecene, 1-hexadecene, 1-aitocene, norbornene, norbornadiene, ethylidenenorbornene, phenylnorbornene, vinylnorbornene, dicyclopentadiene, 1,4-butadiene, 1, 5-pentadiene, 1,6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene, 3-chloromethyl styrene, etc., These monomers may be mixed and copolymerized. When the polyolefin is a copolymer of ethylene and other comonomers, the monomer constituting the copolymer is one selected from the group consisting of propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, and 1-octene It is preferable that it is the above comonomer.

Here, the polymerization of the polyolefin may be carried out by reacting for 1 to 24 hours at a temperature of 25 to 500 ℃ and a pressure of 1 to 100 kgf / ㎠. At this time, 25-200 degreeC is preferable and, as for the said polymerization reaction temperature, 50-100 degreeC is more preferable. Moreover, 1-70 kgf / cm <2> is preferable and, as for the said polymerization reaction pressure, 5-40 kgf / cm <2> is more preferable. The polymerization reaction time is preferably 1 to 5 hours.

The polymerization process can control the molecular weight range of the resulting polymer product in accordance with hydrogenation or no addition conditions. In particular, a high molecular weight polyolefin can be produced under the condition that hydrogen is not added, and low molecular weight polyolefin can be produced even by adding a small amount of hydrogen when hydrogen is added. At this time, the hydrogen content added to the polymerization process is in the range of 0.07 L to 4 L under 1 atmosphere of the reactor conditions, or is supplied at a pressure of 1 bar to 40 bar or 168 ppm to 8,000 ppm in the hydrogen mole content range relative to the olefin monomer Can be.

According to the present invention, a metallocene compound which can not only exhibit high reactivity in the olefin polymerization reaction but also easily control the properties such as internal structure, mechanical properties, etc. of the olefin polymer to be produced, a catalyst composition comprising the same, and the catalyst composition Method for producing an olefin polymer using may be provided.

The invention is explained in more detail in the following examples. However, the following examples are merely to illustrate the invention, but the content of the present invention is not limited by the following examples.

In Examples, Comparative Examples, and Experimental Examples described later, organic reagents and solvents were purchased from Aldrich and Merck, and purified by standard methods. At all stages of the synthesis, the contact between air and moisture was blocked to increase the reproducibility of the experiment.

< Example Ligand compound and Metallocene Synthesis of Compounds>

(1) Synthesis of 8- (4- ( tert- butyl) phenyl) -6-methyl-1,2,3,5-tetrahydro-s-indacene

8-Bromo-6-methyl-1,2,3,5-tetrahydro-s-indacene (35mmol, 9.8g), (4- ( tert -butyl) phenyl) boronic acid (70mmol, 12.5g), sodium carbonate ( 87.50 mmol, 9.3 g) and tetrakistriphenylphosphine palladium (1.80 mmol, 2 g) were added to 250 mL RBF and toluene (35 mL), ethanol (18 mL) and water (1 mL) were added. And it stirred for 16 hours in the oil bath previously heated to 90 degreeC. The reaction was confirmed by NMR, and if the reaction was less progress, the reaction was performed for 16 hours, or the reactants except for indacene and solvent were further prescribed according to the amount of indacene remaining, followed by reaction for 16 hours. After the reaction, all of the ethanol was removed from the rotary evaporator and worked up with water and hexane. The combined organic layers were dried over MgSO ₄ and all solvent was removed. The crude mixture from which the solvent was removed was removed by silica gel short column to remove black impurities. Again all solvent was removed and methanol was added to give a solid. The resulting solid was filtered and washed with methanol to give 8- (4- ( tert -butyl) phenyl) -6-methyl-1,2,3,5-tetrahydro-s-indacene (8.5 g, 80%, white solid) Obtained.

¹ H NMR (500MHz, in CDCl ₃ ): 7.44 ~ 7.31 (m, 4H), 7.12 (s, 1H), 6.47 (s, 1H), 3.19 (s, 2H), 2.97 (t, 2H), 2.09 ~ 2.02 (m, 5H), 1.38 (s, 9H)

(2) (6- (tert-butoxy) hexyl) bis (4- (4- (tert-butyl) phenyl) -2-methyl-1,5,6,7-tetrahydro-s-indacen-1-yl) Synthesis of (methyl) silane Ligands

8- (4- ( tert -butyl) phenyl) -6-methyl-1,2,3,5-tetrahydro-s-indacene (16.40 mmol, 5 g) and CuCN (0.82 mmol, 0.07 g) were added to a 100 mL Schlenk flask. Put in argon state. When argon was formed, anhydrous toluene (45 mL) and anhydrous THF (5 mL) were added thereto, and the mixture was cooled to -25 ° C. n- BuLi (2.5M in Hexane, 18mmol, 7.23mL) was slowly injected. After the injection was completed, the temperature was raised to room temperature and stirred for 3 hours. Then, Tether silane (7.80 mmol, 2.1 g) was injected into the flask as a shot at room temperature and stirred for 16 hours. Worked up with MTBE and water, and the organic layers were collected to remove the solvent. Column (6- (tert-butoxy) hexyl) bis (4- (4- (tert-butyl) phenyl) -2-methyl-1,5,6,7-tetrahydro-s-indacen-1-yl) ( Methyl) silane ligand (4 g, 64%, light yellow solid) was obtained.

¹ H NMR (500MHz, in CDCl ₃ ): 7.45 ~ 7.34 (m, 8H), 7.26 (s, 1H), 7.19 (s, 1H), 3.70 ~ 3.65 (m, 2H), 3.26 ~ 3.24 (m, 2H ), 2.97-2.83 (m, 8H), 2.17-2.03 (m, 10H), 1.53-0.44 (m, 30H), -0.09 --0.15 (m, 3H)

(3) (6- (tert-butoxy) hexyl) bis (4- (4- (tert-butyl) phenyl) -2-methyl-1,5,6,7-tetrahydro-s-indacen-1-yl) Synthesis of (methyl) silane hafnium Metallocene Compound

(6- (tert-butoxy) hexyl) bis (4- (4- (tert-butyl) phenyl) -2-methyl-1,5,6,7-tetrahydro-s-indacen-1-yl) (methyl) Silane ligand (1.24mmol, 1g) was placed in a 50mL Schlenk flask to make an argon state. When argon was formed, anhydrous diethyl ether (25 mL) was added thereto, and the mixture was cooled to -25 ° C. n- BuLi (2.5M in Hexane, 2.73mmol, 1.1mL) was slowly injected, and after the injection, the temperature was raised to room temperature and stirred for 3 hours. After stirring, the Arlen Schlenk flask containing this solution and HfCl ₄ -2 (THF) (1.24 mmol, 0.58 g) was cooled to -78 ° C, and the ligand solution was transferred to a flask containing hafnium at low temperature. . After slowly warming to room temperature, the mixture was stirred for 16 hours. After stirring, the produced solid was filtered off under argon and the solvent was dried to obtain a crude mixture. It was dissolved in a minimum amount of anhydrous toluene and stored at -25 ° C to -30 ° C to produce a solid. The produced solid was collected by filtration after releasing excess hexane at low temperature. The solid obtained was dried to obtain a clean catalyst (6- (tert-butoxy) hexyl) bis (4- (4- (tert-butyl) phenyl) -2-methyl-1,5,6,7-tetrahydro-s- Indacen-1-yl) (methyl) silane hafnium (0.18 mmol, 0.19 g, 14%, yellow solid) was obtained.

¹ H NMR (500 MHz, in CDCl ₃ ): 7.38-7.26 (m, 10H), 6.62 (s, 2H), 3.38-3.36 (t, 2H), 3.10-2.83 (m, 8H), 2.31-2.30 (d , 6H), 2.05-1.34 (m, 34H), 1.2 (s, 3H)

(4) Preparation of Supported Catalyst

Silica gel (3 g) was placed in a 250 mL Schlenk flask under argon, and methyl aluminoxane (MAO; 23 mL, 30 mmol) was slowly injected at room temperature and stirred at 95 ° C. for 18 hours. After completion of the reaction, the mixture was cooled to room temperature and left for 15 minutes to decant the solvent using cannula. Toluene (25 mL) was added thereto, stirred for 1 minute, and left for 20 minutes to decant the solvent using cannula. Then, the metallocene compound (180 μmol) prepared in (3) was dissolved in toluene (20 mL), and then transferred to a flask using cannula and washed with toluene (5 mL). After stirring for 5 hours at 75 ℃, cooled to room temperature and left for 15 minutes to decant the solvent using cannula. Toluene (25 mL) was added thereto, stirred for 1 minute, and left for 10 minutes to decant the solvent using cannula twice. Hexane (25 mL) was added in the same manner, stirred for 1 minute, left for 20 minutes, decant solvent using cannula and dried under vacuum overnight. It was further dried under vacuum at 45 ° C. for 4 hours.

< Comparative example >

(1) Synthesis of Dimethylbis (2-methyl-4-phenyl-1H-inden-1-yl) silane

To a 77 mL 2-methyl-4-phenylindene toluene / THF = 10/1 solution (49.5 mmol), 21.8 mL of n-butyllithium solution (2.5 M, hexane solvent) were slowly added dropwise at 0 ° C., followed by 1 at 80 ° C. After stirring for an hour, the mixture was stirred at room temperature for one day. Thereafter, 2.98 mL of dichloromethylsilane was slowly added dropwise at 0 ° C. or lower, stirred for about 10 minutes, and heated to 80 ° C. for 1 hour. Then, water was added to separate the organic layer, and the silica column was purified and dried in vacuo to give a sticky yellow oil in a yield of 61%.

¹ H NMR (500 MHz, CDCl ₃ , 7.24 ppm): 0.02 (6H, s), 2.37 (6H, s), 4.00 (2H, s), 6.87 (2H, t), 7.83 (2H, t), 7.45 ( 2H, t), 7.57 (4H, d), 7.65 (4H, t), 7.75 (4H, d)

(2) Synthesis of Dimethylbis (2-methyl-4-phenyl-1H-inden-1yl) silane Zirconium dichloride

To a 240 mL dimethylbis (2-methyl-4-phenylindenyl) silane ether / hexane = 1/1 solution (12.4 mmol), 10.9 mL of n-butyllithium solution (2.5M in hexane) was slowly added dropwise at -78 ° C. . Thereafter, the mixture was stirred at room temperature for one day, filtered and dried in vacuo to give a pale yellow solid. Ligand salt and bis (N, N'-diphenyl-1,3-propanediamido) dichlorozirconiumbis (tetrahydrofuran) synthesized in a glove box were used in a Schlenk flask. After weighing), ether was slowly added dropwise at -78 ° C and stirred for 1 day at room temperature. The red solution was separated by filtration, dried in vacuo and a toluene / ether = 1/2 solution was added to obtain a clean red solution. 1.5-2 equivalents of HCl ether solution (1M) was slowly added dropwise at -78 ° C, followed by stirring at room temperature for 3 hours. After filtration and vacuum drying, an orange solid catalyst was obtained in a yield of 70% (racemic only).

¹ H NMR (500MHz, C6D6, 7.24ppm): 1.32 (6H, s), 2.24 (6H, s), 6.93 (2H, s), 7.10 (2H, t), 7.32 (2H, t), 7.36 (2H , d), 7.43 (4H, t), 7.60 (4H, d), 7.64 (2H, d)

< Experimental Example >

(1) Homopolymerization of propylene

The 2 L stainless reactor was vacuum dried at 65 ° C. and then cooled, and 3 mL of triethylaluminum, 2 bar of hydrogen, and 770 g of propylene were sequentially added at room temperature. After stirring for 10 minutes, each of the metallocene catalysts prepared in Examples and Comparative Examples was dissolved in 20 mL of TMA-prescribed hexane and introduced into a reactor under nitrogen pressure. The reactor temperature was then slowly raised to 70 ° C. and then polymerized for 1 hour. After the reaction was completed, unreacted propylene was vented.

(2) Random Polymerization of Propylene

The 2 L stainless reactor was vacuum dried at 65 ° C. and then cooled, and 3 mL of triethylaluminum and 770 g of propylene were sequentially added at room temperature. After stirring for 10 minutes, each of the metallocene catalysts prepared in Examples and Comparative Examples was dissolved in 20 mL of TMA-prescribed hexane and introduced into a reactor under nitrogen pressure. Then, the reactor temperature was slowly raised to 70 ° C. while adding 15 g of ethylene in total, and then polymerized for 1 hour. After the reaction was completed, unreacted propylene and ethylene were vented.

(3) measuring method of physical properties of polymers

1) Catalyst activity: Calculated as the ratio of the weight (kg PP) of the resulting polymer per mg of supported catalyst (mg) used, based on unit time (h).

2) Melting point (Tm) of the polymer: The melting point of the polymer was measured using a differential scanning calorimeter (DSC, device name: DSC 2920, manufacturer: TA instrument). Specifically, the polymer was heated to 220 ° C. and then maintained at that temperature for 5 minutes, cooled to 20 ° C. again, and then increased in temperature, wherein the rate of rise and fall of the temperature was adjusted to 10 ° C./min, respectively. It was.

3) Particle Size Distribution (PSD):

After the sample was injected into the hopper of the optical diffraction particle size analyzer (HELOS, Symatec), the method was set in the range of 50 ~ 3500㎛ to confirm the APS (Acerage Particle Size), Span value and the content of 75㎛ or less (differential).

(4) Measurement result of physical properties of polymer

The results of measuring the properties of the homo and random polymerization processes and the resulting polypropylene prepared using the respective metallocene supported catalysts prepared in Examples and Comparative Examples are shown in Tables 1 (homo polymerization) and Table 2 (random polymerization). ).

Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Liquid propylene (g) 770 770 770 770 770 Supported catalyst amount (mg) 45 45 45 146 146 Hydrogen (ppm) 0 372 703 0 372 Yield (g) 265 395 482 80.3 80 Activity (kg / gCat · hr) 5.9 8.8 10.7 0.55 0.55 MFR 1.3 3.6 11.8 - - Tm (℃) 154.6 156.5 156.8 150.2 150.1 PSD Μm 651.3 788.6 919.2 520 535 Span 0.5 0.6 0.6 - - <74 μm (%) 0 0 0.6 10.2 9.5 <210 μm (%) 0 0 0.6 - - <500 µm (%) 6.9 2.1 1.4 97.5 96.4

Example 1 Example 2 Example 3 Liquid propylene (g) 770 770 770 Supported catalyst amount (mg) 23 23 23 Hydrogen (ppm) 0 372 703 Yield (g) 240 299 437 Activity (kg / gCat · hr) 10.4 13.0 19.0 MFR 1.0 6.9 16.2 Tm (℃) 144.5 151.1 151.7 PSD Μm 746.7 950.6 1094.8 Span 0.5 0.5 0.6 <74 μm (%) 0.3 0.5 0.9 <210 μm (%) 0.4 0.5 0.9 <500 μm (%) 3.5 0.7 1.1

As shown in Table 1 and Table 2, according to the embodiment, an embodiment using a metallocene compound having a specific substituent in an indene group and a bridge group as a supported catalyst shows a generally high activity in preparing polyolefin. It was confirmed that the homopolypropylene prepared in Examples 1 to 3 showed a high melting point of 153 ° C. or higher.

In addition, referring to the results of particle size distribution (PSD) measurement, in the case of the metallocene compound prepared in Example, the chain structure bonded to silicon enables the catalyst to be effectively bonded to the carrier, thereby providing a catalyst without the chain structure. Compared to the generation of fine powder is significantly reduced it can be seen that the polymerization process can be carried out stably.

Claims

A metallocene compound represented by Formula 1 below:
[Formula 1]

In Chemical Formula 1,
R ₁ to R ₁₁ are each independently hydrogen, an alkyl group of 1 to 10 carbon atoms, an alkenyl group of 2 to 10 carbon atoms, an alkynyl group of 2 to 10 carbon atoms, an alkoxy group of 1 to 20 carbon atoms, or an aryl group of 6 to 20 carbon atoms , A cycloalkyl group having 3 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, and an arylalkyl group having 7 to 20 carbon atoms,
R ₁₂ is an alkyl group having 1 to 20 carbon atoms substituted with alkoxy having 1 to 20 carbon atoms,
R ₁₃ is hydrogen, an alkyl group having 1 to 10 carbon atoms, or an alkenyl group having 2 to 20 carbon atoms,
A is silicon or carbon,
Each X is independently halogen or an alkyl group having 1 to 20 carbon atoms.

The method of claim 1,
The R ₂ , R ₃ and R ₄ is a metallocene compound, characterized in that each independently hydrogen or an alkyl group having 1 to 10 carbon atoms.

The method of claim 1,
R ₁₀ is a metallocene compound, characterized in that an alkyl group having 1 to 10 carbon atoms.

The method of claim 1,
A is a metallocene compound, characterized in that silicon.

The method of claim 1,
R ₂ , R ₃ and R ₄ are each independently hydrogen, methyl or tert-butyl, R ₁₂ is tert-butoxy-hexyl, and R ₁₀ is methyl.

The method of claim 1,
The compound represented by Chemical Formula 1 is one of the following structural formula metallocene compound:

,

,

Catalyst composition for olefin polymerization comprising a metallocene compound represented by the formula (1) of claim 1 and a promoter.

A method for producing an olefin polymer, comprising the step of polymerizing the olefin monomer in the presence of the catalyst composition for olefin polymerization of claim 7.