KR101310592B1 - Method for Preparing Supported Metallocene Catalyst for Polymerizing Olefin - Google Patents

Abstract

The present invention relates to a supported catalyst for olefin polymerization, comprising: reacting a cocatalyst with an organic solvent on a carrier under an inert gas pressure of 2 to 20 bar to prepare a carrier on which a promoter is supported (a); And (b) preparing a supported catalyst by reacting a metallocene compound with an organic solvent on a carrier on which the promoter is supported under an inert gas pressure of 2 to 20 bar. Provide a method. According to the present invention, in the preparation of the supported metallocene catalyst, by increasing the pressure of the inert gas in the reactor, the supporting speed of the promoter and the metallocene catalyst is increased, the amount of the catalyst supported on the carrier is increased, and the supported metallocene is increased. The activity of the catalyst is increased, and when the supported metallocene catalyst prepared according to the present invention is used in the polyolefin production method, foreign matter does not adhere or occur inside the reactor, thereby increasing productivity.

Description

Method for preparing supported metallocene catalyst for olefin polymerization {Method for Preparing Supported Metallocene Catalyst for Polymerizing Olefin}

The present invention relates to a method for preparing a supported metallocene catalyst for olefin polymerization, and more particularly, to prepare a carrier on which a promoter is supported by reacting a promoter with an organic solvent on a carrier under an inert gas pressure of 2 to 20 bar. Step (a); And (b) preparing a supported catalyst by reacting a metallocene compound with an organic solvent on a carrier on which the promoter is supported under an inert gas pressure of 2 to 20 bar. It is about a method.

Homogeneous polymerization using an aluminoxane cocatalyst and a metallocene catalyst is known to have high activity against polyolefins. Despite these advantages, in the case of homogeneous polymerization, the problem of forming deposits on the reactor wall, agitator, etc. is serious, and therefore it cannot be used commercially in the gas polymerization or slurry polymerization process. In addition, the polymer material thus formed has the disadvantage of having a very low apparent density, which causes additional cost and process problems. In order to solve these problems, methods of attaching a promoter and a metallocene catalyst to the carrier have been developed.

For example, Korean Unexamined Patent Publication No. KR10-1992-0021589 and Korean Unexamined Patent Publication No. KR10-1996-0034234 describe a method for generating a promoter by reacting alkyl aluminum with silica containing water, but this method requires temperature control. And it has a problem that can not be applied to silica having a long time or low moisture production.

Korean Patent Laid-Open Publication No. 10-2000-0023611 describes a method of efficiently supporting aluminoxane by using silica containing a lot of surface hydroxy groups, but this method is not preferable for silica having a small surface hydroxy group, and there is a lot of reaction of aluminoxane. The efficiency of the catalyst is not maximized by reducing the efficiency.

The various supporting methods up to now have complexities such as sufficient time after mixing the materials in each step or washing the material several times. Alternatively, there is a problem in that an excessive amount of the promoter and the solvent or the catalyst precursor is washed out and sufficient activity does not come out compared to the input catalyst.

The present invention increases the supporting speed of the promoter and the metallocene catalyst by increasing the pressure of the inert gas in the reactor during the preparation of the supported metallocene catalyst, and increases the amount of the supported metallocene catalyst and the activity of the supported metallocene catalyst. This increases, to reduce the multiple washing step in the manufacturing process of the supported metallocene catalyst, to reduce the amount of solvent used, to provide a method for producing a supported metallocene catalyst that can reduce the amount of the promoter.

In addition, by using the supported metallocene catalyst prepared according to the present invention in the polyolefin production method, it is possible to increase the productivity without attaching or generating foreign substances inside the reactor for olefin polymerization, and to manufacture the polyolefin which can control the apparent density of the polyolefin. To provide a method.

The present invention comprises the steps of (a) to prepare a carrier on which the promoter is supported by reacting the promoter with the organic solvent to the carrier under an inert gas pressure of 2 to 20 bar; And

(B) preparing a supported catalyst by reacting a metallocene compound represented by the following Chemical Formula 1, 2 or 3 with an organic solvent on a carrier supported by the promoter under an inert gas pressure of 2 to 20 bar (b)

It provides a method for producing a supported metallocene catalyst for olefin polymerization comprising a.

[Formula 1]

[Formula 2]

(3)

In the above formula (1), (2) or (3)

Cp and Cp 'are one or more 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, and b' are each independently 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 and 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.

The present invention also provides a step of preparing a carrier on which a promoter is supported by reacting a promoter with an organic solvent on a carrier under an inert gas pressure of 2 to 20 bar;

(D) mixing a metallocene compound represented by Formula 1, 2 or 3 and a cocatalyst together with an organic solvent to form a catalyst mixture; And

A supported metallocene catalyst for olefin polymerization comprising the step (e) of preparing a supported catalyst by reacting the catalyst mixture of step (d) with an organic solvent on a carrier supported by the promoter under an inert gas pressure of 2 to 20 bar. It provides a method of manufacturing.

The present invention also comprises the steps of mixing the metallocene compound represented by the formula (1), (2) or (3) and the cocatalyst with an organic solvent to form a catalyst mixture (f); And

Provided is a method for preparing a supported metallocene catalyst for olefin polymerization comprising the step (g) of preparing a supported catalyst by reacting the catalyst mixture of step (f) with an organic solvent on a carrier under an inert gas pressure of 2 to 20 bar. .

In the present invention, the inert gas is characterized in that one or more selected from the group consisting of helium, neon and argon gas.

In the present invention, M is titanium, zirconium or hafnium, Q is halogen, and k is 2.

In the present invention, the carrier is characterized in that at least one member selected from the group consisting of silica, alumina, titanium oxide, zirconia, magnesium chloride, and crosslinked polystyrene, preferably silica.

In the present invention, the promoter is characterized in that the compound represented by the formula (4).

[Formula 4]

In Formula 4, 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.

Here, the compound represented by Formula 4 may be at least one selected from the group consisting of methyl aluminoxane (MAO), ethyl aluminoxane, isobutyl aluminoxane and butyl aluminoxane.

In the present invention, the organic solvent may be at least one selected from the group consisting of benzene, toluene, xylene, hexane, heptane, isobutane, pentane and dichloromethane.

In the present invention, the amount of the promoter supported is 1 to 10,000 moles of Group 13 metals contained in the promoter relative to 1 mole of the transition metal contained in the metallocene compound.

The present invention provides a method for producing a polyolefin, wherein the olefin monomer is polymerized in the presence of a supported metallocene catalyst prepared by the method for producing a supported metallocene of the present invention.

In the method for producing a polyolefin of the present invention, the polymerization is characterized in that carried out in a slurry process or a gas phase process.

In the method for preparing a polyolefin of the present invention, the supported metallocene catalyst is prepared by diluting an aliphatic hydrocarbon solvent having 5 to 12 carbon atoms, an aromatic hydrocarbon solvent, an aliphatic hydrocarbon solvent substituted with chlorine atoms, or an aromatic hydrocarbon solvent substituted with chlorine atoms. It is characterized in that it is injected into the olefin monomer in a slurry state.

In the method for producing a polyolefin of the present invention, the olefin monomer is characterized in that at least one member selected from the group consisting of alpha olefin, cyclic olefin, diene olefin monomer and triene olefin monomer.

In the method of the supported metallocene catalyst of the present invention, by increasing the pressure of the inert gas in the reactor during the preparation of the supported metallocene catalyst, the supporting speed of the promoter and the metallocene catalyst is increased and the amount of the supported metallocene catalyst is increased. In addition, the activity of the supported metallocene catalyst is increased, the number of multiple washing steps in the manufacturing process of the supported metallocene catalyst is reduced, the amount of solvent used is reduced, and the amount of promoter is reduced. In addition, if the supported metallocene catalyst prepared according to the present invention is used in the polyolefin production method, productivity can be increased without foreign matter being attached or generated inside the reactor, and the apparent density of the polyolefin can be controlled.

Hereinafter, the present invention will be described in detail with reference to examples.

The method for preparing a supported metallocene catalyst for olefin polymerization of the present invention comprises the steps of: (a) preparing a carrier on which a promoter is supported by reacting a promoter with an organic solvent on a carrier under an inert gas pressure of 2 to 20 bar; And (b) preparing a supported catalyst by reacting a metallocene compound represented by the following Chemical Formula 1, 2 or 3 with an organic solvent on a carrier supported by the promoter under an inert gas pressure of 2 to 20 bar. .

The present invention also provides a step of preparing a carrier on which a promoter is supported by reacting a promoter with an organic solvent on a carrier under an inert gas pressure of 2 to 20 bar;

(D) mixing a metallocene compound represented by Chemical Formula 1, 2 or 3 and a cocatalyst together with an organic solvent to form a catalyst mixture; And

A supported metallocene catalyst for olefin polymerization comprising the step (e) of preparing a supported catalyst by reacting the catalyst mixture of step (d) with an organic solvent on a carrier supported by the promoter under an inert gas pressure of 2 to 20 bar. It provides a method of manufacturing.

The present invention also comprises the steps of mixing the metallocene compound represented by the following formula (1), (2) or (3) and the cocatalyst with an organic solvent to form a catalyst mixture; And

Provided is a method for preparing a supported metallocene catalyst for olefin polymerization comprising the step (g) of preparing a supported catalyst by reacting the catalyst mixture of step (f) with an organic solvent on a carrier under an inert gas pressure of 2 to 20 bar. .

In the above formula (1), (2) or (3)

Cp and Cp 'are one or more 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, and b' are each independently an integer of 1 to 4;

M is a transition metal of Groups 4B, 5B, or 6B of the periodic table, more preferably titanium, zirconium or hafnium;

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, more preferably a halogen radical, k is 2 or 3, more preferably 2, 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.

The metallocene compound refers to a substance having a cyclopentadienyl, indenyl, or fluorenyl anion and derivatives thereof as a transition metal compound.

Examples of the metallocene compound of formula 1 include bis (cyclopentadienyl) zirconium (IV) dichloride, bis (methylcyclopentadienyl) zirconium (IV) dichloride, bis (n-butylcyclopentadienyl) zirconium (IV) dichloride, bis (t-butylcyclopentadienyl) zirconium (IV) dichloride, bis (pentamethylcyclopentadienyl) zirconium (IV) dichloride, bisindenyl zirconium (IV) dichloride, bis Florenyl zirconium (IV) dichloride, cyclopentadienyl zirconium (IV) trichloride, and each of the titanium (IV) and hafnium (IV) compounds, and the respective methyl chloride, dihydro, dibenzyl, dimethyl compounds, and the like. The present invention is not limited thereto.

Examples of bridged metallocene compounds of formula 3 or 4 include dimethylsilyl-biscyclopentadienyl zirconium (IV) dichloride, dimethylsilyl-bis (tetramethylcyclopentadienyl) zirconium (IV) dichloride, Dimethylsilyl-bis (n-butylcyclopentadienyl) zirconium (IV) dichloride, dimethylsilyl-bis (t-butylcyclopentadienyl) zirconium (IV) dichloride, dimethylsilyl-bisindenyl zirconium ( IV) Dichloride, Isopropylidene-cyclopentadienyl-florenyl zirconium (IV) dichloride, dimethylsilyl- (t-butylamino) (indenyl) zirconium (IV) dichloride, dimethylsilyl- (t-butyl Amino) (tetramethylcyclopentadienyl) zirconium (IV) dichloride and respective titanium (IV), hafnium (IV) compounds, respective methyl chloride, dihydro, dibenzyl, dimethyl compounds and the like. This is not limited to this.

In the method for preparing the supported metallocene catalyst of the present invention, the carrier, the promoter, and the metallocene catalyst can be mixed and reacted in various ways. Generally, each material is suspended and then mixed with an appropriate organic solvent. Do it. Suitable organic solvents may be aromatic or aliphatic solvents, for example benzene, toluene, xylene, hexane, heptane, isobutane, pentane, dichloromethane may be used alone or in admixture of two or more thereof, preferably double toluene.

The components are generally mixed at -50 to 200 ° C, preferably 0 to 100 ° C. The stirring time after mixing is generally 5 minutes to 48 hours, with 30 minutes to 6 hours being preferred.

In general, when the promoter or a mixture thereof is mixed with the carrier, an excess is added to react with all of the hydroxyl groups on the surface of the carrier, followed by washing with a solvent. However, silica has a lot of pores on the surface, and the inside of the pores is known to have a high concentration of silanol structure and forms a strong hydrogen bond. Even if the aluminoxane promoter is used in excess, it is not easy to penetrate and react.

Increasing the pressure of the inert gas in the reaction vessel during the mixing of the cocatalyst or the metallocene catalyst mixture with the carrier promotes penetration into the pores of the liquid material and results in the adsorption of more aluminoxane promoter onto the surface. I found that. As a result, it has been found that a large amount of promoter can be attached to the carrier even if the contact time is reduced to 1 hour or less in order to sufficiently react when supporting the aluminoxane promoter as in the related art. In addition, since it is possible to increase the weight of the aluminoxane cocatalyst and the metallocene catalyst precursor, it has been found that the catalyst activity can be increased compared to the conventional one, and in particular, the apparent density is increased.

Examples of the inert gas used in the preparation of the supported metallocene catalyst of the present invention include helium, neon, and argon group 18 elements. In the catalyst preparation method of the present invention, the pressure of the inert gas in the reactor is increased to 2 to 20 bar in the step of reacting and supporting the promoter, the metallocene catalyst, or the promoter and the metallocene mixture on the carrier. If the pressure is less than 2bar, the supported amount and the supporting speed are insignificant, and if it exceeds 20bar, it may cause safety problems of the reactor due to the high pressure, and it is not recommended to use it because the effect of the invention is not large compared to 2-20bar.

After each mixing step, each solvent is used to wash off the substances that do not adhere to the carrier, and the more the amount is not attached, the greater the amount or number of solvents used to wash off.

As a carrier in the preparation of the supported metallocene catalyst of the present invention, porous materials such as inorganic oxides, chlorides and organic polymer materials can be used. The carrier is dried at high temperature to remove moisture from the surface before use. The inorganic oxide may be an oxide of Group 2, 3, 4, 5, 13, 14 elements of the periodic table, more specifically silica, alumina, titanium oxide, zirconia, magnesium chloride, or crosslinked polystyrene alone or two or more. It can mix and use, More preferably, silica can be used.

Silica has a surface area in the range of 10 to 1000 m ² / g and preferably uses a material in the range of 100 to 600 m ² / g. The pore volume of the silica may be in the range of 0.05 to 4.0 cm ³ / g and preferably 0.2 to 2.0 cm ³ / g may be used. Although the particle size is not determined, it can usually use 0.1-200 micrometers.

In the case of silica, drying is carried out at a high temperature to reduce the amount of moisture and hydroxyl groups on the surface. As for a drying temperature, 100-800 degreeC is preferable. Drying proceeds with inert gas or reduced pressure.

As a cocatalyst in the preparation of the supported metallocene catalyst of the present invention, a compound represented by the following formula (4) can be used, and a catalyst generally used in the production of a metallocene catalyst can also be used.

In Formula 4, 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.

Compound represented by the formula (4) may be present in a linear, circular or reticular form, and as such a compound by mixing alumina methyl acid (MAO), ethyl aluminoxane, isobutyl aluminoxane or butyl aluminoxane alone or two or more Can be used.

The amount of the promoter supported in the preparation of the supported metallocene catalyst of the present invention is 1 to 10,000 mol, more preferably 1 to 1,000 mol of Group 13 metals contained in the promoter relative to 1 mol of the transition metal contained in the metallocene compound. And even more preferably 10 to 100 moles. The supported metallocene catalyst is less active than 1 mol of the Group 13 metal in the promoter relative to 1 mol of the transition metal contained in the metallocene compound. It is very low, and when it exceeds 10,000, the cocatalyst MAO may act as a catalyst poison, and there is a concern that the economic efficiency may be lowered.

The content ratio of the carrier and the promoter to be used is preferably 1 to 50 mmol of the Group 13 metal component of the promoter relative to 1 g of the carrier, and when smaller than that, the silanol of the carrier may react less, and in many cases, the promoter may be due to unreaction. Aluminoxane can be wasted.

The present invention provides a method for producing polyolefin, wherein the olefin monomer is polymerized in the presence of the supported metallocene catalyst prepared by the above method.

The polymerization process for carrying out the method for producing a polyolefin using the supported metallocene catalyst of the present invention may include both a solution process and a slurry or gas phase process, and a slurry and gas phase mixing process. It depends on the process.

The supported metallocene catalyst of the present invention is an aliphatic hydrocarbon solvent having 5 to 12 carbon atoms suitable for the olefin polymerization process, for example, pentane, hexane, heptane, nonane, decane and isomers thereof and aromatic hydrocarbon solvents such as toluene and benzene, dichloro Dilution in the form of slurry in hydrocarbon solvents substituted with chlorine atoms, such as methane and chlorobenzene, is possible. 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.

The olefinic monomers which can be polymerized using the supported metallocene catalyst of the present invention include ethylene, propylene, alpha olefins, cyclic olefins, and the like, and also diene olefin monomers or triene olefin monomers having two or more double bonds. Polymerization is 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-chloromethylstyrene, and the like, and these monomers may be mixed and copolymerized.

The olefin polymerization reaction using the supported metallocene catalyst of the present invention may use bulk polymerization, suspension polymerization, gas phase polymerization, polymerization with a critical fluid, and the like, and the polymerization reactor may be a reactor such as a known batch method or continuous method. Can be. The polymerization reaction is generally carried out at a temperature of 0 to 300 ° C. and a pressure of 0.5 to 3000 bar. Additives may be added at the time of polymerization in accordance with applications such as water removal and antistatic.

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the present invention. Such variations and modifications are intended to be within the scope of the appended claims.

[Example]

Example 1

1-1) Preparation of silica supported catalyst component

2 g of silica gel (XPO2410, Grace Davison) is placed in a 150 ml volume glass pressure reactor (Endless Glass Company) and suspended under 20 ml toluene under argon. The pressure regulator is used to maintain the internal argon pressure at 0.5 bar and the oil bath temperature at 70 ° C. 18 ml of methylaluminoxane (10 wt% toluene solution) was added thereto, the valve was closed, and the pressure was raised to 5 bar. After stirring for 2 hours, 20 ml of toluene was used three times to wash the silica and dried under vacuum at 70 ° C. to obtain 2.98 g of the supported silica. ICP analysis showed that the Al element content was 10.6 mmol / g silica.

Comparative Example 1

C1-1) Preparation of silica supported catalyst component

2 g of silica gel (XPO2410, Grace Davison) is placed in a 150 ml volume glass pressure reactor (Endless Glass Company) and suspended under 20 ml toluene under argon. The pressure regulator is used to maintain the internal argon pressure at 0.5 bar and the oil bath temperature at 70 ° C. 18 ml of methylaluminoxane (10wt% toluene solution) is added and the valve is closed. After stirring for 2 hours, the silica was washed with 20 ml of toluene three times and dried under vacuum at 70 ° C. to obtain 2.81 g of silica supported thereon. ICP analysis showed that the Al element content was 8.9 mmol / g silica.

Example 2

2-1) Preparation of Supported Silica Catalyst

2 g of silica gel (XPO2410, Grace Davison) was placed in a 150 ml glass pressure reactor (Endless Glass Company) and the pressure regulator was used to maintain an internal argon pressure of 0.5 bar and maintain the temperature of the oil bath at 80 ° C. do. 15 ml of methylaluminoxane (10 wt% toluene solution) was added thereto, and the mixture was stirred for 1 hour while raising the pressure to 5 bar. The remaining suspension was washed once with 20 ml of toluene and almost no aluminoxane was seen in the washed solution. After the temperature was lowered to 40 ° C., 64.8 mg of bis (n-butylcyclopentadienyl) zirconium (IV) dichloride was dissolved in toluene, and stirred for an additional 1 hour while raising the pressure to 5 bar. Washed once with 20 ml toluene and dried under vacuum at 70 ℃ to obtain 3.12 g of a pale yellow catalyst.

2-2) Ethylene Polymerization Reaction

2 l high pressure reactor was replaced with nitrogen at 60 ° C. for 1 hour and 1 l of purified hexane was added thereto. 0.6 ml of triethylaluminum (1M hexane solution) for water removal is injected and then 30 mg of the catalyst prepared in Example 2-1) is suspended in hexane and fed through a sample vessel connected to the reactor. After raising the reactor to 80 ° C, when the temperature becomes constant, ethylene is added and the internal pressure is kept constant at 9 bar. After 1 hour, the remaining ethylene is discharged to stop the polymerization. The remaining suspension was filtered and dried in an oven to give 25.1 g (BD 0.378 g / ml ³ ) of polyethylene powder. No deposits or clumps were found on the reactor walls and inside.

Comparative Example 2

C2-1) Preparation of Supported Silica Catalyst

2 g of silica gel (XPO2410, Grace Davison) was placed in a 150 ml glass pressure reactor (Endless Glass Company) and the pressure regulator was used to maintain an internal argon pressure of 0.5 bar and maintain the temperature of the oil bath at 80 ° C. do. 15 ml of methylaluminoxane (10 wt% toluene solution) was added thereto and stirred for 1 hour. Wash the remaining suspension three times with 20 ml toluene and lower the temperature to 40 ° C. 64.8 mg of bis (n-butylcyclopentadienyl) zirconium (IV) dichloride is dissolved in toluene, and further stirred for 1 hour. 20 ml toluene was washed three times and dried in vacuo at 70 ° C. to obtain 2.88 g of a catalyst.

C2-2) Ethylene Polymerization

The polymerization was carried out in the same manner as in Example 2-2, to obtain 19.3 g (BD 0.263 g / ml ³ ) of polyethylene powder. Agglomerated and coated materials have been found in and on the reactor walls.

Example 3

3-1) Preparation of Supported Silica Catalyst

In a glove box filled with argon, 64.8 mg of bis (n-butylcyclopentadienyl) zirconium (IV) dichloride is placed in a flask and dissolved in 5 ml of purified toluene. Seal the flask out and connect it to the Schlenk line. 4 ml of methylaluminoxane (10 wt% toluene solution) is added to the flask and shaken to dissolve it. On the other hand, 2 g of silica gel (XPO2410, Grace Davison) was placed in a 150 ml volume glass pressure reactor (endrous glass company), and the pressure regulator was used to maintain an internal argon pressure of 0.5 bar and the temperature of the oil bath was 80. Keep at ℃. 9 ml of methylaluminoxane (10 wt% toluene solution) was added thereto, and the mixture was stirred for 1 hour while raising the pressure to 5 bar. The previously mixed methylaluminoxane-precursor solution is introduced into a glass pressure reactor and stirred at 40 ° C. for 1 hour while raising the pressure to 5 bar. 20 ml toluene was washed once and dried under vacuum at 70 ° C. to obtain 3.05 g of catalyst.

3-2) Ethylene Polymerization Reaction

The polymerization was carried out in the same manner as in Example 2-2, to obtain 30.9 g (BD 0.389 g / ml ³ ) of polyethylene powder. No deposits or clumps were found on the reactor walls and inside.

Comparative Example 3

C3-1) Preparation of silica supported catalyst

In a glove box filled with argon, 64.8 mg of bis (n-butylcyclopentadienyl) zirconium (IV) dichloride is placed in a flask and dissolved in 5 ml of purified toluene. Seal the flask out and connect it to the Schlenk line. 4 ml of methylaluminoxane (10 wt% toluene solution) is added to the flask and shaken to dissolve it. On the other hand, 2 g of silica gel (XPO2410, Grace Davison) was placed in a 150 ml volume glass pressure reactor (endrous glass company), and the pressure regulator was used to maintain an internal argon pressure of 0.5 bar and the temperature of the oil bath was 80. Keep at ℃. 9 ml of methylaluminoxane (10 wt% toluene solution) was added thereto and stirred for 1 hour. Subsequently, the previously mixed methylaluminoxane-precursor solution is added to a glass pressure reactor and stirred at 40 ° C. for 1 hour. 20 ml toluene was washed three times and dried in vacuo at 70 ° C. to obtain 2.91 g of a catalyst.

C3-2) Ethylene Polymerization

The polymerization was carried out in the same manner as in Example 2-2, to obtain 21 g (BD 0.314 g / ml ³ ) of polyethylene powder. No deposits were found on the reactor walls and inside.

Example 4

4-1) Preparation of Supported Silica Catalyst

In a glove box filled with argon, 64.8 mg of bis (n-butylcyclopentadienyl) zirconium (IV) dichloride is placed in a flask and dissolved in 5 ml of purified toluene. Seal the flask out and connect it to the Schlenk line. Add 14 ml of methylaluminoxane (10wt% toluene solution) to the flask and shake to dissolve it. On the other hand, 2 g of silica gel (XPO2410, Grace Davison) is placed in a 150 ml volume glass pressure reactor (Endless Glass Company) and suspended with 20 ml toluene under argon. The pressure regulator is used to maintain the internal argon pressure at 0.5 bar and the oil bath temperature at 80 ° C. After putting the mixture solution in front of it, the pressure was raised to 5 bar and stirred for 1 hour. 20 ml toluene was washed three times and dried in vacuo at 70 ° C. to obtain 2.62 g of a pale yellow catalyst.

4-2) Ethylene Polymerization Reaction

The polymerization was carried out in the same manner as in Example 2-2, to obtain 30.2 g (BD 0.220 g / ml ³ ) of polyethylene powder. No deposits or clumps were found on the reactor walls and inside.

Comparative Example 4

C4-1) Preparation of Supported Silica Catalyst

In a glove box filled with argon, 64.8 mg of bis (n-butylcyclopentadienyl) zirconium (IV) dichloride is placed in a flask and dissolved in 5 ml of purified toluene. Seal the flask out and connect it to the Schlenk line. Add 14 ml of methylaluminoxane (10wt% toluene solution) to the flask and shake to dissolve it. On the other hand, 2 g of silica gel (XPO2410, Grace Davison) is placed in a 150 ml volume glass pressure reactor (Endless Glass Company) and suspended with 20 ml toluene under argon. The pressure regulator is used to maintain the internal argon pressure at 0.5 bar and the oil bath temperature at 80 ° C. After putting the previous mixed solution here, the valve was closed and stirred for 1 hour. 20 ml toluene was washed three times and dried in vacuo at 70 ° C. to obtain 2.53 g of a pale yellow catalyst.

C4-2) Ethylene Polymerization

The polymerization was carried out in the same manner as in Example 2-2, to obtain 25.8 g (BD 0.145 g / ml ³ ) of polyethylene powder. Agglomerated and coated materials have been found in the reactor walls, coils, and agitators.

Silica gel
(g) Methyl Aluminoxane Solution
(10wt% toluene solution, ml) Bis (n-butylcyclopentadienyl) zirconium (IV) dichloride (mg) Argon pressure
(bar) Manufactured Supported Catalyst
(g) Polyethylene (g) Apparent density
(g / ml ₃ ) Presence of foreign substances on the wall inside the reactor Example 2 2 15 64.8 5 3.12 25.1 0.378 X Example 3 2 4 + 9 64.8 5 3.05 30.9 0.389 X Example 4 2 14 64.8 5 2.62 30.2 0.220 X Comparative Example 2 2 15 64.8 0 2.88 19.3 0.263 O Comparative Example 3 2 4 + 9 64.8 0 2.91 21.0 0.314 X Comparative Example 4 2 14 64.8 0 2.53 25.8 0.145 O

[Reference] X: Foreign substance inside the reactor wall after polymerization reaction, O: Foreign substance inside the reactor wall after polymerization reaction

As shown in Table 1, the catalyst prepared by increasing the pressure of the inert gas using the present invention can increase the apparent density and activity of the polymer compared with the catalyst prepared at low pressure, and at the same time, foreign matter on the inner wall of the reactor during polymerization. The effect of reducing the adhesion can be seen. In addition, when the pressure is increased when the promoter is reacted to the carrier, there is no promoter that is washed off in toluene, and it was confirmed through analysis that the supporting amount and efficiency of the promoter and the catalyst precursor are improved. As a result, it is possible to reduce the amount of solvent used incidentally in the preparation of the supported catalyst.

Claims (15)

Cocatalyst represented by the following formula (4) is added to a carrier which is at least one member selected from the group consisting of silica, alumina, titanium oxide, zirconia, magnesium chloride, and crosslinked polystyrene under an inert gas pressure of 2 to 20 bar. Reacting with at least one organic solvent selected from the group consisting of hexane, heptane, isobutane, pentane and dichloromethane to prepare a carrier on which the promoter is supported; And
(B) preparing a supported catalyst by reacting a metallocene compound represented by the following Chemical Formula 1, 2 or 3 with the organic solvent on a carrier supported by the promoter under an inert gas pressure of 2 to 20 bar (b).
Method for producing a supported metallocene catalyst for olefin polymerization comprising a.
[Formula 1]

(2)

(3)

[Chemical Formula 4]

In Chemical Formula 1, 2 or 3,
Cp and Cp 'are one or more 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, and b' are each independently 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 and 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, and
In Formula 4, 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, n is an integer of 2 or more. Cocatalyst represented by the following formula (4) is added to a carrier which is at least one member selected from the group consisting of silica, alumina, titanium oxide, zirconia, magnesium chloride, and crosslinked polystyrene under an inert gas pressure of 2 to 20 bar. Reacting with at least one organic solvent selected from the group consisting of hexane, heptane, isobutane, pentane and dichloromethane to prepare a carrier on which the promoter is supported (c);
(D) mixing a metallocene compound represented by Chemical Formula 1, 2 or 3 and a cocatalyst with the organic solvent to form a catalyst mixture; And
(E) preparing a supported catalyst by reacting the catalyst mixture of step (d) with the organic solvent on a carrier supported by the promoter under an inert gas pressure of 2 to 20 bar (e).
Method for producing a supported metallocene catalyst for olefin polymerization comprising a.
[Chemical Formula 4]

In Formula 4, 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. Claim 1 selected from the group consisting of benzene, toluene, xylene, hexane, heptane, isobutane, pentane and dichloromethane, the metallocene compound represented by Formula 1, 2 or 3 and the promoter represented by Formula 4 (F) mixing with at least two organic solvents to form a catalyst mixture; And
The catalyst mixture of step (f) is reacted with said organic solvent to at least one carrier selected from the group consisting of silica, alumina, titanium oxide, zirconia, magnesium chloride, and crosslinked polystyrene under an inert gas pressure of 2 to 20 bar. Preparing a catalyst (g)
Method for producing a supported metallocene catalyst for olefin polymerization comprising a.
[Chemical Formula 4]

In Formula 4, 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 method for producing an supported metallocene catalyst for olefin polymerization according to any one of claims 1 to 3, wherein the inert gas is at least one selected from the group consisting of helium, neon, and argon gas. The method for producing a supported metallocene catalyst for olefin polymerization according to any one of claims 1 to 3, wherein M is titanium, zirconium or hafnium, Q is halogen, and k is 2. delete The method for producing a supported metallocene catalyst for olefin polymerization according to any one of claims 1 to 3, wherein the carrier is silica. delete According to any one of claims 1 to 3, wherein the compound represented by the formula (4) is one or more selected from the group consisting of methyl aluminoxane (MAO), ethyl aluminoxane, isobutyl aluminoxane and butyl aluminoxane A method for producing a supported metallocene catalyst for olefin polymerization, which is characterized by the above-mentioned. delete The olefin according to any one of claims 1 to 3, wherein the amount of the promoter supported is 1 to 10,000 moles of Group 13 metals contained in the promoter relative to 1 mole of the transition metal contained in the metallocene compound. Method for producing a supported metallocene catalyst for polymerization. A method for producing a polyolefin, wherein the olefin monomer is polymerized in the presence of a supported metallocene catalyst prepared by the method according to any one of claims 1 to 3. The method for producing polyolefin according to claim 12, wherein the polymerization is carried out in a slurry process or a gas phase process. The method of claim 12, wherein the supported metallocene catalyst is prepared in a slurry prepared by diluting with an aliphatic hydrocarbon solvent having 5 to 12 carbon atoms, an aromatic hydrocarbon solvent, an aliphatic hydrocarbon solvent substituted with chlorine atoms, or an aromatic hydrocarbon solvent substituted with chlorine atoms. A method for producing a polyolefin, which is injected into an olefin monomer. The method for producing a polyolefin according to claim 12, wherein the olefin monomer is at least one selected from the group consisting of alpha olefins, cyclic olefins, diene olefin monomers and triene olefin monomers.