KR100248437B1 - Catalyst for olefin polymerization and method of olefin polymerization - Google Patents

Abstract

The catalyst system for olefin polymerization of the present invention comprises a metallocene catalyst as a catalyst and a supported cocatalyst as a cocatalyst, and the supported cocatalyst is crosslinked with an alkylaluminoxane as a crosslinking agent, and the crosslinked alkylaluminoxane is supported on the carrier. It is characterized by being manufactured. The metallocene catalyst used as a catalyst in the present invention is a cyclopentadienyls or substituted cyclopentadienyl groups in which transition metals (eg, titanium, zirconium, hafnium, etc.) of the Group 4 of the periodic table generate η ⁵ bonds. Substituted cyclopentadienyls, indenyls (indenyls), substituted indenyls (substituted indenyls), fluorenyls (fluorenyls), a substituted fluorenyl group (substituted fluorenyls) has a structure that is bonded. The alkylaluminoxanes used to prepare the supported cocatalysts in the present invention are methylaluminoxane, methylaluminoxane, n-butylaluminoxane, n-hexyl aluminoxane ( n-hexylaluminoxane and modified alkylaluminoxane, the crosslinking agent is a compound having a reactive group such as diamine or triamine, and the carrier is silica, alumina, magnesium compound, zeolite, cray, aluminum phosphate, zirconia and polymer There is.

Description

Catalyst system for olefin polymerization and polymerization method of olefin using the same

Field of invention

The present invention relates to a catalyst system for producing olefin polymers or copolymers. More specifically, the present invention provides a novel supported co-catalyst capable of producing polyolefin having high activity and particle shape and good molecular weight distribution even using a small amount of cocatalyst, and a method for preparing the same and polymerization and copolymerization of olefin using the same. It is about.

Background of the Invention and Prior Art

In general, polymerization and copolymerization of 1-olefins including ethylene have been prepared by heterogeneous catalyst systems composed of titanium compounds and alkylaluminum compounds. Recently, metallocene catalysts, which are homogeneous catalysts with extremely high catalytic activity, have been developed to prepare polyolefins. Metallocene catalysts are compounds of transition metals of Group 4 of the periodic table (e.g., titanium, zirconium, hafnium) and the metal compound and at least one cycloalkanedienyl groups (e.g. : It has a structure combined with a ligand consisting of cyclopentadienyl groups, indenyls, and fluorenyls. This type of metallocene catalyst is used for polymerization in combination with a cocatalyst. The cocatalyst used is an alkylaluminoxane (e.g. methylaluminoxane), which is a reaction product of water and an alkylaluminum compound, unlike that used in conventional heterogeneous catalysts, Ziegler-Natta Catalysts. have. When the olefin is polymerized using such a metallocene catalyst, the metallocene catalyst is applied to the inner wall of the reactor, the resulting polyolefin particles are too small, and the bulk density is low, so there are many problems in commercial production. . The particle size and the solid phase density of the polyolefin are determined by the formation of the catalyst component itself (eg, the carrier).

European Patent Nos. EP 367503 and US Pat. Nos. 5240894 and 5633419 disclose that supported metallocene catalysts are used to solve this problem and to improve uniform particle shape, narrow particle size distribution, high solid phase density, and the like. have. However, these supported metallocene catalysts are disadvantageous in commercialization because they are complicated to manufacture and do not have sufficient activity, and also because alkylaluminoxane (eg, methylaluminoxane) used as a co-catalyst is expensive and used in large amounts.

The method of preparing the cocatalyst of the present invention has a different feature from the method of preparing the silica, alkylaluminoxane and bisphenol A at the same time (for example, European Patent 787746 A1).

Therefore, it is necessary to develop a new catalyst system using existing metallocenes and carrying a cocatalyst.

In order to solve the above problems, the present inventors have conducted a lot of research on the development of the supported cocatalyst to more efficiently prepare the polyolefin polymer and copolymer. As a result, co-catalysts have been developed for the production of polyolefin polymers and copolymers which maintain high catalytic activity even with a small amount of cocatalyst, have rounded particle shapes, uniform particle size distribution and narrow molecular weight distribution.

It is an object of the present invention to provide a novel catalyst system consisting of a metallocene catalyst and a cocatalyst for producing a polymer or copolymer of 1-olefin comprising ethylene.

Another object of the present invention is to provide a novel cocatalyst used for polymerizing or copolymerizing olefins and a method for producing the same.

Still another object of the present invention is to provide a novel cocatalyst capable of producing a polyolefin having excellent activity and particle shape and good molecular weight distribution even using a small amount of a cocatalyst and a method for producing the same.

Still another object of the present invention is to provide a polymerization or copolymerization method of olefins capable of producing polyolefins having high activity and particle shape and good molecular weight distribution even with a small amount of cocatalyst.

The above and other objects of the present invention can be achieved by the present invention described below.

The catalyst system for olefin polymerization of the present invention is composed of a metallocene catalyst as a catalyst and a supported cocatalyst as a cocatalyst, and the supported cocatalyst is crosslinked with an alkylaluminoxane as a crosslinking agent, and the crosslinked alkylaluminoxane is supported on the carrier. It is characterized by being manufactured.

The metallocene catalyst used as a catalyst in the present invention includes a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group, and a transition metal (eg, titanium, zirconium, and hafnium) of Group 4 of the periodic table, which generate η ⁵ bonds. Indenyl group, fluorenyl group, substituted fluorenyl group has a structure in which two bonded. Examples of metallocene catalysts include bis (cyclopentadienyl) zirconium dichloride, bis (cyclopentadienyl) zirconium methylchloride, bis (cyclopentadienyl) zirconium dimethyl, bis (methylcyclopentadienyl) zirconium dichloride , Bis (methylcyclopentadienyl) zirconium methyl chloride, bis (methylcyclopentadienyl) zirconium dimethyl, bis (ethylcyclopentadienyl) zirconium dichloride, bis (ethylcyclopentadienyl) zirconium methyl chloride, bis ( Ethylcyclopentadienyl) zirconium dimethyl, bis (pentamethylcychloride) zirconium dichloride, bis (pentamethylcyclopentadienyl) zirconium methyl chloride, bis (pentamethylcyclopentadiethyl) zirconium dimethyl, bis (n-butyl -Cyclopentadienyl) zirconium dichloride, bis (n-butyl-cyclopentadienyl) zirconium methyl chlor Id, bis (n-butyl-cyclopentadienyl) zirconium dimethyl, bis (indenyl) zirconium dichloride, bis (indenyl) zirconium methyl chloride, bis (indenyl) zirconium dimethyl, bis (2-methyl-indenyl Zirconium dichloride, bis (2-methyl-indenyl) zirconium methyl chloride, bis (2-methyl-indenyl) zirconium dimethyl, bis (2-phenyl-indenyl) zirconium dichloride, bis (2-phenyl-inde Nil) zirconium methyl chloride, bis (2-phenyl-indenyl) zirconium dimethyl, dimethylsilylbis (cyclopentadienyl) zirconium dichloride, dimethylsilbis (cyclopentadienyl) zirconium methyl chloride, dimethylsilylbis (cyclolyi) Pentadienyl) zirconium dimethyl, dimethylsilylbis (indenyl) zirconium dichloride, dimethylsilbis (indenyl) zirconium methyl chloride, dimethylsilbis (indenyl) zirconium dimethyl, di Tylsilylbis (2-methyl-indenyl) zirconium dichloride, dimethylsilylbis (2-methyl-indenyl) zirconium methyl chloride, dimethylsilylbis (2-methyl-indenyl) zirconium dimethyl, dimethylsilbis (indenyl Cyclopentadienyl) zirconium dichloride, dimethylsilyl (indenylcyclopentadienyl) zirconium methyl chloride, dimethylsilyl (indenylcyclophenkadienyl) zirconium dimethyl, dimethylsilyl (fluorenylcyclopentadienyl) zirconium di Chloride, dimethylsilyl (fluorenylcyclopentadienyl) zirconium methyl chloride, dimethylsilyl (fluorenylcyclopentadienyl) zirconium dimethyl, ethylenebis (cyclopentadienyl) zirconium dichloride, ethylenebis (cyclopentadienyl Zirconium methyl chloride, ethylenebis (cyclopentadienyl) zirconium dimethyl, ethylenebis (indenyl) zirconium dichloride, Ethylenebis (indenyl) zirconium methyl chloride, ethylenebis (indenyl) zirconium dimethyl, ethylenebis (2-methyl-indenyl) zirconium dichloride, ethylenebis (2-methyl-indenyl) zirconium methyl chloride, ethylenebis ( 2-methyl-indenyl) zirconium dimethyl, ethylene (indenylcyclopentadienyl) zirconium dichloride, ethylene (indenylcyclopentadienyl) zirconium methyl chloride, enylene (indenylcyclopentadienyl) zirconium dimethyl, ethylene (Fluorenylcyclopentadienyl) zirconium dichloride, ethylene (fluorenylcyclopentadienyl) zirconium methyl chloride, ethylene (gluorenylcyclopentadienyl) zirconium dimethyl, isopropylbis (cyclopentadienyl) zirconium Dichloride, Isopropylbis (cyclopentadienyl) zirconium methyl chloride, Isopropylbis (cyclopentadienyl) zir Dimethyl dimethyl, isopropylbis (indenyl) zirconium dichloride, isopropylbis (indenyl) zirconium methyl chloride, isopropylbis (indenyl) zirconium dimethyl, isopropylbis (2-methyl-indenyl) zirconium dichloride, Isopropylbis (2-methyl-indenyl) zirconium methyl chloride, isopropyl (2-methyl-indenyl) zirconium dimethyl, isopropyl (indenylcyclopentadienyl) zirconium dichlorite, isopropyl (indenylcyclopenta Dienyl) zirconium methyl chloride, isopropyl (indenylcyclopentadienyl) zirconium dimethyl, isopropyl (fluorenylcyclopentadienyl) zirconium dichloride, isopropyl (fluorenylcyclopentadienyl) zirconium methyl chloride, Isopropyl (fluorenylcyclopentadienyl) zirconium dimethyl.

The alkylaluminoxanes used to prepare the supported cocatalysts in the present invention are methylaluminoxane, methylaluminoxane, n-butylaluminoxane, n-hexyl aluminoxane ( n-hexylaluminoxane and modified alkylaluminoxane, the crosslinking agent is a compound having a reactive group such as diamine or triamine, and the carrier is silica, alumina, magnesium compound, zeolite, cray, aluminum phosphate, zirconia and polymer There is. Polymers in the carrier include styrene homopolymers and copolymers.

The diamine compound in the cross-linked agent in the present invention has the following structure.

H ₂ NR-NH ₂ , H ₂ NR ₁ -OR ₂ -NH ₂ , H ₂ NR ₁ -CO-R ₂ -NH ₂ , H ₂ NR ₁ -COO-R ₂ -NH ₂ , H ₂ -R _1- C (CH ₃ ) ₂ -R ₂ -NH ₂ , and H ₂ NR ₁ -C (CH ₃ ) ₂ -R ₂ -C (CH ₃ ) ₂ -R ₃ -NH ₂

In the structural formula, R ₁ , R ₂ , R ₃ are each independently an aliphatic alkyl group having 1 to 12 carbon atoms (aliphatic alkyl group), an aromatic alkyl group (aromatic alkyl group).

The triamine compound in the crosslinking agent in the present invention has the following structure.

Structural Formula 1

In Formula 1, R ₁ , R ₂ , and R ₃ are each independently an aliphatic alkyl group having 1 to 12 carbon atoms, and an aromatic alkyl group.

The method for producing a supported cocatalyst according to the present invention is as follows.

Diamine or triamine as a crosslinking agent is dissolved in toluene, and alkylaluminoxane is gradually added to the solution and crosslinked for 5 to 20 minutes at 10 to 100 ° C. The crosslinked alkylaluminoxane is slowly added to the toluene solution in which the carrier is dispersed and reacted at 5 to 100 ° C. for 5 to 20 hours.

The diamine or triamine as the alkylaluminoxane and the crosslinking agent preferably has a concentration ratio ([Al] / [amine]) in the range of 5 to 100, and the hydroxyl group or water of the alkylaluminoxane and the carrier is in the concentration ratio {[Al]. / ([OH] or [H ₂ O])} is preferably in the range of 3 to 50. After the completion of the reaction, to remove the unreacted product, it was washed with toluene, extracted with toluene for 5 hours at 80-100 ° C, and dried to prepare a supported cocatalyst.

The olefin is polymerized using the catalyst system of the present invention. The monomers to be polymerized in the process of the present invention are olefins or cycloolefins, olefins are α-olefins having 2 to 20 carbon atoms, and cycloolefins are cyclobutene, cyclopentene, cyclohexene, cyclooctene, norbornene, vinylnorbornene Etc. can be mentioned. The polymerization method in the present invention may be carried out by a conventional polymerization method carried out in the polymerization technology of olefins. The polymerization temperature for polymerizing olefin polymerization and copolymer is 0-150 degreeC, Preferably it is 30-120 degreeC. As a result of olefin polymerization and copolymerization using the new supported co-catalyst and the metallocene catalyst, even when a small amount of the supported co-catalyst was used, it showed high activity and had good molecular weight distribution. Preparation was possible.

The novel supported cocatalyst of the present invention can be more clearly understood by the following examples and the following examples are merely for illustrative purposes of the present invention and are not intended to limit the scope of the invention.

Example

Some representative examples of the novel supported cocatalysts according to the present invention will be described as follows, for example, the preparation method and the polymerization thereof.

Example 1

Preparation of Supported Cocatalyst (A) Using Phenylenediamine

3 g of silica (SiO ₂ , 4 mmol-OH, Grace Davison 948) dried at 600 ° C. for 8 hours was added to a flask, and 40 ml of toluene was added and dispersed. The reaction vessel was then adjusted to 50 ° C. 1.2 mmol (0.065 g) of phenylenediamine was added to another flask, and 40 ml of toluene was added to completely dissolve. Then, 24 mmol (12 ml) of methylaluminoxane (6.4 wt% -Al, Tosoh Akzo) was slowly added at 50 ° C for 5 minutes. Reacted. This was slowly added to the flask in which silica was dispersed, and reacted with stirring at 50 ° C. for 5 hours. After completion of the reaction was extracted with toluene at 60 ℃ and dried to prepare a supported cocatalyst.

Ethylene Polymerization Using Supported Cocatalyst (A)

1 L of heptane was charged into a 2 L high-pressure reactor, 1 mmol of triethylaluminum was added, and the mixture was polymerized at 80 ° C for 1 hour. As a metallocene catalyst, 0.012 mmol (5 mg) of bis (butylcyclopentadienyl) zirconium dichloride was used, and as a cocatalyst, polymerization was carried out at 115 ethylene pressure of 75 g of polyethylene using 0.05 g of a supported cocatalyst (A). Got. The molecular weight (melt index, MI) of the produced polyethylene was 0.25, and the molecular weight distribution (melt flow rate, MFR) was 16, showing a narrow molecular weight distribution. The particle size distribution of polyethylene was narrow and most of the particle size was 400-700 μm.

Example 2

Preparation of Supported Cocatalyst (B) Using Diaminonaphthalene

3 g of silica (SiO ₂ , 4 mmol-OH, Grace Davison) dried at 600 ° C. for 8 hours was added to a flask, and 40 ml of toluene was added and dispersed. The reaction vessel was then adjusted to 50 ° C. To another flask, 1.2 mmol (0.1 g) of diaminonaphthalene was added and 40 ml of toluene was completely dissolved. Then, 24 mmol (12 ml) of methylaluminoxane (6.4 wt% -Al, Tosoh Akzo) was slowly added at 50 ° C for 5 minutes. Reacted. This was slowly added to a flask in which silica was dispersed and reacted at 50 ° C. for 5 hours with stirring. After completion of the reaction was extracted with toluene at 60 ℃ and dried to prepare a supported cocatalyst (B).

Ethylene Polymerization Using Supported Cocatalyst (B)

1 L of heptane was charged into a 2 L high-pressure reactor, 1 mmol of triethylaluminum was added, and the mixture was polymerized at 80 ° C for 1 hour. As a metallocene catalyst, 0.012 mmol (5 mg) of bis (n-butylcyclopentadienyl) zirconium dichloride was used. The cocatalyst was polymerized at 115 ethylene pressure using 0.05 g of a supported cocatalyst (B). 90 g of polyethylene was obtained. The molecular weight (melt index, MI) of the resulting polyethylene was 0.15, and the molecular weight distribution (melt flow rate, MFR) was 16, showing a narrow molecular weight distribution. The particle size distribution of polyethylene was narrow and most of the particle size was 500-700 μm.

Example 3

Preparation of supported cocatalyst (C) using 4,4'-diaminodiphenyl ether

3 g of silica (SiO ₂ , 4 mmol-OH, Grace Davison) dried at 600 ° C. for 8 hours was added to the flask, and 40 ml of toluene was added and dispersed. The reaction vessel was then adjusted to 50 ° C. In another flask, 1.2 mmol (0.12 g) of 4,4'-diaminodiphenyl ether was added, and 40 ml of toluene was added thereto to completely dissolve. 24 mmol of methylaluminoxane (methylaluminoxane, 6.4 wt% -Al, Tosoh Akzo) was added at 50 ° C. 12 ml) was added slowly and reacted for 5 minutes. This was slowly added to a flask in which silica was dispersed and reacted at 50 ° C. for 5 hours with stirring. After completion of the reaction was extracted with toluene at 60 ℃ and dried to prepare a supported cocatalyst (C).

Ethylene Polymerization Using Supported Cocatalyst (C)

1 L of heptane was charged into a 2 L high-pressure reactor, 1 mmol of triethylaluminum was added, and the mixture was polymerized at 80 ° C for 1 hour. As a metallocene catalyst, 0.012 mmol (5 mg) of bis (n-butylcyclopentadienyl) zirconium dichloride was used, and as a cocatalyst, polymerization was performed at 115 ethylene pressure using 0.05 g of a supported cocatalyst (C). 49 g of polyethylene was obtained. The molecular weight (melt index, MI) of the produced polyethylene was 0.30, and the molecular weight distribution (melt flow rate, MFR) was 16, showing a narrow molecular weight distribution. The particle size distribution of polyethylene was narrow and most of the particle size was 300 ~ 600㎛.

Example 4

α, α ¹ - bis (4-aminophenyl) -1,4-diisopropylbenzene (α, α ¹ - bis (4-aminophenyl) - 1,4- diisopropylbenzene) supported cocatalyst (D) using a prepared

3 g of silica (SiO ₂ , 4 mmol-OH, Grace Davison) dried at 600 ° C. for 8 hours was added to a flask, and 40 ml of toluene was added and dispersed. The reaction vessel was then adjusted to 50 ° C. To another flask, 1.2 mmol (0.20 g) of α, α'-bis (4-aminophenyl) -1,4-diisopropylbenzene was added, and 40 ml of toluene was added thereto to completely dissolve. Methylaluminoxane (6.4) wt% -Al, Tosoh Akzo) 24 mmol (12 ml) was slowly added to react for 5 minutes. This was slowly added to a flask in which silica was dispersed and reacted at 50 ° C. for 5 hours with stirring. After completion of the reaction was extracted with toluene at 80 ℃ and dried to prepare a supported cocatalyst (D).

Ethylene Polymerization Using Supported Cocatalyst (D)

1 L of heptane was charged into a 2 L high-pressure reactor, 1 mmol of triethylaluminum was added, and the mixture was polymerized at 80 ° C for 1 hour. As a metallocene catalyst, 0.012 mmol (5 mg) of bis (n-butylcyclopentadienyl) zirconium dichloride was used, and the cocatalyst was polymerized at 115 ethylene pressure using 0.05 g of a supported cocatalyst (D). 120 g of polyethylene was obtained. The molecular weight (melt index, MI) of the resulting polyethylene was 0.14, and the molecular weight distribution (melt flow rate, MFR) was 16, showing a narrow molecular weight distribution. The particle size distribution of polyethylene was narrow and most of the particle size was 400-800 μm.

Example 5

Preparation of Supported Cocatalyst (E) Using 2,2'-bis (4- (4-aminophenoxy) phenyl) propane (2,2'-bis (4- (4-aminophenoxy) phenyl) propane)

3 g of silica (SiO ₂ , 4 mmol-OH, Grace Davison) dried at 600 ° C. for 8 hours was added to a flask, and 40 ml of toluene was added and dispersed. The reaction vessel was then adjusted to 50 ° C. In another flask, 1,2 mmol (0.25 g) of 2,2 ¹ -bis (4- (4-aminophenoxy) phenyl) propane was added, and 40 ml of toluene was added thereto to completely dissolve. Methylaluminoxane (6.4) was added at 50 ° C. wt% -Al, Tosho Akzo) 24 mmol (12 ml) was slowly added to react for 5 minutes. This was slowly added to a flask in which silica was dispersed and reacted at 50 ° C. for 5 hours with stirring. After completion of the reaction was extracted with toluene at 80 ℃ and dried to prepare a supported cocatalyst (D).

Ethylene Polymerization Using Supported Cocatalyst (E)

1 L of heptane was charged into the 2 L high-pressure reactor, and 1 mmol of triethylaluminum was added thereto, followed by polymerization at 80 ° C for 1 hour. As a metallocene catalyst, 0.012 mmol (5 mg) of bis (n-butylcyclopentadienyl) zirconium dichloride was used, and the cocatalyst was polymerized at 115 ethylene pressure using 0.05 g of a supported cocatalyst (E). 55 g of polyethylene was obtained. The molecular weight (melt index, MI) of the produced polyethylene was 0.25, and the molecular weight distribution (melt flow rate, MFR) was 16, showing a narrow molecular weight distribution. The particle size distribution of polyethylene was narrow and most of the particle size was 300-800 μm.

Comparative Example

In order to compare the properties of the novel supported cocatalyst of the present invention, ethylene polymerization was carried out using a cocatalyst prepared by a conventional method (eg, European Patent 787746 A1). In addition to the supported cocatalyst, polymerization was also carried out using methylaluminoxane, which is a homogeneous cocatalyst, to investigate the crosslinking agent effect of diamine.

Comparative Example 1

Homogeneous polymerization using diamine as a crosslinking agent

1 L of heptane was charged into a 2 L high-pressure reactor, 1 mmol of triethylaluminum was added, and the mixture was polymerized at 80 ° C for 1 hour. The catalyst used was 0.012 mmol of bis (n-butylcyclopentadienyl) zirconium dichloride, and 6 mmol of methylaluminoxane (6.4 wt% -Al, Tosoh Akzo) and α, α ¹ -bis (co) as co-catalysts. 1.2 mmol (0.20 g) of 4-aminophenyl) -1,4-diisopropylbenzene was used by reacting at 50 ° C.

In this case, 170 g of polyethylene was produced, and the molecular weight (melt index, MI) was 0.5 g / 10 min. However, when methylaluminoxane alone was used as the cocatalyst, 110 g of polyethylene was produced, and the molecular weight (MI) was 2.5 g / 10 min. As a result, the use of diamine as a crosslinking agent was effective in increasing the activity and molecular weight of the catalyst.

Comparative Example 2

In the preparation of the supported cocatalyst, the same conditions as in Example 1 were prepared without using diamine to carry out ethylene polymerization.

The polymerization was carried out under the same conditions as in Example 1, but as a result of using a supported cocatalyst prepared without using diamine, the amount of polyethylene produced was only 5 g, and the particle size was 150-500 µm.

Comparative Example 3

In contrast to the preparation method of Example 4, 1.2 mmol of methylaluminoxane and α, α'-bis (4-aminophenyl) -1,4-diisopropylbenzene were first pre-reacted on silica as in the method shown in European Patent 787746 A1. The supported cocatalyst was prepared by reacting at the same time without making.

Using the supported cocatalyst thus prepared, ethylene polymerization was carried out in the same manner as in Example 4. As a result, 42 g of polyethylene was produced, and the molecular weight (MI) was also low as 0.35 g / 10 min.

Comparative Example 4

Bisphenol A (bisphenol) was used in the same manner as in Examples 1 to 4 without using α, α'-bis (4-aminophenyl) 1,4-diisopropylbenzene as a crosslinking agent, as described in European Patent No. 787746 A1. The supported cocatalyst was prepared using A) and subjected to ethylene polymerization.

As a result of the polymerization, 55 g of polyethylene was produced, resulting in lower catalytic activity than in Examples 1-4. Moreover, molecular weight (MI) was also low as 0.30g / 10min.

The present invention provides a novel catalyst system consisting of a metallocene catalyst and a cocatalyst for preparing a polymer or copolymer of 1-olefin comprising ethylene, and a novel cocatalyst used for polymerizing or copolymerizing olefins and The present invention provides a process for producing a new polycatalyst capable of producing a polyolefin having high activity and particle shape and good molecular weight distribution even with a small amount of cocatalyst. Have

Simple modifications or changes of the present invention can be easily carried out by those skilled in the art, and all such modifications or changes can be seen to be included in the scope of the present invention.

Claims (9)

Alkylaluminoxane is crosslinked with diamine or triamine as a crosslinking agent at 10 to 100 DEG C for 5 to 20 minutes; And Supporting the crosslinked alkylaluminoxane for 5 to 20 hours at 5 to 100 ° C. in the carrier; And a concentration ratio of [Al] / [amine] in the solution is 5 to 100, and a concentration ratio of [Al] / ([OH] or [H ₂ O]) is 3 to 50. Method for producing a supported cocatalyst for olefin polymerization. According to claim 1, wherein the alkylaluminoxane (methylaluminoxane), methylaluminoxane (methylaluminoxane), ethylaluminoxane (ethylaluminoxane), n-butylaluminoxane (n-butylaluminoxane), n-hexylaluminoxane (n-hexylaluminoxane) Method for producing a supported co-catalyst for olefin polymerization, characterized in that it is selected from the group consisting of an improved alkylaluminoxane (modified alkylaluminoxane). The method of claim 1, wherein the diamine is H ₂ NR-NH ₂ , H ₂ NR ₁ -OR ₂ -NH ₂ , H ₂ NR ₁ -CO-R ₂ -NH ₂ , H ₂ NR ₁ -COO-R _2- NH ₂ , H ₂ -R ₁ -C (CH ₃ ) ₂ -R ₂ -NH ₂ , H ₂ NR ₁ -C (CH ₃ ) ₂ -R ₂ -C (CH ₃ ) ₂ -R ₃ -NH ₂ Method for producing a supported co-catalyst for olefin polymerization, characterized in that it is selected from the group consisting of. The method according to claim 1, wherein the triamine is selected from the group consisting of the following structural formulas (1). Structural Formula 1 The method of claim 1, wherein the carrier is selected from the group consisting of silica, alumina, magnesium compounds, zeolite, cray, aluminum phosphate, zirconia, and polymers. An olefin polymerization method comprising contacting an olefin under a catalyst system comprising a supported cocatalyst prepared according to any one of claims 1 to 5 and a metallocene catalyst. The method for olefin polymerization according to claim 6, wherein the olefin is C2-C12 alpha-olefin or cycloolefin. The metallocene catalyst of claim 6, wherein the metallocene catalyst is bis (cyclopentadienyl) zirconium dichloride, bis (cyclopentadienyl) zirconium methyl chloride, bis (cyclopentadienyl) zirconium dimethyl, bis (methylcyclopentadiene Nil) zirconium dichloride, bis (methylcyclopentadienyl) zirconium methyl chloride, bis (methylcyclopentadienyl) zirconium dimethyl, bis (ethylcyclopentadienyl) zirconium dichloride, bis (ethylcyclopentadienyl) zirconium Methyl chloride, bis (ethylcyclopentadienyl) zirconium dimethyl, bis (pentamethylcichloride) zirconium dichloride, bis (pentamethylcyclopentadienyl) zirconium methyl chloride, bis (pentamethylcyclopentadiethyl) zirconium dimethyl, Bis (n-butyl-cyclopentadienyl) zirconium dichloride, bis (n-butyl-cyclopentadienyl) zir Methyl chloride, bis (n-butyl-cyclopentadienyl) zirconium dimethyl, bis (indenyl) zirconium dichloride, bis (indenyl) zirconium methyl chloride, bis (indenyl) zirconium dimethyl, bis (2-methyl- Indenyl) zirconium dichloride, bis (2-methyl-indenyl) zirconium methyl chloride, bis (2-methyl-indenyl) zirconium dimethyl, bis (2-phenyl-indenyl) zirconium dichloride, bis (2-phenyl Indenyl) zirconium methyl chloride, bis (2-phenyl-indenyl) zirconium dimethyl, dimethylsilylbis (cyclopentadienyl) zirconium dichloride, dimethylsilbis (cyclopentadienyl) zirconium methyl chloride, dimethylsilylbis ( Cyclolaipentadienyl) zirconium dimethyl, dimethylsilylbis (indenyl) zirconium dichloride, dimethylsilbis (indenyl) zirconium methyl chloride, dimethyldimethylbis (indenyl) zirco Dimethyl, dimethylsilylbis (2-methyl-indenyl) zirconium dichloride, dimethylsilylbis (2-methyl-indenyl) zirconium methyl chloride, dimethylsilylbis (2-methyl-indenyl) zirconium dimethyl, dimethylsilbis ( Indenylcyclopentadienyl) zirconium dichloride, dimethylsilyl (indenylcyclopentadienyl) zirconium methyl chloride, dimethylsilyl (indenylcyclopentadienyl) zirconium dimethyl, dimethylsilyl (fluorenylcyclopentadienyl) Zirconium Dichloride, Dimethylsilyl (Fluorenylcyclopentadienyl) Zirconium Methyl Chloride, Dimethylsilyl (Fluorenylcyclopentadienyl) zirconium Dimethyl, Ethylenebis (cyclopentadienyl) zirconium Dichloride, Ethylenebis (cyclopenta Dienyl) zirconium methyl chloride, ethylenebis (cyclopentadienyl) zirconium dimethyl, ethylenebis (indenyl) zirconium Chloride, ethylenebis (indenyl) zirconium methyl chloride, ethylenebis (indenyl) zirconium dimethyl, ethylenebis (2-methyl-indenyl) zirconium dicollide, ethylenebis (2-methyl-indenyl) zirconium methyl chloride, Ethylenebis (2-methyl-indenyl) zirconium dimethyl, ethylene (indenylcyclopentadienyl) zirconium dichloride, ethylene (indenylcyclopentadienyl) zirconium methyl chloride, enylene (indenylcyclopentadienyl) zirconium Dimethyl, Ethylene (Fluorenylcyclopentadienyl) zirconium dichloride, Ethylene (Fluorenylcyclopentadienyl) zirconium methyl chloride, Ethylene (Cluorenylcyclopentadienyl) zirconium dimethyl, Isopropylbis (cyclopentadiene Nyl) zirconium dichloride, isopropylbis (cyclopentadienyl) zirconium methyl chloride, isopropylbis (cyclophene Dienyl) zirconium dimethyl, isopropylbis (indenyl) zirconium dichloride, isopropylbis (indenyl) zirconium methyl chloride, isopropylbis (indenyl) zirconium dimethyl, isopropylbis (2-methyl-indenyl) zirconium Dichloride, isopropylbis (2-methyl-indenyl) zirconium methyl chloride, isopropyl (2-methyl-indenyl) zirconium dimethyl, isopropyl (indenylcyclopentadienyl) zirconium dichlorite, isopropyl Nylcyclopentadienyl) zirconium methyl chloride, isopropyl (indenylcyclopentadienyl) zirconium dimethyl, isopropyl (fluorenylcyclopentadienyl) zirconium dichloride, isopropyl (fluorenylcyclopentadienyl) zirconium Methyl chloride, and isopropyl (fluorenylcyclopentadienyl) zirconium dimethyl The olefin polymerization method of the gong. A supported cocatalyst for olefin polymerization prepared according to any one of claims 1 to 5.