KR100361889B1 - Supported metallocene catalyst and method for producing the same - Google Patents

Abstract

PURPOSE: Provided are a supported metallocene catalyst which retains a catalyst activity corresponding to that of catalyst of homogeneous system, and which can polymerize high molecular homopolymer or copolymer, and a method for producing the same. CONSTITUTION: The supported metallocene catalyst is produced by supporting a metallocene catalyst(to which transition metal is ligand-bonded) and an alkyl aluminum or a condensate of water and alkyl aluminum as a co-catalyst, on carrier having surfaces modified by contacting with silane compound represented by formula I(wherein A, B and C are the same or different each other, at least one of A, B and C are -R1HN-(R2)x-, the others are -H(R2)x-, R1 is at least one selected from hydrogen, alkyl of C1-C8, or aryl of C6-C20, R2 is one or two or more selected from C20 or less of alkyl, or C6-C20 of aryl, C1-C10 of iso-alkyl comprising one or two or more of N, O, S, P, Si atoms, and C6-C20 of iso-aryl, x is 0-15, y is 0-10, z is 0-3, D is a halogen, and each of x, y, z and (3-z) is the same or different, respectively).

Description

Metallocene supported catalyst and its manufacturing method

The present invention relates to a metallocene supported catalyst used for the single polymerization or copolymerization of various olefins and styrene monomers and a method for producing the same.

Metallocene catalysts are also referred to as single-site catalysts, and their general structure is a form in which transition metal atoms are coordinated with at least one cyclopentadienyl derivative group. These transition metal compounds are paired with a bulky, noncoordinating anion. To form a cationic species that is active in the coordination polymerization of a monomer having a double bond.

Since metallocene catalysts were discovered to have high activity in 1980 when methylaluminoxane was used as a promoter (H. Sinn, W. Kaminsky, HJ Vollmer and R. Woldt, Angew Chem., 92, 396 ( 1980), research on the development of various catalysts and products is being carried out worldwide.

Metallocene catalysts have various advantages, such as high polymerization activity, uniform molecular weight and distribution of polymers, excellent copolymerization performance, and stereoregular polymerization, as compared with conventional Ziegler-Natta catalysts.

Metallocene catalysts are commonly used as homogeneous catalysts dissolved in solvents in commercial processes, but in some existing processes such as suspension or gas phase processes, metallocene catalysts are used as supported catalysts by adsorption or chemical bonding to carriers (M , Kaminska and K. Soga, Polymer, 33, 1105 (1992)). Supporting the metallocene catalyst in addition to the necessity of such a process has the advantage of excellent thermal stability and shelf life of the catalyst and control of the shape of the polymer. In addition, when the supported catalyst, methylaluminoxane as a co-solvent, is previously contacted with a carrier, the amount of methylaluminoxane can be reduced, and there are many advantages such as general alkyl aluminum can be used during polymerization.

The method of preparing the metallocene supported catalyst reported in the patent or literature so far is classified as follows.

A. A method of supporting a metallocene catalyst by first contacting a promoter with a carrier, for example, by directly reacting trimethylaluminum with water adsorbed on the surface of silica to form methylaluminoxane on the surface of silica or hydride on the surface of silica or modified silica. After reacting the hydroxy group with methylaluminoxane, the metallocene catalyst is adsorbed or chemically bonded (US 4912075, US 5086205, EPA 206794, EP 452520, JP 04008704, M. kaminaka, Soga, Makromol. Chem., Rapid Commun. , 12, 367 (1991).

N. Method of contacting the cocatalyst after first supporting the metallocene catalyst on the carrier: For example, a method of contacting methylaluminoxane after making a supported metallocene catalyst by reacting a metallocene catalyst with a hydroxy group on the surface of silica (W kaminsky, F. Renner, Makromol.Chem., Rapid Commun., 14, 239 (1993).

C. A method in which the metallocene catalyst and the promoter are activated by first contacting or activated by contacting the carrier at once (US 5240894).

D. A method of first reacting a ligand compound with a carrier and then reacting it with a transition metal compound to form a metallocene catalyst chemically bonded to the surface of the carrier (EP 293815, k. Soga, HJ kim, and T. Shiono, Macromol , Rapid Commun., 15, 139 (1994)).

M. A method of making a polymer of a metallocene catalyst using a polymerizable ligand or chemically bonding a polymer reactor with a ligand reactor of a metal catalyst (US 5262498, CA 2004419),

Iii. A method of adsorbing or chemically bonding a metallocene catalyst to alumina or magnesium chloride having a Lewis acid group and treating with trialkylaluminum to form active cationic species on the surface of the carrier (EPA 336593, EP 436399).

A. Diol having a suitable hydrocarbon number is reacted with methylaluminoxane to make a solid methylaluminoxane and used as a carrier (C. Janiak, B. Rieger, R. Voelkel and H. Braun, J. of Polym. Sci. , Part A: Polym. Chem., 31, 2959 (1993)).

As described above, many studies and patents on supported metallocene catalysts have been reported, but the activity of the catalysts is still lower than that of homogeneous metallocene catalysts (EP 128045, US 4871705, EP 420436), and US 4871705, US 5006500, EP 436399), the molecular weight of the polymer does not exceed the range of hundreds of thousands. Moreover, the activity and molecular weight of the copolymer is further reduced, and the mass average molecular weight of the produced copolymer is in the range of tens of thousands to hundreds of thousands. In either case, no polymerization has been reported for copolymers having a molecular weight of millions. The present inventors earnestly studied in order to solve the above problems, the metallocene catalyst by the method of contacting the metallocene catalyst and the promoter simultaneously or sequentially after deforming the surface of the carrier to a silane compound containing an amine group New metallocenes capable of polymerizing high molecular weight homopolymers or copolymers as well as maintaining the activity of the catalyst at homogeneous catalyst levels by preventing the change of inactive species by reaction with hydroxyl groups liberated on the surface of the carrier The supported catalyst and its manufacturing method have been developed.

Hereinafter, the present invention will be described in detail.

The distinction between the catalyst of the present invention and the prior art is that the catalyst activity, as well as the structure, physical properties and shape control ability of the polymer, which are generally specific to the existing supported catalysts, are maintained at the same level as the homogeneous metallocene catalyst, and the molecular weight of the polymer is Higher molecular weight polymers can be produced than with homogeneous catalysts or other heterogeneous catalysts.

The supported catalyst of the present invention is prepared to have activity by physically or chemically bonding one or two or more metallocene catalysts to a surface-modified carrier, and there is a clear difference in the supported catalysts of the prior art and the preparation method thereof. . Representative methods of modifying the surface of the carrier are silane compounds, which react with a hydroxy group liberated on the silica surface with trimethylsilanol or the like, or after reacting with a dichlorodimethylsilane, substitute a chloride group with a hydroxy group, and then silanol. Methods of transformation to compounds are known (Makromol. Chem., Rapid Commun. 14, 765-770 (1993) and Makromol. Chem. 194, 3499 (1993)).

However, these methods do not react fully with the hydroxy group and the promoter when treating the modified carrier surface with a promoter and free hydroxy is present. In this case, the metallocene catalyst reacts with the remaining hydroxyl group to become an inactive species (Makromol. Chem., Rapid Commun. 12, 367-372 (1991), Macromol. Rapid Commun. 15, 139-143 (1994)). , Makromol. Chem. Phys. 195, 1369-1379 (1993)) During polymerization, all of the catalysts bound to the carrier do not become polymeric active species, resulting in reduced activity. In addition, by treating the chloride group of the silanol compound reacted on the silica surface with a water-soluble NaHCO ₃ solution and substituting a hydroxyl group, it becomes an impurity itself to reduce the activity of the promoter or metallocene catalyst. However, in the present invention, the hydroxyl group on the surface of the carrier can be substituted with an amine group to prevent the metallocene catalyst from reacting with the hydroxyl group and converting into inactive species, thereby obtaining a high molecular weight polymer.

What can be used as a carrier in the present invention are various inert solids, in particular, it is preferable that the surface and the inside of the particles are porous. Examples of inert solids include various inorganic oxides, such as silica, alumina, silica-alumina, magnesia, titania, zirconia, and the like, and talc, zeolite, and the like may also be used as a carrier.

In the present invention, one or two or more kinds of groups are used to satisfy the desired structure and physical properties, and the number of hydroxyl groups should be controlled. As a method of releasing a hydroxyl group, there is a method of heating under vacuum or heating while flowing an inert gas such as nitrogen or argon. Heating temperature is 100-1000 degreeC, More preferably, it is 200-800 degreeC. The usual heating method is to raise the temperature to the desired temperature at a rate of 0.5-8 ° C / minute, hold for 2 hours to 48 hours, and then cool slowly at room temperature. A method of heating the hydroxyl group as a method of liberating a chemical treatment thereof is also used. Representative compounds include trimethylchlorosilane and tetrachloride silane. These compounds react with and remove moisture or hydroxyl groups from the surface of the carrier.

In the present invention, the surface of the carrier is modified by contacting the silane compound containing the amine group with the carrier directly or under an inert solvent, wherein the amount of the added silane compound is used in an amount sufficient to modify the surface of the carrier. . In the present invention, the silane compound containing the amine group may be represented by the following general formula (I).

In the above formula (I), A, B and C are the same or different from each other, at least one of A, B and C is in the form of R ¹ HN- (R ² ) x-, and the rest is H (R ² x-form. From here,

R ¹ = hydrogen, one alkyl selected from 1 to 8 carbon atoms, or one aryl having 6 to 20 carbon atoms

R ² = Alkyl having 20 or less carbon atoms, or aryl having 6-20 carbon atoms, or C1-10 heteroalkyl having 6 or more carbon atoms containing 1, 2 or more atoms of N, O, S, P, Si. 1 type or 2 or more types selected from isomers of 2

x = 0-15 and all x are the same or different

y = 0-10 and y are all the same or different

z = 0-3 and all z are the same or different

D = halogen with all (3-z) identical or different

Examples of the alkyl group include -CH _2- , -CH (CH ₃ ) CH _2- , -CH ₂ CH ₂ (CH ₃ ) CH _2- , -CH (CH ₃ )-, -C (CH ₃ ) _2- , -C (CH ₃ ) (CH ₂ CH ₃ )-, -C (CH ₂ CH ₃ ) _2- , and the like. Examples of isoalkyl are -NHCH2-, -NHCH2CH2-, -OCH3-, -OCH2CH3, and examples of isoaryl having 6 to 20 carbon atoms There is a back. Examples of the alkyl reason is _{-NHCH 2 -, -NHCH 2 CH 2} -, -OCH 3 -, -OCH 2 CH 3 , and an example of this, the number of carbon atoms of 6-20, such as rational aryl is _{- (CH 2) nNH (CH} 2 m (CH ₂ ) ₁ -and the like, where n, m, and l are each 0-4. Examples of halogens are chloride, bromide and the like.

Representative examples of the silane compound containing such an amine group include 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, aminophenoxytrimethoxysilane, (aminoethylaminomethyl) pentyltrimethoxysilane Etc.

The supported catalyst is prepared by the following three methods in a modified carrier prepared by the above method under an inert organic solvent.

A. Method of supporting metallocene catalyst after first contacting promoter to carrier

N. Method of contacting cocatalyst after first supporting metallocene catalyst on carrier

C. Activated by first contacting the metallocene catalyst with the promoter or by contacting the carrier at once

In addition, fouling may be prevented during polymerization by prepolymerizing the supported catalyst with olefins or by adding a small amount of cocatalyst or alkylaluminum to remove the remaining solvent or impurities.

As the metallocene catalyst used in the above, the same catalysts as those of the homogeneous metallocene catalyst may be used. Typically, a cyclopentadienyl having a transition metal such as titanium, zirconium and hafnium, a cyclopentadienyl having a substituent, and a modification Cyclopentadienyl, indenyl, indenyl with substituents, florenyl, florenyl with substituents, and the like are bound by the following method.

A. One or more ligands π-bond to the transition metal

N. A two-bond ligand compound in which two ligands, which are identical or different, are linked by a compound such as hydrocarbon, silane, sulfur, amide, and phosphorus is π-bonded to the transition metal.

C. The two-bond ligand compound in which silane, sulfur, amide, phosphorus, etc. are substituted in one ligand is a π- and σ-bond to the transition metal.

Examples of such metallocene catalysts include biscyclopentadienyl zirconium dichloride, bispentamethylcyclopentadienyl zirconium dichloride, rac-dimethylsilylbistetrahydroindenyl zirconium dichloride, ethylenebisindenyl zirconium dichloride, Ethylene bistetrahydroindenyl zirconium dichloride, iso-propyl (florenyl) (cyclopentadienyl) zirconium dichloride, and the like are the most representative. However, it can be used in the present invention is not limited thereto.

And examples of the cocatalyst used with the metallocene catalyst include trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, tributylaluminum, triisobutylaluminum, dimethylchloroaluminum, diethylchloroaluminum or water. Condensation products of alkylaluminum compounds are also used, and representative examples thereof include methylaluminoxane, and methylaluminoxane, which is generally purchased and used, contains a small amount of trimethylaluminum.

The amount of alkyl aluminum in the prepared metallocene supported catalyst is 0.05-40 mmol per gram of carrier, more preferably 0.5-20 mmol per gram of carrier. The molar ratio of the transition metal to the alkyl aluminum is from 1: 10 to 1: 1000, and the total weight of the transition metal and aluminum is used at 30% or less with respect to the carrier.

When the carrier and the silane compound are reacted or when the modified carrier and the catalyst, the promoter, or the mixed product of the catalyst and the promoter are stirred in a slurry state, the stirring temperature is 0-130 ° C, and the stirring time is 20 minutes- Although it is 48 hours, it can be carried out above or below this temperature depending on the reactivity of the silane compound used with the hydroxyl group on the surface of the carrier, the reactivity of the modified carrier with the catalyst or promoter, and with air at all stages of catalyst preparation. To prevent contact, it should be carried out under high purity nitrogen gas.

The amount of the organic solvent used in the experiment does not particularly affect the preparation of the catalyst of the present invention, and the unreacted substance is preferably removed by washing five or more times with the organic solvent. The prepared supported catalyst is dried in a vacuum for 2 to 48 hours, and is suitably performed in a range in which the properties of the catalyst of the present invention do not change. As the inert solvent used in the present invention, a hydrocarbon solvent having a relatively low boiling point, an inert aromatic solvent, and the like may be used as a solvent that does not contain oxygen, water, or impurities that may be adsorbed on the surface of the carrier. Examples of the hydrocarbon solvent include hexane having 5 to 10 carbon atoms, cyclohexane, pentane, cyclopentane, isopentane, heptane, octane and nonane, and aromatic solvents include benzene, toluene, ethylbenzene and diethylbenzene. .

When the transition metal catalyst is adsorbed on the surface-modified carrier, or when the transition metal catalyst and methylaluminoxane react with each other to generate active species, the color of the transition metal is changed to yellow or pink, and is completely dried and in contact with water and oxygen. The catalysts retain activity as well as color for at least six months. In addition, the activity of the catalyst is different depending on the time when the supported catalyst is aged while stirring in a solvent in a slurry (slurry) state. The high activity is maintained at a aging time of 30 minutes-2 months. It shows the highest activity when aging time. In addition, the hydroxy group and the amine group in the preparation process of the supported catalyst can be analyzed by FT-IR instrument, and the amount of aluminum and the amount of transition metal supported can be analyzed by ICP and element separator.

The supported catalyst prepared by the above methods and alkylaluminum are added to carry out olefin homopolymerization or copolymerization. As the alkylaluminum used herein, the same catalyst as used for preparing the supported catalyst is used. Alkyl aluminum not only serves as a promoter but also removes impurities in the reactor. The polymerization process is carried out under an inert organic solvent. First, an appropriate amount of inert organic solvent and alkylaluminum are added to the glass reactor to remove impurities in the reactor, and monomers dissolved in a solvent are dissolved in a solvent or a gaseous monomer is used in a reactor. Apply supported catalyst while flowing into the inside of The polymerization time is limited to within 2 hours for comparison, the polymerization temperature is 40 ℃-70 ℃ to select the appropriate temperature and reaction time according to the type of monomer.

The polymerization is terminated by adding 5% HCl / CH ₃ OH solution to remove the remaining catalyst, precipitated in methanol, washed and dried in a vacuum oven to obtain a white polymer. Analysis of the molecular weight and molecular weight distribution of the polymerized polymer can be carried out by high temperature gel permeation chromatography.

Hereinafter, the present invention will be described with reference to Examples, but the present invention is not limited by these Examples.

Analysis of the polymerized polymer in Example was performed after making a universal calibration curve of a polystyrene standard sample using a 150 CV model of Waters Co., Ltd. equipped with a concentration detector capable of simultaneously measuring the refractive index and the viscosity.

Organic reagents and solvents necessary for preparing the supported catalyst were purchased from Aldrich and purified by standard methods, and carriers were purchased from Aldrich and Fuji Silysia. The alkylaluminum compound and the metallocene catalyst were purchased from Aldrich and used without further purification, and the monomer was purchased from Applied Gas Technology Co., Ltd., a high-purity gaseous monomer, and the main polymerization was carried out through a water and oxygen filtration device. The reproducibility of the experiment was improved by blocking the contact of air at all stages of the preparation and polymerization of the supported catalyst.

Example 1

(1) Preparation of catalyst

In a glove box substituted with high purity nitrogen gas, 6 g of dried silica (Fuji Silysia, P-10; dried at 200 ° C for 24 hours) is placed in a Schlenk tube, completely sealed, and then I took it out of the box. And a hose was connected to the Schlenk tube so that argon gas of high purity may be supplied to silica gradually. 100 ml of purified toluene solvent and 5.34 ml (22.72 mmol) of 3-aminopropyltriethoxysilane were added at room temperature and stirred in a slurry state for 5 hours.

Then, the toluene solvent was refluxed for 24 hours, and then excess solvent and unreacted material were removed. The silica was washed five times with 30 ml of toluene solvent and then dried in a vacuum oven at 60 ° C. for 48 hours.

6 ml of methylaluminoxane toluene solution having an amount of aluminum of 10.3% was placed in a 50 ml Schlenk tube and dried in vacuo to remove trimethylaluminum and toluene solvent to obtain white methylaluminoxane powder. This powder was dissolved again in 20 ml of toluene solution to form a methylaluminoxane solution from which trimethylaluminum was removed.

1 g of silica and 10 ml of toluene solution prepared as above were added to a 50 ml Schlenk tube under high purity argon gas and stirred. And 11 ml of methylaluminoxane solution from which trimethylaluminum was removed were added at room temperature, followed by stirring for 1 hour. Excess toluene solvent and unreacted substance were removed, and silica was washed 5 times with 30 ml of toluene solvent to make the amount of toluene 10 ml. 4 ml of biscyclopentadienyl zirconium dichloride (0.02 mmol) dissolved in a heptane solvent was added to this Schlenk tube at room temperature, followed by stirring for 1 hour. Excess toluene solvent and unreacted substances were removed, silica was washed 5 times with 30 ml of toluene solvent, and then vacuum dried and stored in a glove box.

(2) polymerization 1

200 ml of the glass reactor was replaced with nitrogen and then replaced with ethylene, and 113 ml of toluene was injected. The reactor was immersed in a 40 ° C. thermostat and stirred for 30 minutes under ethylene atmosphere to saturate ethylene in toluene solvent. 10 ml of triisobutylaluminum solution (concentration 1 mmol / ml) was injected, and after 5 minutes, 0.004 mmol (200 mg of Cp ₂ ZrCl ₂ supported on modified silica + 4 ml of toluene) prepared above was added to initiate polymerization.

Ethylene pressure during the polymerization was maintained at 1 atmosphere, and the polymerization temperature was 40 ° C., and after 1 hour, 5% HCl / CH ₃ OH solution was added to stop the reaction. The reaction product was precipitated in 500 ml of 5% HCl / CH ₃ OH solution, filtered and dried under vacuum at 60 ° C. to obtain 1.43 g of white polyethylene. The mass average molecular weight measured by the gel permeation chromatography method using the trichlorobenzene solvent of 140 degreeC was 6,426,000, and molecular weight distribution was 5.84.

(3) polymerization 2

The polymerization was carried out in the same manner as in the polymerization 1 except that trimethylaluminum was used as the cocatalyst. At this time, 1.43 g of white polyethylene was obtained, having a mass average molecular weight of 6,344,000 and a molecular weight distribution of 5.77.

(4) polymerization 3

The 200 ml glass reactor was first replaced with nitrogen using a vacuum line and then replaced with ethylene, and 113 ml of toluene and 1.5 ml of 1-hexene were injected. The reactor was immersed in a 40 ° C. thermostat and stirred for 30 minutes under ethylene atmosphere to allow ethylene to be saturated in toluene solvent. 10 ml of trimethylaluminum solution (concentration 1 mmol / ml) was injected and 5 minutes later, polymerization was started by adding 0.004 mmol (200 mg of Cp ₂ ZrCl ₂ + 4 toluene supported on modified silica) prepared above. Ethylene pressure during the polymerization was maintained at 1 atmosphere, the polymerization temperature was 40 ℃ and after 30 minutes, 5% HCl / CH ₃ OH solution was added to stop the reaction. The reaction product was precipitated in 500 ml of 5% HCl / CH ₃ OH solution, filtered and dried under vacuum at 60 ° C. to obtain 0.938 g of polyethylene. The mass average molecular weight measured by the gel permeation chromatography method using the trichlorobenzene solvent of 140 degreeC was 2,946,000, and molecular weight distribution was 4.55.

Example 2

(1) Preparation of catalyst

The drying conditions of the silica were changed to 600 ° C. (10 hours), except that 5.34 ml (22.72 mmol) of 3-aminopropyltriethoxysilane and 10 ml (0.04 mmol) of bispentamethylcyclopentadienyl zirconium dichloride were used. And it carried out similarly to Example 1.

(2) polymerization

The polymerization was carried out in the same manner as in Example 1, except that 300 mg of the supported catalyst prepared above was used. At this time, 2.71 g of polyethylene was obtained, having a mass average molecular weight of 3,419,000 and a molecular weight distribution of 5.18.

Example 3

(1) Preparation of catalyst

Under a high purity nitrogen gas, 6 g of dried silica (Fuji silysia, P-10: dried at 200 ° C. for 24 hours) and 100 ml of purified toluene solvent were placed in a Schlenk tube and stirred. 3.97 ml (22.72 mmol) of 3-aminopropyltrimethoxysilane was added at room temperature and stirred in a slurry for 4 hours. Then, the toluene solvent was refluxed for another 24 hours, and excess solvent and unreacted substance were removed. The silica was washed five times with 30 ml of toluene solvent and then dried in a vacuum oven at 60 ° C. for 48 hours. The dried silica was stored in a glove box.

6 ml of methylaluminoxane toluene solution having an amount of aluminum of 10.3% was placed in a 50 ml Schlenk tube and dried in vacuo to remove trimethylaluminum and toluene solvent to obtain white methylaluminoxane powder. The powder was again dissolved in 20 ml of toluene solution to form a methylaluminoxane solution in which methyl aluminum was removed, and then 10 ml of this solution and 4 ml of zirconocene dichloride (0.02 mmol) dissolved in heptane solvent were mixed with 10 ml of toluene solvent. It was placed in a 50 ml Schlenk tube at room temperature and stirred for 10 minutes under argon gas. 1 g of the above modified silica was added to the Schlenk tube, followed by stirring for 1 hour while raising the temperature to 40 ° C. The excess toluene solvent and the unreacted substance were removed, the silica was washed five times with 30 ml of toluene solvent, and then vacuum dried and stored in a glove box.

(2) polymerization

The polymerization was carried out in the same manner as in Example 1, except that 300 mg of the supported catalyst prepared above was used. At this time, 4.24 g of polyethylene was obtained, with a mass average molecular weight of 4,251,000 and a molecular weight distribution of 5.73.

Comparative Example 1

(1) Preparation of catalyst

Under a high purity nitrogen gas, 1 g of dried silica (Fuji silysis, P-10: dried at 200 ° C. for 24 hours) and 10 ml of purified toluene solvent were placed in a 50 ml Schlenk tube and stirred. And 11 ml of methylaluminoxane solution from which trimethylaluminum was removed through the same method as Example 1 was added at room temperature, followed by stirring for 1 hour. Excess toluene solvent and unreacted substance were removed, and silica was washed 5 times with 30 ml of toluene solvent to make the amount of toluene 10 ml. 4 ml of biscyclopentadienyl zirconium dichloride (0.02 mmol) dissolved in heptane solvent was added at room temperature, stirred for 1 hour, the excess toluene solvent and the unreacted substance were removed, and the silica was washed 5 times with 30 ml of toluene solvent. After vacuum drying it was stored in a glove box.

(2) polymerization

200 ml of the glass reactor was first replaced with nitrogen using a vacuum line, and then again with ethylene, and 113 ml of toluene and 1.5 ml of 1-hexene were added thereto. After immersing this reactor in a 40 degreeC thermostat, it stirred for 30 minutes in ethylene atmosphere, and made it saturate in toluene solvent. 50 ml of trimethylaluminum solution (concentration 1 mmol / ml) was injected and after 5 minutes, 0.008 mmol of the catalyst prepared above (200 ml of Cp ₂ ZrCl ₂ supported on modified silica + 4 ml of toluene) was added to initiate polymerization. Ethylene pressure during the polymerization was maintained at 1 atmosphere, polymerization temperature was 40 ℃, after 60 minutes, 5% HCl / CH ₃ OH solution was added to stop the reaction. The precipitate was poured into 500 ml of a 5% HCl / CH ₃ OH solution, precipitated, filtered, and dried in vacuo at 60 ° C. to obtain 3.65 g of polyethylene. The mass average molecular weight was 19,510 and the molecular weight distribution was 6.78 measured by gel permeation chromatography using a trichlorobenzene solvent at 140 ° C.

Comparative Example 2

(1) Preparation of catalyst

Under a high purity nitrogen gas, 1 g of dried silica (Fuji silysia, P-10; dried at 200 ° C. for 24 hours) and 10 ml of purified toluene solvent were placed in a 50 ml Schlenk tube and stirred. 3.2 ml of methylaluminoxane solution (8.4 wt% toluene solution) was added at room temperature, followed by stirring for 30 minutes. Excess toluene solvent and unreacted substance were removed, and silica was washed 5 times with 30 ml of toluene solvent to make the amount of toluene 10 ml. 4 ml of biscyclopentadienyl zirconium dichloride (0.02 mmol) dissolved in heptane solvent was added at room temperature, stirred for 1 hour, and then excess toluene solvent and unreacted substance were removed, and silica was washed 5 times with 30 ml of toluene solvent. After vacuum drying it was stored in a glove box.

(2) polymerization

500 ml of the glass reactor was first replaced with nitrogen using a vacuum line, and then again with ethylene and 250 ml of toluene was injected. The reactor was immersed in a thermostat at 50 ° C. and stirred for 30 minutes under a pressure of 10 psi to allow ethylene to be saturated in the toluene solvent. 4.68 ml of triisobutylaluminum solution (5mmol, concentration 25wt% toluene) was injected, and 5 minutes later, 0.04 mmol of the catalyst prepared above (200 mg of Cp ₂ ZrCl ₂ + 4 ml toluene supported on modified silica) was added to initiate polymerization. . Ethylene pressure during the polymerization was maintained at 10 psi, the polymerization temperature was 50 ℃, after 50 minutes, the reaction was stopped by adding 5% HCl / CH ₃ OH solution. And precipitated in 500ml of 5% HCl / CH ₃ OH solution, filtered and dried in vacuo at 60 ℃ to obtain 4.939g of polyethylene. The mass average molecular weight measured by the gel permeation chromatography method using the trichlorobenzene solvent of 140 degreeC was 117,000, and molecular weight distribution was 4.33.

Claims (9)

The condensation product of alkyl aluminum or water and alkyl aluminum, which is a metallocene catalyst and a cocatalyst having a transition metal ligand, and a promoter is supported on a carrier in which surface modification occurs by contact with a silin compound containing an amine group represented by the following general formula (I) Metallocene supported catalyst, characterized in that. In the above formula (I), A, B and C are the same or different groups from each other, at least one of A, B and C is in the form of R ¹ HN- (R ² ) x-, and the rest is H (R ² x-form. From here, R ¹ = hydrogen, one alkyl selected from 1 to 8 carbon atoms, or one aryl having 6 to 20 carbon atoms R ² = Alkyl having 20 or less carbon atoms, or aryl having 6 to 20 carbon atoms, or C1-10 isoalkyl having 6 or more carbon atoms containing one or two or more N, O, S, P and Si atoms. One or two isomers selected from x = 0-15 and all x are the same or different y = 0-10 and y are all the same or different z = 0-3 and all z are the same or different D = halogen with all (3-z) identical or different The supported metallocene catalyst according to claim 1, wherein the amount of alkyl aluminum is 0.05-40 mmol per gram of carrier. The supported metallocene catalyst according to claim 1, wherein the molar ratio of the transition metal to the alkyl aluminum of the metallocene catalyst is from 1: 10 to 1: 1000. The supported metallocene catalyst according to claim 1, wherein the total weight of the transition metal of the metallocene catalyst and the alkyl aluminum is 30% or less of the carrier. The supported metallocene catalyst according to claim 1, wherein the carrier is one or two or more selected from silica, alumina, silica-alumina, magnesia, titania, zirconia, talc, and zeolite. After modifying the surface of the carrier by directly contacting the silin compound containing the amine group represented by the following general formula (I) or under an inert solvent, the carrier is supported with a metallocene catalyst and a cocatalyst. Method for producing a metallocene supported catalyst. In the above formula (I), A, B and C are the same or different groups from each other, at least one of A, B and C is in the form of R ¹ HN- (R ² ) x-, and the rest is H (R ² x-form. From here, R ¹ = hydrogen, one alkyl selected from 1 to 8 carbon atoms, or one aryl having 6 to 20 carbon atoms R ² = Alkyl having 20 or less carbon atoms, or aryl having 6 to 20 carbon atoms, or 1 to 10 isoalkyl alkyl having 6 or more carbon atoms containing N, O, S, P, Si atoms and 6 to 20 carbon atoms. 1 type or 2 or more types selected from isomers of 2 x = 0-15 and all x are the same or different y = 0-10 and y are all the same or different z = 0-3 and all z are the same or different D = halogen with all (3-z) identical or different The silinic compound used in modifying the surface of the carrier is 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, aminophenoxytrimethoxysilane, (aminoethylaminomethyl A method for producing a metallocene supported catalyst, characterized in that one selected from phenyltrimethoxysilane is used. The method of claim 6, wherein the cocatalyst is trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, tributylaluminum, triisobutylaluminum, dimethylchloroaluminum, diethylchloroaluminum or water and an alkylyl aluminum compound. A method for producing a metallocene supported catalyst, characterized in that at least one selected from condensation products is used. 7. The method for preparing a metallocene supported catalyst according to claim 6, wherein the carrier is a free hydroxyl group.