KR20170082917A - Metallocene compounds, catalyst compositions comprising the same, and method for preparing olefin polymers using the same - Google Patents

Abstract

The present invention relates to a metallocene compound having a novel structure capable of exhibiting high reactivity in the olefin polymerization reaction and easily controlling the properties such as the internal structure and mechanical properties of the synthesized olefin polymer, And to a process for preparing an olefin polymer using the catalyst composition.

Description

TECHNICAL FIELD [0001] The present invention relates to a metallocene compound, a catalyst composition containing the metallocene compound, and a process for producing the olefin polymer using the same. BACKGROUND ART [0002]

The present invention relates to a metallocene compound having a novel structure capable of controlling the microstructure of an olefin-based polymer while having high activity, a catalyst composition containing the metallocene compound, and a process for producing an olefin polymer using the metallocene compound.

Ziegler-Natta catalysts of titanium or vanadium compounds have been widely used for the commercial production of polyolefins. Although the Ziegler-Natta catalysts have high activity, they have a wide molecular weight distribution of the produced polymers because of their high activity, The uniformity of the composition is not uniform and there is a limit in ensuring desired physical properties.

Recently, a metallocene catalyst in which a transition metal such as titanium, zirconium, or hafnium and a ligand containing a cyclopentadiene functional group are bonded has been developed and widely used. The metallocene compound is generally activated by using aluminoxane, borane, borate or other activator. For example, a metallocene compound having a ligand containing a cyclopentadienyl group and two sigma chloride ligands uses aluminoxane as an activator. These metallocene catalysts are single active site catalysts having one kind of active site. The molecular weight distribution of the produced polymer is narrow and the molecular weight, stereoregularity, crystallinity, especially reactivity of the comonomer can be greatly controlled depending on the structure of the catalyst and the ligand There is an advantage. However, since the polyolefin polymerized with the metallocene catalyst has a low melting point and a narrow molecular weight distribution, it is difficult to apply the polyolefin in a field where the productivity is remarkably decreased due to the influence of the extrusion load, I have done a lot of effort to adjust.

In particular, in order to solve the problems of the above-mentioned metallocene catalysts, many metallocene compounds coordinated with a ligand compound containing a hetero atom have been introduced. Specific examples of such a metallocene compound containing a hetero atom include an azaferrocene compound having a cyclopentadienyl group containing a nitrogen atom, a functional group such as a dialkylamine is connected to a cyclopentadienyl group as an additional chain Or a titanium (lV) metallocene compound into which a cyclic alkylamine functional group is introduced such as piperidine, and the like.

However, among all of these attempts, the metallocene catalysts that are actually applied to commercial plants are only a few levels, and the anthra-metallocene compounds capable of controlling the microstructure of the olefinic polymer, Research is still needed.

The present invention is to provide a ligand compound and a metallocene compound having a novel structure capable of controlling the microstructure of an olefin-based polymer while having high activity.

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

The present invention also provides a process for producing an olefin polymer using the catalyst composition.

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

The present invention also provides a metallocene compound represented by the following general formula (2).

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

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

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

According to one embodiment of the present invention, a ligand compound represented by the following formula (1) may be provided.

[Chemical Formula 1]

In Formula 1,

R ₁ is a C _6-20 aryl substituted with C _6-20 aryl or C _1-20 alkyl,

R ₂ is C _1-20 alkoxy,

R ₃ is C _1-20 alkyl,

R ₄ is hydrogen, halogen, C _1-20 alkyl, C _2-20 alkenyl, C _1-20 alkylsilyl, C _1-20 alkyl silyl, C _1-20 alkoxysilyl, C _1-20 ether, C _{1- 20} silyl ether, C _1-20 alkoxy, C _6-20 aryl, C _7-20 alkylaryl, or C _7-20 arylalkyl,

A is carbon, silicon or germanium,

R ₅ is C _1-20 alkyl substituted by C _1-20 alkoxy,

R ₆ is hydrogen, C _1-20 alkyl or C _2-20 alkenyl.

The present inventors have found that by virtue of the inherent chemical structure of the ligand compound of Formula 1, the electronic / stereoscopic environment around the transition metal that can be bonded thereto can be easily controlled, and the microstructure and mechanical properties of the synthesized polyolefin It is possible to provide a metallocene catalyst capable of easily controlling the characteristics of the catalyst.

The ligand compound of formula (1) has a crosslinked structure in which two indene groups are connected by a carbon, silicon or germanium bridge. Particularly, a ligand compound having a functional group such as an aryl group, an alkyl group and an alkoxy group at a specific position of an indene group , The ligand compound can exhibit high activity upon olefin polymerization and can provide a catalyst capable of producing a polyolefin having a high molecular weight and a low melt flow index (MFR).

In particular, the ligand compound of this embodiment has a structure in which not only an aryl group which is a bulky group is bonded to a specific position of an indene group but also an alkyl group and an alkoxy group are combined to enhance an electron donating effect, It is possible to increase the electron density around the polymer and thus exhibit high activity in the polymerization of olefins.

In addition, the ligand compound includes a bridge group connecting two indene groups, and an alkyl group having 1 to 20 carbon atoms substituted with an alkoxy group having 1 to 20 carbon atoms to form a metallocene compound containing a ligand compound The yield of the supported catalyst can be increased, and the activity of the catalyst can be increased.

Each of the substituents defined in Formula 1 will be described in detail as follows.

The C _1-20 alkyl may include straight chain or branched chain alkyl, and the C _2-20 alkenyl may include straight chain or branched chain alkenyl.

The aryl group is preferably an aromatic ring having _{6 to 20} carbon atoms. Specific examples thereof include phenyl, naphthyl, anthracenyl, pyridyl, dimethylanilinyl, and anisole. However, the aryl group is not limited thereto.

The alkylsilyl and alkoxysilyl mean a silyl functional group introduced with C _1-20 alkyl or C _1-20 alkoxy, and the silylalkyl, silyl ether means an alkyl or ether in which silyl is introduced.

The alkylaryl means an aryl in which at least _one C _1-20 linear or branched alkyl is introduced, and the arylalkyl means straight-chain or branched alkyl having at least one C _6-20 aryl introduced therein.

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

In the ligand compounds of this embodiment, R ₁ is preferably phenyl or phenyl substituted with C _1-10 alkyl.

And R < ₂ > is preferably methoxy.

It is preferable that R ₃ is C _1-4 alkyl, and it is more preferably tert-butyl.

It is preferable that A is silicon, R ₅ is 6-tert-butoxy-hexyl, and R ₆ is methyl.

Preferable examples of the ligand compound represented by the above formula (1) include the following compounds:

,

,

,

,

,

,

The compound represented by the formula (1) can be synthesized by the following reaction scheme 1, but is not limited thereto. The method for preparing the compound represented by the formula (1) will be described in more detail in the following examples.

[Reaction Scheme 1]

The step 1 is a step of reacting the compound represented by the formula 3 with the compound represented by the formula 4 to prepare the compound represented by the formula 1. It is preferable to use alkyllithium (for example, n-butyllithium) in the above reaction, and the reaction temperature is -200 to 0 占 폚, more preferably -150 to 0 占 폚. As the solvent, toluene, THF and the like can be used. At this time, the organic layer may be separated from the product, and then the separated organic layer may be vacuum dried and excess reactant may be removed.

The compound represented by formula (I) prepared according to the above method may be a ligand compound capable of forming a chelate with a metal.

According to another embodiment of the present invention, a metallocene compound represented by the following general formula (2) may be provided.

(2)

In Formula 2,

R ₁ is a C _6-20 aryl substituted with C _6-20 aryl or C _1-20 alkyl,

R ₂ is C _1-20 alkoxy,

R ₃ is C _1-20 alkyl,

R ₄ is hydrogen, halogen, C _1-20 alkyl, C _2-20 alkenyl, C _1-20 alkylsilyl, C _1-20 alkyl silyl, C _1-20 alkoxysilyl, C _1-20 ether, C _{1- 20} silyl ether, C _1-20 alkoxy, C _6-20 aryl, C _7-20 alkylaryl, or C _7-20 arylalkyl,

A is carbon, silicon or germanium,

R ₅ is C _1-20 alkyl substituted by C _1-20 alkoxy,

R ₆ is hydrogen, C _1-20 alkyl or C _2-20 alkenyl,

M is a Group 4 transition metal compound,

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

The present inventors have found that the electronic / stereoscopic environment around the transition metal can be easily controlled owing to the chemical structure of the metallocene compound of Formula 2 wherein a ligand compound of a specific structure is bonded to the transition metal, Microstructure, mechanical properties, and the like can be easily controlled.

As described above, the metallocene compound of Formula 2 has a crosslinked structure in which two indene groups are connected by a carbon, silicon or germanium bridge. In particular, the metallocene compound of Formula 2 has an aryl group, An alkoxy group and the like, the metallocene compound can exhibit high activity in olefin polymerization and can produce a high molecular weight polyolefin having a low melt flow index (MFR).

And, as described above, in the metallocene compound of this embodiment, R ₁ is preferably phenyl or phenyl substituted with C _1-10 alkyl.

And R < ₂ > is preferably methoxy.

It is preferable that R ₃ is C _1-4 alkyl, and it is more preferably tert-butyl.

It is preferable that A is silicon, R ₅ is 6-tert-butoxy-hexyl, and R ₆ is methyl.

Further, it is preferable that M is zirconium and X is chloro.

On the other hand, preferred examples of the metallocene compound represented by the above formula (2) include the following compounds.

,

,

,

,

,

,

The metallocene compound represented by Formula 2 may be formed by reacting the ligand compound of Formula 1 with a metallocene compound. Specifically, the metallocene compound represented by the formula (3) can be synthesized by a method similar to the following reaction scheme 2, but is not limited thereto. The method for preparing the compound represented by the above formula (2) will be described in more detail in the following examples.

[Reaction Scheme 2]

The step 2 is a step of reacting the compound represented by the formula 1 with the compound represented by the formula 5 to prepare the compound represented by the formula 2. It is preferable to use alkyllithium (for example, n-butyllithium) in the above reaction, and the reaction temperature is -200 to 0 占 폚, more preferably -150 to 0 占 폚. As the solvent, ether, hexane and the like can be used.

According to another embodiment of the present invention, there can be provided a catalyst composition for olefin polymerization comprising the metallocene compound represented by Formula 2 and the cocatalyst.

The cocatalyst is not particularly limited as it is customary in the art to which the present invention belongs, but alkyl aluminoxane may be preferably used, and silica, silica-alumina, organoaluminum compound and the like may be further included. When such a cocatalyst is used, the catalyst may be used in which X bonded to the metal element of the compound represented by Formula 3 is substituted with an alkyl group, for example, C _1-20 alkyl.

The catalyst composition may include a metallocene compound represented by Formula 2; And cocatalyst; In addition, a solvent may be further included.

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

The catalyst for olefin polymerization may be a catalyst supported on a support. The carrier may be any of those generally used in the technical field to which the present invention belongs, so that it is not particularly limited, but preferably at least one carrier selected from the group consisting of silica, silica-alumina and silica-magnesia may be used.

On the other hand, when supported on a support such as silica, since the silica carrier and the functional group of the compound represented by Chemical Formula 2 are chemically bonded and supported, there is almost no catalyst liberated from the surface in the olefin polymerization process, and thus polyolefin The fouling phenomenon of the wall surface of the reactor or the polymer particles tangling with each other may be small.

As such a carrier, silica, silica-alumina and the like, which are dried at a high temperature, may be preferably used. These carriers are usually oxides such as Na ₂ O, K ₂ CO ₃ , BaSO ₄ and Mg (NO ₃ ) ₂ , A nitrate component may be included.

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

As described above, the metallocene compound of the above formula (2) can easily control the electronic / stereoscopic environment around the metal, so that the characteristics such as the internal structure and the mechanical properties of the synthesized polyolefin can be easily controlled.

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

Examples of olefin monomers that can be polymerized using the metallocene compounds and the cocatalyst include ethylene, alpha-olefin, cyclic olefin, etc., and diene olefin monomers or triene olefin monomers having two or more double bonds Can also be polymerized. Specific examples of the monomer include ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, Butene, dicyclopentadiene, 1,4-butadiene, 1,4-butadiene, 1,3-butadiene, 1,3-butadiene, Pentadiene, 1,6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene, 3-chloromethylstyrene and the like. These two or more monomers may be mixed and copolymerized. When the polyolefin is a copolymer of ethylene and another comonomer, the monomer constituting the copolymer is selected from the group consisting of propylene, 1-butene, 1-hexene, 4-methyl- Or more of the comonomer.

Here, the polymerization of the polyolefin can be carried out by reacting at a temperature of 25 to 500 ° C and a pressure of 1 to 100 kgf / cm 2 for 1 to 24 hours. At this time, the polymerization reaction temperature is preferably 25 to 200 ° C, more preferably 50 to 100 ° C. The polymerization reaction pressure is preferably 1 to 70 kgf / cm 2, and more preferably 5 to 40 kgf / cm 2. The polymerization reaction time is preferably 1 to 5 hours.

The polymerization process can control the molecular weight range of the finally produced polymer product according to the hydrogenation or not added conditions. In particular, a polyolefin having a high molecular weight can be produced under a condition that hydrogen is not added, and a low molecular weight polyolefin can be produced even with a small amount of hydrogen addition by adding hydrogen. At this time, the hydrogen content added to the polymerization process is 0.07 L to 4 L under 1 atm of the reactor condition, or is supplied at a pressure of 1 bar to 40 bar or in a range of 168 ppm to 8,000 ppm in terms of the molar amount of hydrogen relative to the olefin monomer .

According to the present invention, a ligand compound, a metallocene compound, a catalyst composition containing the metallocene compound and the like, which can easily exhibit high reactivity in the olefin polymerization reaction and can easily control the properties such as the internal structure and mechanical properties of the produced olefin polymer A method for producing an olefin polymer using the catalyst composition may be provided.

The invention will be described in more detail in the following examples. However, the following examples are illustrative of the present invention, and the present invention is not limited by the following examples.

< Example : A ligand compound and Metallocene  Synthesis of Compound &gt;

(1) Synthesis of 5- ( tert- butyl) -6-methoxy-2-methyl-7-phenyl- 1H- indene

7-Bromo-5- (tert -butyl ) -6-methoxy-2-methyl-1 H -indene (18.5mmol, 5.5g), phenylboronic acid (29mmol, 3.6g), sodium carbonate (59.4mmol, 6.3g) , tetrakistriphenylphosphine palladium (0.87 mmol, 1 g) were placed in 250 mL RBF and toluene (30 mL), ethanol (15 mL) and water (15 mL) were added. Then, the mixture was stirred in an oil bath preheated to 75 캜 for 16 hours. When the reaction was complete, remove all of the ethanol from the rotary evaporator and work up with water and hexane. Combined organic layers were dried over MgSO ₄ and remove all the solvent. The crude mixture was purified by silica gel short column to obtain 5- ( tert- butyl) -6-methoxy-2-methyl-7-phenyl- 1H- indene (3.1 g, 57%, colorless oil) .

^{1 H NMR (500 MHz, CDCl} 3, 7.24 ppm): 1.45 (9H, s), 2.07 (3H, s), 3.13 (2H, s), 6.45 (1H, s), 7.23 (1H, s), 7.35 (1H, t), 7.44 (2H, t), 7.49 (2H, d)

Synthesis of (6- (tert-butoxy) hexyl) bis (6- (tert-butyl) -5-methoxy-2-methyl-4-phenyl-1H-inden-

Put 5- (tert -butyl) -6-methoxy -2-methyl-7-phenyl-1 H -indene (4.65mmol, 1.4g), CuCN (0.23mmol, 0.02g) in 50mL Schlenk flask made argon state gave. When the argon state was established, anhydrous toluene (13.5 mL) and anhydrous THF (1.5 mL) were added and cooled to -25 ° C. n- BuLi (2.5 M in Hexane, 0.8 mmol, 2.00 mL) was slowly poured into the flask. When the flask was completely poured into the flask, the flask was heated to room temperature and stirred for 3 hours. When stirring was completed, the mixture was cooled to -25 ° C again, and a 6- (tert-butoxy) hexyl dichloro (methyl) silane (2.32 mmol, 0.63 g) was poured into the flask with one shot and stirred for 16 hours. Work up with MTBE and water and collect organic layers to remove solvent. Hexane) bis (6- (tert-butyl) -5-methoxy-2-methyl-4-phenyl-1H-inden-1-yl) (methyl) silane ligand as a silica column (1.3 g, 71%, light yellow solid).

¹ H NMR (500 MHz, CDCl ₃ , 7.24 ppm): {-0.07 (d), 0.04 (s) (3H)}, 0.40-1.50 (10H, m), 1.15 m), 1.88 (d), 2.06 (d) (6H)}, 3.21 (6H, s), 3.25-3.52 (2H, m), 6.29-6.43 (2H, m), 7.31-7.49 )

(3) Synthesis of 6- (tert-butoxy) hexyl (methyl) silanyl-bis (6- tert -butyl) -5-methoxy-2-methyl-4-phenyl-1-indenyl) zirconium dichloride Synthesis of

t-Butylamine (88 μL, 0.84 mmol) was dissolved in toluene (2 mL) and THF (68 μL) in a 50 mL Schlenk flask under argon. The temperature was lowered to -30 ° C, n- BuLi (1.6M in Hexane, 0.53mL) was added, and the mixture was stirred for 3 hours.

Then, ZrCl ₄ (THF) ₂ (289 mg, 0.77 mmol) was added to another Schlenk flask under argon, toluene (1 mL) was added, and the mixture was stirred in a slurry state. The temperature was reduced to -30 &lt; 0 &gt; C and stirred. Then, Li-t-butylamide prepared above was added to a flask containing ZrCl ₄ (THF) ₂ through a cannula, washed with toluene (1 mL), and stirred at room temperature for 3 hours.

Then, another ligand compound (600 mg, 0.77 mmol) prepared in the above (1) was added to another Schlenk flask under argon, and toluene (1.2 mL) and THF (0.12 mL) were dissolved therein. The temperature was lowered to -30 ° C and n- BuLi (1.6 M in Hexane, 1.0 mL) was added, followed by stirring at room temperature for 3 hours. After stirring at room temperature, the temperature was lowered to -30 ° C and the above-prepared solution of ZrCl ₃ (THF) ₂ NHtBu was injected through the cannula. After the addition was completed, the temperature was raised to room temperature and stirred overnight. After the reaction was terminated, the reaction was filtered to remove the solid and cooled to 0 &lt; 0 &gt; C. HCl (2M in ethylether, 0.38 mL) was added to the solution, and the mixture was stirred at room temperature for 2 hours. After the reaction was completed, it was dried under reduced pressure. The pentane was added to the solid obtained, and the material was removed by filtration. The obtained pentane solution was stored in a refrigerator and recrystallized. The precipitate was filtered to obtain an orange solid (6- (tert-butoxy) hexyl) (methyl) silanyl-bis (6- (tert- butyl) -5- methoxy- 2-methyl-4- phenyl- 1-indenyl) zirconium dichloride (126 mg, 17%).

^{1 H NMR (500 MHz, CDCl} 3, 7.24 ppm): 1.20 (9H, s), 1.29 (3H, s), 1.39 (18H, s), 1.42 ~ 1.90 (10H, m), 2.16 (6H, s) , 3.37 (2H, t), 3.40 (6H, s), 6.59 (2H, s), 7.26-7.62

(4) Preparation of supported catalyst

Silica gel (3 g) was placed in a 250 mL Schlenk flask under argon and methylaluminoxane (MAO; 23 mL, 30 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 (25 mL) was added, stirred for 1 minute, left to stand for 20 minutes, and the solvent was decanted with a cannula. Then, the metallocene compound (180 μmol) prepared in the above (3) was dissolved in toluene (20 mL), and the flask was transferred using a cannula and washed with toluene (5 mL). 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 (25 mL) was added, stirred for 1 minute, left for 10 minutes, and the solvent was decanted with a cannula twice. In the same manner, hexane (25 mL) was added, stirred for 1 minute, left to stand for 20 minutes, the solvent was decanted with a cannula and dried under vacuum overnight. Lt; RTI ID = 0.0 &gt; 45 C &lt; / RTI &gt; for 4 hours.

< Comparative Example  1>

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

First, 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 over 3 hours, And the mixture was stirred at room temperature for 3 hours. After separating the transparent organic layer from the mixed solution, the separated transparent organic layer was vacuum-dried to remove excess trichloromethylsilane to obtain transparent liquid (6-t-butoxyhexyl) dichloromethylsilane.

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

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)

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

To a 50 mL of the previously prepared (6-tert-butoxyhexyl) (methyl) bis (2-methyl-4-phenyl) indenylsilane ether / hexane = 1/1 solution (3.37 mmol) M in hexane) was slowly added dropwise at -78 ° C, stirred at room temperature for about 2 hours, and then vacuum-dried. The salt was washed with hexane and then filtered and vacuum dried to give 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 NC ₅ H ₆ ) Cl ₂ (C ₄ H ₈ O) ₂ ] was weighed into a shrinking flask, ether was slowly added dropwise at -78 ° C., and the mixture was stirred at room temperature for one day. Thereafter, the red reaction solution was separated by filtration, 4 equivalents of a 1 M solution of HCl in ether was slowly added dropwise at -78 ° C, and the mixture was stirred at room temperature for 3 hours. Filtration and vacuum drying afforded the anthra-metallocene compound as an orange solid in 85% yield (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

(3) Preparation of supported catalyst

([(6-t-butoxyhexylmethylsilane-diyl) -bis (2-methyl-4-phenylindenyl)] zirconium dichloride synthesized in the same manner as in Example 4, ) Was used to prepare a silica-supported metallocene catalyst.

< Comparative Example  2>

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

21.8 mL of a n-butyllithium solution (2.5 M, hexane solvent) was slowly added dropwise to 77 mL of 2-methyl-4-phenylindene toluene / THF = 10/1 solution (49.5 mmol) at 0 ° C, And the mixture was stirred at room temperature for one day. Thereafter, 2.98 mL of dichloromethylsilane was slowly added dropwise at 0 DEG C or lower, stirred for about 10 minutes, then heated to 80 DEG C and stirred for 1 hour. The organic layer was separated by adding water, and the silica column was purified and vacuum dried to obtain a sticky yellow oil (yield: racemic: meso = 1: 1).

_{^{1 H NMR (500MHz, CDCl 3}} , 7.24ppm): 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

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

10.9 mL of a n-butyllithium solution (2.5 M in hexane) was slowly added dropwise to 240 mL of a dimethyl bis (2-methyl-4-phenylindenyl) silane ether / hexane = 1/1 solution (12.4 mmol) . Thereafter, the mixture was stirred at room temperature for one day, filtered and vacuum dried to obtain a pale yellow solid. The ligand salt synthesized in a glove box and bis (N, N'-diphenyl-1,3-propanediamido) dichloro zirconium bis (tetrahydrofuran) were dissolved in a Schlenk flask ), Ether was slowly added dropwise at -78 ° C, and the mixture was stirred at room temperature for one day. The red solution was separated by filtration, dried in vacuo, and a toluene / ether = 1/2 solution was added to obtain a clear red solution. 1.5-2 equivalent of HCl ether solution (1M) was slowly added dropwise at -78 deg. C, followed by stirring at room temperature for 3 hours. After filtration and vacuum drying, the catalyst of orange solid component 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 , 7.43 (4H, t), 7.60 (4H, d), 7.64 (2H, d)

< Experimental Example >

(1) homopolymerization of propylene

The 2 L stainless steel reactor was vacuum dried at 65 占 폚, cooled, and then 1.5 mmol of triethylaluminum, 2 bar of hydrogen and 770 g of propylene were sequentially added at room temperature. After stirring for 10 minutes, 0.048 g of each metallocene catalyst prepared in the above Examples and Comparative Examples was dissolved in 20 mL of TMA-prescribed hexane and introduced into the reactor under a nitrogen pressure. The temperature of the reactor was then slowly raised to 70 ° C and then polymerized for 1 hour. After the completion of the reaction, unreacted propylene was bubbled.

(2) Random polymerization of propylene

The 2 L stainless steel reactor was vacuum dried at 65 占 폚, cooled, and then 1.5 mmol of triethylaluminum and 770 g of propylene were sequentially introduced at room temperature. After stirring for 10 minutes, 0.048 g of each metallocene catalyst prepared in the above Examples and Comparative Examples was dissolved in 20 mL of TMA-prescribed hexane and introduced into the reactor under a nitrogen pressure. After 15 g of ethylene was added, the temperature of the reactor was slowly raised to 70 ° C., and the reactor was polymerized for 1 hour. After completion of the reaction, unreacted propylene and ethylene were vented.

(3) Method of measuring physical properties of polymer

1) Catalytic activity: Calculated as the ratio of the weight of polymer produced (kg PP) per unit time (h) to the catalyst content (mmol and g of catalyst) used.

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

3) Melt Flow Rate (MFR): Measured under the conditions of a load of 230 kg and a load of 2.16 kg according to ASTM D-1238.

(4) Measurement results of physical properties of polymer

The homo and random polymerization process conditions and physical properties of polypropylene produced using the metallocene supported catalysts prepared in Examples and Comparative Examples were measured and the results are shown in Table 1 (homopolymerization) and Table 2 ).

Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Amount of supported catalyst (mg) 45 45 45 60 240 Hydrogen (ppm) 0 372 703 372 372 Yield (g) 92 463 396 428 78 Activity (kg / gCat · hr) 2 10.3 8.8 7.1 0.32 MFR <1 0.8 6.6 9.8 Tm (占 폚) 142.2 144.8 145.5 148.7

Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Amount of supported catalyst (mg) 23 23 23 45 60 Hydrogen (ppm) 0 372 703 0 0 Yield (g) 145 456 479 433 505 Activity (kg / gCat · hr) 6.3 19.8 20.8 9.6 8.4 MFR 0.09 1.3 5.0 19.6 12.6 Tm (占 폚) 131.6 139.2 140.4 139.9 140.3

As shown in the above Tables 1 and 2, the metallocene compound having a specific substituent group in the indene group and the bridge group as a supported catalyst according to this embodiment exhibited substantially higher activity in the production of the polyolefin And it was confirmed that a polymer exhibiting a low melt flow index (MFR) and high molecular weight can be produced.

Claims (11)

A ligand compound represented by the following formula (1):
[Chemical Formula 1]

In Formula 1,
R ₁ is a C _6-20 aryl substituted with C _6-20 aryl or C _1-20 alkyl,
R ₂ is C _1-20 alkoxy,
R ₃ is C _1-20 alkyl,
R ₄ is hydrogen, halogen, C _1-20 alkyl, C _2-20 alkenyl, C _1-20 alkylsilyl, C _1-20 alkyl silyl, C _1-20 alkoxysilyl, C _1-20 ether, C _{1- 20} silyl ether, C _1-20 alkoxy, C _6-20 aryl, C _7-20 alkylaryl, or C _7-20 arylalkyl,
A is carbon, silicon or germanium,
R ₅ is C _1-20 alkyl substituted by C _1-20 alkoxy,
R ₆ is hydrogen, C _1-20 alkyl or C _2-20 alkenyl.
The method according to claim 1,
Wherein R ₁ is a ligand compound, it characterized in that the phenyl is substituted by phenyl or C _1-10 alkyl.
The method according to claim 1,
Wherein R &lt; ₂ &gt; is methoxy.
The method according to claim 1,
Wherein R ₃ is a ligand compound, characterized in that C _1-4 alkyl.
The method according to claim 1,
Said R &lt; ₅ &gt; is 6-tert-butoxy-hexyl and R &lt; ₆ &gt; is methyl.
2. The compound according to claim 1, wherein the compound represented by the formula (1) is a ligand compound represented by the following structural formula:

,

,

,

A metallocene compound represented by the following formula (2): &lt; EMI ID =
(2)

In Formula 2,
R ₁ is a C _6-20 aryl substituted with C _6-20 aryl or C _1-20 alkyl,
R ₂ is C _1-20 alkoxy,
R ₃ is C _1-20 alkyl,
R ₄ is hydrogen, halogen, C _1-20 alkyl, C _2-20 alkenyl, C _1-20 alkylsilyl, C _1-20 alkyl silyl, C _1-20 alkoxysilyl, C _1-20 ether, C _{1- 20} silyl ether, C _1-20 alkoxy, C _6-20 aryl, C _7-20 alkylaryl, or C _7-20 arylalkyl,
A is carbon, silicon or germanium,
R ₅ is C _1-20 alkyl substituted by C _1-20 alkoxy,
R ₆ is hydrogen, C _1-20 alkyl or C _2-20 alkenyl,
M is a Group 4 transition metal compound,
Each X independently represents a halogen or an alkyl group having 1 to 20 carbon atoms.
8. The method of claim 7,
Wherein M is zirconium and X is chloro.
8. The method of claim 7,
The compound represented by Formula 2 is a metallocene compound represented by the following structural formula:

,

,

,

A catalyst composition for olefin polymerization comprising a metallocene compound represented by the general formula (2) of claim 7 and a cocatalyst.
A process for producing an olefin polymer, comprising the step of polymerizing an olefin monomer in the presence of the catalyst composition for olefin polymerization of claim 10.