KR20170073463A - 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 polymer having high activity and exhibiting a high activity catalyst and a process for producing an olefin polymer using the same.

Description

TECHNICAL FIELD [0001] The present invention relates to a hybrid supported catalyst and a method for producing an olefinic polymer using the same. BACKGROUND ART < RTI ID = 0.0 >

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

Olefin polymerization catalyst systems can be classified into Ziegler-Natta and metallocene catalyst systems, both of which have been developed for their respective characteristics. The Ziegler-Natta catalyst has been widely applied to commercial processes since its invention in the 1950's. However, since it is a multi-site catalyst having a plurality of active sites, the molecular weight distribution of the polymer is broad and the composition of the comonomer There is a problem that the desired physical properties can not be secured because the distribution is not uniform.

The metallocene catalyst consists of a combination of a main catalyst, which is the main component of the transition metal compound, and a cocatalyst, which is an organometallic compound mainly composed of aluminum. Such a catalyst is a single site catalyst as a homogeneous complex catalyst, According to the single active site characteristic, the molecular weight distribution is narrow, the polymer having uniform composition distribution of comonomer is obtained, and the stereoregularity of the polymer, copolymerization characteristics, molecular weight, crystallinity And the like.

On the other hand, the ansa-metallocene compound is an organometallic compound containing two ligands connected to each other by a bridge group. The bridge group prevents the rotation of the ligand, Activity and structure are determined.

These anisometallocene compounds are used as catalysts in the production of olefinic homopolymers or copolymers. In particular, it is known that an anisometallocene compound containing a cyclopentadienyl-fluorenyl ligand can produce a high molecular weight polyethylene, thereby controlling the microstructure of the polypropylene have. It is also known that an anisometallocene compound containing an indenyl ligand can produce an olefin polymer having excellent activity and improved stereoregularity.

The present inventors have disclosed an anthra-metallocene compound having a novel structure capable of providing various selectivity and activity to olefin polymers in Korean Patent Publication No. 10-2013-0125311.

On the other hand, in the case of bis-indenyl-ligand in an anisometallocene catalyst, two types of ligand, i.e., racemate and mirror-symmetrical meso-diastereomer, symmetric meso diastereomer) can be formed. In the case of racemates, mirror-symmetric meso-diastereomers are preferred because they produce isotactic polymers with high crystallinity and melting points and high specific gravity and mechanical strength, while atactic polymers It is a catalyst that should be avoided because it is manufactured. However, since the racemate and the mirror-symmetric meso-diastereomer are simultaneously produced in the process of preparing the anisma-metallocene catalyst, the structure of the anthra-metallocene catalyst, in which an excess of the racemate can be produced, Should be considered.

Accordingly, the present inventors have carried out various studies on a catalyst capable of producing an olefin polymer having a broad molecular weight distribution (PDI) so as to exhibit the same or higher activity as a conventional catalyst and exhibit high porosity, The present inventors have completed the present invention by confirming that olefinic polymers can be prepared simultaneously using hybrid supported catalysts comprising two kinds of catalysts having the structures described in the specification of the present invention.

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

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

In order to solve the above-mentioned problems, the present invention provides a method for producing a metal complex comprising at least one first metallocene compound represented by the following general formula (1) At least one second metallocene compound selected from compounds represented by the following general formulas (2), (3) and (4); And a carrier.

[Chemical Formula 1]

In Formula 1,

M ¹ is a Group 4 transition metal,

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

A ¹ is carbon, silicon or germanium,

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

R ² , R ³ and R ⁴ are the same or different and each independently represents hydrogen, halogen, alkyl of 1 to 20 carbon atoms, alkenyl of 2 to 20 carbon atoms, alkylsilyl of 1 to 20 carbon atoms, Alkyl having 1 to 20 carbon atoms, alkoxysilyl having 1 to 20 carbon atoms, ether having 1 to 20 carbon atoms, silyl ether having 1 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, alkylaryl having 7 to 20 carbon atoms, or arylalkyl having 7 to 20 carbon atoms,

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

R ⁶ is hydrogen, alkyl having 1 to 20 carbon atoms or alkenyl having 2 to 20 carbon atoms,

 (2)

In Formula 2,

M ² is a Group 4 transition metal,

X ³ and X ⁴ are the same or different and are each independently halogen,

A ² is carbon, silicon or germanium,

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

R ⁸ is hydrogen, alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, alkylaryl having 7 to 30 carbon atoms, arylalkyl having 7 to 30 carbon atoms, or aryl having 6 to 30 carbon atoms,

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

(3)

In Formula 3,

M ³ is a Group 4 transition metal,

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

A ³ is carbon, silicon or germanium,

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

R ¹² is hydrogen, alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, alkylaryl having 7 to 30 carbon atoms, arylalkyl having 7 to 30 carbon atoms, or aryl having 6 to 30 carbon atoms,

R ¹³ and R ¹⁴ are the same or different and are each independently hydrogen and alkyl having 1 to 20 carbon atoms,

R ¹⁵ and R ¹⁶ are the same or different and are each independently aryl having 6 to 20 carbon atoms substituted with alkyl having 1 to 20 carbon atoms.

[Chemical Formula 4]

In Formula 4,

M ⁴ is a Group 4 transition metal,

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

A ⁴ is carbon, silicon or germanium,

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

R ¹⁸ is alkoxy having 1 to 20 carbon atoms,

R < ¹⁹ > is alkyl having 1 to 20 carbon atoms,

R ²⁰ is hydrogen, halogen, alkyl of 1 to 20 carbon atoms, alkenyl of 2 to 20 carbon atoms, alkylsilyl of 1 to 20 carbon atoms, silylalkyl of 1 to 20 carbon atoms, alkoxysilyl of 1 to 20 carbon atoms, An aryl of 1 to 20 carbon atoms, an alkoxy of 1 to 20 carbon atoms, an aryl of 6 to 20 carbon atoms, an alkylaryl of 7 to 20 carbon atoms, or an arylalkyl of 7 to 20 carbon atoms,

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

R ²² is hydrogen, alkyl of 1 to 20 carbon atoms or alkenyl of 2 to 20 carbon atoms.

The present invention also provides a process for producing an olefinic polymer using the hybrid supported catalyst.

The hybrid supported catalyst according to the present invention has high catalytic activity and exhibits a low melting temperature (Tm), a high melt flow rate ratio (MFRR), and a broad molecular weight distribution (PDI) when olefinic polymers are prepared using the catalysts. The olefinic polymer can be easily produced.

The terminology used herein is for the purpose of describing exemplary embodiments only and is not intended to be limiting of the invention. The singular expressions include plural expressions unless the context clearly dictates otherwise.

While the invention is susceptible to various modifications and alternative forms, specific embodiments thereof are shown by way of example in the drawings and will herein be described in detail. It should be understood, however, that the invention is not intended to be limited to the particular forms disclosed, but includes all modifications, equivalents, and alternatives falling within the spirit and scope of the invention.

A hybrid supported catalyst according to a specific embodiment of the present invention and a method for producing an olefin 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 the following formula (1) At least one second metallocene compound selected from compounds represented by the following general formulas (2), (3) and (4); And a carrier.

[Chemical Formula 1]

In Formula 1,

M ¹ is a Group 4 transition metal,

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

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

R ² , R ³ and R ⁴ are the same or different and each independently represents hydrogen, halogen, alkyl of 1 to 20 carbon atoms, alkenyl of 2 to 20 carbon atoms, alkylsilyl of 1 to 20 carbon atoms, Alkyl having 1 to 20 carbon atoms, alkoxysilyl having 1 to 20 carbon atoms, ether having 1 to 20 carbon atoms, silyl ether having 1 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, alkylaryl having 7 to 20 carbon atoms, or arylalkyl having 7 to 20 carbon atoms,

A ¹ is carbon, silicon or germanium,

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

R ⁶ is hydrogen, alkyl having 1 to 20 carbon atoms or alkenyl having 2 to 20 carbon atoms,

(2)

In Formula 2,

M ² is a Group 4 transition metal,

X ³ and X ⁴ are the same or different and are each independently halogen,

A ² is carbon, silicon or germanium,

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

R ⁸ is hydrogen, alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, alkylaryl having 7 to 30 carbon atoms, arylalkyl having 7 to 30 carbon atoms, or aryl having 6 to 30 carbon atoms,

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

(3)

In Formula 3,

M ³ is a Group 4 transition metal,

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

A ³ is carbon, silicon or germanium,

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

R ¹² is hydrogen, alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, alkylaryl having 7 to 30 carbon atoms, arylalkyl having 7 to 30 carbon atoms, or aryl having 6 to 30 carbon atoms,

R ¹³ and R ¹⁴ are the same or different and are each independently hydrogen and alkyl having 1 to 20 carbon atoms,

R ¹⁵ and R ¹⁶ are the same or different and are each independently aryl having 6 to 20 carbon atoms substituted with alkyl having 1 to 20 carbon atoms.

[Chemical Formula 4]

In Formula 4,

M ⁴ is a Group 4 transition metal,

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

A ⁴ is carbon, silicon or germanium,

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

R ¹⁸ is alkoxy having 1 to 20 carbon atoms,

R < ¹⁹ > is alkyl having 1 to 20 carbon atoms,

R ²⁰ is hydrogen, halogen, alkyl of 1 to 20 carbon atoms, alkenyl of 2 to 20 carbon atoms, alkylsilyl of 1 to 20 carbon atoms, silylalkyl of 1 to 20 carbon atoms, alkoxysilyl of 1 to 20 carbon atoms, An aryl of 1 to 20 carbon atoms, an alkoxy of 1 to 20 carbon atoms, an aryl of 6 to 20 carbon atoms, an alkylaryl of 7 to 20 carbon atoms, or an arylalkyl of 7 to 20 carbon atoms,

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

R ²² is hydrogen, alkyl of 1 to 20 carbon atoms or alkenyl of 2 to 20 carbon atoms.

Unless defined otherwise herein, the following terms may be defined as follows.

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

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

The alkenyl having 2 to 20 carbon atoms may be straight-chain, branched-chain or cyclic alkenyl. Specific examples of the alkenyl having 2 to 20 carbon atoms include straight chain alkenyl having 2 to 20 carbon atoms, straight chain alkenyl having 2 to 10 carbon atoms, straight chain alkenyl having 2 to 5 carbon atoms, branched alkenyl having 3 to 20 carbon atoms, Branched chain alkenyl having 3 to 10 carbon atoms, cyclic alkenyl having 5 to 20 carbon atoms, or cyclic alkenyl having 5 to 10 carbon atoms. More specifically, the alkenyl having 2 to 20 carbon atoms can be ethenyl, propenyl, butenyl, pentenyl or cyclohexenyl, and the like.

The aryl having from 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 an anthracenyl group.

Alkylaryl having 7 to 30 carbon atoms can mean a substituent wherein at least one hydrogen of the aryl is substituted by alkyl. Specifically, the alkylaryl having 7 to 30 carbon atoms may be methylphenyl, ethylphenyl, n-propylphenyl, isopropylphenyl, n-butylphenyl, iso-butylphenyl, tert-butylphenyl or cyclohexylphenyl.

Arylalkyl having 7 to 30 carbon atoms can mean a substituent wherein at least one hydrogen of the alkyl is substituted by aryl. Specifically, arylalkyl having 7 to 30 carbon atoms may be a benzyl group, phenylpropyl, phenylhexyl, or the like.

(Tm), a broad molecular weight distribution (PDI), and a high molecular weight distribution (PDI) in the case of using a hybrid supported catalyst in which the first metallocene compound of Formula 1 and the second metallocene compound of Formula 2 are simultaneously carried. The olefin polymer showing porosity can be produced with high activity.

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

In addition, since a bulky group such as an aryl (R ¹ ) having 6 to 20 carbon atoms substituted with an alkyl having 1 to 20 carbon atoms is substituted for the indenyl group, a steric hindrance is imparted to inhibit formation of the meso form do. Accordingly, when the first metallocene compound represented by Formula 1 is supported on a carrier and used as a catalyst in the production of polyolefin, polyolefin having desired properties can be produced more easily with high activity.

In the above formula (1), preferably, R ¹ may be phenyl substituted with tert-butyl, more preferably R ¹ may be 4-tert-butyl-phenyl.

Also preferably, M ¹ can be hafnium (Hf) or zirconium (Zr), and X ¹ and X ² can 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 can be 6-tert-butoxy-hexyl and R ⁶ can be methyl.

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

The first metallocene compound represented by Formula 1 may be prepared according to the following Reaction Scheme 1, but the present invention is not limited thereto.

[Reaction Scheme 1]

Step 1 is a step of reacting a compound represented by Formula 1-2 with a compound represented by Formula 1-3 to prepare a compound represented by Formula 1-4. 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.

Step 2 is a step of reacting the compound represented by Formula 1-4 with the compound represented by Formula 1-5 to prepare the compound represented by 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, ether, hexane and the like can be used.

Among the second metallocene compounds, the second metallocene compound represented by Formula 2 includes two benzoindenyl groups as a ligand, and a bridge group connecting the two ligands And an oxygen-donor, which contains a functional group capable of serving as a Lewis base. For example, when the compound of Formula 2 having such a specific structure is activated and supported on a carrier by a suitable method and used as a polymerization catalyst for olefin monomers, a low melting temperature (Tm) and a high melt index (MFR) An olefin polymer excellent in energy saving effect can be produced. In particular, this effect can be maximized in the polymerization of propylene.

More specifically, in the second metallocene compound represented by Formula 2, the benzoindenyl ligand may be substituted with a substituent which is not substituted or is less sterically hindered. As a result, an olefin polymer having a desired stereoregular structure can be easily produced while exhibiting good catalytic activity.

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

The bridge group connecting the benzoindenyl ligand in the above 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 a branched chain alkoxy having 3 to 6 carbon atoms, preferably 6-tert-butoxy-hexyl.

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

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

Also preferably, A ² may be silicon.

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

,

,

The second metallocene compound represented by Formula 2 may be prepared according to the following Reaction Scheme 2, but the present invention is not limited thereto.

[Reaction Scheme 2]

Step 1 is a step of reacting the compounds represented by Formulas 2-1 and 2-2 with the compound represented by Formula 2-3 to prepare the compound represented by Formula 2-4. 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.

Step 2 is a step of reacting the compound represented by Formula 2-4 with the compound represented by Formula 2-5 to prepare the compound represented by 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.

Among the second metallocene compounds, the second metallocene compound represented by the general formula (3) includes two 2- (2-furyl) indene as a ligand, and a bridge group connecting two ligands It has an oxygen-donor structure including a functional group capable of acting as a Lewis base. In the case of the existing metallocene catalyst precursors, the selectivity for each stereoisomer was similar during the synthesis, and the meso compound and the racemic mixture were produced in almost similar proportions. However, the metallocene compound of formula (3) according to one embodiment of the present invention exhibits a high selectivity to an optical isomer when synthesized by the specific stereochemical structure described above, and thus a racemic mixture is obtained. It has been found that the metallocene compound of formula (3) having the specific stereoregular structure described above is excellent in hydrogen reactivity and can provide an olefin polymer having a higher fluidity than the conventional catalyst with the same amount of hydrogen. That is, the use of the metallocene compound of formula (3) having the specific structure described above makes it possible to easily produce a highly flowable olefin polymer that is very suitable for producing melt blown fibers.

Specifically, in the second metallocene compound represented by 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 can exhibit good catalytic activity while exhibiting good structural stability. For example, in Formula 3, R ¹⁵ and R ¹⁶ each independently may be phenyl substituted by tert-butyl, more preferably R ¹⁵ and R ¹⁶ may be 4-tert-butyl-phenyl.

In the second metallocene compound represented by Formula 3, the 5-position of furyl may be unsubstituted or substituted with alkyl having 1 to 20 carbon atoms. More specifically, the 5-position of the furyl may be substituted with a substituent having a small steric hindrance to further improve the structural stability. For example, R ¹³ and R ¹⁴ in Formula 3 may each independently be any of linear alkyl having 1 to 3 carbon atoms, preferably methyl.

The bridge group connecting 2- (2-furyl) indene in the above formula (3) may affect the loading stability of the metallocene compound. For example, R ¹¹ in formula (3) may be alkyl substituted with a branched chain alkoxy having 3 to 6 carbon atoms, preferably 6-tert-butoxy-hexyl, for improved loading efficiency. R ¹² in the general formula (3) is straight chain alkyl having 1 to 6 carbon atoms, preferably 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 the general formula (3) are as follows, but the present invention is not limited thereto:

The compound represented by the above formula (3) can be synthesized using known synthesis reactions, and a more detailed synthesis method can be referred to the following embodiments.

Among the second metallocene compounds, the metallocene compound represented by the general formula (4) has a crosslinking structure in which two indene groups are connected by a carbon, silicon or germanium bridge. Particularly, , An alkyl 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).

In the second metallocene compound of Formula 4 of this embodiment, R ¹⁷ is preferably phenyl or phenyl substituted with alkyl having 1 to 10 carbon atoms.

And R < ¹⁸ > is preferably methoxy.

R ¹⁹ is preferably an alkyl having 1 to 4 carbon atoms, more preferably tert-butyl.

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

It is preferable that M ⁴ is zirconium (Zr), and X ⁷ and X ⁸ are chloro (Cl).

Meanwhile, preferred examples of the second metallocene compound represented by Formula 4 include the following compounds.

,

,

,

,

,

,

The second metallocene compound represented by the general formula (4) can be synthesized using known synthesis reactions, and a more detailed synthesis method can be referred to the following embodiments.

When an olefinic polymer is prepared by a conventional metallocene catalyst, there is a difficulty in the process such as the reduction of the melting temperature, the polymerization activity is low, or the olefinic polymer having a high melting temperature is obtained although the polymerization activity is high, It is not easy to simultaneously realize these properties with a single metallocene catalyst.

In the hybrid supported catalyst of the present invention, the second metallocene compounds represented by the above Chemical Formulas (2) to (4) are obtained by polymerization of a highly porous olefinic polymer having a high melt flow rate ratio and a large molecular weight distribution (PDI) However, it has a disadvantage in that the catalytic activity is relatively low. On the other hand, by using a hybrid supported catalyst in which the first metallocene compound and the second metallocene compound are carried together as in the present invention, it is advantageous to produce a highly porous olefin polymer with high activity. In addition, an olefin-based polymer having an appropriate range of melt index is obtained, and both the processability and the mechanical properties can be satisfied.

The molar ratio of the first metallocene compound to the second metallocene compound is in the range of about 10: 1 to about 2: 1, preferably about 3: 1 to about 2: 1, 5: 1. And exhibits optimum catalytic activity and physical properties at the above-mentioned molar ratio, which is advantageous from the viewpoints of maintaining the activity of the catalyst and economical efficiency.

In the hybrid supported catalyst according to the present invention, a carrier containing a hydroxy group on its surface may be used as the carrier, and preferably a carrier having a hydroxyl group and a siloxane group, Can be used. Silica-alumina, silica-magnesia, and the like, which are usually dried at high temperature, and which are usually made of oxides such as Na ₂ O, K ₂ CO ₃ , BaSO ₄ , and Mg (NO ₃ ) ₂ , Sulfate, and nitrate components.

The drying temperature of the carrier is preferably 200 to 800 ° C, more preferably 300 to 600 ° C, and most preferably 300 to 400 ° C. If the drying temperature of the carrier is less than 200 ° C, moisture is excessively large and the surface moisture reacts with the cocatalyst. When the temperature exceeds 800 ° C, the pores on the surface of the carrier are combined to reduce the surface area. And only the siloxane group is left, and the reaction site with the co-catalyst is reduced, which is not preferable.

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

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

In the hybrid supported catalyst according to the present invention, the mass ratio of the catalyst (the first and second metallocene compounds) to the support is preferably 1: 1 to 1: 1000. When the carrier and the catalyst are contained in the above-described mass ratio, they exhibit appropriate supported catalyst activity, which may be advantageous from the standpoint of maintaining the activity of the catalyst and economical efficiency.

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

[Chemical Formula 5]

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

In Formula 5,

R 'may be the same or different from each other and are 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;

[Chemical Formula 6]

J (R ') ₃

In Formula 6,

R " is as defined in Formula 5 above;

J is aluminum or boron;

(7)

[EH] ⁺ [ZQ ₄ ] ^- or [E] ⁺ [ZQ ₄ ] ^-

In 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 independently at least one hydrogen atom is an aryl group having 6 to 20 carbon atoms or an alkyl group having 1 to 20 carbon atoms, which is substituted with halogen, a hydrocarbon having 1 to 20 carbon atoms, alkoxy or phenoxy .

Examples of the compound represented by the general formula (5) include methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, and butylaluminoxane. A more preferred compound is methylaluminoxane.

Examples of the compound represented by Formula 6 include trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, dimethylchloroaluminum, triisopropylaluminum, tri-s-butylaluminum, tricyclopentylaluminum , Tripentyl aluminum, triisopentyl aluminum, trihexyl aluminum, trioctyl aluminum, ethyl dimethyl aluminum, methyldiethyl aluminum, triphenyl aluminum, tri-p-tolyl aluminum, dimethyl aluminum methoxide, dimethyl aluminum ethoxide, Boron, triethylboron, triisobutylboron, tripropylboron, tributylboron and the like, and more preferred compounds are selected from trimethylaluminum, triethylaluminum and triisobutylaluminum.

Examples of the compound represented by Formula 7 include triethylammonium tetraphenylboron, tributylammonium tetraphenylboron, trimethylammonium tetraphenylboron, tripropylammonium tetraphenylboron, trimethylammonium tetra (p-tolyl) Boron, trimethylammoniumtetra (o, p-dimethylphenyl) boron, tributylammoniumtetra (p -trifluoromethylphenyl) boron, trimethylammoniumtetra (ptrifluoromethylphenyl) boron, tributylammoniumtetra N, N-diethylanilinium tetraphenylboron, N, N-diethylanilinium tetrapentafluorophenylboron, diethylammonium tetrapentafluorophenylboron, triphenylphosphonium Tetraphenylboron, trimethylphosphonium tetraphenylboron, triethylammonium tetraphenyl aluminum, tributylammonium tetraphenyl aluminum, trimethylammonium tetraphenyl aluminum (P-tolyl) aluminum, triethylammoniumtetra (o, p-dimethylphenyl) aluminum, tributylammonium tributylammonium (P-trifluoromethylphenyl) aluminum, trimethylammonium tetra (p-trifluoromethylphenyl) aluminum, tributylammonium tetrapentafluorophenyl aluminum, N, N-diethylanilinium tetraphenyl aluminum, N , N-diethylanilinium tetrapentafluorophenyl aluminum, diethylammonium tetrapentatetraphenyl aluminum, triphenylphosphonium tetraphenyl aluminum, trimethylphosphonium tetraphenyl aluminum, tripropylammonium tetra (p-tolyl) Boron, triethylammoniumtetra (o, p-dimethylphenyl) boron, tributylammoniumtetra (p -trifluoromethylphenyl) boron, triphenylcarboniumtetra (p- Phenyl) boron and the like, triphenylamine car I phenylboronic as Titanium tetra-penta flow.

The hybrid supported catalyst according to the present invention is characterized in that it comprises a step of supporting a promoter compound on a support, supporting the first metallocene compound on the support, and supporting the second metallocene compound on the support can do.

In the preparation of the hybrid supported catalyst, a hydrocarbon solvent such as pentane, hexane, heptane or the like, or an aromatic solvent such as benzene, toluene or the like may be used as a reaction solvent. In addition, the metallocene compound and the co-catalyst compound may be used in the form supported on silica or alumina.

The present invention also provides a process for producing an olefin-based polymer comprising polymerizing an olefin-based monomer in the presence of the hybrid supported catalyst.

In the process for preparing an olefin polymer according to the present invention, specific examples of the olefin monomer include ethylene, propylene, 1-butene, 1-pentene, 4-methyl- Octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-eicosene and the like. Preferably, the olefinic polymer may be a propylene homopolymer or a random copolymer of propylene and ethylene.

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

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

Here, the polymerization may 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 above-mentioned polymerization process can control the molecular weight range of the olefin-based polymer finally produced according to the hydrogenation or not-added conditions. In particular, an olefin polymer having a high molecular weight can be produced under hydrogen-free conditions, and if hydrogen is added, a low molecular weight olefin polymer can be produced even with a small amount of hydrogenation. 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 Can be supplied.

The olefin-based polymer prepared using the hybrid supported catalyst comprising the first and second metallocenes according to the present invention has a higher molecular weight distribution (PDI) than the conventional metallocene catalyst, The polymer can be produced with higher activity.

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

< 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 placed in a 3 L Schlenk flask and dissolved in toluene / THF (10: 1, 1.73 L) at room temperature . After cooling the solution to -20 캜, 240 mL of n-butyllithium solution (n-BuLi, 2.5 M in hexane) was slowly added dropwise, and the mixture was stirred at room temperature for 3 hours. Thereafter, the reaction solution was cooled to -20 캜, and then 82 g of (6-t-butoxyhexyl) dichloromethylsilane and 512 mg of CuCN were slowly added dropwise. The reaction solution was warmed to room temperature, stirred for 12 hours, and 500 mL of water was added. Thereafter, the treated organic layer was separated, washed, dehydrated, and filtered through a MgSO _4. 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

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 previously in a 3 L Schlenk flask, 1 L of ethyl ether was added and dissolved at room temperature. After the solution was cooled to -20 ° C, 240 mL of a n-butyllithium solution (n-BuLi, 2.5 M in hexane) was slowly added dropwise and the mixture was stirred at room temperature for 3 hours. Thereafter, the reaction solution was cooled to -78 deg. C, and then 92 g of hafnium chloride was added thereto. The reaction solution was warmed to room temperature, stirred for 12 hours, and the solvent was removed under reduced pressure. 1 L of dichloromethane was added, and then the insoluble inorganic salts and the like were removed by filtration. The filtrate was dried under reduced pressure, and again 300 mL of dichloromethane was added 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- butylphenylindenyl) silane

(20.0 g, 76 mmol) was dissolved in toluene / THF = 10/1 solution (230 mL), and a solution of n-butyllithium (2.5 M in hexane solvent, 22 g) at 0 &lt; 0 &gt; C slowly 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. Thereafter, water was added to separate the organic layer, and the solvent was distillated under reduced pressure to obtain (6-t-butoxyhexyl) (methyl) -bis (2-methyl-4-tert-butylphenylindenyl) 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 (2H, m), 6.89-6.91 (2H, m), 7.19-7.61 (14H, m) m)

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

(6-t-butoxyhexyl) (methyl) -bis (2-methyl-4-tert-butylphenylindenyl) silane prepared in the above step 1 was dissolved in a toluene / THF = After dissolution, a n-butyllithium solution (2.5 M, hexane solvent, 22 g) was slowly added dropwise at -78 占 폚, and the mixture was stirred at room temperature for one day. To the reaction solution of bis (N, N'- diphenyl-1,3-propane dia shown) dichloro zirconium 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 the mixture was stirred at room temperature for one day. After the reaction solution was cooled to -78 ° C, a HCl ether solution (1 M, 183 mL) was slowly added dropwise thereto, followed by stirring at 0 ° C for 1 hour. After filtration and vacuum drying, hexane was added and stirred to precipitate crystals. The precipitated crystals were filtered off and dried under reduced pressure to obtain 20.5 g of [(6-t-butoxyhexylmethylsilane-diyl) -bis (2-methyl-4-tert- butylphenylindenyl)] zirconium dichloride %).

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 , 2.26 (3H, s), 3.38 (2H, t), 7.00 (2H, s), 7.09-7.13 ), 7.59 (2H, d), 7.65 (2H, d)

Second Metallocene  Preparation of compounds

Synthetic example  3

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

1.1 g of NaH and 9.1 mL of diethylmethyl malonate were added to 55 mL of THF (tetrahydrofuran) and refluxed for 1 hour. Thereafter, the reaction mixture was cooled to room temperature, 10 g of 2-bromomethylnaphthalene was added to the reaction mixture, and the mixture was refluxed for 3 hours to prepare Compound A.

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

Then, HCl was added to the reaction mixture containing the compound B, and then the organic layer was extracted with ethyl acetate. Thereafter, the organic layer was dried, and heated until the gas was not discharged (heated to about 175 캜) to obtain a compound C.

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

Then, the reaction mixture containing the compound D was dried to remove the solvent. The remaining solute was added to 10 mL of dichloromethane and then cooled to 0 占 폚. To the cooled reaction mixture, 5.2 g of aluminum chloride was dispersed in 40 mL of dichloromethane and slowly added for 30 minutes. Then, the obtained reaction mixture was refluxed for 30 minutes, and the organic layer was extracted with an aqueous solution of HCl and dichloromethane to obtain a compound E.

Then, 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 the container containing 809 mg of NaBH ₄ powder at a temperature of 0 캜 for 1 hour. Subsequently, the reaction mixture was stirred at room temperature for 1 hour, and the organic layer was extracted with water to obtain Compound F. [

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

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

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

On the other hand, after the reactor was washed and dried 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 캜. Then, the filtrate prepared above was slowly dropped to the reactor while maintaining the temperature at -5 ° C for 2 hours. The temperature of the reactor was raised to 25 DEG C and stirred at about 130 rpm for 16 hours. Thereafter, the reaction mixture was distilled under reduced pressure at 25 캜, dispersed in 4.3 L of hexane, and stirred for 30 minutes. Thereafter, the solid was filtered from the reaction mixture, and further washed with 1.0 L of hexane and filtered. The filtrate was distilled under reduced pressure at 25 캜 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-benzoindan-1-yl) (6- (t-butoxy) hexyl) (methyl)

2-methyl-1H-benzoindene (2 g, 11.1 mmol) 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 DEG C, and 4.7 mL of a 2.5 M solution in hexane solution was slowly added dropwise to the reaction mixture. The resulting reaction mixture was then stirred at ambient temperature for 3 hours. Then 9.9 mg of CuCN was dissolved in a small amount of toluene and added to the reaction mixture in the form of a slurry, followed by stirring for 30 minutes. Subsequently, 1.6 g of the above-prepared (6-t-butoxyhexyl) dichloromethylsilane was added to the reaction mixture, and the resulting reaction mixture was stirred at room temperature for one day. Then, the obtained reaction product was extracted with water and methyl t-butyl ether, and dried to obtain a ligand.

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

3.1 g (5.55 mmol) of bis (2-methyl-1H-benzoindene-1-yl) (6- (t-butoxy) hexyl) (methyl) silane prepared above was dissolved in 55.5 mL of diethyl ether, To the solution was added slowly 4.7 mL of a solution of n-butyllithium (2.5 M solution in hexane) at -25 ° C. Thereafter, the obtained reaction mixture was stirred at room temperature for about 3 hours, and then cooled again to -25 ° C. 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 the mixture was stirred at room temperature for one day. Then, the reaction mixture was dried to remove the solvent, and dichloromethane was then injected. Then, the obtained mixed solution was filtered and the filtrate was dried. The solid obtained by drying was recrystallized with toluene at -30 캜 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 ~ 1.52 (2H, m), 1.59 ~ 1.62 (2H, m), 1.66 ~ 1.67 (2H, m), 1.84 ~ (2H, d), 7.56 (2H, dd), 7.76 (2H, d), 1.86 (4H, m), 2.35 (2 H, d), 7.94 (2 H, d).

Synthetic example  4

Step 4: Preparation of bis (2-methyl-1H-benzoindene-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.

3.1 g (5.55 mmol) of bis (2-methyl-1H-benzoindene-1-yl) (6- (t-butoxy) hexyl) (methyl) silane prepared above was dissolved in 55.5 mL of diethyl ether, -25, 4.7 mL of n-butyllithium solution (2.5 M solution in hexane) was slowly added dropwise to the solution. Then, the obtained reaction mixture was stirred at room temperature for about 3 hours, and then cooled again to -25. 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 dichloromethane was then injected. Then, the obtained mixed solution was filtered and the filtrate was dried. The solid obtained by drying was recrystallized with toluene at -30 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 ~ (2H, t), 7.50 (2H, t), 7.60 (2H, t), 1.87 (4H, m) (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)

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

Then, p-toluenesulfonic acid (p-TsOH) was dissolved in toluene, and the mixture was refluxed for 0.5 hours.

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

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

Then, after 4-indazol added along with Pd (PPh _{3) 4} (Tetrakis (triphenylphosphine) palladium) and a mixed solvent (toluene / ethanol / water), the Na ₂ CO ₃ and the non-stirred, 4- 4-tert-butylphenylboronic acid was added and the mixture was stirred at 80 ° C for 16 hours to obtain 4- (4-t-butylphenyl) -2-indanone.

On the other hand, 2-methylfuran and THF were added to a separate reactor, and the temperature of the reactor was cooled to -25 ° C. Subsequently, a n-butyllithium solution was slowly added dropwise to the resulting reaction mixture, and the mixture was stirred for 4 hours while the temperature was raised to room temperature.

Then, the temperature of the resulting reaction mixture was cooled again to -25 캜. 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-toluenesulfonic acid (p-TsOH) was added to the resulting reaction mixture and refluxed for 10 minutes to prepare 2- [2- (5-methyl) furyl] -4- (4- Respectively.

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

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

On the other hand, after the reactor was washed and dried 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 캜. Then, the filtrate prepared above was slowly dropped to the reactor while maintaining the temperature at -5 ° C for 2 hours. The temperature of the reactor was raised to 25 DEG C and stirred at about 130 rpm for 16 hours. Thereafter, the reaction mixture was distilled under reduced pressure at 25 캜, dispersed in 4.3 L of hexane, and stirred for 30 minutes. Thereafter, the solid was filtered from the reaction mixture, and further washed with 1.0 L of hexane and filtered. The filtrate was distilled under reduced pressure at 25 캜 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-methylpuryl) -4- (4-t-butylphenyl) inden-

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 DEG C, and 4.7 mL of a 2.5 M solution in hexane solution was slowly added dropwise to the reaction mixture. The resulting reaction mixture was then stirred at ambient temperature for 3 hours. Then, the temperature of the obtained reaction mixture was cooled to 0 캜 again, 1.6 g of the previously prepared (6-t-butoxyhexyl) dichloromethylsilane was added, and the resulting reaction mixture was stirred at room temperature for 15 hours. Then, from the reaction product obtained, an organic layer was extracted with water and methyl t-butyl ether and dried. The thus-obtained dried product was purified by column chromatography to obtain a ligand in a yield of 79%. At this time, hexane / EA (ethyl acetate) = 20/1 was used as an elution solvent.

Step 4: Synthesis of bis (2- [2- (5-methyl) furyl] -4- (4-t-butylphenyl) inden- Manufacturing

(6-t-butoxyhexyl) (methyl) silane prepared above was reacted with diethyl (2-ethylphenyl) After dissolving in ether, 4.7 mL of n-butyllithium solution (2.5 M solution in hexane) was slowly added dropwise to the solution at 0 ° C. Then, the obtained reaction mixture was stirred at room temperature for about 3 hours, and then cooled again to 0 占 폚. 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. Then, the reaction mixture was dried to remove the solvent, and dichloromethane was then injected. Then, the obtained mixed solution was filtered and the filtrate was dried. The racemic compounds were predominantly 5 times more abundant than the meso compounds in the crude transition metal compounds obtained in this way. The transition metal compound in the crude state was recrystallized from a mixed solvent (dichloromethane / hexane: volume ratio = 1: 5) to obtain a transition metal compound at a yield of 44% (racemic: meso = 99: 1).

Synthesis Example 6

(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

Preparation of Supported Catalyst

Production Example 1

3 g of silica L203F was preliminarily weighed in a shrinking flask, and 13 mmol of methylaluminoxane (MAO) was added thereto, followed by reaction at 95 ° C. for 24 hours. After precipitation, the upper layer was removed and washed once with toluene. 60 占 퐉 ol of the compound prepared in Synthesis Example 1 was dissolved in toluene and reacted at 75 占 폚 for 5 hours. After the completion of the reaction, the upper layer solution was removed and the remaining reaction product was washed once with toluene. Then, 20 mu mol of the compound prepared in Synthesis Example 3 was dissolved in toluene, and the mixture was further reacted at 75 DEG C for 2 hours.

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

Production Example 2

3 g of silica L203F was preliminarily weighed in a shrinking flask, and 13 mmol of methylaluminoxane (MAO) was added thereto, followed by reaction at 95 ° C. for 24 hours. After precipitation, the upper layer was removed and washed once with toluene. 60 占 퐉 ol of the compound prepared in Synthesis Example 1 was dissolved in toluene and reacted at 75 占 폚 for 5 hours. After the completion of the reaction, the upper layer solution was removed and the remaining reaction product was washed once with toluene. Then, 20 mu mol of the compound prepared in Synthesis Example 5 was dissolved in toluene and further reacted at 75 DEG C for 2 hours.

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

Production Example 3

3 g of silica L203F was preliminarily weighed into a shrinkage flask, and 13 mmol of methylaluminoxane (MAO) was added thereto, followed by reaction at 95 ° C. for 24 hours. After precipitation, the upper layer was removed and washed once with toluene. 60 mu mol of the compound prepared in Synthesis Example 2 was dissolved in toluene, and the mixture was reacted at 75 DEG C for 5 hours. After the completion of the reaction, the upper layer solution was removed and the remaining reaction product was washed once with toluene. Then, 20 mu mol of the compound prepared in Synthesis Example 4 was dissolved in toluene, and the mixture was further reacted at 75 DEG C for 2 hours.

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

Production Example 4

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

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

Example of olefin polymerization

Example 1

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, the hybrid supported catalyst prepared in Preparation Example 1 was dissolved in 20 mL of TMA-formulated hexane in the following Table 1 and introduced into the reactor under 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.

<Experimental Example>

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

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

(2) Polydispersity Index (PDI): The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the polymer were measured 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 160 캜, trichlorobenzene was used as a solvent, and the molecular weight was measured by standardizing with polystyrene.

(3) Melt Index (MFR, 2.16 kg): Measuring temperature 230 占 폚, ASTM 1238

(4) Melt Flow Rate Ratio (MFRR): The MFR ₂₀ was calculated by dividing the melt index (21.6 kg load) by the 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, 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 lowered to 20 ° C., the temperature was increased again. The temperature rising rate and the falling rate were controlled at 10 ° C./min.

The results of measurement of the physical properties of the olefinic polymers prepared in the examples are shown in Table 1 below.

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

As shown in Table 1, the examples of the present invention show that not only the catalytic activity is high, but also the low melting temperature, the high melt flow rate ratio and the wide molecular weight distribution are shown, and it is confirmed that it is suitable for producing 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 general formulas (2), (3) and (4); And
Hybrid supported catalyst comprising carrier:
[Chemical Formula 1]

In Formula 1,
M ¹ is a Group 4 transition metal,
X ¹ and X ² are the same or different from each other and each independently halogen,
R ¹ is aryl having 6 to 20 carbon atoms substituted with alkyl having 1 to 20 carbon atoms,
R ² , R ³ and R ⁴ are the same or different and each independently represents hydrogen, halogen, alkyl of 1 to 20 carbon atoms, alkenyl of 2 to 20 carbon atoms, alkylsilyl of 1 to 20 carbon atoms, Alkyl having 1 to 20 carbon atoms, alkoxysilyl having 1 to 20 carbon atoms, ether having 1 to 20 carbon atoms, silyl ether having 1 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, alkylaryl having 7 to 20 carbon atoms, or arylalkyl having 7 to 20 carbon atoms,
A ¹ is carbon, silicon or germanium,
R ⁵ is alkyl having 1 to 20 carbon atoms substituted with alkoxy having 1 to 20 carbon atoms,
R ⁶ is hydrogen, alkyl having 1 to 20 carbon atoms or alkenyl having 2 to 20 carbon atoms,
(2)

In Formula 2,
M ² is a Group 4 transition metal,
X ³ and X ⁴ are the same or different and are each independently halogen,
A ² is carbon, silicon or germanium,
R ⁷ is alkyl having 1 to 20 carbon atoms substituted with alkoxy having 1 to 20 carbon atoms,
R ⁸ is hydrogen, alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, alkylaryl having 7 to 30 carbon atoms, arylalkyl having 7 to 30 carbon atoms, or aryl having 6 to 30 carbon atoms,
R ⁹ and R ¹⁰ are the same or different from each other and each independently represents hydrogen or alkyl having 1 to 20 carbon atoms,
(3)

In Formula 3,
M ³ is a Group 4 transition metal,
X ⁵ and X ⁶ are the same or different from each other and each independently halogen,
A ³ is carbon, silicon or germanium,
R ¹¹ is alkyl having 1 to 20 carbon atoms substituted with alkoxy having 1 to 20 carbon atoms,
R ¹² is hydrogen, alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, alkylaryl having 7 to 30 carbon atoms, arylalkyl having 7 to 30 carbon atoms, or aryl having 6 to 30 carbon atoms,
R ¹³ and R ¹⁴ are the same or different and are each independently hydrogen and alkyl having 1 to 20 carbon atoms,
R ¹⁵ and R ¹⁶ are the same or different and are each independently an aryl having 6 to 20 carbon atoms and substituted with alkyl having 1 to 20 carbon atoms,
[Chemical Formula 4]

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

,

The method according to claim 1,
R ⁷ in the above formula (2) is 6-tert-butoxy-hexyl,
The method according to claim 1,
Wherein R ⁸ , R ⁹ , and R ¹⁰ in Formula 2 are methyl.
The method according to claim 1,
Wherein the second metallocene compound represented by Formula 2 is one of the following compounds:

,

The method according to claim 1,
Wherein R &lt; ¹¹ &gt; in the above formula (3) is 6-tert-butoxy-hexyl.
The method according to claim 1,
Wherein R ¹² , R ¹³ and R ¹⁴ in the above formula (3) are methyl.
The method according to claim 1,
Wherein R ¹⁵ and R ¹⁶ in Formula 3 are 4-tert-butyl-phenyl.
The method according to claim 1,
The second metallocene compound represented by the above-mentioned general formula (3) is the following compound, mixed carrier catalyst:

The method according to claim 1,
Wherein R ¹⁸ in the formula (4) is methoxy and R ¹⁹ is tert-butyl.
The method according to claim 1,
Wherein R ²¹ in Formula 4 is 6-tert-butoxy-hexyl, hybrid supported catalyst.
The method according to claim 1,
Wherein the second metallocene compound represented by Formula 4 is one of the following compounds:

,

,

,

The method according to claim 1,
Wherein the carrier is silica, alumina, magnesia or a mixture thereof.
The method according to claim 1,
Wherein the first metallocene compound and the second metallocene compound are present in a molar ratio of 10: 1 to 2: 1, based on the molar ratio of metal.
The method according to claim 1,
A hybrid supported catalyst further comprising at least one cocatalyst selected from a compound represented by the following general formula (5), a compound represented by the general formula (6) and a compound represented by the general formula (7)
[Chemical Formula 5]
- [Al (R ') - O] _m -
In Formula 5,
R 'may be the same or different from each other and are 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;
[Chemical Formula 6]
J (R ') ₃
In Formula 6,
R &quot; is as defined in Formula 5 above;
J is aluminum or boron;
(7)
[EH] ⁺ [ZQ ₄ ] ^- or [E] ⁺ [ZQ ₄ ] ^-
In 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 independently at least one hydrogen atom is an aryl group having 6 to 20 carbon atoms or an alkyl group having 1 to 20 carbon atoms substituted or unsubstituted with halogen, a hydrocarbon having 1 to 20 carbon atoms, an alkoxy or a phenoxy .
A process for producing an olefin-based polymer, which comprises polymerizing at least one olefin monomer in the presence of the hybrid supported catalyst of any one of claims 1 to 18.
20. The method of claim 19,
The olefins may be selected from the group consisting of ethylene, propylene, 1-butene, 1-pentene, 1-hexene, Octadecene, 1-octadecene, 1-eicosene, and mixtures thereof.
20. The method of claim 19,
Wherein the olefinic polymer is a propylene homopolymer or a copolymer of propylene and ethylene.