KR101116699B1 - Hybrid Supported Metallocene Catalyst, Method for Preparing the Same, and Method for Preparing Polyolefin using the Same - Google Patents

Abstract

The present invention relates to a hybrid supported metallocene catalyst, a method for preparing the same, and a method for preparing a polyolefin using the same, comprising: a promoter; an organic metal compound comprising aluminum in a carrier; Cocatalyst component 2, which is an organometallic compound comprising boron; Metallocene compound 1; And it provides a hybrid supported metallocene catalyst, its preparation method, and a method for producing a polyolefin using the metallocene compound 2 is supported. The hybrid supported metallocene catalyst of the present invention includes two or more different metallocene compounds having a ligand substituted with an alkoxide or an aryl oxoxide in the existing supported metallocene catalyst and a borate compound as a second promoter. By supporting, the catalytic activity is remarkably high compared to the existing metallocene supported catalyst and the molecular weight distribution can be easily controlled.

Description

Hybrid supported metallocene catalyst, method for preparing the same, and method for preparing polyolefin using the same {Hybrid Supported Metallocene Catalyst, Method for Preparing the Same, and Method for Preparing Polyolefin using the Same}

The present invention relates to a hybrid supported metallocene catalyst, and more particularly, to a highly active hybrid supported metallocene catalyst, a method for preparing the same, and a method for producing a polyolefin using the same.

In 1976, Professor Kaminsky of Germany reported that methylaluminoxane (MAO) compounds obtained by partial hydrolysis of trimethylaluminum can be used as cocatalysts and zirconocenedichloride compounds as catalysts for olefin polymerization. (A.Anderson, JG Corde, J. Herwig, W. Kaminsky, A. Merck, R. Mottweiler, J. Pein, H. Sinn, and HJ Vollmer, Angew. Chem. Int. Ed. Engl., 15, 630 , 1976).

Exon subsequently filed a patent (US Pat. No. 5,324,800) for olefin polymerization using metallocene compounds having various substituents on cyclopentadienyl ligands.

Since the metallocene catalyst has a uniform active site, the molecular weight distribution of the polymer is narrow, the copolymerization is easy, and the distribution of the second monomer is uniform, and in the case of propylene polymerization, the steric structure of the polymer can be adjusted according to the symmetry of the catalyst. There is an advantage. In particular, existing Ziegler-Natta catalysts can only produce isotactic polypropylene, but with metallocene catalysts, isotactic, syndiotactic, atactic and of course hemiisotactic Various polypropylenes, such as hemisotactic, can be produced stereoregularly. For example, the syndiotactic polypropylene synthesized using metallocene has low crystallinity, moderate stiffness and hardness, transparency, and high impact resistance. That is, when the metallocene catalyst is used, three-dimensional control is possible in the production of polyolefin, and since there is an advantage in that physical properties of the polymer are easily controlled, studies on the metallocene catalyst have been actively conducted.

However, in the olefin polymerization technique using such a homogeneous catalyst, it is difficult to maintain the shape of the polymer in a gas phase process or a slurry process, and there is a problem in that an excessive amount of MAO is required to exhibit the maximum activity of the metallocene catalyst. In order to solve this problem, the metallocene catalyst should be supported on a suitable carrier. In the case of supporting the catalyst, not only the shape of the produced polymer can be adjusted, but also the molecular weight distribution can be adjusted according to the use. The apparent density can be improved, and fouling in the reactor can be reduced.

In general, a method for preparing a supported metallocene catalyst is a method for preparing a metallocene compound by physically and chemically bonding a metallocene compound to a carrier and then contacting aluminoxane, and reacting the metallocene compound after supporting the aluminoxane on a carrier. And a method of contacting a metallocene compound with an aluminoxane first and then supporting it on a carrier. In order for the supported catalyst to have the same high activity and copolymerization efficiency as the homogeneous catalyst, the single active site catalyst structure must be maintained even after supporting, and the catalyst must not be separated from the carrier during the polymerization process to prevent reactor fouling. In addition, the particle size, particle size distribution, and apparent density of the polymer depend on the particle shape and the mechanical properties of the supported catalyst.

Korean Patent Publication No. 10-0404780 discloses a metallocene compound having a silacycloalkyl substituent and a supported catalyst using the same, but when used in a gas phase process or a slurry process, a reactor fouling phenomenon occurs because the catalyst is liberated in a carrier. This may occur.

On the other hand, Japanese Patent Application Laid-open No. Hei 6-56928 discloses a method of preparing a supported metallocene catalyst by first supporting a ligand by a chemical bond on the surface of a carrier and then bonding a metal to the ligand. This method has the disadvantage that the process of making the catalyst is very complicated and it is difficult to support a large amount of catalyst on the carrier.

Of the various supported catalyst preparation methods described above, the method of reacting aluminoxane on a carrier and reacting with a metallocene compound is the oldest method of making a heterogeneous single activity catalyst. For example, silica is reacted with an aluminoxane solution and the filtrate is filtered and then reacted with zirconocene dissolved in toluene or an aliphatic hydrocarbon solvent to form a supported catalyst, which can be used directly for ethylene polymerization or copolymerization in gas phase or slurry processes. have. This supporting method shows relatively high activity because the promoter is physically and chemically fixed on the surface of the carrier and the catalyst is present in the form of an ionic bond with the promoter as in a homogeneous system, and requires the use of an additional aluminoxane in the polymerization reactor. Single-phase catalysts can be prepared, making them easy to apply to existing slurry or gas phase processes. However, reactor fouling may occur because the glass of the catalyst may not be completely blocked, and aluminoxanes that may be bonded to silica may have limitations, and thus, metallocene compounds that may bind to the catalysts may have limitations. .

WO2002 / 040549 discloses an olefin polymerization catalyst comprising a metallocene compound and a supported activator such as MAO, an ionizing activator such as dimethylanilinium tetra (pentafluorophenyl) borate, triphenylcarbeniumtetra (pentafluorophenyl) borate and a carrier. 2008-121027 discloses a catalyst for preparing an olefin polymer comprising a carrier such as silica, a transition metal compound such as methylaluminoxane and bis (indenyl) zirconium dichloride, and [PhNMe ₂ H] [B (C ₆ F ₅ ) ₄ ]. U.S. Patent Application Publication No. 2006/0116490 discloses a metallocene catalyst for olefin polymerization including a cocatalyst and a metallocene compound, which is a combination of a carrier, an ionic compound such as aluminoxane and tetrakis (pentafluorophenyl) borate, and Akihiro. Yano has published dimethylanilinium tetrakis (pentafluorophenyl) borate (Me ₂ PhNH? B (C ₆ F ₅ ) ₄ ) / triisobutylaluminum (i-B in the Journal of Molecular Catalysis A: Chemical 156_2000.133-141. u ₃ Al) An ethylene polymerization catalyst comprising a cocatalyst and a metallocene compound was disclosed. However, these catalysts have a problem of low activity and difficult to control the molecular weight distribution.

In order to solve this problem, the present invention includes two or more metallocene compounds of different structures having ligands substituted with alkoxides or aryloxanes in existing supported metallocene catalysts, It is intended to provide a highly active hybrid supported metallocene catalyst having catalytic activity significantly higher than that of a conventional metallocene supported catalyst by supporting with a cocatalyst.

It is also an object of the present invention to provide a method for preparing a highly active hybrid supported metallocene catalyst.

In addition, by using the hybrid supported metallocene catalyst prepared according to the present invention in the polyolefin production method, it can be applied in the polyolefin polymerization process polymerized at a low or high pressure, it is easy to control the molecular weight distribution of the polyolefin produced, An object of the present invention is to provide a method for preparing polyolefin to prevent fouling.

The present invention to achieve the first technical problem,

Carrier; on

Promoter component 1, which is an organometallic compound comprising aluminum;

Cocatalyst component 2, which is an organometallic compound comprising boron;

Metallocene compound 1 represented by Formula 1; And

It provides a hybrid hybrid supported metallocene catalyst, characterized in that the metallocene compound 2 represented by the formula (2) or (3) is supported.

 [Formula 1]

[Formula 2]

(3)

In Formula 1, 2 or 3,

Cp and Cp 'are either selected from the group consisting of the same or different cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl and fluorenyl radicals; R ^m and R ⁿ are the same or different hydrogen radicals, alkyl having 1 to 20 carbon atoms, cycloalkyl, aryl, alkenyl, alkylaryl, arylalkyl, arylalkenyl radicals or alkylsilyl radicals; R ¹ and R ² are the same or different hydrogen or hydrocarbyl radicals having 1 to 6 carbon atoms; a, a ', b or b' are each an integer of 1 to 4;

M is a transition metal of Groups 4B, 5B, or 6B of the Periodic Table;

Q is a halogen radical or an alkyl radical having 1 to 20 carbon atoms, an alkenyl radical, an aryl radical, an alkylaryl radical, an arylalkyl radical; Or an alkylidene radical of 1 to 20 carbon atoms, k is 2 or 3, z is 0 or 1, and z is 0 when k is 3;

B is any one selected from the group consisting of alkyl radicals having 1 to 4 carbon atoms or hydrocarbyl radicals containing silicon, germanium, phosphorus, nitrogen, boron or aluminum;

In formula 3, J is any one selected from the group consisting of NR ^s , O, PR ^s and S, wherein R ^s is an alkyl radical or substituted alkyl radical having 1 to 20 carbon atoms;

Any one of the hydrogen radicals present in the R ^m , R ⁿ , B or R ^s is a compound of formula 4, 5 or 6,

[Formula 4]

In Formula 4,

Z is an oxygen atom or a sulfur atom, or preferably an oxygen atom;

R and R 'are the same or different hydrogen radicals; Alkyl having 1 to 20 carbon atoms, cycloalkyl, aryl, alkenyl, alkylaryl, arylalkyl; Or an arylalkenyl radical, preferably an alkyl radical having 1 to 20 carbon atoms, the same as or different from each other; Two R ′s can be linked together to form a ring,

G is alkoxy, aryloxy, alkylthio, arylthio, phenyl, or substituted phenyl or preferably alkoxy having 1 to 20 carbon atoms, which may be linked to R 'to form a ring;

If Z is a sulfur atom, G is necessarily alkoxy or aryloxy;

If G is alkylthio, arylthio, phenyl, or substituted phenyl, Z is necessarily an oxygen atom,

[Chemical Formula 5]

In Formula 5,

Z 'is an oxygen atom or a sulfur atom or preferably an oxygen atom and at least one of the two Z' is an oxygen atom;

R and R ″ are the same or different from each other, a hydrogen radical; Alkyl, cycloalkyl, aryl, alkenyl, alkylaryl, arylalkyl, or arylalkenyl radicals of 1 to 20 carbon atoms, preferably alkyl radicals of 1 to 20 carbon atoms, the same or different,

R and R ″ or two R ″ can be linked together to form a ring,

[Formula 6]

In Chemical Formula 6,

Z ″ is an oxygen, sulfur, nitrogen, phosphorus or arsenic atom or preferably an oxygen atom;

R ′ '' is a hydrogen radical, alkyl having 1 to 40 carbon atoms, cycloalkyl, aryl, alkenyl, alkylaryl, arylalkyl or arylalkenyl radicals, which are the same as or different from each other, and are preferably the same or different Is an alkyl radical of;

R '' '' is a hydrogen radical, alkyl of 1 to 40 carbon atoms, aryl, alkenyl, alkylaryl, alkylsilyl, arylsilyl, phenyl or substituted phenyl or preferably an alkyl radical of 1 to 40 carbon atoms;

n is 1 or 2 or preferably 1, n is 1 if Z "is oxygen or sulfur, n is 2 if Z" is nitrogen, phosphorus or arsenic.

The present invention to achieve the second technical problem,

Preparing a carrier on which promoter 1 is supported by reacting promoter 1, which is an organometallic compound containing aluminum, with the carrier;

Promoter 1 and metallocene compounds 1 and 2 are reacted by reacting the metallocene compound 1 represented by the formula (1) and the metallocene compound 2 represented by the formula (2) or (3) according to the present invention to a carrier on which the promoter 1 is supported. Preparing a supported carrier; And

Co-catalyst 1 and the supported metal carrier 2, an organic metal compound of the boron-containing cocatalyst 2 is reacted with a carrier on which the promoters 1, 2, metallocene compound 1, and the hybrid supported metal supported on Preparing a rosene catalyst;

It provides a method for producing a hybrid supported metallocene catalyst comprising a.

The hybrid supported metallocene catalyst of the present invention includes two or more different metallocene compounds having a ligand substituted with an alkoxide or an aryl oxoxide in the existing supported metallocene catalyst and a borate compound as a second promoter. By supporting, the catalytic activity has a remarkably high effect compared to the existing metallocene supported catalyst.

In addition, the method for producing a highly active hybrid supported metallocene catalyst of the present invention can produce a highly active hybrid supported metallocene catalyst in a simple process.

In addition, the polyolefin production method of the present invention using a hybrid supported metallocene catalyst prepared according to the present invention is applicable to a polyolefin polymerization process polymerized at a low or high pressure, it is easy to control the molecular weight distribution of the produced polyolefin, It has the effect of preventing fouling in the process.

Hereinafter, the present invention will be described in detail including examples.

According to a preferred embodiment of the present invention, in the compounds represented by Formulas 1 to 3, M is titanium, zirconium or hafnium, Q is preferably halogen, most preferably chlorine, and k is preferably 2.

On the other hand, a representative example of the metallocene compound represented by Formula 1 of the present invention is [AO- (CH ₂ ) _a -C ₅ H ₄ ] ₂ ZrCl ₂ or [AO- (CH ₂ ) _a -C ₉ H ₆ ] ZrCl ₃ , wherein a is an integer of 4 to 8, A is methoxymethyl, t-butoxymethyl, tetrahydropyranyl, tetrahydrofuranyl, 1-ethoxyethyl, 1-methyl-1- It may be any one selected from the group consisting of methoxyethyl and t-butyl.

Meanwhile, in the compound of Formula 2, B are both substituted by a structural bridge, and of a metallocene catalyst C _p rings are essentially in a different manner between the two C _p rings to impart steric rigidity to the C _p rings within the catalyst And there is a steric difference between the C _p rings in which R ¹ _a R ^m _b is _a ring in which (C _p R ¹ _a R ^m _b ) is essentially different from (C _p R ² _a R ⁿ _b ) Is selected.

According to a preferred embodiment of the present invention, a representative example of the metallocene compound represented by Formula 2 is [AO- (CH ₂ ) _a -C ₅ H ₄ ] C (CH ₃ ) ₂ [C ₁₃ H ₈ ] ZrCl ₂ , [AO- (CH ₂ ) _a -C ₅ H ₄ ] Si (CH ₃ ) ₂ [C1 ₃ H ₈ ] ZrCl ₂ , [C ₅ H ₅ ] C (CH ₃ ) (AO- (CH ₂ ) _a ) [C1 ₃ H ₈ ] ZrCl ₂ or [C ₅ H ₅ ] Si (CH ₃ ) (AO- (CH ₂ ) _a ) [C ₁₃ H ₈ ] ZrCl ₂ , where a is an integer from 4 to 8 , A is any one selected from the group consisting of methoxymethyl, t-butoxymethyl, tetrahydropyranyl, tetrahydrofuranyl, 1-ethoxyethyl, 1-methyl-1-methoxyethyl and t-butyl Can be.

According to a preferred embodiment of the present invention, a representative example of the metallocene compound represented by Formula 3 is [(A'-D- (CH ₂ ) _a )] (CH ₃ ) X (C ₅ Me ₄ ) (NCMe ₃ )] TiCl ₂ , X is methylene, ethylene or silicon, D is an oxygen or nitrogen atom, A ′ is hydrogen, alkyl of 1 to 20 carbon atoms, alkenyl, aryl, alkylaryl, arylalkyl, alkylsilyl, Any one selected from the group consisting of arylsilyl, methoxymethyl, t-butoxymethyl, tetrahydropyranyl, tetrahydrofuranyl, 1-ethoxyethyl, 1-methyl-1-methoxyethyl and t-butyl Can be.

The carrier used in the present invention has a highly reactive hydroxyl group and a siloxane group after drying to remove water from the surface. Specifically, silica, silica-alumina, silica-magnesia, etc., dried at a high temperature may be used, and these are usually oxides, carbonates, sulfates, such as Na ₂ O, K ₂ CO ₃ , BaSO ₄ , and Mg (NO ₃ ) ₂ . And nitrate components. The drying temperature at this time is 200 to 800 ℃, preferably 300 to 600 ℃, more preferably 300 to 400 ℃, when less than 200 ℃ water is too much to react with the surface moisture and the promoter, 800 ℃ It is not preferable to exceed the amount of hydroxy groups on the surface and only siloxane groups remain to reduce the reaction site with the promoter.

The dried carrier may be mixed with the cocatalyst 1 represented by Formula 7 to form a carrier on which the cocatalyst 1 is supported. Cocatalyst 1 is an organometallic compound containing aluminum and is the same as the cocatalyst used when polymerizing olefins under a general metallocene catalyst. When the promoter 1 is supported, a bond is generated between the hydroxyl group of the carrier and the aluminum metal.

[Formula 7]

 In formula 7, R 3 is the same or different from each other, a halogen radical, a hydrocarbyl radical having 1 to 20 carbon atoms, or a hydrocarbyl radical having 1 to 20 carbon atoms substituted with halogen, n is an integer of 2 or more.

The compound of Formula 7 may be present in a linear, circular or reticulated form, and examples of such compounds include methylaluminoxane (MAO), ethylaluminoxane, isobutylaluminoxane, and butylaluminoxane.

After supporting the metallocene compounds 1 and 2 of the present invention on the carrier on which the cocatalyst 1 was loaded to prepare a carrier on which the promoter 1 and the metallocene compounds 1 and 2 were supported, the cocatalyst 2 of Formula 8 By mixing the cocatalyst 1, 2, the metallocene compound 1, and the hybrid supported metallocene catalyst supported on 2 can be prepared.

[Formula 8]

T ⁺ [BQ ₄ ] ^-

In formula (8), T ⁺ is a + monovalent polyatomic ion; B is boron in the +3 type oxidation state; Each Q is independently selected from hydride, dialkylamido, halide, alkoxide, aryloxide, hydrocarbyl, halocarbyl and halo-substituted-hydrocarbyl radicals, provided that Q has up to 20 carbons, provided that In one or less positions Q is a halide.

Non-limiting examples of ion-forming compounds comprising proton-providing cations that can be used as activating promoters in the preparation of the catalysts of the present invention as examples of compounds of formula 8 are trisubstituted ammonium salts such as trimethylammonium tetra Phenylborate, methyldioctadecylammonium tetraphenylborate, triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tri (n-butyl) ammonium tetraphenylborate, methyltetracyclooctadecylammonium tetraphenylborate, N, N-dimethylaniline tetraphenylborate, N, N-diethylaninynium tetraphenylborate, N, N-dimethyl (2,4,6-trimethylaninium) tetraphenylborate, trimethylammonium tetrakis (pentafluorophenyl Borate, methyl ditetradecyl ammonium tetrakis (pentaphenyl) borate, methyl dioctadecyl ammonium tetrakis (pen Fluorophenyl) borate, triethylammonium tetrakis (pentafluorophenyl) borate, tripropylammonium tetrakis (pentafluorophenyl) borate, tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, tri (Secondary-butyl) ammonium tetrakis (pentafluorophenyl) borate, N, N-dimethylaninium tetrakis (pentafluorophenyl) borate, N, N-diethylaninium tetrakis (pentafluorophenyl) Borate, N, N-dimethyl (2,4,6-trimethylaninynium) tetrakis (pentafluorophenyl) borate, trimethylammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate, triethyl Ammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate, tripropylammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate, tri (n-butyl) ammonium tetrakis ( 2,3,4,6-tetrafluorophenyl) borate, dimethyl (t-butyl) ammonium te Trakis (2,3,4,6-tetrafluorophenyl) borate, N, N-dimethylaninynium tetrakis (2,3,4,6-tetrafluorophenyl) borate, N, N-diethylaniyl Tetrakis (2,3,4,6-tetrafluorophenyl) borate and N, N-dimethyl- (2,4,6-trimethylaninynium) tetrakis- (2,3,4,6-tetrafluoro Rophenyl) borate; Dialkyl ammonium salts such as dioctadecylammonium tetrakis (pentafluorophenyl) borate, ditetradecylammonium tetrakis (pentafluorophenyl) borate and dicyclohexylammonium tetrakis (pentafluorophenyl) borate; And trisubstituted phosphonium salts such as triphenylphosphonium tetrakis (pentafluorophenyl) borate, methyldioctadecylphosphonium tetrakis (pentafluorophenyl) borate and tri (2,6-dimethylphenyl) Phosphonium tetrakis (pentafluorophenyl) borate. Long-chain alkyl mono- and disubstituted ammonium complexes, especially C ₁₄ -C ₂₀ alkyl ammonium complexes, especially methyldi (octadecyl) ammonium tetrakis (pentafluorophenyl) borate and methyldi (tetradecyl) -ammonium tetrakis (penta) Preference is given to fluorophenyl) borate or mixtures comprising them. This mixture comprises a protonated ammonium cation derived from an amine comprising two C ₁₄ , C ₁₆ or C ₁₈ alkyl groups and one methyl group. Such amines are available from Witco Corp. under the tradename Kemamine® T9701 and from Akzo-Nobel under the tradename amine (Armeen® M2HT).

Meanwhile, the molar ratio of [boron] / [transition metal] in the hybrid supported metallocene catalyst may be 0.01 to 1,000, preferably 0.1 to 100, more preferably 0.2 to 10, wherein the molar ratio is less than 0.01. When boron content is too small, the effect of increasing activity is very low, and when it exceeds 1,000, the activity is no longer increased and the content of borate compound remaining unsupported is high, which may cause fouling in the reactor during polymerization. .

In addition, the hybrid supported metallocene catalyst of the present invention can be used by itself for olefin polymerization, and is separately polymerized by contacting the catalyst with an olefin monomer such as ethylene, propylene, 1-butene, 1-hexene, 1-octene, or the like. It can also be prepared and used as a catalyst.

The method for preparing a hybrid supported metallocene catalyst for polyolefin polymerization according to the present invention includes the steps of preparing a carrier on which promoter 1 is supported by reacting promoter 1, which is an organometallic compound containing aluminum, with a carrier; Promoter 1 and metallocene compounds 1 and 2 are reacted by reacting the metallocene compound 1 represented by the formula (1) and the metallocene compound 2 represented by the formula (2) or (3) according to the present invention to a carrier on which the promoter 1 is supported. (B) preparing a supported carrier; And a promoter supported by the promoter 1 and the metallocene compounds 1 and 2, and the promoter 2, which is an organometallic compound containing boron, by reacting the promoters 1, 2, the metallocene compound 1, and the hybrid supported thereon. Step (c) to prepare a metallocene catalyst; characterized in that it comprises a.

According to the present invention, after reacting Cocatalyst 1, which is an organometallic compound including aluminum, to a carrier, a functional group such as alkoxy, which can act as a Lewis base as an oxygen donor, is cyclopentadiene and cyclopentadiene. Two or more different metallocene compounds substituted in a derivative or bridge group are reacted with the supported promoter to prepare a carrier on which promoter 1 and the metallocene compounds 1 and 2 are supported, including boron Reacting the cocatalyst 2, which is an organometallic compound, to prepare a hybrid supported metallocene catalyst on which cocatalysts 1, 2, metallocene compounds 1, and 2 are supported, and are supported when the olefin is polymerized. It is possible to provide a hybrid supported metallocene catalyst having no polymerization and not causing reactor fouling and having excellent polymerization activity.

In the reaction (a) of the carrier and the promoter 1, a solvent may be used or may be reacted without a solvent. Solvents that can be used are aliphatic hydrocarbon solvents such as hexane, pentane, and aromatic hydrocarbon solvents such as toluene.

The reaction temperature of step (a) may be -20 ℃ to 100 ℃, because the range in which the reaction solvent is present as a liquid is within the temperature range, preferably -10 ℃ to 100 ℃, more preferably 0 ° C. to 80 ° C., since the reaction can proceed optimally in this temperature range. On the other hand, the reaction time may be 10 minutes to 24 hours.

The prepared catalyst-supported catalyst can be used as it is by removing the reaction solvent through filtration or distillation under reduced pressure, and if necessary, soxhlet filtering with an aromatic hydrocarbon such as toluene.

The solvent that can be used in the reaction (b) of the carrier supported with the promoter 1 and the metallocene catalyst is an aliphatic hydrocarbon solvent such as hexane or pentane, an aromatic hydrocarbon solvent such as toluene or benzene, or a chlorine atom such as dichloromethane. Mostly organic solvents such as hydrocarbon solvent, diethyl ether, ether solvent such as THF, acetone, ethyl acetate and the like, with hexane, heptane and toluene being preferred.

The reaction temperature of step (b) may be 0 ℃ to 100 ℃ and the reaction time is preferably 5 minutes to 24 hours.

The solvent that can be used in the step (c) of preparing a hybrid supported metallocene catalyst by reaction of the promoter supported by the promoter 1, the metallocene compounds 1 and 2 with the promoter 2 is an aliphatic hydrocarbon solvent such as hexane and pentane. , Aromatic hydrocarbon solvents such as toluene, benzene, hydrocarbon solvents substituted with chlorine atoms such as dichloromethane, ether solvents such as diethyl ether, THF, acetone, ethyl acetate and most organic solvents, such as hexane, heptane, toluene desirable.

The reaction temperature of step (c) may be 0 ℃ to 100 ℃ and the reaction time is preferably 5 minutes to 24 hours.

The metallocene supported catalyst thus prepared may be used as it is by removing the reaction solvent through filtration or distillation under reduced pressure, and may be used by soxhlet filtering with an aromatic hydrocarbon such as toluene if necessary.

Polymerization process of the polyolefin using the hybrid supported metallocene catalyst of the present invention can be used both a solution process, a slurry or a gas phase process, and a slurry and gas phase mixing process, preferably by a slurry or gas phase process.

The hybrid supported metallocene catalyst of the present invention is an aliphatic hydrocarbon solvent having 5 to 12 carbon atoms suitable for the olefin polymerization process, for example, pentane, hexane, heptane, nonane, decane and isomers thereof and aromatic hydrocarbon solvents such as toluene and benzene, Dilution in the form of slurry in hydrocarbon solvents substituted with chlorine atoms such as dichloromethane and chlorobenzene can be injected. The solvent used herein is preferably used by removing a small amount of water, air and the like acting as a catalyst poison by treating a small amount of alkylaluminum, and may be carried out by further using a promoter.

Olefin monomers which can be polymerized using the hybrid supported metallocene catalyst of the present invention include ethylene, propylene, alpha olefins, cyclic olefins, etc., and diene olefin monomers or triene olefin monomers having two or more double bonds. Polymerization is also possible. Examples of such monomers are ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-decene, 1-undecene, 1-dodecene, 1-tetra Decene, 1-hexadecene, 1-icocene, norbornene, norbornadiene, ethylidenenorbornene, vinylnorbornene, dcclopentadiene, 1,4-butadiene, 1,5-pentadiene, 1,6- Hexadiene, styrene, alpha-methylstyrene, divinylbenzene, 3-romethylmethyl styrene, and the like, and these monomers may be mixed and copolymerized.

Hereinafter, the present invention will be described in more detail with reference to preferred examples, but the present invention is not limited thereto.

In the following examples, the organic reagents and solvents required for catalyst preparation and polymerization were purified by standard methods from Aldrich, and ethylene was passed through a high-purity product from Applied Gas Technology through a water and oxygen filtration device. After the polymerization, the polymerization was carried out, and the contact between air and water was blocked at all stages of catalyst synthesis, loading, and polymerization, thereby increasing the reproducibility of the experiment.

On the other hand, in order to prove the structure of the catalyst was obtained spectrum using 300 MHz NMR (Bruker).

On the other hand, ICP-AES (Inductively Coupled Plasma-Atomic Emission Spectrometer) model of XMP integra manufactured by GBC was used for analysis of the supported catalyst. Through this ICP analysis, we could know the contents of zirconium and boron in the filtrate after reaction with the supported catalyst.

Hereinafter, preferred examples are provided to aid the understanding of the present invention, but the following examples are merely for exemplifying the present invention, and it will be apparent to those skilled in the art that various changes and modifications can be made within the scope and spirit of the present invention. It is natural that such variations and modifications fall within the scope of the appended claims.

[Example]

The organic reagents and solvents required for catalyst preparation and polymerization were purified by Aldrich's standard method, and ethylene was used by applying high purity products from Applied Gas Technology through water and oxygen filtration devices. It was. The reproducibility of the experiment was enhanced by blocking contact between air and moisture at all stages of catalyst synthesis, loading and olefin polymerization.

< Manufacturing example  1> [t- This -O- ( CH ₂ ) ₆ - C ₅ H ₄ ] ₂ ZrCl ₂ Synthesis of

Using 6-chlorohexanol, t-Butyl-O- (CH ₂ ) ₆ -Cl was prepared by the method shown in Tetrahedron Lett. 2951 (1988), and reacted with NaCp. t-Butyl-O- (CH ₂ ) ₆ -C ₅ H ₅ was obtained (yield 60%, bp 80 ° C./0.1 mmHg). Further, t-Butyl-O- (CH ₂ ) ₆ -C ₅ H ₅ was dissolved in THF at -78 ° C, and normal butyllithium (n-BuLi) was slowly added, and the temperature was raised to room temperature, followed by reaction for 8 hours. . The solution was again slowly added a lithium salt solution synthesized to a suspension solution of ZrCl ₄ (THF) ₂ (1.70 g, 4.50 mmol) / THF (30 mL) at -78 ° C. The reaction was further reacted at room temperature for 6 hours. All volatiles were dried in vacuo and the resulting oily liquid material was filtered off by addition of hexane solvent. The filtered solution was dried in vacuo and hexane was added to induce precipitate at low temperature (-20 ° C). The obtained precipitate was filtered at low temperature to give a [tBu-O- (CH ₂ ) ₆ -C ₅ H ₄ ] ₂ ZrCl ₂ compound as a white solid (yield 92%).

1 H NMR (300 MHz, CDCl ₃ ): 6.28 (t, J = 2.6 Hz, 2H), 6.19 (t, J = 2.6 Hz, 2H), 3.31 (t, 6.6 Hz, 2H), 2.62 ( t, J = 8 Hz), 1.7-1.3 (m, 8 H), 1.17 (s, 9 H).

13 C NMR (CDCl ₃ ): 135.09, 116.66, 112.28, 72.42, 61.52, 30.66, 30.61, 30.14, 29.18, 27.58, 26.00.

< Manufacturing example  2> [ methyl (6-t- buthoxyhexyl ) silyl (η ⁵ - tetramethylCp ) (t- Butylamido )] TiCl ₂ Synthesis of

50 g of Mg (s) was added to a 10 L reactor at room temperature, followed by 300 mL of THF. After adding 0.5 g of I ₂ , the reactor temperature was maintained at 50 ° C. After the reactor temperature was stabilized, 250 g of 6-t-butoxyhexyl chloride was added to the reactor at a rate of 5 mL / min using a feeding pump. As the 6-t-butoxyhexyl chloride was added, it was observed that the reactor temperature increased by about 4 to 5 ° C. The mixture was stirred for 12 hours while adding 6-t-butoxyhexyl chloride. After 12 hours of reaction, a black reaction solution was obtained. After taking 2 mL of the resulting black solution, water was added to obtain an organic layer, and 6-t-butoxyhexane was confirmed by 1 H-NMR, and Grignard from 6-t-butoxyhexane. The reaction proceeded well. Thus, 6-t-butoxyhexyl magnesium chloride was synthesized.

500 g of MeSiCl ₃ and 1 L of THF were added to the reactor, and the reactor temperature was cooled to -20 ° C. 560 g of the synthesized 6-t-butoxyhexyl magnesium chloride was added to the reactor at a rate of 5 mL / min using an infusion pump. After completion of the Grignard reagent injection, the reaction mixture was stirred for 12 hours while slowly raising the temperature to room temperature. After 12 hours, it was confirmed that a white MgCl ₂ salt was produced. 4 L of hexane was added to remove the salt through a laboratory pressure dewatering filtration apparatus (labdori, Han River Engineering Co., Ltd.) to obtain a filter solution. The resultant filter solution was added to the reactor, and hexane was removed at 70 ° C. to obtain a pale yellow liquid. The obtained liquid was confirmed to be the desired methyl (6-t- methoxyhexyl) dichlorosilane compound through 1 H-NMR.

1 H-NMR (CDCl ₃ ): 3.3 (t, 2H), 1.5 (m, 3H), 1.3 (m, 5H), 1.2 (s, 9H), 1.1 (m, 2H), 0.7 (s, 3H) .

1.2 mol (150 g) of tetramethylcyclopentadiene and 2.4 L of THF were added to the reactor, and the reactor temperature was cooled to -20 ° C. 480 mL of n-BuLi was added to the reactor at a rate of 5 mL / min using an infusion pump. After n-BuLi was added, the reaction mixture was stirred for 12 hours while slowly raising the temperature to room temperature. After 12 hours of reaction, an equivalent amount of Methyl (6-t-buthoxyhexyl) dichlorosilane (326 g, 350 mL) was quickly added to the reactor. After stirring for 12 hours while slowly raising the reactor temperature to room temperature, the reactor temperature was further cooled to 0 ° C., and then 2 equivalents of t-BuNH ₂ was added thereto. Stirring for 12 hours while slowly raising the reactor temperature to room temperature. After 12 hours of reaction, THF was removed and 4 L of hexane was added to obtain a filter solution from which salt was removed through labdori. After the filter solution was added to the reactor again, hexane was removed at 70 ° C. to obtain a yellow solution. The obtained yellow solution was confirmed to be Methyl (6-t-buthoxyhexyl) (tetramethylCpH) t-Butylaminosilane compound through 1H-NMR.

TiCl ₃ (THF) ₃ (10 mmol) was quickly added to the dilithium salt of a ligand of −78 ° C. synthesized in THF solution from n-BuLi and ligand Dimethyl (tetramethylCpH) t-Butylaminosilane. The reaction solution was slowly stirred at -78 ° C to room temperature for 12 hours. After stirring for 12 hours, an equivalent amount of PbCl ₂ (10 mmol) was added to the reaction solution at room temperature, followed by stirring for 12 hours. After stirring for 12 hours, a dark black solution was obtained. After removing THF from the resulting reaction solution, hexane was added to filter the product. After removing hexane from the obtained filter solution, it was confirmed by 1 H-NMR that the desired [methyl (6-t-buthoxyhexyl) silyl (η ⁵ -tetramethylCp) (t-Butylamido)] TiCl ₂ compound.

1 H-NMR (CDCl ₃ ): 3.3 (s, 4H), 2.2 (s, 6H), 2.1 (s, 6H), 1.8 to 0.8 (m), 1.4 (s, 9H), 1.2 (s, 9H), 0.7 (s, 3H)

< Manufacturing example  3> [( CH ₂ ) ₄ - C ₅ H ₄ ] ₂ ZrCl ₂ Manufacture

It was purchased from Aldrich.

Preparation Example 4 Synthesis of 6-t-butoxyhexylmethylsilylbisindenyl zirconium dichloride

17.5 ml of 2.5M n-BuLi solution was added to 5 ml of indene dissolved in 20 ml ether at 0 ° C. for 20 minutes, followed by stirring at room temperature for 2 hours. 5.25 g of t-butoxyhexylmethyldichlorosilane is dissolved in 10 ml hexane and then added to indenylithium solution at −78 ° C. over 10 minutes. After stirring the reaction solution at room temperature for 3 hours, lithium chloride is filtered off and the solvent is dried in vacuo to obtain a product in which the structural isomers are mixed. Structural isomers were confirmed by ¹ H NMR.

¹ H NMR (500 MHz, CDCl 3): 1.17 (t-BuO, 9H, s), 3.59 (Indene, 2H, m), 0.21 (MeSi, 3H, s), 0.47 (CH ₂ , 2H, m), 0.89 ( CH ₂ , 2H, m), 1.28 (CH ₂ , 2H, m), 1.56 (CH ₂ , 4H, m), 3.26 (OCH ₂ , t, J _HH = 0.014), 7.48 (ArH, 2H, m), 7.38 (ArH, 2H, m), 7.26 (ArH, 2H, m), 7.16 (ArH, 2H, m), 6.90 (indene, H, m), 6.60 (ArH, 2H, m).

Dissolve the material identified by ¹ H NMR in 40 ml of ether and 17.5 ml of 2.5M n-BuLi solution at -78 ℃ 20 minutes. After stirring for 3 hours at room temperature, Hexane was added to make a solid and filtered to obtain a material.

1 g of zirconium chloride is added to 20 ml of toluene and stirred. 30 ml of the toluene / ether 1: 2 solution was added to 2.3 g of the ligand solid prepared above, and the mixture was added to the zirconium chloride mixed solution for 20 minutes at a temperature of −78 ° C. It is filtered after stirring for 16 hours at room temperature. The material is recrystallized from hexane to give the final catalyst.

¹ H NMR (500 MHz, C ₆ D ₆ ): 1.15 (t-BuO, 9H, s), 1.12 (MeSi, 3H, s), 1.34 (CH ₂ , 6H, m), 1.47 (CH ₂ , 2H, m ), 1.60 (CH ₂ , 2H, m), 3.26 (OCH ₂ , t, J _HH = 0.014, 7.40 (ArH, 2H, m), 7.33 (ArH, 2H, m), 7.28 (ArH, 2H, m) , 7.16 (ArH, 2H, m), 6.90 (indene, H, m), 5.83 (ArH, 2H, m)

< Manufacturing example  5> [t- This -O- ( CH ₂ ) ₆ - C ₅ H ₄ ] ₂ HfCl ₂ Synthesis of

Using 6-chlorohexanol, t-Butyl-O- (CH2) ₆ -Cl was prepared by the method shown in Tetrahedron Lett. 2951 (1988), and NaCp was reacted with t -Butyl-O- (CH ₂ ) ₆ -C ₅ H ₅ was obtained (yield 60%, bp 80 ° C./0.1 mmHg). Further, t-Butyl-O- (CH ₂ ) ₆ -C ₅ H ₅ was dissolved in THF at -78 ° C, and normal butyllithium (n-BuLi) was slowly added, and the reaction mixture was heated to room temperature for 8 hours. The solution was added slowly to a suspension solution of HfCl 4 (1.44 g, 4.50 mmol) / THF (30 mL) at −78 ° C., and slowly stirred at room temperature for 6 hours. Reacted further. All volatiles were dried in vacuo and the resulting oily liquid material was filtered off by addition of hexane solvent. The filtered solution was dried in vacuo and hexane was added to induce precipitate at low temperature (-20 ° C). The obtained precipitate was filtered at low temperature to give a [tBu-O- (CH ₂ ) 6 -C ₅ H ₄ ] ₂ HfCl ₂ compound as a white solid (yield 88%).

¹ H-NMR (300 MHz, CDCl ₃ ): 6.19 (t, J = 2.6 Hz, 2H), 6.08 (t, J = 2.6 Hz, 2H), 3.31 (t, 6.6 Hz, 2H), 2.65 (t, J = 8 Hz), 1.56-1.48 (m, 4H), 1.34 (m, 4H), 1.17 (s, 9H).

¹³ C-NMR (CDCl ₃ ): 134.09, 116.06, 111.428, 72.42, 61.33, 30.42, 30.67, 30.14, 29.20, 27.52, 26.01.

<Catalyst preparation>

Example  One

10 ml of Toluene was added to 3 g of calcined silica (Sylopol 2212, Grace Davison) having a pore volume of 1.47 ml / g at a surface area of 280 m ² / g, and reacted with 15 ml of MAO (10 wt% Toluene solution) at 70 ° C. for 2 hours. Washing with toluene to remove unreacted MAO solution. 0.48mmole of the metallocene compound of Preparation Example 1 having a tert butoxy-group and 0.24mmole of the metallocene compound of Preparation Example 2 were reacted at 50 ° C. for 1 hour and then washed with toluene. Trityl tetrakis (penta-fluoro-phenyl) borate (TB) was reacted with 1.2mmole at 50 ° C. for 1 hour and then dried under reduced pressure at 50 ° C. to prepare a solid catalyst.

Comparative example  One

Except for using the metallocene compound of Preparation Example 1 and 0.72mmole of the metallocene compound of Preparation Example 1 having a tert butoxy-group instead of the metallocene compound of Preparation Example 1 and the metallocene compound of Preparation Example 2 and the same.

Comparative example  2

Except for using the metallocene compound of Preparation Example 2 and 0.72mmole of the metallocene compound of Preparation Example 2 having a tert butoxy-group instead of the metallocene compound of Preparation Example 1 and the metallocene compound of Preparation Example 2 and the same.

Comparative example  3

It is the same as Example 1 except not performing TB treatment.

<Production of polyethylene and evaluation of properties>

1) Melt index (MI, 2.16kg): Measured based on the measurement temperature 190 ℃, ASTM 1238.

2) High Load Melt Index (HLMI, 21.16kg): Measured based on measurement temperature 190 ° C and ASTM 1238.

3) MFR (HLMI / MI): The ratio of the HLMI melt index (MI, 21.6kg load) divided by MI (MI, 2.16kg load).

<Low Pressure Polymerization>

Example  2

3 liters of normal hexane was added to prevent the contact of air and oxygen in a 5 liter high pressure reactor, and triethylaluminum was added so that the triethylaluminum concentration was 0.6 mmol / L relative to normal hexane. 30 mg of the prepared solid catalyst was added thereto. Thereafter, ethylene was continuously added at 80 ° C. and polymerized for 2 hours while maintaining a pressure of 9 bar. This was terminated after the supply of ethylene was stopped and the pressure was removed. The suspension obtained therefrom was separated and dried to produce polyethylene particles.

Comparative example  4

It is the same as Example 2 except for using the catalyst prepared from Comparative Example 1 having a tert-butoxy group instead of the catalyst prepared from Example 1.

Comparative example  5

It is the same as Example 2 except using the catalyst prepared from Comparative Example 2 having a tert-butoxy group instead of the catalyst prepared from Example 1.

Comparative example  6

Same as Example 2 except that the catalyst prepared from Comparative Example 3 was used instead of the catalyst prepared from Example 1.

<High Pressure Polymerization>

Example  3

Same as Example 2 except for the ethylene polymerization at 40 bar.

Comparative example  7

It is the same as Comparative Example 4 except for ethylene polymerization at 40 bar.

Comparative example  8

It is the same as Comparative Example 6 except for ethylene polymerization at 40 bar.

Table 1 is a table showing the low-pressure polymerization characteristics of 9bar pressure in the ethylene polymerization reaction, Table 2 is a table showing the high-pressure polymerization characteristics of 40bar pressure in the ethylene polymerization reaction.

division
Metallocene Catalyst (Manufacturing Example) Borate promoter Supported Metallocene Catalyst activation
(KgPE / gCat) MI (2.16Kg)
(g / 10 min) MFR
Example 2 1 and 2 TB Example 1 36 1.1 21 Comparative Example 4 One TB Comparative Example 1 39 1.2 17 Comparative Example 5 2 TB Comparative Example 2 3.5 <0.1 - Comparative Example 6 1 and 2 - Comparative Example 3 2.7 0.74 23

In Table 1 TB is trityl tetrakis (penta-fluoro-phenyl) borate.

In Table 1, in the case of Comparative Example 5, the molecular weight of the produced polyethylene was too high to accurately measure not only MI but also HLMI.

division
Metallocene Catalyst (Manufacturing Example) Borate promoter Supported Metallocene Catalyst activation
(KgPE / gCat) HLMI (21.6 kg)
g / 10min MFR Example 3 1 and 2 TB Example 1 87 1.2 22 Comparative Example 7 One TB Comparative Example 1 78 1.8 18 Comparative Example 8 1 and 2 - Comparative Example 3 10 0.35 23

Referring to Table 1 and Table 2, when preparing the metallocene supported catalyst in the case of further supporting the borate as in Example 2 and Example 3 than when using only MAO as in Comparative Example 6 and Comparative Example 8 The activity of the catalyst could be increased by a factor of ten.

On the other hand, in the case of the supported catalyst carrying a single metallocene compound as in Comparative Example 4 and Comparative Example 7, there is a disadvantage that the MFR of the polymer using the same. However, when ethylene is polymerized using a hybrid supported metallocene catalyst simultaneously supporting two or more metallocene compounds as in Examples 2 and 3, not only can the MFR of the polymer be increased, but also various 2 When using a catalyst that simultaneously supports more than one metallocene compound, the MFR of the polymer can be controlled.

Therefore, by adjusting the composition ratio of each metallocene catalyst in the hybrid supported metallocene catalyst of the present invention, it is possible to control the activity of the catalyst, to prepare a polymer having a variety of physical properties and molecular weight distribution, which in turn is a single reactor This means that a metallocene supported catalyst capable of controlling molecular weight distribution can be prepared.

Claims (20)

On the carrier,
Promoter component 1, which is an organometallic compound comprising aluminum;
A metallocene compound 1 represented by Formula 1 and a metallocene compound 2 represented by Formula 2 or 3 below; And
A hybrid supported metallocene catalyst, characterized in that the promoter component 2 which is an organometallic compound containing boron is sequentially supported.
[Formula 1]

(2)

(3)

In Formula 1, 2 or 3,
Cp and Cp 'are either selected from the group consisting of the same or different cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl and fluorenyl radicals; R ^m and R ⁿ are the same or different hydrogen radicals, alkyl having 1 to 20 carbon atoms, cycloalkyl, aryl, alkenyl, alkylaryl, arylalkyl, arylalkenyl radicals or alkylsilyl radicals; R ¹ and R ² are the same or different hydrogen or hydrocarbyl radicals having 1 to 6 carbon atoms; a, a ', b or b' are each an integer of 1 to 4;
M is a transition metal of Groups 4B, 5B, or 6B of the Periodic Table;
Q is a halogen radical or an alkyl radical having 1 to 20 carbon atoms, an alkenyl radical, an aryl radical, an alkylaryl radical, an arylalkyl radical; Or an alkylidene radical of 1 to 20 carbon atoms, k is 2 or 3, z is 0 or 1, and z is 0 when k is 3;
B is any one selected from the group consisting of alkyl radicals having 1 to 4 carbon atoms or hydrocarbyl radicals containing silicon, germanium, phosphorus, nitrogen, boron or aluminum;
In formula 3, J is any one selected from the group consisting of NR ^s , O, PR ^s and S, wherein R ^s is an alkyl radical or substituted alkyl radical having 1 to 20 carbon atoms;
Any one hydrogen radical present in R ^m , R ⁿ , B or R ^s is substituted with a radical of Formula 4, 5 or 6,
[Chemical Formula 4]

In Formula 4,
Z is an oxygen atom;
R and R 'are the same or different hydrogen radicals; Alkyl having 1 to 20 carbon atoms, cycloalkyl, aryl, alkenyl, alkylaryl, arylalkyl; Or an arylalkenyl radical; Two R's may be linked to each other to form a ring;
G is alkoxy, aryloxy, alkylthio, arylthio, phenyl, or substituted phenyl having 1 to 20 carbon atoms, and can be linked to R 'to form a ring;
[Chemical Formula 5]

In Formula 5,
Z 'is an oxygen atom;
R and R ″ are the same or different from each other, a hydrogen radical; Alkyl, cycloalkyl, aryl, alkenyl, alkylaryl, arylalkyl, or arylalkenyl radicals having 1 to 20 carbon atoms,
R and R ″ or two R ″ can be linked together to form a ring,
[Formula 6]

In Chemical Formula 6,
Z "is oxygen;
R ′ '' are the same or different hydrogen radicals, alkyl of 1 to 40 carbon atoms, cycloalkyl, aryl, alkenyl, alkylaryl, arylalkyl or arylalkenyl radicals;
R '''' is a hydrogen radical, alkyl having 1 to 40 carbon atoms, aryl, alkenyl, alkylaryl, alkylsilyl, arylsilyl, phenyl or substituted phenyl;
n is 1. The compound of claim 1, wherein in formula 4, R and R ′ are alkyl radicals having 1 to 20 carbon atoms, the same as or different from each other; G is alkoxy having 1 to 20 carbon atoms; In formula (5), R and R ″ are the same or different alkyl radicals having 1 to 20 carbon atoms; In formula (6), R '' 'is an alkyl radical having 1 to 40 carbon atoms, the same as or different from each other; R '' '' is a hybrid supported metallocene catalyst, characterized in that it is an alkyl radical having 1 to 40 carbon atoms. The hybrid supported metallocene catalyst according to claim 1, wherein M is titanium, zirconium or hafnium, Q is halogen, and k is 2. According to claim 1, wherein the compound represented by the formula (1) is [AO- (CH ₂ ) _a -C ₅ H ₄ ] ₂ ZrCl ₂ or [AO- (CH ₂ ) _a -C ₉ H ₆ ] ZrCl ₃ , Where a is an integer from 4 to 8, A is methoxymethyl, t-butoxymethyl, tetrahydropyranyl, tetrahydrofuranyl, 1-ethoxyethyl, 1-methyl-1-methoxyethyl and t- Hybrid supported metallocene catalyst, characterized in that any one selected from the group consisting of butyl. According to claim 1, wherein the compound represented by formula 2 is [AO- (CH ₂ ) _a -C ₅ H ₄ ] C (CH ₃ ) ₂ [C ₁₃ H ₈ ] ZrCl ₂ , [AO- (CH ₂ ) _a -C ₅ H ₄ ] Si (CH ₃ ) ₂ [C1 ₃ H ₈ ] ZrCl ₂ , [C ₅ H ₅ ] C (CH ₃ ) (AO- (CH ₂ ) _a ) [C1 ₃ H ₈ ] ZrCl ₂ or [C ₅ H ₅ ] Si (CH ₃ ) (AO- (CH ₂ ) _a ) [C ₁₃ H ₈ ] ZrCl ₂ , where a is an integer from 4 to 8 and A is methoxymethyl, t-part Hybrid supported metallocene, characterized in that any one selected from the group consisting of methoxymethyl, tetrahydropyranyl, tetrahydrofuranyl, 1-ethoxyethyl, 1-methyl-1-methoxyethyl and t-butyl catalyst. The compound represented by the formula (3) is [(A'-D- (CH ₂ ) _a ) (CH ₃ ) X (C ₅ Me ₄ ) (NCMe ₃ )] TiCl ₂ , X is methylene, Ethylene or silicon, D is an oxygen or nitrogen atom, A 'is hydrogen, alkyl having 1 to 20 carbon atoms, alkenyl, aryl, alkylaryl, arylalkyl, alkylsilyl, arylsilyl, methoxymethyl, t-butoxy A hybrid supported metallocene catalyst, characterized in that any one selected from the group consisting of methyl, tetrahydropyranyl, tetrahydrofuranyl, 1-ethoxyethyl, 1-methyl-1-methoxyethyl and t-butyl. The hybrid supported metallocene catalyst according to claim 1, wherein the carrier is dried at 200 ° C to 800 ° C. The hybrid supported metallocene catalyst according to claim 1, wherein the carrier is at least one member selected from the group consisting of silica, silica-alumina, and silica-magnesia. The hybrid supported metallocene catalyst according to claim 1, wherein the promoter 1 is a compound represented by the formula (7).
[Formula 7]

In formula 7, R ³ is the same as or different from each other, a halogen radical, a hydrocarbyl radical having 1 to 20 carbon atoms, or a hydrocarbyl radical having 1 to 20 carbon atoms substituted with halogen, and n is an integer of 2 or more. The hybrid supported metallocene catalyst according to claim 9, wherein the compound represented by the formula (7) is any one selected from the group consisting of methyl aluminoxane (MAO), ethyl aluminoxane, isobutyl aluminoxane and butyl aluminoxane. . The hybrid supported metallocene catalyst according to claim 1, wherein the promoter 2 is a borate compound represented by the formula (8).
[Chemical Formula 8]
T ⁺ [BQ ₄ ] ^-
In formula (8), T ⁺ is a + monovalent polyatomic ion; B is boron in the +3 type oxidation state; Each Q is independently selected from hydride, dialkylamido, halide, alkoxide, aryloxide, hydrocarbyl, halocarbyl and halo-substituted-hydrocarbyl radicals, provided that Q has up to 20 carbons In one or less positions Q is a halide. 12. The method of claim 11, wherein promoter 2 is trimethylammonium tetraphenylborate, methyldioctadecylammonium tetraphenylborate, triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tri (n-butyl) ammonium tetraphenylborate, Methyltetracyclocyclodecylammonium tetraphenylborate, N, N-dimethylaninium tetraphenylborate, N, N-diethylaninynium tetraphenylborate, N, N-dimethyl (2,4,6-trimethylaninium) Tetraphenylborate, trimethylammonium tetrakis (pentafluorophenyl) borate, methylditetradecylammonium tetrakis (pentaphenyl) borate, methyldioctadecylammonium tetrakis (pentafluorophenyl) borate, triethylammonium tetrakis ( Pentafluorophenyl) borate, tripropylammonium tetrakis (pentafluorophenyl) borate, tri (n-butyl) ammonium tetraki S (pentafluorophenyl) borate, tri (secondary-butyl) ammonium tetrakis (pentafluorophenyl) borate, N, N-dimethylaninium tetrakis (pentafluorophenyl) borate, N, N-diethyl Aninium tetrakis (pentafluorophenyl) borate, N, N-dimethyl (2,4,6-trimethylaninium) tetrakis (pentafluorophenyl) borate, trimethylammonium tetrakis (2,3,4,6 -Tetrafluorophenyl) borate, triethylammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate, tripropylammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate, Tri (n-butyl) ammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate, dimethyl (t-butyl) ammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate, N, N-dimethylaninium tetrakis (2,3,4,6-tetrafluorophenyl) borate, N, N-diethylaninynium tetrakis (2,3,4,6-tetrafluorophenyl) Late, N, N-dimethyl- (2,4,6-trimethylaninynium) tetrakis- (2,3,4,6-tetrafluorophenyl) borate, dioctadecylammonium tetrakis (pentafluorophenyl) Borate, ditetradecylammonium tetrakis (pentafluorophenyl) borate, dicyclohexylammonium tetrakis (pentafluorophenyl) borate, triphenylphosphonium tetrakis (pentafluorophenyl) borate, methyldioctadecylphosphonium Tetrakis (pentafluorophenyl) borate, tri (2,6-dimethylphenyl) phosphonium tetrakis (pentafluorophenyl) borate, methyldi (octadecyl) ammonium tetrakis (pentafluorophenyl) borate, and methyl A hybrid supported metallocene catalyst, characterized in that at least one member selected from the group consisting of di (tetradecyl) -ammonium tetrakis (pentafluorophenyl) borate. The hybrid supported metallocene catalyst according to claim 1, wherein the supported amount of the promoter 2 is 0.1 to 10,000 moles based on the boron contained in the promoter 2, based on 1 mole of the transition metal contained in the metallocene compound. Preparing a carrier on which promoter 1 is supported by reacting promoter 1, which is an organometallic compound containing aluminum, with the carrier;
Promoter 1 by reacting the metallocene compound 1 represented by the formula (1) according to any one of claims 1 to 6 and the metallocene compound 2 represented by the formula (2) or 3 on the carrier supported by the promoter 1 And preparing a carrier on which the metallocene compounds 1 and 2 are supported; And
Co-catalyst 1 and the supported metal carrier 2, an organic metal compound of the boron-containing cocatalyst 2 is reacted with a carrier on which the promoters 1, 2, metallocene compound 1, and the hybrid supported metal supported on Preparing a rosene catalyst;
Method of producing a hybrid supported metallocene catalyst comprising a. 15. The method for producing a hybrid supported metallocene catalyst according to claim 14, wherein the carrier is silica, silica-alumina, or silica-magnesia. 15. The method for producing a hybrid supported metallocene catalyst according to claim 14, wherein the promoter 1 is methyl aluminoxane (MAO), ethyl aluminoxane, isobutyl aluminoxane or butyl aluminoxane. The method of claim 14, wherein the promoter 2 is trimethylammonium tetraphenylborate, methyldioctadecylammonium tetraphenylborate, triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tri (n-butyl) ammonium tetraphenylborate, Methyltetracyclocyclodecylammonium tetraphenylborate, N, N-dimethylaninium tetraphenylborate, N, N-diethylaninynium tetraphenylborate, N, N-dimethyl (2,4,6-trimethylaninium) Tetraphenylborate, trimethylammonium tetrakis (pentafluorophenyl) borate, methylditetradecylammonium tetrakis (pentaphenyl) borate, methyldioctadecylammonium tetrakis (pentafluorophenyl) borate, triethylammonium tetrakis ( Pentafluorophenyl) borate, tripropylammonium tetrakis (pentafluorophenyl) borate, tri (n-butyl) ammonium tetraki S (pentafluorophenyl) borate, tri (secondary-butyl) ammonium tetrakis (pentafluorophenyl) borate, N, N-dimethylaninium tetrakis (pentafluorophenyl) borate, N, N-diethyl Aninium tetrakis (pentafluorophenyl) borate, N, N-dimethyl (2,4,6-trimethylaninium) tetrakis (pentafluorophenyl) borate, trimethylammonium tetrakis (2,3,4,6 -Tetrafluorophenyl) borate, triethylammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate, tripropylammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate, Tri (n-butyl) ammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate, dimethyl (t-butyl) ammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate, N, N-dimethylaninium tetrakis (2,3,4,6-tetrafluorophenyl) borate, N, N-diethylaninynium tetrakis (2,3,4,6-tetrafluorophenyl) Late, N, N-dimethyl- (2,4,6-trimethylaninynium) tetrakis- (2,3,4,6-tetrafluorophenyl) borate, dioctadecylammonium tetrakis (pentafluorophenyl) Borate, ditetradecylammonium tetrakis (pentafluorophenyl) borate, dicyclohexylammonium tetrakis (pentafluorophenyl) borate, triphenylphosphonium tetrakis (pentafluorophenyl) borate, methyldioctadecylphosphonium Tetrakis (pentafluorophenyl) borate, tri (2,6-dimethylphenyl) phosphonium tetrakis (pentafluorophenyl) borate, methyldi (octadecyl) ammonium tetrakis (pentafluorophenyl) borate, and methyl A method for producing a hybrid supported metallocene catalyst, characterized in that at least one member selected from the group consisting of di (tetradecyl) -ammonium tetrakis (pentafluorophenyl) borate. A method for producing a polyolefin, comprising polymerizing an olefinic monomer in the presence of a hybrid supported metallocene catalyst according to claim 1. 19. The process for producing polyolefin according to claim 18, wherein the polymerization is carried out in a slurry process or a gas phase process. 19. The method of claim 18, wherein the hybrid supported metallocene catalyst is injected into the olefin monomer in a slurry prepared by diluting in an aliphatic hydrocarbon solvent having 5 to 12 carbon atoms, an aromatic hydrocarbon solvent, or a hydrocarbon solvent substituted with a chlorine atom. A method for producing a polyolefin, characterized in that.