KR20170075533A - 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 exhibiting a high active catalyst and having a low melting temperature, and a process for producing an olefin-based 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. In addition, there is a need for an anhydride-metallocene catalyst capable of producing olefinic polymers of higher molecular weight.

Accordingly, the present inventors have conducted various studies on a catalyst capable of producing an olefin-based polymer having a higher activity than the above-described catalyst while having a low melting temperature and a melt index, Based catalyst, the present inventors have completed the present invention by confirming that the olefin-based polymer can be simultaneously prepared.

The present invention is to provide a hybrid supported catalyst capable of producing an olefin polymer having a low melting temperature and high porosity at 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 problems, the present invention provides a hybrid supported catalyst comprising a transition metal compound represented by the following formula (1), a transition metal compound represented by the following formula (2), and a carrier.

[Chemical Formula 1]

In Formula 1,

X is the same or different 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, alkoxysilyl having 1 to 20 carbon atoms, ether having 1 to 20 carbon atoms, silyl ether having 1 to 20 carbon atoms, alkoxy having 1 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, alkylaryl having 7 to 20 carbon atoms, Lt; / RTI > to 20,

A 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 is a Group 4 transition metal,

X 'are the same or different from each other and are each independently halogen or alkyl of 1 to 20 carbon atoms,

A 'is carbon, silicon or germanium,

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

n is an integer between 1 and 20;

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 can easily produce an olefin polymer having a low melting temperature (Tm) and a melt index (MFR) when an olefinic polymer is prepared using the catalyst.

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 a transition metal compound represented by the following formula (1), a transition metal compound represented by the following formula (2), and a carrier:

[Chemical Formula 1]

In Formula 1,

X is the same or different 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, alkoxysilyl having 1 to 20 carbon atoms, ether having 1 to 20 carbon atoms, silyl ether having 1 to 20 carbon atoms, alkoxy having 1 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, alkylaryl having 7 to 20 carbon atoms, Lt; / RTI > to 20,

A 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 is a Group 4 transition metal,

X 'are the same or different from each other and are each independently halogen or alkyl of 1 to 20 carbon atoms,

A 'is carbon, silicon or germanium,

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

n is an integer between 1 and 20;

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.

When a hybrid supported catalyst in which the transition metal compound represented by Formula 1 and the transition metal compound represented by Formula 2 are carried together, an olefin polymer exhibiting a low melting temperature (Tm) and high porosity can be produced. In addition, it has been confirmed that the transition metal compound of the above formula (1) can complement the disadvantage that the catalyst for preparing an olefin polymer having a low melting point is low in activity, and thus an olefin polymer having the above properties can be produced with high activity.

The transition metal compound of Formula 1 has an anis-metallocene structure and contains 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 transition metal compound represented by the formula (1) is supported on a carrier and used as a catalyst in the production of polyolefins, a polyolefin having a desired property 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, X may be chloro (Cl).

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

Also preferably, A may be silicon.

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

Representative examples of the transition metal compound represented by the formula (1) are as follows, but the present invention is not limited thereto.

The 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.

The transition metal compound represented by the general formula (2) includes two benzoindenyl groups as a ligand and a bridge group connecting the two ligands with an Lewis base as an oxygen-donor And a functional group capable of acting as a substituent. For example, when the transition metal 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) is exhibited, Can be produced. In particular, this effect can be maximized in the polymerization of propylene.

More specifically, in the transition metal compound represented by the general formula (2), the benzoindenyl ligand may be substituted with a substituent which is not substituted or has a low steric hindrance. 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 deposition stability of the transition metal compound.

For example, R ₇ of formula (1) may be any of branched alkyl having 3 to 6 carbon atoms, preferably tert-butyl, for improved loading efficiency.

Also, n is an integer of 4 to 8, preferably 6.

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

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

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

,

,

The 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 (Stpe 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.

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 transition metal compound represented by the above formula (2) has a disadvantage that the olefin polymer having a low melting temperature (Tm) can be polymerized due to structural specificity, but the catalytic activity is relatively low. On the other hand, the transition metal compound represented by the formula (1) contains zirconium (Zr) as a metal atom, so that the activity of the catalyst is very high. Thus, by using the hybrid supported catalyst carrying the transition metal compounds represented by the above formulas (1) and (2) as the present invention, it is possible to obtain an olefin polymer having a low melting temperature, for example, ) Can be produced 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 transition metal compound represented by Formula 1 and the transition metal compound represented by Formula 2 may be in the range of about 1: 1 to about 1: 1,000, preferably about 1: : 1 to about 1: 10. 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. When the drying temperature of the carrier is lower than 200 ° C, water is too much to cause the cocatalyst to react with moisture on the surface. When the drying temperature exceeds 800, the pores on the surface of the carrier are combined to reduce the surface area. It is not preferable because only the excess siloxane group is left and the reaction site with the co-catalyst is reduced.

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 transition metal compound represented by Formula 1 and the transition metal compound represented by Formula 2) 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 transition metal compound represented by the formula (1) and the transition metal compound represented by the formula (2). The cocatalyst may include at least one of the following cocatalyst compounds represented by the following formulas (3), (4) and (5).

(3)

- [Al (R ₁₁ ) -O] _m -

In Formula 3,

R ₁₁ 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;

[Chemical Formula 4]

J (R ₁₂ ) ₃

In Formula 4,

R ₁₂ is as defined in Formula 3 above;

J is aluminum or boron;

[Chemical Formula 5]

[EH] ⁺ [ZQ ₄ ] ^- or [E] ⁺ [ZQ ₄ ] ^-

In Formula 5,

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 (3) include methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, butylaluminoxane and the like. A more preferred compound is methylaluminoxane.

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

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

The hybrid supported catalyst according to the present invention comprises a support having a promoter compound supported thereon, supporting the compound represented by Formula 1 on the support, and supporting the compound represented by Formula 2 on the support And the order of loading can be changed as needed.

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 olefinic polymer prepared using the hybrid supported catalyst comprising the transition metal compound represented by Formula 1 and the transition metal compound represented by Formula 2 according to the present invention can be produced by using a conventional metallocene catalyst The olefin polymer having a lower melting temperature 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.

<Examples>

Preparation of first transition metal compound

Synthesis Example 1

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), 7.19-7.61 (14H, m), 1.36 (2H, m), 2.19-2.23 (6H, m), 3.30-3.34 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)

Preparation of second transition metal compound

Synthesis Example 2

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.

(1H, m), 3.33 (2H, t), 1.32 (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 hafnium 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 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 캜 to obtain a transition metal compound in a yield of 12%.

(2H, m), 1.67-1.69 (2H, m), 1.81-1.87 (2H, m), 1.50-1.54 (2H, t), 7.43 (2H, t), 7.60 (2H, t), 7.39 , &lt; / RTI &gt; dd), 7.77 (2H, d), 7.92 (2H, d).

Synthesis Example 3

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

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)

Preparation of Supported Catalyst

Production Example 1

3 g of silica L203F was preliminarily weighed into 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 1 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.

Comparative Preparation Example 1

3 g of silica L203F was preliminarily weighed in a shrinking flask, and 10 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. Dimethyl anilinium tetrakis (pentafluorophenyl) borate (48 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.

Comparative Production Example 2

3 g of silica L203F was preliminarily weighed in a shrinking flask, and 10 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. Dimethyl anilinium tetrakis (pentafluorophenyl) borate (48 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.

Comparative Production Example 3

3 g of silica L203F was preliminarily weighed in a shrinking flask, and 10 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 3 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 1 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.

Example of olefin polymerization

Example 1

1) Propylene homopolymerization

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

2) random polymerization of propylene

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

Comparative Example 1

Propylene homopolymerization and random polymerization were carried out in the same manner as in Example 1, except that the supported catalyst of Comparative Production Example 1 was used instead of the hybrid supported catalyst of Example 1.

Comparative Example 2

Propylene homopolymerization and random polymerization were carried out in the same manner as in Example 1, except that the supported catalyst of Comparative Production Example 2 was used instead of the hybrid supported catalyst of Example 1.

Comparative Example 3

Propylene homopolymerization and random polymerization were carried out in the same manner as in Example 1, except that the supported catalyst of Comparative Production Example 3 was used instead of the hybrid supported catalyst of Example 1 above.

<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 (mmol and g of catalyst) based on unit time (h).

(2) 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.

(3) Crystallization temperature (Tc): The crystallization temperature was determined from the curve obtained by decreasing the temperature under the same conditions as the melting point using DSC.

(4) Melt index (MFR, 2.16 kg): Measuring temperature 230 占 폚, ASTM 1238

The results of physical properties of the homo and random propylene polymers prepared in Examples and Comparative Examples are shown in Table 1 below.

catalyst Category ¹⁾ Bearing
Amount of catalyst
(mg) yield
(g) activation
(kg PP / g Cat.hr) MFR
(g / 10 min) Tm
(° C) Tc
(° C) Example 1 H 45 396.6 8.8 12.4 148.6 99.7 R 45 433.9 9.6 5.8 140.0 86.7 Comparative Example 1 H 45 375.6 8.3 8.3 150.3 99.2 R 45 332.0 7.4 6.6 143.3 93.5 Comparative Example 2 H 80 94.1 1.2 Not measurable 144.7 100.2 R 80 163.2 2.0 4.0 138.4 86.5 Comparative Example 3 H 45 437.4 9.7 9.1 152.6 101.1 R 30 369.4 12.3 5.1 142.5 89.4

1) H: homopolymerization, R: random polymerization

As shown in Table 1, both the homopolymerization and the random polymerization showed that the embodiments of the present invention were significantly improved in activity and physical properties as compared with Comparative Examples 1 and 2 using each of the transition metal compound catalysts alone.

Specifically, in Comparative Examples 1 and 3, the catalyst activity was relatively high but the melting temperature of the polymer was high, so that it could not be used for a film having a low melting temperature. In Comparative Example 2, .

On the other hand, Example 1 exhibited a higher catalytic activity as compared with Comparative Example 2, exhibited a lower melting temperature than Comparative Examples 1 and 3, and was suitable for producing an olefin polymer excellent in energy saving effect during processing or molding .

Claims (17)

A transition metal compound represented by the following formula (1);
A transition metal compound represented by the following formula (2); And
Hybrid supported catalyst comprising carrier:
[Chemical Formula 1]

In Formula 1,
X is the same or different 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 each independently 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, Alkoxy of 1 to 20 carbon atoms, ether of 1 to 20 carbon atoms, silyl ether of 1 to 20 carbon atoms, alkoxy of 1 to 20 carbon atoms, aryl of 6 to 20 carbon atoms, alkylaryl of 7 to 20 carbon atoms, ego,
A 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 is a Group 4 transition metal,
X 'are the same or different from each other and are each independently halogen or alkyl of 1 to 20 carbon atoms,
A 'is carbon, silicon or germanium,
R ₇ is an alkyl having 1 to 20 carbon atoms, an alkenyl having 2 to 20 carbon atoms, an alkylaryl having 7 to 30 carbon atoms, an arylalkyl having 7 to 30 carbon atoms or an aryl having 6 to 30 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,
n is an integer between 1 and 20;
The method according to claim 1,
R &lt; _{1 &gt;} is phenyl substituted with tert-butyl.
The method according to claim 1,
R ₂ , R ₃ and R ₄ are hydrogen.
The method according to claim 1,
A is a silicone, hybrid supported catalyst.
The method according to claim 1,
R ₅ is 6-tert-butoxy-hexyl, and R ₆ is methyl.
The method according to claim 1,
The transition metal compound represented by the above-mentioned formula (1) is the following compound, mixed carrier catalyst:

The method according to claim 1,
R &lt; ₇ &gt; is a tert-butyl, hybrid supported catalyst
The method according to claim 1,
R ₈ , R ₉ and R ₁₀ are methyl.
The method according to claim 1,
And A 'is silicon.
The method according to claim 1,
M is hafnium (Hf) or zirconium (Zr).
The method according to claim 1,
The transition metal compound represented by Formula 2 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 transition metal compound represented by Formula 1 and the transition metal compound represented by Formula 2 are contained in a molar ratio of 1: 1 to 1: 1,000 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 (3), a compound represented by the general formula (4) and a compound represented by the general formula (5)
(3)
- [Al (R ₁₁ ) -O] _m -
In Formula 3,
R ₁₁ 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;
[Chemical Formula 4]
J (R ₁₂ ) ₃
In Formula 4,
R ₁₂ is as defined in Formula 3 above;
J is aluminum or boron;
[Chemical Formula 5]
[EH] ⁺ [ZQ ₄ ] ^- or [E] ⁺ [ZQ ₄ ] ^-
In Formula 5,
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 14.
16. The method of claim 15,
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.
16. The method of claim 15,
Wherein the olefinic polymer is a propylene homopolymer or a random copolymer of propylene and ethylene.