KR102124102B1 - Supported hybrid catalyst and method for preparing of olefin based polymer using the same - Google Patents

Abstract

The present invention relates to a hybrid supported catalyst for producing an olefin-based polymer having a high activity and exhibiting high activity, and a method for producing the olefin-based polymer using the same.

Description

Hybrid supported catalyst and manufacturing method of olefin polymer using the same{SUPPORTED HYBRID CATALYST AND METHOD FOR PREPARING OF OLEFIN BASED POLYMER USING THE SAME}

The present invention relates to a hybrid supported catalyst for producing an olefin-based polymer exhibiting a high activity catalyst and having a low melting temperature, and a method for producing the olefin-based polymer using the same.

Olefin polymerization catalyst systems can be classified into Ziegler-Natta and metallocene catalyst systems, and these two highly active catalyst systems have been developed to suit each characteristic. The Ziegler Natta catalyst has been widely applied to existing commercial processes since it was invented in the 50s, but because it is a multi-site catalyst with multiple active sites, the molecular weight distribution of the polymer is characterized by a wide range of comonomers. There is a problem that there is a limit to securing desired physical properties because the distribution is not uniform.

The metallocene catalyst is composed of a combination of a main catalyst having a transition metal compound as a main component and a cocatalyst having an organometallic compound having aluminum as a main component. Such a catalyst is a homogeneous complex catalyst and is a single site catalyst. The molecular weight distribution is narrow according to the properties of a single active point, a polymer having a uniform composition distribution of a comonomer is obtained, and the stereoregularity, copolymerization characteristics, molecular weight, crystallinity, etc. of the polymer are changed according to modification of the ligand structure and polymerization conditions of the catalyst. It has the characteristics that can change the.

On the other hand, the ansa-metallocene (ansa-metallocene) compound is an organometallic compound comprising two ligands connected to each other by a bridge group, the rotation of the ligand is prevented by the bridge group, and the metal center Activity and structure are determined.

Such ansa-metallocene compounds are used as catalysts in the production of olefinic homopolymers or copolymers. In particular, the ansa-metallocene compound containing a cyclopentadienyl-fluorenyl ligand is capable of producing high molecular weight polyethylene, through which it is known that the microstructure of polypropylene can be controlled. have. In addition, it is known that an ansa-metallocene compound containing an indenyl ligand has excellent activity and can produce an olefin-based polymer with improved stereoregularity.

The present inventors have disclosed a novel structured ansa-metallocene compound capable of providing various selectivities and activities for olefinic polymers in Korean Patent Publication No. 10-2013-0125311.

On the other hand, in the case of having an bis-indenyl-ligand in an ansa-metallocene catalyst, depending on the steric arrangement of the two ligands, two forms, namely racemate and mirror-symmetrical meso diastereomer (mirror-) symmetric meso diastereomers) can be formed. In the case of racemates, it is preferred because it produces an isotactic polymer having a high crystallinity and melting point and a high specific gravity and mechanical strength, whereas a mirror-symmetrical meso diastereomer is an atactic polymer. It is a catalyst that should be avoided because it is manufactured. However, in the process of preparing the ansa-metallocene catalyst, the structure of the ansa-metallocene catalyst in which the racemate can be excessively produced is important because the racemate and the mirror-symmetric mesodiastereomer are simultaneously produced. Should be considered.

Accordingly, the present inventors, while exhibiting activity equivalent to or higher than that of a conventional catalyst, while performing various studies on a catalyst capable of producing an olefin-based polymer having a wide molecular weight distribution (PDI) to exhibit high processability, When preparing an olefin-based polymer using a hybrid supported catalyst comprising two types of catalysts having the structure as described in the specification of the present invention, it was confirmed that it can be satisfied at the same time to complete the present invention.

The present invention is to provide a hybrid supported catalyst capable of producing an olefin-based polymer having a wide molecular weight distribution (PDI) with high activity.

In addition, the present invention is to provide a method for producing an olefin-based polymer using the hybrid supported catalyst.

In order to solve the above problems, the present invention is at least one first metallocene compound represented by Formula 1 below; At least one second metallocene compound selected from compounds represented by the following Chemical Formula 2, Chemical Formula 3, or Chemical Formula 4; And it provides a hybrid supported catalyst comprising a carrier.

[Formula 1]

In Chemical Formula 1,

M ¹ is a Group 4 transition metal,

X ¹ and X ² are the same or different from each other and are each independently halogen,

A ¹ is carbon, silicon or germanium,

R ¹ is aryl having 6 to 20 carbons substituted with alkyl having 1 to 20 carbons,

R ² , R ³ and R ⁴ are the same or different from each other, and each independently hydrogen, halogen, alkyl having 1 to 20 carbons, alkylsilyl having 1 to 20 carbons, silylalkyl having 1 to 20 carbons, alkoxy having 1 to 20 carbons Silyl, ether having 1 to 20 carbons, silyl ether having 1 to 20 carbons, aryl having 6 to 20 carbons, alkylaryl having 7 to 20 carbons, or arylalkyl having 7 to 20 carbons,

R ⁵ is alkyl having 1 to 20 carbons substituted with alkoxy having 1 to 20 carbons,

R ⁶ is hydrogen, alkyl having 1 to 20 carbons,

[Formula 2]

In Chemical Formula 2,

M ² is a Group 4 transition metal,

X ³ and X ⁴ are the same as or different from each other, and each independently halogen.

A ² is carbon, silicon or germanium,

R ⁷ is alkyl having 1 to 20 carbons substituted with alkoxy having 1 to 20 carbons,

R ⁸ is hydrogen, alkyl having 1 to 20 carbons, alkyl aryl having 7 to 30 carbons, arylalkyl having 7 to 30 carbons, or aryl having 6 to 30 carbons,

R ⁹ and R ¹⁰ are the same as or different from each other, and each independently hydrogen or alkyl having 1 to 20 carbons,

[Formula 3]

In Chemical Formula 3,

M ³ is a Group 4 transition metal,

X ⁵ and X ⁶ are the same as or different from each other, and each independently halogen.

A ³ is carbon, silicon or germanium,

R ¹¹ is alkyl having 1 to 20 carbons substituted with alkoxy having 1 to 20 carbons,

R ¹² is hydrogen, alkyl having 1 to 20 carbons, alkyl aryl having 7 to 30 carbons, arylalkyl having 7 to 30 carbons, or aryl having 6 to 30 carbons,

R ¹³ and R ¹⁴ are the same as or different from each other, and each independently hydrogen and alkyl having 1 to 20 carbons,

R ¹⁵ and R ¹⁶ are the same or different from each other, and each independently is aryl having 6 to 20 carbons, substituted with alkyl having 1 to 20 carbons.

[Formula 4]

In Chemical Formula 4,

M ⁴ is a Group 4 transition metal,

X ⁷ and X ⁸ are the same or different from each other, each independently halogen.

A ⁴ is carbon, silicon or germanium,

R ¹⁷ is aryl having 6 to 20 carbons or aryl having 6 to 20 carbons substituted with alkyl having 1 to 20 carbons,

R ¹⁸ is alkoxy having 1 to 20 carbon atoms,

R ¹⁹ is alkyl having 1 to 20 carbons,

R ²⁰ is hydrogen, halogen, alkyl having 1 to 20 carbons, alkylsilyl having 1 to 20 carbons, silylalkyl having 1 to 20 carbons, alkoxysilyl having 1 to 20 carbons, ether having 1 to 20 carbons, carbon having 1 to 20 carbons Silyl ether, alkoxy having 1 to 20 carbons, aryl having 6 to 20 carbons, alkylaryl having 7 to 20 carbons, or arylalkyl having 7 to 20 carbons,

R ²¹ is alkyl having 1 to 20 carbons substituted with alkoxy having 1 to 20 carbons,

R ²² is hydrogen, alkyl having 1 to 20 carbons.

In addition, the present invention provides a method for producing an olefin-based polymer using the hybrid supported catalyst.

The hybrid supported catalyst according to the present invention has high catalytic activity and exhibits low process temperature (Tm), high melt flow rate ratio (MFRR), and wide molecular weight distribution (PDI) when producing an olefin-based polymer using it, thereby exhibiting high processability. Branches can easily produce olefinic polymers.

The terminology used herein is only used to describe exemplary embodiments, and is not intended to limit the present invention. Singular expressions include plural expressions unless the context clearly indicates otherwise.

The present invention can be applied to various changes and may have various forms, and specific embodiments will be illustrated and described in detail below. However, this is not intended to limit the present invention to a specific disclosure form, and it should be understood that it includes all modifications, equivalents, and substitutes included in the spirit and scope of the present invention.

Hereinafter, a hybrid supported catalyst according to a specific embodiment of the present invention and a method for preparing an olefin-based polymer using the hybrid supported catalyst will be described.

The hybrid supported catalyst according to an embodiment of the present invention includes at least one first metallocene compound represented by Formula 1 below; At least one second metallocene compound selected from compounds represented by the following Chemical Formula 2, Chemical Formula 3, or Chemical Formula 4; And carriers:

[Formula 1]

In Chemical Formula 1,

M ¹ is a Group 4 transition metal,

X ¹ and X ² are the same or different from each other and are each independently halogen,

R ¹ is aryl having 6 to 20 carbons substituted with alkyl having 1 to 20 carbons,

R ² , R ³ and R ⁴ are the same or different from each other, and each independently hydrogen, halogen, alkyl having 1 to 20 carbons, alkylsilyl having 1 to 20 carbons, silylalkyl having 1 to 20 carbons, alkoxy having 1 to 20 carbons Silyl, ether having 1 to 20 carbons, silyl ether having 1 to 20 carbons, aryl having 6 to 20 carbons, alkylaryl having 7 to 20 carbons, or arylalkyl having 7 to 20 carbons,

A ¹ is carbon, silicon or germanium,

R ⁵ is alkyl having 1 to 20 carbons substituted with alkoxy having 1 to 20 carbons,

R ⁶ is hydrogen, alkyl having 1 to 20 carbons,

[Formula 2]

In Chemical Formula 2,

M ² is a Group 4 transition metal,

X ³ and X ⁴ are the same as or different from each other, and each independently halogen.

A ² is carbon, silicon or germanium,

R ⁷ is alkyl having 1 to 20 carbons substituted with alkoxy having 1 to 20 carbons,

R ⁸ is hydrogen, alkyl having 1 to 20 carbons, alkyl aryl having 7 to 30 carbons, arylalkyl having 7 to 30 carbons, or aryl having 6 to 30 carbons,

R ⁹ and R ¹⁰ are the same or different from each other, and each independently is hydrogen or alkyl having 1 to 20 carbon atoms,

[Formula 3]

In Chemical Formula 3,

M ³ is a Group 4 transition metal,

X ⁵ and X ⁶ are the same as or different from each other, and each independently halogen.

A ³ is carbon, silicon or germanium,

R ¹¹ is alkyl having 1 to 20 carbons substituted with alkoxy having 1 to 20 carbons,

R ¹² is hydrogen, alkyl having 1 to 20 carbons, alkyl aryl having 7 to 30 carbons, arylalkyl having 7 to 30 carbons, or aryl having 6 to 30 carbons,

R ¹³ and R ¹⁴ are the same as or different from each other, and each independently hydrogen and alkyl having 1 to 20 carbons,

R ¹⁵ and R ¹⁶ are the same or different from each other, and each independently is aryl having 6 to 20 carbons, substituted with alkyl having 1 to 20 carbons.

[Formula 4]

In Chemical Formula 4,

M ⁴ is a Group 4 transition metal,

X ⁷ and X ⁸ are the same or different from each other, each independently halogen.

A ⁴ is carbon, silicon or germanium,

R ¹⁷ is aryl having 6 to 20 carbons or aryl having 6 to 20 carbons substituted with alkyl having 1 to 20 carbons,

R ¹⁸ is alkoxy having 1 to 20 carbon atoms,

R ¹⁹ is alkyl having 1 to 20 carbons,

R ²⁰ is hydrogen, halogen, alkyl having 1 to 20 carbons, alkylsilyl having 1 to 20 carbons, silylalkyl having 1 to 20 carbons, alkoxysilyl having 1 to 20 carbons, ether having 1 to 20 carbons, carbon having 1 to 20 carbons Silyl ether, alkoxy having 1 to 20 carbons, aryl having 6 to 20 carbons, alkylaryl having 7 to 20 carbons, or arylalkyl having 7 to 20 carbons,

R ²¹ is alkyl having 1 to 20 carbons substituted with alkoxy having 1 to 20 carbons,

R ²² is hydrogen, alkyl having 1 to 20 carbons.

In the present specification, unless otherwise specified, the following terms may be defined as follows.

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

The alkyl having 1 to 20 carbons may be straight chain, branched chain or cyclic alkyl. Specifically, alkyl having 1 to 20 carbons is linear alkyl having 1 to 20 carbons; Straight-chain alkyl having 1 to 10 carbon atoms; Straight-chain alkyl having 1 to 5 carbon atoms; Branched or cyclic alkyl having 3 to 20 carbon atoms; Branched or cyclic alkyl having 3 to 15 carbons; Or it may be a branched or cyclic alkyl having 3 to 10 carbon atoms. More specifically, alkyl having 1 to 20 carbon atoms is methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, tert-butyl group, n-pentyl group, iso-pentyl group or Cyclohexyl group, and the like.

The alkenyl having 2 to 20 carbon atoms may be straight chain, branched chain or cyclic alkenyl. Specifically, alkenyl having 2 to 20 carbon atoms includes straight alkenyl having 2 to 20 carbon atoms, straight alkenyl having 2 to 10 carbon atoms, straight alkenyl having 2 to 5 carbon atoms, branched alkenyl having 3 to 20 carbon atoms, and 3 carbon atoms. It may be a branched chain alkenyl having 15 to 15, a branched chain alkenyl having 3 to 10 carbons, a cyclic alkenyl having 5 to 20 carbons, or a cyclic alkenyl having 5 to 10 carbons. More specifically, alkenyl having 2 to 20 carbon atoms may be ethenyl, propenyl, butenyl, pentenyl or cyclohexenyl.

Aryl having 6 to 30 carbon atoms may mean a monocyclic, bicyclic or tricyclic aromatic hydrocarbon. Specifically, aryl having 6 to 30 carbon atoms may be a phenyl group, a naphthyl group, or anthracenyl group.

The alkylaryl having 7 to 30 carbon atoms may mean a substituent in which one or more hydrogens of aryl are substituted by alkyl. Specifically, the alkylaryl having 7 to 30 carbon atoms may be methylphenyl, ethylphenyl, n-propylphenyl, iso-propylphenyl, n-butylphenyl, iso-butylphenyl, tert-butylphenyl, or cyclohexylphenyl.

Arylalkyl having 7 to 30 carbon atoms may mean a substituent in which one or more hydrogens of alkyl are substituted by aryl. Specifically, arylalkyl having 7 to 30 carbon atoms may be a benzyl group, phenylpropyl or phenylhexyl.

In the case of using a hybrid supported catalyst in which the first metallocene compound of Formula 1 and the second metallocene compound of Formulas 2 to 4 are supported together, a low melting temperature (Tm), a wide molecular weight distribution (PDI), and high cost The olefin polymer exhibiting porosity can be produced with high activity.

The first metallocene compound of Chemical Formula 1 has an ansa-metallocene structure and includes two indenyl groups as ligands. In particular, a functional group capable of acting as a Lewis base as an oxygen-donor is substituted in a bridge group connecting the ligand, thereby maximizing activity as a catalyst.

In addition, since a bulky group such as an aryl group having 6 to 20 carbon atoms (R ¹ ) substituted with an alkyl group having 1 to 20 carbon atoms is substituted, it imparts a steric hindrance to suppress the formation of mesoforms. do. Accordingly, when the first metallocene compound represented by Chemical Formula 1 is supported on a carrier and used as a catalyst in the production of polyolefin, it is highly active and polyolefin having desired physical properties can be more easily produced.

In Chemical Formula 1, preferably R ¹ may be phenyl substituted with tert-butyl, and more preferably, R ¹ may be 4-tert-butyl-phenyl.

Also preferably, M ¹ may be hafnium (Hf) or zirconium (Zr), and X ¹ and X ² may be chloro (Cl).

Also preferably, R ² , R ³ and R ⁴ may be hydrogen.

Also preferably, A ¹ may be silicon.

Also preferably, R ⁵ may be 6-tert-butoxy-hexyl, and R ⁶ may be methyl.

Representative examples of the first metallocene compound represented by Chemical Formula 1 are as follows, but the present invention is not limited thereto:

In addition, the first metallocene compound represented by Formula 1 may be prepared by the same method as in Scheme 1 below, but the present invention is not limited thereto.

[Scheme 1]

Step 1 (Step 1) is a step of preparing a compound represented by Formula 1-4 by reacting the compound represented by Formula 1-3 with the compound represented by Formula 1-3. It is preferable to use alkyl lithium (for example, n-butyl lithium) for the reaction, and the reaction temperature is -200 to 0°C, more preferably -150 to 0°C. As the solvent, toluene, THF, or the like can be used. In this case, after separating the organic layer from the product, the step of vacuum drying the separated organic layer and removing excess reactants may be further performed.

Step 2 (Step 2) is a step of preparing a compound represented by Formula 1 by reacting the compound represented by Formula 1-5 with the compound represented by Formula 1-4. It is preferable to use alkyl lithium (for example, n-butyl lithium) for the reaction, and the reaction temperature is -200 to 0°C, more preferably -150 to 0°C. As the solvent, ether, hexane, or the like can be used.

Of the second metallocene compound, the second metallocene compound represented by Formula 2 includes two benzoindenyl groups as ligands, and a bridge group connecting the two ligands. Oxygen-donor (oxygen-donor) has a structure containing a functional group that can act as a Lewis base. For example, when the compound of Formula 2 having such a specific structure is activated and supported on a carrier in an appropriate manner and used as a polymerization catalyst for an olefin monomer, it exhibits a low melting temperature (Tm) and a high melting index (MFR), thereby processing or molding. At this time, an olefin polymer having an excellent energy saving effect can be produced. In particular, this effect can be maximized during polymerization of propylene.

More specifically, in the second metallocene compound represented by Chemical Formula 2, the benzoindenyl ligand may be unsubstituted or substituted with a substituent having little steric hindrance. Thereby, an olefin polymer having a desired steric structure can be easily produced while exhibiting good catalytic activity.

For example, R ⁹ and R ¹⁰ in Chemical Formula 2 may be independently hydrogen or straight chain alkyl having 1 to 5 carbon atoms.

In addition, the bridge group connecting the benzoindenyl ligand in Chemical Formula 2 may affect the loading stability of the metallocene compound.

For example, for improved loading efficiency, R ⁷ in Formula 2 is alkyl substituted with branched chain alkoxy having 3 to 6 carbon atoms, and may be preferably 6-tert-butoxy-hexyl.

Further, R ⁸ , R ⁹ , and R ¹⁰ are straight-chain alkyl having 1 to 6 carbon atoms, and may preferably be methyl.

Also preferably, M ² may be hafnium (Hf) or zirconium (Zr), and X ³ and X ⁴ may be chloro (Cl).

Also preferably, A ² may be silicon.

Representative examples of the compound represented by Formula 2 are as follows, but the present invention is not limited thereto.

,

,

In addition, the second metallocene compound represented by Formula 2 may be prepared by the same method as in Scheme 2 below, but the present invention is not limited thereto.

[Scheme 2]

Step 1 (Step 1) is a step of preparing a compound represented by Formula 2-4 by reacting a compound represented by Formula 2-3 with a compound represented by Formula 2-1 and 2-2. It is preferable to use alkyl lithium (for example, n-butyl lithium) for the reaction, and the reaction temperature is -200 to 0°C, more preferably -150 to 0°C. As the solvent, toluene, THF, or the like can be used. In this case, after separating the organic layer from the product, the step of vacuum drying the separated organic layer and removing excess reactants may be further performed.

Step 2 (Step 2) is a step of preparing a compound represented by Formula 2 by reacting the compound represented by Formula 2-5 with the compound represented by Formula 2-4. It is preferable to use alkyl lithium (for example, n-butyl lithium) for the reaction, and the reaction temperature is -200 to 0°C, more preferably -150 to 0°C. As the solvent, ether, hexane, or the like can be used.

Among the second metallocene compounds, the second metallocene compound represented by Chemical Formula 3 includes two 2-(2-furyl)indenes as ligands, and a bridge group connecting two ligands. Oxygen-donor (oxygen-donor) has a structure containing a functional group that can act as a Lewis base. In the case of the conventional metallocene catalyst precursor, the meso compounds and racemic mixtures were generated at almost the same ratio as the selectivity for each stereoisomer was similar during synthesis. However, the metallocene compound of Formula 3 according to the above embodiment exhibits high selectivity for optical isomers when synthesized by the specific stereostructure described above, thereby obtaining a racemic mixture. In addition, it was confirmed that the metallocene compound of Chemical Formula 3 having a specific three-dimensional structure described above has excellent hydrogen reactivity and thus can provide an olefin polymer having a high fluidity compared to a conventional catalyst with the same amount of hydrogen. That is, by using the metallocene compound of Chemical Formula 3 having a specific three-dimensional structure described above, it is possible to easily produce a highly fluid olefin polymer that is very suitable for producing melt blown fibers.

Specifically, in the second metallocene compound represented by Chemical Formula 3, the 4-position of 2-(2-furyl)indene may be substituted with a substituent having a large steric hindrance. The metallocene compound having such a structure may exhibit excellent catalytic activity while exhibiting good structural stability. For example, in Formula 3, R ¹⁵ and R ¹⁶ may each independently be substituted phenyl with tert-butyl, and more preferably, R ¹⁵ and R ¹⁶ may be 4-tert-butyl-phenyl.

In the second metallocene compound represented by Chemical Formula 3, the fifth position of furyl may be unsubstituted or substituted with alkyl having 1 to 20 carbons. More specifically, the fifth position of the furyl may be replaced with a substituent having a small steric hindrance to further improve structural stability. For example, in Formula 3, R ¹³ and R ¹⁴ may each independently be any one of straight chain alkyl having 1 to 3 carbon atoms, preferably methyl.

In addition, the bridge group connecting 2-(2-furyl)indene in Chemical Formula 3 may affect the loading stability of the metallocene compound. For example, for improved loading efficiency, R ¹¹ in Formula 3 is alkyl substituted with branched chain alkoxy having 3 to 6 carbon atoms, and may be preferably 6-tert-butoxy-hexyl. Further, R ¹² in Chemical Formula 3 is a straight chain alkyl having 1 to 6 carbon atoms, and preferably may be methyl.

Also preferably, M ³ may be hafnium (Hf) or zirconium (Zr), and X ⁵ and X ⁶ may be chloro (Cl).

Also preferably, A ³ may be silicon.

Representative examples of the second metallocene compound represented by Chemical Formula 3 are as follows, but the present invention is not limited thereto:

The compound represented by Chemical Formula 3 may be synthesized using known synthetic reactions, and detailed examples of synthesis may be referred to examples described later.

Of the second metallocene compound, the metallocene compound represented by Chemical Formula 4 has a crosslinked structure in which two indene groups are connected by carbon, silicon, or germanium bridges, in particular, an aryl group at a specific position of the indene group , Introduced into a functional group such as an alkyl group, an alkoxy group, etc., the metallocene compound may exhibit high activity during olefin polymerization, and in particular, a high molecular weight polyolefin having a low melt flow index (MFR) may be prepared.

In addition, in the second metallocene compound of Chemical Formula 4 of the above embodiment, R ¹⁷ is preferably phenyl or phenyl substituted with alkyl having 1 to 10 carbons.

And, it is preferable that R ¹⁸ is methoxy.

Moreover, it is preferable that said R ¹⁹ is C1-C4 alkyl, and it is more preferable that it is tert-butyl.

And, it is preferable that A ⁴ is silicon, R ²¹ is 6-tert-butoxy-hexyl, and R ²² is preferably methyl.

In addition, M ⁴ is zirconium (Zr), and X ⁷ and X ⁸ are preferably chloro (Cl).

On the other hand, as a preferred example of the second metallocene compound represented by Chemical Formula 4, the following compounds may be mentioned.

,

,

,

,

,

,

The second metallocene compound represented by Chemical Formula 4 may be synthesized using known synthetic reactions, and detailed examples of synthesis may be referred to examples described later.

When manufacturing an olefin-based polymer with a conventional metallocene catalyst, there is a difficulty in processing, such as obtaining an olefin-based polymer having a low melting temperature or a high polymerization temperature but having a high polymerization activity instead of decreasing the melting temperature, It is not easy to realize these properties simultaneously with a single metallocene catalyst.

In the hybrid supported catalyst of the present invention, the second metallocene compound represented by Chemical Formulas 2 to 4 is polymerized of a highly processable olefin-based polymer having a high melt flow rate ratio and a large molecular weight distribution (PDI) due to structural specificity. This is possible, but has the disadvantage of relatively low catalytic activity. On the other hand, as in the present invention, there is an advantage that a highly processable olefin polymer can be produced with high activity by using a hybrid supported catalyst carrying the first metallocene compound and the second metallocene compound together. In addition, an olefin-based polymer having an appropriate range of melt index can be obtained to satisfy both processability and mechanical properties.

The molar ratio of the first metallocene compound and the second metallocene compound is about 10:1 to about 2:1, preferably about 3:1 to about, based on the molar ratio of the metal contained in each metal compound It may be 5:1. It can be advantageous in terms of maintaining the activity and economical efficiency of the catalyst by showing the optimum catalyst activity and physical properties in the molar ratio.

In the hybrid supported catalyst according to the present invention, a carrier containing a hydroxy group on the surface may be used as the carrier, and preferably a carrier having a highly reactive hydroxy group and a siloxane group that has been dried to remove moisture on the surface. Can be used. For example, silica dried at high temperature, silica-alumina, and silica-magnesia can be used, and these are usually oxides, carbonates, 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 200 to 800°C, more preferably 300 to 600°C, and most preferably 300 to 400°C. When the drying temperature of the carrier is less than 200°C, there is too much moisture so that the surface moisture and the co-catalyst react, and when it exceeds 800°C, the surface area decreases as the pores of the carrier surface are combined, and there are many hydroxyl groups on the surface. It is not preferable because the reaction site with the co-catalyst decreases because the siloxane group disappears and disappears.

The amount of hydroxy groups on the surface of the carrier is preferably 0.1 to 10 mmol/g, and more preferably 0.5 to 5 mmol/g. The amount of hydroxy groups on the surface of the carrier can be controlled by the method and conditions of the carrier or drying conditions, such as temperature, time, vacuum or spray drying.

When the amount of the hydroxy group is less than 0.1 mmol/g, there are few reaction sites with the cocatalyst, and if it exceeds 10 mmol/g, it is not preferable because it may be due to moisture other than the hydroxy group present on the surface of the carrier particle. not.

In the hybrid supported catalyst according to the present invention, the mass ratio of the catalyst (the first and second metallocene compounds) to the carrier is preferably 1:1 to 1:1000. When the carrier and the catalyst are included in the above mass ratio, it can be advantageous in terms of maintaining the activity and economical efficiency of the catalyst by exhibiting appropriate supported catalyst activity.

The hybrid supported catalyst according to the present invention may further include a cocatalyst in addition to the first metallocene compound represented by Chemical Formula 1 and the second metallocene compound represented by Chemical Formulas 2 to 4. The cocatalyst may include one or more of the cocatalyst compounds represented by the following Chemical Formula 5, Chemical Formula 6 or Chemical Formula 7.

[Formula 5]

-[Al(R')-O] _m-

In Chemical Formula 5,

R'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;

m is an integer of 2 or more;

[Formula 6]

J(R'') ₃

In Chemical Formula 6,

R'' is the same as R'defined in Formula 5 above;

J is aluminum or boron;

[Formula 7]

_{^{[EH] + [ZQ 4]}} - or _{^{[E] + [ZQ 4]}} -

In Chemical Formula 7,

E is a neutral or cationic Lewis base;

H is a hydrogen atom;

Z is a group 13 element;

Q may be the same as or different from each other, and each independently one or more hydrogen atoms are halogen, a hydrocarbon having 1 to 20 carbon atoms, an alkoxy or phenoxy substituted or unsubstituted aryl group having 6 to 20 carbon atoms or an alkyl group having 1 to 20 carbon atoms. .

Examples of the compound represented by the formula (5) include methyl aluminoxane, ethyl aluminoxane, isobutyl aluminoxane, butyl aluminoxane, and more preferred compounds are methyl aluminoxane.

Examples of the compound represented by Chemical Formula 6 include trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, tripropyl aluminum, tributyl aluminum, dimethylchloro aluminum, triisopropyl aluminum, tri-s-butyl aluminum, and tricyclopentyl aluminum. , Tripentyl aluminum, triisopentyl aluminum, trihexyl aluminum, trioctyl aluminum, ethyl dimethyl aluminum, methyl diethyl aluminum, triphenyl aluminum, tri-p-tolyl aluminum, dimethyl aluminum methoxide, dimethyl aluminum ethoxide, trimethyl Boron, triethyl boron, triisobutyl boron, tripropyl boron, tributyl boron, and the like, and more preferable compounds are selected from trimethyl aluminum, triethyl aluminum, and triisobutyl aluminum.

Examples of the compound represented by Chemical Formula 7 include triethylammonium tetraphenylboron, tributylammonium tetraphenylboron, trimethylammonium tetraphenylboron, tripropylammonium tetraphenylboron, and trimethylammoniumtetra(p-tolyl). Boron, trimethylammoniumtetra(o,p-dimethylphenyl)boron, tributylammoniumtetra(p-trifluoromethylphenyl)boron, trimethylammoniumtetra(p-trifluoromethylphenyl)boron, tributylammoniumtetra Pentafluorophenylboron, N,N-diethylanilinium tetraphenylboron, N,N-diethylanilinium tetrapentafluorophenylboron, diethylammonium tetrapentafluorophenylboron, triphenylphosphonium Tetraphenylboron, trimethylphosphoniumtetraphenylboron, triethylammoniumtetraphenylaluminum, tributylammoniumtetraphenylaluminum, trimethylammoniumtetraphenylaluminum, tripropylammoniumtetraphenylaluminum, trimethylammoniumtetra(p-tolyl Aluminium, tripropylammoniumtetra(p-tolyl)aluminum, triethylammoniumtetra(o,p-dimethylphenyl)aluminum, tributylammoniumtetra(p-trifluoromethylphenyl)aluminum, trimethylammoniumtetra( p-trifluoromethylphenyl)aluminum, tributylammonium tetrapentafluorophenylaluminum, N,N-diethylanilinium tetraphenylaluminum, N,N-diethylanilinium tetrapentafluorophenylaluminum, di Ethylammonium tetrapentatetraphenylaluminum, triphenylphosphoniumtetraphenylaluminum, trimethylphosphoniumtetraphenylaluminum, tripropylammoniumtetra(p-tolyl)boron, triethylammoniumtetra(o,p-dimethylphenyl)boron , Tributyl ammonium tetra (p-trifluoromethylphenyl) boron, triphenylcarbonium tetra (p-trifluoromethylphenyl) boron, triphenylcarbonium tetrapentafluorophenyl boron, and the like.

The hybrid supported catalyst according to the present invention is prepared by supporting a cocatalyst compound on a carrier, supporting the first metallocene compound on the carrier, and supporting the second metallocene compound on the carrier. can do.

When preparing the hybrid supported catalyst, a hydrocarbon-based solvent such as pentane, hexane, heptane, or the like, or an aromatic-based solvent such as benzene and toluene may be used. In addition, the metallocene compound and the cocatalyst compound can also be used in a form supported on silica or alumina.

In addition, the present invention provides a method for producing an olefin-based polymer comprising the step of polymerizing an olefin-based monomer in the presence of the hybrid supported catalyst.

In the method for producing an olefin-based polymer according to the present invention, specific examples of the olefin-based monomer are ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1 -Octen, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-eicocene, and the like, and may be copolymerized by mixing two or more of them. Preferably, the olefin-based polymer may be a propylene homopolymer, or a random copolymer of propylene and ethylene.

The polymerization reaction may be carried out by homopolymerizing one olefinic monomer or copolymerizing two or more monomers using one continuous slurry polymerization reactor, loop slurry reactor, gas phase reactor, or solution reactor.

The hybrid supported catalyst is 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, and chlorine atoms such as dichloromethane and chlorobenzene. It can be injected by dissolving or diluting a substituted hydrocarbon solvent. 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 alkyl aluminum, and it is also possible to further use a cocatalyst.

Here, the polymerization may be performed by reacting for 1 to 24 hours under a temperature of 25 to 500°C and a pressure of 1 to 100 kgf/cm 2. At this time, the polymerization reaction temperature is preferably 25 to 200°C, more preferably 50 to 100°C. Further, 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 may control the molecular weight range of the olefin-based polymer finally produced according to hydrogenation or non-addition conditions. In particular, high-molecular-weight olefin-based polymers can be produced under the condition that no hydrogen is added, and low-molecular-weight olefin-based polymers can be produced 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 condition, or supplied at a pressure of 1 bar to 40 bar, or 168 ppm to 8,000 ppm in the hydrogen molar content range compared to the olefinic monomer. Can be supplied.

The olefin-based polymers prepared using the hybrid supported catalysts comprising the first and second metallocenes according to the present invention have olefins having a broader molecular weight distribution (PDI) than when using the conventional metallocene catalysts. The system polymer can be produced with higher activity.

Hereinafter, preferred embodiments are provided to help understanding of the present invention. However, the following examples are only provided to more easily understand the present invention, and the contents of the present invention are not limited thereby.

< Example >

1st Metallocene Preparation of compounds

Synthetic example One

Step 1: Preparation of (6-t-butoxyhexyl)(methyl)-bis(2-methyl-4-(4-t-butylphenyl)indenyl))silane

150 g of 2-methyl-4-(4-t-butylphenyl)-indene was added to a 3 L schlenk flask, and a toluene/THF (10:1, 1.73 L) solution was added and dissolved at room temperature. . After the solution was cooled to -20°C, 240 mL of an n-butyllithium solution (n-BuLi, 2.5 M in hexane) was slowly added dropwise and stirred at room temperature for 3 hours. Thereafter, the reaction solution was cooled to -20°C, and then 82 g of (6-t-butoxyhexyl)dichloromethylsilane and 512 mg of CuCN were slowly added dropwise. The reaction solution was heated to room temperature, stirred for 12 hours, and 500 mL of water was added. Thereafter, the organic layer was separated, and dehydrated with MgSO ₄ and filtered. The filtrate was distilled under reduced pressure to obtain a yellow oil.

¹ H NMR (500 MHz, CDCl ₃ , 7.26 ppm): -0.09--0.05 (3H, m), 0.40-0.60 (2H, m), 0.80-1.51 (26H, m), 2.12-2.36 (6H, m ), 3.20-3.28 (2H, m), 3.67-3.76 (2H, m), 6.81-6.83 (2H, m), 7.10-7.51 (14H, m)

Step 2: Preparation of rac-[(6-t-butoxyhexylmethylsilanediyl)-bis(2-methyl-4-(4-t-butylphenyl)indenyl)]hafnium dichloride

(6-t-butoxyhexyl)(methyl)bis(2-methyl-4-(4-t-butylphenyl))indenylsilane prepared in 3 L of a Schlenk flask was added, and di 1 L of ethyl ether was added and dissolved at room temperature. After the solution was cooled to -20°C, 240 mL of an n-butyllithium solution (n-BuLi, 2.5 M in hexane) was slowly added dropwise and stirred at room temperature for 3 hours. Thereafter, the reaction solution was cooled to -78°C, and then 92 g of hafnium chloride was added. After heating the reaction solution to room temperature, the mixture was stirred for 12 hours, and the solvent was removed under reduced pressure. After adding 1 L of dichloromethane, inorganic salts and the like that were not dissolved were filtered off. The filtrate was dried under reduced pressure, and 300 mL of dichloromethane was added again to precipitate crystals. The precipitated crystals were filtered and dried to obtain 80 g of rac-[(6-t-butoxyhexylmethylsilanediyl)-bis(2-methyl-4-(4-t-butylphenyl)indenyl)]hafnium dichloride. (Rac:meso = 50:1).

¹ H NMR (500 MHz, CDCl ₃ , 7.26 ppm): 1.19-1.78 (37H, m), 2.33 (3H, s), 2.34 (3H, s), 3.37 (2H, t), 6.91 (2H, s) , 7.05-7.71 (14H, m)

Synthetic example 2

Step 1: Preparation of (6-t-butoxyhexyl)(methyl)-bis(2-methyl-4-tert-butyl-phenylindenyl)silane

2-Methyl-4-tert-butylphenylindene (20.0 g, 76 mmol) was dissolved in a toluene/THF=10/1 solution (230 mL), followed by n-butyllithium solution (2.5 M, hexane solvent, 22 g) was slowly added dropwise at 0° C., and then stirred at room temperature for one day. Then, (6-t-butoxyhexyl)dichloromethylsilane (1.27 g) was slowly added dropwise to the mixed solution at -78°C, stirred for about 10 minutes, and then stirred at room temperature for one day. Then, water was added to separate the organic layer, and then the solvent was distilled under reduced pressure to obtain (6-t-butoxyhexyl)(methyl)-bis(2-methyl-4-tert-butyl-phenylindenyl)silane.

¹ H NMR (500 MHz, CDCl ₃ , 7.26 ppm): -0.20-0.03 (3H, m), 1.26 (9H, s), 0.50-1.20 (4H, m), 1.20-1.31 (11H, m), 1.40 -1.62 (20H, m), 2.19-2.23 (6H, m), 3.30-3.34 (2H, m), 3.73-3.83 (2H, m), 6.89-6.91 (2H, m), 7.19-7.61 (14H, m)

Step 2: Preparation of [(6-t-butoxyhexylmethylsilane-diyl)-bis(2-methyl-4-tert-butylphenylindenyl)] zirconium dichloride

The (6-t-butoxyhexyl)(methyl)-bis(2-methyl-4-tert-butyl-phenylindenyl)silane prepared in Step 1 above was added to a toluene/THF=5/1 solution (95 mL). After dissolution, n-butyllithium solution (2.5 M, hexane solvent, 22 g) was slowly added dropwise at -78°C, followed by stirring at room temperature for one day. 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 dissolved in toluene (229 mL), then slowly added dropwise at -78°C and stirred at room temperature for one day. After the reaction solution was cooled to -78°C, HCl ether solution (1 M, 183 mL) was slowly added dropwise, followed by stirring at 0°C for 1 hour. After filtering and drying under vacuum, hexane was added and stirred to precipitate crystals. The precipitated crystals were filtered and dried under reduced pressure to [(6-t-butoxyhexylmethylsilane-diyl)-bis(2-methyl-4-tert-butylphenylindenyl)] zirconium dichloride (20.5 g, total 61 %).

¹ H NMR (500 MHz, CDCl ₃ , 7.26 ppm): 1.20 (9H, s), 1.27 (3H, s), 1.34 (18H, s), 1.20-1.90 (10H, m), 2.25 (3H, s) , 2.26 (3H, s), 3.38 (2H, t), 7.00 (2H, s), 7.09-7.13 (2H, m), 7.38 (2H, d), 7.45 (4H, d), 7.58 (4H, d ), 7.59 (2H, d), 7.65 (2H, d)

2nd Metallocene Preparation of compounds

Synthetic example 3

Step 1: Preparation of 2-methyl-1H-benzoindene

After adding 1.1 g of NaH and 9.1 mL of diethyl methylmalonate to 55 mL of tetrahydrofuran (THF), it was refluxed for 1 hour. Thereafter, the reaction mixture was cooled to room temperature, and 10 g of 2-bromomethylnaphthalene was added to the reaction mixture, followed by refluxing for 3 hours to prepare Compound A.

Subsequently, 30 mL of ethanol and 9.7 g of KOH were dissolved in 29 mL of water to 13.6 g of the reaction mixture containing Compound A, and refluxed for 4 hours to obtain Compound B.

Then, after adding HCl to the reaction mixture containing the compound B, the organic layer was extracted using ethyl acetate. Thereafter, the organic layer was dried, and then heated until no gas was released (heated to about 175°C) to obtain Compound C.

Then, the compound C was dissolved in 24.5 mL of dichloromethane, 7.2 mL of thionyl chloride was added, and refluxed for 30 minutes to obtain compound D.

Then, the reaction mixture containing the compound D was dried to remove the solvent. Then, the remaining solute was added to 10 mL of dichloromethane, and then cooled to 0°C. To the cooled reaction mixture, 5.2 g of aluminum chloride was dispersed in 40 mL of dichloromethane and then slowly added for 30 minutes. Subsequently, the obtained reaction mixture was refluxed for 30 minutes, and compound E was obtained by extracting an organic layer using an aqueous HCl solution and dichloromethane.

Thereafter, 2.1 g of the compound E was dissolved in 12 mL of THF and 6 mL of methanol to prepare a reaction mixture. Then, the reaction mixture was slowly injected into a container containing 809 mg of NaBH ₄ powder at a temperature of 0° C. for 1 hour. Subsequently, the reaction mixture was stirred at room temperature for 1 hour, and compound F was obtained by extracting the organic layer with water.

Thereafter, 2.1 g of the compound F was dissolved in 13 mL of toluene, and 102 mg of p-toluenesulfonic acid was added thereto and refluxed. 2-methyl-1H-benzoindene was obtained by extracting an organic layer using a NaCO ₃ aqueous solution and diethyl ether when the reaction was completed by using TLC (thin layer chromatography).

Step 2: Preparation of (6-t-butoxyhexyl)dichloromethylsilane

Into a 1 L flask, 95 g of Mg was added, washed three times with 1.0M HCl three times with MeOH and three times with acetone, and then dried under reduced pressure at 25° C. for 3 hours. To a reactor containing Mg, THF 1.0L and 1,2-DBE (1,2-dibromoethane) 5.0 mL were sequentially added and stirred. After adding 500 g of t-butoxyhexyl chloride to the dropping funnel, about 5% of them were added to the reactor for 5 minutes. Thereafter, the temperature of the reactor was raised to 70° C., and the reaction mixture was stirred for 30 minutes. Subsequently, the remaining amount of t-butoxyhexyl chloride was slowly added to the reactor over about 3 hours, and the reaction mixture was stirred at a temperature of 70° C. for about 15 hours. Thereafter, the temperature of the reactor was cooled to 25°C, and the reaction mixture was filtered to remove excess Mg, and the filtrate was transferred to a 3L flask.

Meanwhile, after washing and drying under reduced pressure, 583 g of trichloromethylsilane and 3.3 L of THF were added to the reactor, and the temperature of the reactor was cooled to -15°C. Subsequently, the filtrate prepared above was slowly added dropwise to the reactor at -5°C for 2 hours. The temperature of the reactor was raised to 25° C. and stirred at about 130 rpm for 16 hours. Thereafter, the reaction mixture was distilled under reduced pressure at 25° C., dispersed in 4.3 L of hexane, and then stirred for 30 minutes. Thereafter, the solid was filtered from the reaction mixture, then washed and filtered with 1.0 L of hexane, and the filtrate was distilled under reduced pressure at 25° C. to obtain (6-t-butoxyhexyl)dichloromethylsilane in 85% yield.

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)

Step 3: Preparation of bis(2-methyl-1H-benzoinden-1-yl)(6-(t-butoxy)hexyl)(methyl)silane

2 g (11.1 mmol) of 2-methyl-1H-benzoindene was dissolved in a mixed solvent of 101 mL of toluene and 10.1 mL of THF. Thereafter, the reaction mixture was cooled to -25°C, and 4.7 mL of n-butyllithium solution (2.5M solution in hexane) was slowly added dropwise to the reaction mixture. Then, the resulting reaction mixture was stirred at room temperature for 3 hours. Then, 9.9 mg of CuCN was dissolved in a small amount of toluene, added to the reaction mixture in the form of a slurry, and stirred for 30 minutes. Subsequently, 1.6 g of (6-t-butoxyhexyl)dichloromethylsilane prepared above was added to the reaction mixture, and the resulting reaction mixture was stirred at room temperature for one day. Thereafter, an organic layer was extracted from the obtained reaction product using water and methyl t-butyl ether, and dried to obtain a ligand.

Step 4: Preparation of bis(2-methyl-1H-benzoinden-1-yl)(6-(t-butoxy)hexyl)(methyl)silane zirconium dichloride

After dissolving 3.1 g (5.55 mmol) of bis(2-methyl-1H-benzoinden-1-yl)(6-(t-butoxy)hexyl)(methyl)silane prepared above in 55.5 mL of diethyl ether, 4.7 mL of n-butyl lithium solution (2.5M solution in hexane) was slowly added dropwise to the solution at -25°C. Then, the obtained reaction mixture was stirred at room temperature for about 3 hours, and then cooled to -25°C again. Then, the reaction mixture was added to a reaction vessel containing 2.09 g of bis(tetrahydrofuran) zirconium tetrachloride [ZrCl ₄ (C ₄ H ₅ O) ₂ ] and stirred at room temperature for one day. Then, the reaction mixture was dried to remove the solvent, and then dichloromethane was injected. Then, the obtained mixed solution was filtered to dry the filtrate. Then, the solid obtained by drying was recrystallized at -30°C using toluene to obtain a transition metal compound in a yield of 17%.

¹ H NMR (500 MHz, CDCl ₃ , 7.26 ppm): 1.19 (9H, s), 1.49 to 1.52 (2H, m), 1.59 to 1.62 (2H, m), 1.66 to 1.67 (2H, m), 1.84 to 1.86 (4H, m), 2.35 (6H, s), 3.37 (2H, t), 7.36 (2H, dd), 7.48 (2H, t), 7.50 (2H, d), 7.55 (2H, dd), 7.76 (2H, d), 7.94 (2H, d).

Synthetic example 4

Step 4: Preparation of bis(2-methyl-1H-benzoinden-1-yl)(6-(t-butoxy)hexyl)(methyl)silane hafnium dichloride

Steps 1 to 3 were the same as steps 1 to 3 of Synthesis Example 3.

After dissolving 3.1 g (5.55 mmol) of bis(2-methyl-1H-benzoinden-1-yl)(6-(t-butoxy)hexyl)(methyl)silane prepared above in 55.5 mL of diethyl ether, At -25, 4.7 mL of n-butyllithium solution (2.5M solution in hexane) was slowly added dropwise to the solution. Thereafter, the obtained reaction mixture was stirred at room temperature for about 3 hours, and then cooled to -25 again. Then, the reaction mixture was added to a reaction vessel containing 1.78 g of hafnium tetrachloride (HfCl ₄ ) and stirred at room temperature for one day. Then, the reaction mixture was dried to remove the solvent, and then dichloromethane was injected. Then, the obtained mixed solution was filtered to dry the filtrate. Then, the solid obtained by drying was recrystallized at -30 using toluene to obtain a transition metal compound in a yield of 12%.

¹ H NMR (500 MHz, CDCl ₃ , 7.26 ppm): 1.20 (9H, s), 1.50~1.54 (2H, m), 1.59~1.63 (2H, m), 1.67~1.69 (2H, m), 1.81~ 1.87 (4H, m), 2.45 (6H, d), 3.38 (2H, t), 7.19 (2H, s), 7.33 (2H, dd), 7.48 (2H, t), 7.53 (2H, t), 7.60 (2H, dd), 7.77 (2H, d), 7.92 (2H, d)

Synthetic example 5

Step 1: Preparation of 2-[2-(5-methyl)furyl]-4-(4-t-butylphenyl)indene

Ethanol and dichloromethane were added to a reactor containing 7-bromo-1-indanone, and the temperature of the reactor was cooled to 0°C. Then, NaBH ₄ was added dropwise to the reactor, and stirred at room temperature for 3 hours to reduce the carbonyl group.

Subsequently, p-toluenesulfonic acid (p-TsOH) was dissolved in toluene and added dropwise to the reactor, and refluxed for 0.5 hour.

Then, after the obtained reaction product was cooled to 0° C., NaHCO ₃ and meta-chloroperoxybenzoic acid (m-CPBA) were added together with dichloromethane and stirred at room temperature for 3 hours.

Thereafter, after cooling the obtained reaction product to 0° C. again, ZnI ₂ was added together with toluene and stirred at room temperature for 4 hours to obtain 4-bromo-2-indanone.

Subsequently, Pd(PPh ₃ ) ₄ (Tetrakis(triphenylphosphine) palladium) and Na ₂ CO ₃ were added to 4-bromo-2-indanone together with a mixed solvent (toluene/ethanol/water) and stirred, and then 4- Then, 4-(4-t-butylphenyl)-2-indone was obtained by adding t-butylphenyl boronic acid (4-tert-butylphenylboronic acid) and stirring at 80°C for 16 hours.

Meanwhile, 2-methylfuran and THF were added to separate reactors, and the temperature of the reactor was cooled to -25°C. Subsequently, an n-butyllithium solution was slowly added dropwise to the obtained reaction mixture, and the mixture was stirred for 4 hours while raising the temperature to room temperature.

Then, the temperature of the obtained reaction mixture was again cooled to -25°C. Subsequently, 4-(4-t-butylphenyl)-2-indanone prepared above was added to the reaction mixture, and the mixture was stirred for 16 hours while raising the temperature to room temperature.

Then, p-toluene sulfonic acid (p-TsOH) was added to the resulting reaction mixture, and refluxed for 10 minutes to prepare 2-[2-(5-methyl)furyl]-4-(4-t-butylphenyl)indene. Did.

Step 2: Preparation of (6-t-butoxyhexyl)dichloromethylsilane

Into a 1 L flask, 95 g of Mg was added, washed three times with 1.0M HCl three times with MeOH and three times with acetone, and then dried under reduced pressure at 25° C. for 3 hours. To a reactor containing Mg, THF 1.0L and 1,2-DBE (1,2-dibromoethane) 5.0 mL were sequentially added and stirred. After adding 500 g of t-butoxyhexyl chloride to the dropping funnel, about 5% of them were added to the reactor for 5 minutes. Thereafter, the temperature of the reactor was raised to 70° C., and the reaction mixture was stirred for 30 minutes. Subsequently, the remaining amount of t-butoxyhexyl chloride was slowly added to the reactor over about 3 hours, and the reaction mixture was stirred at a temperature of 70° C. for about 15 hours. Thereafter, the temperature of the reactor was cooled to 25°C, and the reaction mixture was filtered to remove excess Mg, and the filtrate was transferred to a 3L flask.

Meanwhile, after washing and drying under reduced pressure, 583 g of trichloromethylsilane and 3.3 L of THF were added to the reactor, and the temperature of the reactor was cooled to -15°C. Subsequently, the filtrate prepared above was slowly added dropwise to the reactor at -5°C for 2 hours. The temperature of the reactor was raised to 25° C. and stirred at about 130 rpm for 16 hours. Thereafter, the reaction mixture was distilled under reduced pressure at 25° C., dispersed in 4.3 L of hexane, and then stirred for 30 minutes. Thereafter, the solid was filtered from the reaction mixture, then washed and filtered with 1.0 L of hexane, and the filtrate was distilled under reduced pressure at 25° C. to obtain (6-t-butoxyhexyl)dichloromethylsilane in 85% yield.

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)

Step 3: Preparation of bis(2-[2-(5-methyl)furyl]-4-(4-t-butylphenyl)inden-1-yl)(6-t-butoxyhexyl)(methyl)silane

2 g of 2-[2-(5-methyl)furyl]-4-(4-t-butylphenyl)indene was dissolved in THF. Thereafter, the reaction mixture was cooled to -25°C, and 4.7 mL of n-butyllithium solution (2.5M solution in hexane) was slowly added dropwise to the reaction mixture. Then, the resulting reaction mixture was stirred at room temperature for 3 hours. Then, the temperature of the obtained reaction mixture was again cooled to 0° C., and 1.6 g of (6-t-butoxyhexyl)dichloromethylsilane prepared above was added, and the obtained reaction mixture was stirred at room temperature for 15 hours. Thereafter, an organic layer was extracted from the obtained reaction product using water and methyl t-butyl ether and dried. The dried product thus obtained was purified by column chromatography to obtain a ligand with a yield of 79%. At this time, hexane/EA (ethyl acetate)=20/1 was used as an elution solvent.

Step 4: Bis(2-[2-(5-methyl)furyl]-4-(4-t-butylphenyl)inden-1-yl)(6-t-butoxyhexyl)(methyl)silane zirconium dichloride Manufacture of

Diethyl bis(2-[2-(5-methyl)furyl]-4-(4-t-butylphenyl)inden-1-yl)(6-t-butoxyhexyl)(methyl)silane prepared above was diethyl. After dissolving in ether, 4.7 mL of n-butyllithium solution (2.5M solution in hexane) was slowly added dropwise to the solution at 0°C. Thereafter, the obtained reaction mixture was stirred at room temperature for about 3 hours, and then cooled to 0°C again. Then, the reaction mixture was added to a reaction vessel containing bis(tetrahydrofuran) zirconium tetrachloride [ZrCl ₄ (C ₄ H ₅ O) ₂ ] and stirred at room temperature for one day. Thereafter, the reaction mixture was dried to remove the solvent, and then dichloromethane was injected. Then, the obtained mixed solution was filtered to dry the filtrate. In the crude metal transition metal compound thus obtained, the racemic compound was more than 5 times more prevalent than the meso compound. The crude transition metal compound was recrystallized with a mixed solvent (dichloromethane/hexane volume ratio = 1:5) to obtain a transition metal compound with a yield of 44% (racemic:meso = 99:1).

Synthesis Example 6

(1) Synthesis of 5-( tert -butyl)-6-methoxy-2-methyl-7-phenyl-1 H -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 (0.87mmol, 1g) was added to 250mL RBF and toluene (30mL), ethanol (15mL), and water (15mL) were added. Then, the mixture was stirred in an oil bath previously heated to 75° C. for 16 hours. After the reaction, all ethanol was removed from the rotary evaporator, and work up with water and hexane. The combined organic layers were dried over MgSO ₄ and all solvents were removed. The crude mixture from which the solvent was removed was purified by silica gel short column to obtain 5-( tert -butyl)-6-methoxy-2-methyl-7-phenyl-1 H -indene (3.1g, 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 (2)(6-(tert-butoxy)hexyl)bis(6-(tert-butyl)-5-methoxy-2-methyl-4-phenyl-1H-inden-1-yl)(methyl)silane ligand

Add 5-( tert -butyl)-6-methoxy-2-methyl-7-phenyl-1 H -indene (4.65mmol, 1.4g), CuCN (0.23mmol, 0.02g) to 50mL Schlenk flask and make argon gave. When the argon state was formed, anhydrous toluene (13.5 mL) and anhydrous THF (1.5 mL) were added and cooled to -25°C. n- BuLi (2.5M in Hexane, 0.8mmol, 2.00mL) was slowly injected, and after the injection, the mixture was heated to room temperature and stirred for 3 hours. After stirring, the mixture was cooled to -25°C, and (6-(tert-butoxy)hexyl)dichloro(methyl)silane (2.32mmol, 0.63g) was added to the flask in one shot and stirred for 16 hours. Work up with MTBE and water and collect the organic layer to remove the solvent. And, with a silica column, (6-(tert-butoxy)hexyl)bis(6-(tert-butyl)-5-methoxy-2-methyl-4-phenyl-1H-inden-1-yl)(methyl)silane ligand (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 to 1.50 (10H, m), 1.15 (9H, m), 1.42 (18H, 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 (12H, m )

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

t-Butylamine (88 μL, 0.84 mmol) was placed in a 50 mL Schlenk flask under argon and dissolved by injecting toluene (2 mL) and THF (68 μL). The temperature was lowered to -30 °C, n -BuLi (1.6M in Hexane, 0.53 mL) was added, followed by stirring 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 slurry was stirred. The temperature was lowered to -30°C and stirred. Then, the above-made Li-t-butylamide was introduced into a flask containing ZrCl ₄ (THF) ₂ through cannula, washed with toluene (1 mL), and stirred at room temperature for 3 hours.

Then, in another Schlenk flask, the ligand compound (600 mg, 0.77 mmol) prepared in (1) was added under argon and toluene (1.2 mL) and THF (0.12 mL) were dissolved. After lowering the temperature to -30°C and adding n -BuLi (1.6M in Hexane, 1.0mL), the mixture was stirred at room temperature for 3 hours. After stirring at room temperature, the temperature was lowered to -30°C, and the ZrCl ₃ (THF) ₂ NHtBu solution prepared above was added through cannula. After the injection was completed, the temperature was raised to room temperature and stirred overnight. After the reaction was completed, the reaction was filtered to remove solids and cooled to 0°C. HCl (2M in ethylether, 0.38 mL) was added to the solution and the temperature was raised and stirred at room temperature for 2 hours. After the reaction was completed, it was dried under reduced pressure. After adding pentane to the obtained solid, it was filtered to remove insoluble substances, and the obtained pentane solution was stored in a refrigerator to recrystallize. The precipitate was filtered to give 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(12H, m)

Preparation of supported catalyst

Preparation Example 1

3 g of silica L203F was pre-weighed in a shrink flask, and 13 mmol of methylaluminoxane (MAO) was added and reacted at 95° C. for 24 hours. After precipitation, the upper layer was removed and washed once with toluene. 60 μmol of the compound prepared in Synthesis Example 1 was dissolved in toluene, and reacted at 75° C. for 5 hours. After the completion of the reaction and the precipitation was over, the upper layer solution was removed and the remaining reaction product was washed once with toluene. Then, 20 μmol of the compound prepared in Synthesis Example 3 was dissolved in toluene, and further reacted at 75° C. for 2 hours.

After the completion of the reaction and the precipitation was over, the upper layer solution was removed and the remaining reaction product was washed once with toluene. Dimethylanilininyltetrakis (pentafluorophenyl) borate 64 μmol was added and reacted at 75° C. for 5 hours. After the reaction was completed, the mixture was washed with toluene, washed again with hexane, and dried under vacuum to obtain a silica-supported metallocene catalyst in the form of solid particles.

Preparation Example 2

3 g of silica L203F was pre-weighed in a shrink flask, and 13 mmol of methylaluminoxane (MAO) was added and reacted at 95° C. for 24 hours. After precipitation, the upper layer was removed and washed once with toluene. 60 μmol of the compound prepared in Synthesis Example 1 was dissolved in toluene, and reacted at 75° C. for 5 hours. After the completion of the reaction and the precipitation was over, the upper layer solution was removed and the remaining reaction product was washed once with toluene. Then, 20 μmol of the compound prepared in Synthesis Example 5 was dissolved in toluene, and further reacted at 75° C. for 2 hours.

After the completion of the reaction and the precipitation was over, the upper layer solution was removed and the remaining reaction product was washed once with toluene. Dimethylanilininyltetrakis (pentafluorophenyl) borate 64 μmol was added and reacted at 75° C. for 5 hours. After the reaction was completed, the mixture was washed with toluene, washed again with hexane, and dried under vacuum to obtain a silica-supported metallocene catalyst in the form of solid particles.

Preparation Example 3

3 g of silica L203F was pre-weighed in a shrink flask, and 13 mmol of methylaluminoxane (MAO) was added and reacted at 95° C. for 24 hours. After precipitation, the upper layer was removed and washed once with toluene. 60 μmol of the compound prepared in Synthesis Example 2 was dissolved in toluene, and reacted at 75° C. for 5 hours. After the completion of the reaction and the precipitation was over, the upper layer solution was removed and the remaining reaction product was washed once with toluene. Then, 20 μmol of the compound prepared in Synthesis Example 4 was dissolved in toluene, and further reacted at 75° C. for 2 hours.

After the completion of the reaction and the precipitation was over, the upper layer solution was removed and the remaining reaction product was washed once with toluene. Dimethylanilininyltetrakis (pentafluorophenyl) borate 64 μmol was added and reacted at 75° C. for 5 hours. After the reaction was completed, the mixture was washed with toluene, washed again with hexane, and dried under vacuum to obtain a silica-supported metallocene catalyst in the form of solid particles.

Preparation Example 4

3 g of silica L203F was pre-weighed in a shrink flask, and 13 mmol of methylaluminoxane (MAO) was added and reacted at 95° C. for 24 hours. After precipitation, the upper layer was removed and washed once with toluene. 60 μmol of the compound prepared in Synthesis Example 2 was dissolved in toluene, and reacted at 75° C. for 5 hours. After the completion of the reaction and the precipitation was over, the upper layer solution was removed and the remaining reaction product was washed once with toluene. Then, 20 μmol of the compound prepared in Synthesis Example 6 was dissolved in toluene, and further reacted at 75° C. for 2 hours.

After the completion of the reaction and the precipitation was over, the upper layer solution was removed and the remaining reaction product was washed once with toluene. Dimethylanilininyltetrakis (pentafluorophenyl) borate 64 μmol was added and reacted at 75° C. for 5 hours. After the reaction was completed, the mixture was washed with toluene, washed again with hexane, and dried under vacuum to obtain a silica-supported metallocene catalyst in the form of solid particles.

Olefin polymerization example

Example 1

The 2 L stainless reactor was vacuum dried at 65° C., cooled, and 1.5 mmol of triethylaluminum and 770 g of propylene were sequentially added at room temperature. Thereafter, after stirring for 10 minutes, the hybrid supported catalyst prepared in Preparation Example 1 was dissolved in 20 mL of TMA-prescribed hexane to the content of Table 1, and then introduced into the reactor under nitrogen pressure. Then, while adding 15 g of ethylene, the reactor temperature was slowly raised to 70° C., followed by polymerization for 1 hour. After the reaction, unreacted propylene and ethylene were vented.

<Experimental Example>

The physical properties of the polymers prepared in Examples and Comparative Examples were measured by the following method.

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

(2) Molecular weight distribution (PDI, polydispersity index): Measure the weight average molecular weight (Mw) and number average molecular weight (Mn) of the polymer using gel permeation chromatography (GPC). The molecular weight distribution (PDI) was calculated by dividing the average molecular weight by the number average molecular weight. At this time, the analysis temperature was set to 160°C, trichlorobenzene was used as the solvent, and molecular weight was measured by standardizing with polystyrene.

(3) Melt Index (MFR, 2.16 kg): Measurement temperature 230℃, ASTM 1238

(4) Melt Flow Rate Ratio (MFRR): The MFR ₂₀ melt index (21.6 kg load) was calculated as the ratio divided by MFR ₂ (MI, 2.16 kg load) (MFR ₂₀ /MFR ₂ ).

(5) Melting temperature (Tm): The melting point of the polymer was measured using a differential scanning calorimeter (DSC, device name: DSC 2920, manufacturer: TA instrument). Specifically, after heating the polymer to 220°C, the temperature was maintained for 5 minutes, the temperature was lowered again to 20°C, and then the temperature was increased again. At this time, the rate of rise and fall of the temperature were respectively adjusted to 10°C/min.

Table 1 shows the results of measuring the physical properties of the olefin-based polymer prepared in Examples.

Example No. Catalyst precursor activation
(kg PP/g Cat.hr) MFR
(g/10 min) MFRR PDI Tm
(℃) Example 1 Preparation Example 1
(Synthesis example 1/
Synthesis Example 3) 8.4 6.4 4.8 3.5 138.5 Example 2 Preparation Example 2
(Synthesis example 1/
Synthesis Example 5) 8.7 5.7 2.9 2.6 139.4 Example 3 Preparation Example 3
(Synthesis example 2/
Synthesis Example 4) 8.8 5.0 4.1 3.0 139.4 Example 4 Preparation Example 4
(Synthesis example 2/
Synthesis Example 6) 9.2 2.0 6.1 4.2 134.8

As shown in Table 1, the embodiment of the present invention not only has a high catalytic activity, but also exhibits a low melting temperature, a high melt flow rate ratio, and a wide molecular weight distribution, confirming that it is suitable for preparing an olefin polymer having excellent processability there was.

Claims (21)

At least one first metallocene compound represented by Formula 1 below;
At least one second metallocene compound selected from compounds represented by the following Chemical Formula 2, Chemical Formula 3, or Chemical Formula 4; And
Hybrid supported catalyst comprising a carrier:
[Formula 1]

In Chemical Formula 1,
M ¹ is a Group 4 transition metal,
X ¹ and X ² are the same or different from each other and are each independently halogen,
R ¹ is aryl having 6 to 20 carbons substituted with alkyl having 1 to 20 carbons,
R ² , R ³ and R ⁴ are the same or different from each other, and each independently hydrogen, halogen, alkyl having 1 to 20 carbons, alkylsilyl having 1 to 20 carbons, silylalkyl having 1 to 20 carbons, alkoxy having 1 to 20 carbons Silyl, ether having 1 to 20 carbons, silyl ether having 1 to 20 carbons, aryl having 6 to 20 carbons, alkylaryl having 7 to 20 carbons, or arylalkyl having 7 to 20 carbons,
A ¹ is carbon, silicon or germanium,
R ⁵ is alkyl having 1 to 20 carbons substituted with alkoxy having 1 to 20 carbons,
R ⁶ is hydrogen, alkyl having 1 to 20 carbons,
[Formula 2]

In Chemical Formula 2,
M ² is a Group 4 transition metal,
X ³ and X ⁴ are the same as or different from each other, and each independently halogen.
A ² is carbon, silicon or germanium,
R ⁷ is alkyl having 1 to 20 carbons substituted with alkoxy having 1 to 20 carbons,
R ⁸ is hydrogen, alkyl having 1 to 20 carbons, alkyl aryl having 7 to 30 carbons, arylalkyl having 7 to 30 carbons, or aryl having 6 to 30 carbons,
R ⁹ and R ¹⁰ are the same as or different from each other, and each independently hydrogen or alkyl having 1 to 20 carbons,
[Formula 3]

In Chemical Formula 3,
M ³ is a Group 4 transition metal,
X ⁵ and X ⁶ are the same as or different from each other, and each independently halogen.
A ³ is carbon, silicon or germanium,
R ¹¹ is alkyl having 1 to 20 carbons substituted with alkoxy having 1 to 20 carbons,
R ¹² is hydrogen, alkyl having 1 to 20 carbons, alkyl aryl having 7 to 30 carbons, arylalkyl having 7 to 30 carbons, or aryl having 6 to 30 carbons,
R ¹³ and R ¹⁴ are the same as or different from each other, and each independently hydrogen and alkyl having 1 to 20 carbons,
R ¹⁵ and R ¹⁶ are the same or different from each other, and each independently is aryl having 6 to 20 carbons, substituted with alkyl having 1 to 20 carbons,
[Formula 4]

In Chemical Formula 4,
M ⁴ is a Group 4 transition metal,
X ⁷ and X ⁸ are the same or different from each other, each independently halogen.
A ⁴ is carbon, silicon or germanium,
R ¹⁷ is aryl having 6 to 20 carbons or aryl having 6 to 20 carbons substituted with alkyl having 1 to 20 carbons,
R ¹⁸ is alkoxy having 1 to 20 carbon atoms,
R ¹⁹ is alkyl having 1 to 20 carbons,
R ²⁰ is hydrogen, halogen, alkyl having 1 to 20 carbons, alkylsilyl having 1 to 20 carbons, silylalkyl having 1 to 20 carbons, alkoxysilyl having 1 to 20 carbons, ether having 1 to 20 carbons, carbon having 1 to 20 carbons Silyl ether, alkoxy having 1 to 20 carbons, aryl having 6 to 20 carbons, alkylaryl having 7 to 20 carbons, or arylalkyl having 7 to 20 carbons,
R ²¹ is alkyl having 1 to 20 carbons substituted with alkoxy having 1 to 20 carbons,
R ²² is hydrogen, alkyl having 1 to 20 carbons.
According to claim 1,
R ¹ in Formula 1 is a phenyl substituted with tert-butyl, a hybrid supported catalyst.
According to claim 1,
R ² , R ³ and R ⁴ in Chemical Formula 1 are hydrogen, and a hybrid supported catalyst.
According to claim 1,
R ⁵ in Formula 1 is 6-tert-butoxy-hexyl, and R ⁶ is methyl, a hybrid supported catalyst.
According to claim 1,
The first metallocene compound represented by Formula 1 is one of the following compounds, a hybrid supported catalyst:

,

According to claim 1,
R ⁷ in Formula 2 is 6-tert-butoxy-hexyl, a hybrid supported catalyst
According to claim 1,
R ⁸ , R ⁹ , and R ¹⁰ in Chemical Formula 2 are methyl, and a hybrid supported catalyst.
According to claim 1,
The second metallocene compound represented by Formula 2 is one of the following compounds, a hybrid supported catalyst:

,

According to claim 1,
R ¹¹ in Chemical Formula 3 is 6-tert-butoxy-hexyl, a hybrid supported catalyst.
According to claim 1,
R ¹² , R ¹³ and R ¹⁴ in Chemical Formula 3 are methyl, and a hybrid supported catalyst.
According to claim 1,
R ¹⁵ and R ¹⁶ of Chemical Formula 3 are 4-tert-butyl-phenyl, hybrid supported catalyst.
According to claim 1,
The second metallocene compound represented by Formula 3 is the following compound, a hybrid supported catalyst:

According to claim 1,
R ¹⁸ of Formula 4 is methoxy, R ¹⁹ is tert-butyl, hybrid supported catalyst.
According to claim 1,
R ²¹ of Formula 4 is 6-tert-butoxy-hexyl, a hybrid supported catalyst.
According to claim 1,
The second metallocene compound represented by Chemical Formula 4 is one of the following compounds, and a hybrid supported catalyst:

,

,

,

According to claim 1,
The carrier is a silica, alumina, magnesia or a mixture thereof, a hybrid supported catalyst.
According to claim 1,
A hybrid supported catalyst comprising the first metallocene compound and the second metallocene compound in a molar ratio of 10:1 to 2:1 based on the molar ratio of metal.
According to claim 1,
A hybrid supported catalyst further comprising one or more cocatalysts of a compound represented by Formula 5, a compound represented by Formula 6, and a compound represented by Formula 7:
[Formula 5]
-[Al(R')-O] _m-
In Chemical Formula 5,
R'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;
m is an integer of 2 or more;
[Formula 6]
J(R'') ₃
In Chemical Formula 6,
R'' is the same as R'defined in Chemical Formula 5 above;
J is aluminum or boron;
[Formula 7]
_{^{[EH] + [ZQ 4]}} - or _{^{[E] + [ZQ 4]}} -
In Chemical Formula 7,
E is a neutral or cationic Lewis base;
H is a hydrogen atom;
Z is a group 13 element;
Q may be the same or different from each other, and each independently one or more hydrogen atoms are halogen, a hydrocarbon having 1 to 20 carbons, an alkoxy or phenoxy substituted or unsubstituted aryl group having 6 to 20 carbon atoms or an alkyl group having 1 to 20 carbon atoms. .
A method for producing an olefinic polymer comprising the step of polymerizing at least one or more olefin monomers in the presence of the hybrid supported catalyst of claim 1.
The method of claim 19,
The olefin is ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, A method for producing an olefin-based polymer, at least one member selected from the group consisting of 1-eicocene and mixtures thereof.
The method of claim 19,
The olefin polymer is a propylene homo polymer, or a copolymer of propylene and ethylene, a method for producing an olefin polymer.