KR101123410B1 - Method for Preparing Supported Multi-site Metallocene Catalyst and Method for Preparing Polyolefin using the Same - Google Patents

Abstract

The present invention relates to a method for preparing a multi-metallocene supported catalyst, and a method for producing a polyolefin using the same, comprising the steps of: reacting a metallocene compound 1 to a carrier to prepare a metallocene compound 1 supported carrier; Preparing a carrier on which the metallocene compound 1 and the promoter 1 are supported by reacting the catalyst on which the metallocene compound 1 is supported with the promoter 1 which is an organometallic compound including aluminum; Preparing a carrier on which the metallocene compound 1, the promoter 1 and the metallocene compound 2 are supported by reacting the metallocene compound 2 on the carrier on which the metallocene compound 1 and the promoter 1 are supported; And a metallocene compound 1, a metallocene compound 2, and a cocatalyst by reacting the metallocene compound 1, the cocatalyst 1, and the cocatalyst 2, which is an organometallic compound containing boron, with a carrier on which the metallocene compound 1, the metallocene compound 2 are supported. It provides a method for producing a multi-metallocene supported catalyst comprising; 1, and preparing a supported metallocene catalyst supported on the promoter 2. In the method for preparing a multimetallocene supported catalyst of the present invention, two or more metallocene compounds each having a ligand substituted with an alkoxide or an aryl oxide may be supported before and after the step of supporting the organometallic compound including aluminum on a carrier. After that, the borate-containing compound containing boron is supported by the second cocatalyst, and the catalytic activity is remarkably higher than that of the conventional metallocene supported catalyst and the molecular weight distribution can be easily controlled.

Description

Method for preparing multi-metallocene supported catalyst and method for preparing polyolefin using same {Method for Preparing Supported Multi-site Metallocene Catalyst and Method for Preparing Polyolefin using the Same}

The present invention relates to a method for preparing a multimetallocene supported catalyst, and more particularly, to a method for preparing a high activity multimetallocene supported catalyst and a method for preparing 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-Bu in Journal of Molecular Catalysis A: Chemical 156_2000.133-141. An ethylene polymerization catalyst comprising a ₃ Al) promoter and a metallocene compound is disclosed. However, these catalysts have a problem of low activity and difficult to control the molecular weight distribution.

In order to solve the above problems, the present invention supports two or more metallocene compounds each having a ligand substituted with an alkoxide or an aryl oxide, before and after the step of supporting the organometallic compound including aluminum on the carrier. The present invention is to provide a method for preparing a highly active multi-metallocene supported catalyst having a significantly higher effect than that of a conventional metallocene supported catalyst by supporting a borate compound containing boron with a second promoter.

In addition, it is easy to control the molecular weight distribution of the polyolefin produced by using the multi-valent metallocene supported catalyst prepared according to the method of preparing the high-active multi-metallocene supported catalyst of the present invention in the polyolefin production method, and fouling during the manufacturing process It is to provide a method for producing a polyolefin to prevent.

The present invention to achieve the first technical problem,

Preparing a carrier on which the metallocene compound 1 is supported by reacting the carrier with at least one metallocene compound 1 selected from the group consisting of compounds represented by Formulas 1 to 3;

Preparing a carrier on which the metallocene compound 1 and the promoter 1 are supported by reacting the catalyst on which the metallocene compound 1 is supported with the promoter 1 which is an organometallic compound including aluminum;

Metallocene compound 1, promoter 1 and metallo are reacted with at least one metallocene compound 2 selected from the group consisting of compounds represented by Formulas 1 to 3 on a carrier on which the metallocene compound 1 and the promoter 1 are supported. Preparing a carrier carrying Sen compound 2; And

Metallocene compound 1, metallocene compound 2, promoter 1 by reacting metallocene compound 1, cocatalyst 1, and cocatalyst 2, an organometallic compound containing boron, with a carrier on which metallocene compound 2 is supported. Preparing a supported metallocene catalyst supported with promoter 2;

It provides a method for producing a multi-metallocene supported catalyst comprising a.

 [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 hydrogen radical present in R ^m , R ⁿ , B or R ^s is substituted with a radical 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;

delete

delete

[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 having 1 to 40 carbon atoms, aryl, alkenyl, alkylaryl, alkylsilyl, arylsilyl, phenyl or substituted phenyl.

delete

The present invention to achieve the second technical problem,

Provided is a method for producing a polyolefin, characterized in that the polymerization of an olefinic monomer in the presence of a multi-metallocene supported catalyst prepared according to the production method of the present invention.

In the method for preparing a multimetallocene supported catalyst of the present invention, at least one metallocene compound having a ligand substituted with an alkoxide or an aryl oxide may be prepared before or after supporting a cocatalyst of an organometallic compound including aluminum on a carrier. Each supported, followed by supporting a borate compound containing boron with a second cocatalyst has a significantly higher effect than the conventional metallocene supported catalyst.

In addition, the polyolefin production method using the multi-metallocene supported catalyst prepared according to the production method of the multi-metallocene supported catalyst of the present invention facilitates the control of molecular weight distribution of the polyolefin and prevents fouling during the manufacturing process. Have

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 [C ₁₃ H ₈ ] ZrCl ₂ , [C ₅ H ₅ ] C (CH ₃ ) (AO- (CH ₂ ) _a ) [C ₁₃ 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, aryl Can be any one selected from the group consisting of silyl, methoxymethyl, t-butoxymethyl, tetrahydropyranyl, tetrahydrofuranyl, 1-ethoxyethyl, 1-methyl-1-methoxyethyl and t-butyl have.

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 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 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.

Before and after the step of supporting the cocatalyst of the organometallic compound including aluminum on the carrier, each of the at least one metallocene compound having a ligand substituted with an alkoxide or aryl oxide, and the like, and thereafter, a borate compound including boron The supported metallocene catalyst on which the metallocene compound 1, the metallocene compound 2, the cocatalyst 1, and the promoter 2 were supported can be prepared by supporting a with a second promoter.

[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).

On the other hand, the molar ratio of [boron] / [transition metal] in the multi-metallocene supported 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 multimetallocene supported catalyst prepared according to the present invention can be used by itself for olefin polymerization, and separately contacting the catalyst with olefinic monomers such as ethylene, propylene, 1-butene, 1-hexene, 1-octene, and the like. It can also be prepared and used as a prepolymerized catalyst.

In the method for preparing a multi-metallocene supported catalyst for polyolefin polymerization according to the present invention, a functional group such as alkoxy, which may serve as a Lewis base as an O-donor, may be used as cyclopentadiene or cyclopentadiene derivative. Or by reacting at least one metallocene compound 1 selected from the compounds represented by Formulas 1 to 3 substituted with a bridge group to prepare a carrier on which the metallocene compound 1 is supported (step a). The metallocene compound 1 is prepared by reacting the cocatalyst 1, which is an organometallic compound containing aluminum, with the support on which the sen compound 1 is supported (step b), and then the metallocene compound 1 And a metallocene compound 1, a promoter 1 and a metallocene by reacting at least one metallocene compound 2 selected from the compounds represented by Formulas 1 to 3 with a carrier on which promoter 1 is supported. After preparing a carrier carrying Compound 2 (step c), the cocatalyst 2, which is an organometallic compound containing boron, is reacted with the metallocene compound 1, the promoter 1, and the carrier carrying the metallocene compound 2 To provide a supported metallocene catalyst on which the metallocene compound 1, the metallocene compound 2, the promoter 1, and the promoter 2 are supported (step d), It is possible to provide a multi-metallocene supported catalyst having no polymerization and not causing reactor fouling and having excellent polymerization activity.

In the reaction of the carrier with the metallocene compound 1 (step a), a solvent may be used, and the solvent may be an aliphatic hydrocarbon solvent such as hexane or pentane, an aromatic hydrocarbon solvent such as toluene or benzene, or a dichloromethane. Mostly organic solvents such as hydrocarbon solvents substituted with chlorine atoms, diethyl ether, ether solvents such as THF, acetone and ethyl acetate, and hexane, heptane and toluene are preferable.

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

Step (b) of preparing a carrier in which the metallocene compound 1 and the promoter 1 are supported by reacting the metallocene compound 1 with the cocatalyst 1, which is an organometallic compound containing aluminum, may be used as a solvent. It 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 (b) may be -20 ° C to 100 ° C, because the range in which the reaction solvent is present as a liquid is within the temperature range, preferably -10 ° C to 100 ° C, 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 carrier carrying the prepared metallocene compound 1 and the cocatalyst 1 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. have.

The metallocene compound 1, the promoter 1, and the metal are reacted by reacting the metallocene compound 1 with the promoter supported by the at least one metallocene compound 2 selected from the group consisting of compounds represented by Formulas 1 to 3 Solvents that may be used in step (c) of preparing the carrier supported by Rosen compound 2 include aliphatic hydrocarbon solvents such as hexane and pentane, aromatic hydrocarbon solvents such as toluene and benzene, and hydrocarbons substituted with chlorine atoms such as dichloromethane. Mostly organic solvents such as a solvent, an ether solvent such as diethyl ether and THF, acetone and ethyl acetate, and hexane, heptane and toluene are preferable.

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

The metallocene compound 1, the metallocene compound 2, the cocatalyst are reacted by reacting the metallocene compound 1, the cocatalyst 1, and the cocatalyst 2, which is an organometallic compound containing boron, on a carrier on which the metallocene compound 1, the cocatalyst 1, and the metallocene compound 2 are supported. The solvent that can be used in step (d) of preparing a supported metallocene catalyst carrying 1, and cocatalyst 2 is an aliphatic hydrocarbon solvent such as hexane and pentane, an aromatic hydrocarbon solvent such as toluene, benzene, dichloromethane and Mostly organic solvents such as hydrocarbon solvents substituted with the same chlorine atom, diethyl ether, ether solvent such as THF, acetone, ethyl acetate, and the like, and hexane, heptane and toluene are preferable.

The reaction temperature of step (d) 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 multi-metallocene supported 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 multi-metallocene supported 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 multi-metallocene supported catalyst of the present invention include ethylene, propylene, alpha olefins, cyclic olefins, and the like, 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)

<Catalyst preparation>

Example  One

30 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 the metallocene compound of Preparation Example 1 having a tert butoxy-group at 70 ° C 0.36 After adding mmole and reacting for 1 hour, the mixture was washed with toluene. After reacting with MAO 15ml (10wt% Toluene solution) at 70 ° C. for 2 hours, it was washed with toluene to remove unreacted MAO solution. Thereafter, 0.36 mmol of the metallocene compound of Preparation Example 2 was 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.

Example  2

Example 1 except that the metallocene compound of Preparation Example 2 was used in place of the metallocene compound of Preparation Example 1, and the metallocene compound of Preparation Example 1 was used in place of the metallocene compound of Preparation Example 2 Is the same as

Example  3

Production Example 1 Instead of 0.36 mmol of the metallocene compound of Preparation Example 1 0.18 mole of the metallocene compound of Preparation Example 1 and 0.18 mmol of the metallocene compound of Preparation Example 2, using the metallocene compound of Preparation Example 2 It is the same as Example 1 except using 0.18 mole of the metallocene compound of 1 and 0.18 mmol of the metallocene compound of Preparation Example 2.

Comparative 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. After washing with toluene to remove the unreacted MAO solution. 0.36mmole of the metallocene compound of Preparation Example 1 having a tert butoxy-group was reacted at 70 ° C. for 1 hour and then washed with toluene. Thereafter, 0.36 mmol of the metallocene compound of Preparation Example 2 was reacted at 70 ° 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.

 <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).

Example  4

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.

Example  5

Same as Example 4 except that the catalyst prepared in Example 2 was used.

Example  6

Same as Example 4 except that the catalyst prepared in Example 3 was used.

Comparative example  2

It is the same as Example 4 except using the catalyst prepared from Comparative Example 1.

division
Metallocene Catalyst (Manufacturing Example) Borate promoter Supported Metallocene Catalyst activation
(KgPE / gCat) MI (2.16Kg)
(g / 10 min) MFR
Example 4 1 and 2 TB Example 1 45 0.2 38 Example 5 1 and 2 TB Example 2 40 0.6 27 Example 6 1 and 2 TB Example 3 42 0.9 32 Comparative Example 2 1 and 2 TB Comparative Example 1 25 1.1 23

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

Referring to Table 1, in the preparation of a metallocene supported catalyst using two metallocene compounds containing an alkoxide ligand, it is compared with a catalyst prepared by carrying a metallocene compound after supporting MAO as in Comparative Example 1. Example of the metallocene supported catalyst prepared by supporting a part of one metallocene compound or two metallocene compounds as shown in 1 to 3 and then supporting MAO followed by the remaining metallocene compound Polyethylene having a high molecular weight and a wide molecular weight distribution, such as 4 to 6 can be prepared. And in the activity of about 70 to 80% increase in activity can be obtained.

Therefore, by adjusting the composition ratio of each metallocene catalyst using the method for preparing a multimetallocene supported catalyst of the present invention, not only the catalyst activity is excellent, but also the activity of the catalyst can be adjusted, and various physical properties and molecular weight distribution can be adjusted. Eggplant can produce polymers, which in turn means that it is possible to produce multimetallocene supported catalysts with significantly higher activity that can control the molecular weight distribution in a single reactor.

Claims (16)

A first step of preparing a carrier on which the metallocene compound 1 is supported by reacting the carrier with at least one metallocene compound 1 selected from the group consisting of compounds represented by Formulas 1 to 3;
A second step of preparing a carrier on which the metallocene compound 1 and the promoter 1 are supported by reacting the metallocene compound 1 with the cocatalyst 1, which is an organometallic compound including aluminum of Formula 7, on the support;
Metallocene compound 1, cocatalyst 1 by reacting the metallocene compound 1 and at least one metallocene compound 2 selected from the group consisting of compounds represented by formulas 1 to 3 on a carrier on which promoter 1 of formula 7 is supported And a third step of preparing a carrier on which the metallocene compound 2 is supported. And
Metallocene Compound 1, Chemical Formula 7 by reacting the metallocene compound 1, the cocatalyst 1 of Formula 7, and the cocatalyst 2, which is an organometallic compound containing boron of Formula 8, on a carrier on which the metallocene compound 2 is supported A fourth step of preparing a multimetallocene supported catalyst having a promoter 1, a metallocene compound 2, and a promoter 2 of Formula 8 sequentially supported;
Method for producing a multi-metallocene supported catalyst comprising a
[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 the 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 an oxygen atom;
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.
[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.
[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.
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 method for producing a multimetallocene supported catalyst, characterized in that an alkyl radical having 1 to 40 carbon atoms. The method of 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- Method for producing a multi-metallocene supported 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 [C ₁₃ H ₈ ] ZrCl ₂ , [C ₅ H ₅ ] C (CH ₃ ) (AO- (CH ₂ ) _a ) [C ₁₃ 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 Multimetallocene supported, characterized in that it is any one selected from the group consisting of methoxymethyl, tetrahydropyranyl, tetrahydrofuranyl, 1-ethoxyethyl, 1-methyl-1-methoxyethyl and t-butyl Method for preparing a 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 Of any of the supported metallocene catalysts, which is selected from the group consisting of methyl, tetrahydropyranyl, tetrahydrofuranyl, 1-ethoxyethyl, 1-methyl-1-methoxyethyl and t-butyl. Manufacturing method. The method of claim 1, wherein the carrier is dried at 200 ° C to 800 ° C. The method of claim 1, wherein the carrier is at least one member selected from the group consisting of silica, silica-alumina, and silica-magnesia. delete The multimetallocene supported catalyst according to claim 1, wherein the compound represented by Formula 7 is any one selected from the group consisting of methyl aluminoxane (MAO), ethyl aluminoxane, isobutyl aluminoxane and butyl aluminoxane. Manufacturing method. delete The method of claim 1, 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 (Pentafluorophenyl) borate, tri (secondary-butyl) ammonium tetrakis (pentafluorophenyl) borate, N, N-dimethylaninium tetrakis (pentafluorophenyl) borate, N, N-diethylaniyl Tetrakis (pentafluorophenyl) borate, N, N-dimethyl (2,4,6-trimethylaninynium) 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-diethylaninium tetrakis (2,3,4,6-tetrafluorophenyl) bo 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 multi-metallocene supported catalyst, characterized in that at least one member selected from the group consisting of di (tetradecyl) -ammonium tetrakis (pentafluorophenyl) borate. The amount of the supported metal catalyst of claim 1, wherein the supported amount of promoter 2 is 0.1 to 10,000 moles with respect to 1 mole of the transition metal contained in the metallocene compound on the basis of boron contained in promoter 2. Manufacturing method. A method for producing a polyolefin, wherein the olefin monomer is polymerized in the presence of a multi-metallocene supported catalyst prepared according to the method of claim 1. The method for producing a polyolefin according to claim 14, wherein the polymerization is carried out in a slurry process or a gas phase process. The method of claim 14, wherein the multi-metallocene supported 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.