KR100235180B1 - Supported-liquid phase metallocene catalyst - Google Patents

Abstract

The present invention relates to a method for conveniently preparing a metallocene liquid supported catalyst and an electrocatalyst in which a solution in which a metallocene catalyst and a promoter is dissolved is supported by a liquid phase in pores of a carrier.

In the metallocene liquid support catalyst of the present invention, a solution in which a metallocene catalyst and a promoter are dissolved in a solvent is supported in the liquid phase in the pores of the carrier, and the electrocatalyst dries the carrier to provide moisture and carriers present in the pores. The OH group present on the surface is removed, a solution obtained by dissolving the metallocene catalyst and the cocatalyst in a solvent is injected into a reactor into which a dried carrier is introduced in an electric process, and the solution is prepared by being supported in the pores of the carrier. Since the metallocene liquid support catalyst of the present invention has a very large activity of the synthesis reaction, it is used in the polymerization reaction of ethylene or propylene and is applied to synthesize polyethylene or polypropylene.

According to the method for producing a metallocene liquid catalyst supported according to the present invention, the amount of the cocatalyst used in polymerization can be greatly reduced, and the liquid catalyst can be easily synthesized, thereby maintaining a low catalyst production price. In addition, the polymer prepared by using the metallocene liquid supported catalyst of the present invention has a spherical shape suitable for a commercial process, and has a particle size, a particle size distribution, and a bulk density suitable for a commercial process.

Description

Metallocene liquid supported catalyst and preparation method thereof

The present invention relates to a supported-liquid phase metallocene catalyst.

More specifically, the present invention relates to a method for conveniently preparing a metallocene liquid supported catalyst and an electrocatalyst in which a solution in which a metallocene catalyst and a promoter is dissolved is supported by a liquid phase in pores of a carrier.

Metallocene catalyst is a catalyst used in the synthesis reaction for the production of polyolefin, and it can be used in various polymerization processes such as high temperature bulk polymerization, solution polymerization, slurry polymerization or gas phase polymerization by supporting, and is one of the most important variables in the polymerization process. Since the shape of one polymer can be controlled, studies on the metallocene catalyst supported on a carrier have been actively conducted.

Conventionally, a method of covalently bonding a metallocene catalyst to the surface of a carrier has been known as a method of supporting a metallocene catalyst, which is a moisture sensitive organometallic complex to a silanol group (Si-OH) on a silica surface. ) Is used.

The electric method can be roughly divided into two types, one is to directly support the metallocene catalyst on the silica carrier, and the other is to support the silica carrier after surface treatment with another compound.

However, the supporting method using a covalent bond has a disadvantage in that the polymerization activity of the catalyst after supporting is very small because it inevitably deforms the form of the metallocene catalyst during the supporting process.

For example, US Pat. Nos. 4808561, 4912075, and 4904631 disclose that a catalyst supported by surface treatment of silica with methylaluminoxane or surface treatment of silica with alkylaluminum, followed by bonding of metallocene. A method of making is disclosed.

However, the supported catalysts produced by the electric method have the disadvantage of low activity and excessive use of a promoter during preparation.

In addition, US Pat. No. 5,088,111 discloses a process for preparing a supported metallocene catalyst using various carriers, namely, coli, clayminerals, ion exchanged layered compounds, silicates and the like. However, since this method also supports the metallocene catalyst on the surface-treated carrier through chemical bonding, the amount of the supported catalyst and the promoter is very small, and the shape of the metallocene catalyst is modified to support the activity of the supported catalyst. There is a drawback to this sharp decrease.

Therefore, a small amount of crude catalysts and electrocatalysts supported with high activity metallocenes and supported catalysts can be used in various polymerization processes such as high temperature bulk polymerization, solution polymerization, slurry polymerization or gas phase polymerization for the production of polyolefins. There is an urgent need for the development of methods that can be produced using catalysts.

Accordingly, the present inventors have made intensive studies to overcome the problems of the catalyst and the method of preparing the metallocene catalyst covalently supported on the surface of the carrier, and as a result, the solution in which the metallocene catalyst and the promoter are dissolved is supported. In the metallocene liquid supported catalyst supported by the liquid phase itself in the pores of the metallocene catalyst, the metallocene catalyst is present in its own form in the pores of the carrier so that the polymerization activity of the supported catalyst is large, and a small amount of a cocatalyst is used when preparing the supported catalyst. The present invention was completed.

As a result, the main object of the present invention is to provide a metallocene liquid supported catalyst in which a solution in which a metallocene catalyst and a promoter are dissolved is supported by a liquid phase in pores of a carrier.

It is another object of the present invention to provide a method for preparing an electrometallic liquid supported catalyst.

1 is a graph showing the size distribution of the polyethylene particles prepared in Example 1-2 using the metallocene liquid supported catalyst of the present invention.

2 is a graph showing the size distribution of the polypropylene particles prepared in Example 2-2 using the metallocene liquid supported catalyst of the present invention.

3 is a graph showing the size distribution of the polypropylene particles prepared in Example 2-3 using the metallocene liquid supported catalyst of the present invention.

4 is a graph showing the size distribution of the polyethylene particles prepared in Example 3-2 using the metallocene liquid supported catalyst of the present invention.

5 is a graph showing the size distribution of the polypropylene particles prepared in Example 4-2 using the metallocene liquid supported catalyst of the present invention.

Hereinafter, a metallocene liquid supported catalyst and a method for preparing the same according to the present invention will be described in more detail.

The metallocene liquid supported catalyst of the present invention has a solution in which a metallocene catalyst and a promoter are dissolved in a solvent in the pores of the carrier, wherein a specific example used as a carrier, a metallocene catalyst, a promoter and a solvent Is as follows.

(1) carrier

As the carrier, all organic and inorganic materials having pores are used as they are, or in the case of inorganic materials, inorganic materials surface-treated with organic compounds having hydrophobic functional groups are used to increase the carrying efficiency. Specific examples are as follows. no.

Inorganic carriers include silica (SiO ₂ ), alumina (Al ₂ O ₃ ), magnesium chloride (MgCl ₂ ), magnesium oxide (MgO), and the most widely used conventionally supported Ziegler-Natta catalysts and metallocene catalysts. Zeolite-based carriers with normal pores; linde type X, linde type Y, sapo-37, CSJ-3 a) or El jet -210 (LZ-210), etc. In addition, eye beuyipi -5 (VPI-5), alpo -8M (ALPO ₄ -8M) or clover light (cloverite) and the like are used.

In particular, the mesoporous molecular sieve in the inorganic carrier (mesoporous molecular sieve) of the M41S (M41S) system having a pore diameter of 15 to 100A, preferably MCM-41, MCM-48, MCM-22, MCM-49, MCM-59, MCM-56 and the like are used. The M 41 S-based carrier has a surface area of 700 m 2 / g or more and an adsorption capacity for hydrocarbons of 0.7 ml / g or more.

In addition, clay, clay minerals, diatomaceous earth or intercalated layer compounds, preferably kaolin, bentonite, kibushi clay, and gyrom clay gairome clay, allophane, hisinerite, pyrophyllite, talc, mica group, montmorillonite group, vermiculite , Chlorite group, palygorskite, kaolinite, nactrite, dickite or halloysite and the like are used.

Examples of silicates in the inorganic carrier include lithium silicate, sodium silicate, potassium silicate, magnesium silicate, calcium silicate and barium silicate. silicate, aluminum silicate, titanium silicate or zirconium silicate and the like.

As the organic carrier, crosslinked polystyrene beads or gels, polyamino acids, acrylic polymers, dextran, or polysiloxanes are used.

The polymers are crosslinked with each other with a crosslinking agent, and there are ion exchangeable functional groups, preferably amine-based anionic groups, sulfonic-based cationic groups, or carbonyl-based cationic groups.

(2) metallocene catalysts

As the metallocene catalyst, ethylene, propylene, styrene, higher alpha olefins or cyclic olefins can be synthesized, and are transition metal organic compounds smaller than the pore size of the carrier to be supported by the supporting method of the present invention. The compound of formula (I), (II) or (III) is used.

R ¹ _m (C _p R ² _n ) (C _p R ² _n ) MR ³ ₂ (n, m = integer); Neutrality (Ⅰ)

[R ¹ _m (C _p R ² _n ) (C _p P ² n) MR ³ R ⁴ ] ⁺ R ^5- (n, m = integer); Cationic type (Ⅱ)

R ¹ _m (C _p R ² _n ) LR ³ _n MR ⁴ ₂ (n, m = integer): Constrained geometry catalyst (CGC) type (III)

Where

C _p R ² _n is a cyclopentene group or a cyclopentene group having a substituent:

R _n ² is a C _{4 ′} C ₁₀ cyclic compound having or without substituents:

R ¹ is a carbon, silicon or germanium compound covalently bonded to C _p R _n ² :

R ³ is a hydrogen, halogen, amine or alkyl group:

R ⁴ is a hydrogen, halogen, amine or alkyl group:

R ^5- is the counter anion that stabilizes the cationic metal:

L is an amine, alkyl or alkoxy group; And,

M is a Group 4, 5, 6 transition metal or a lanthanide metal.

Examples of electrocatalysts include bis (cyclopentadienyl) zirconium dichloride (Cp ₂ ZrCl _2), bis (cyclopentadienyl) zirconium dimethyl (bis) (cyclopentadienyl) zirconium dimethyl, bis (cyclo Pentadienyl) titanium dichloride (bis (cyclopentadienyl) zirconium dichloride), bis (cyclopentadienyl) titanium dimethyl (bis (cyclopentadienyl) zirconium dimethyl), bis (cyclopentadienyl) hafnium dichloride (bis (cyclopentadienyl) hafnium dichloride, bis (cyclopentadienyl) hafnium dimethyl, cyclopentadienyltitanium trichloride, cyclopentadienyltitanium trichloride, ethylenebis (indenyl) Zirconium dichloride, Et (ind) ₂ ZrC1 ₂ , ethylene-bis (indenyl) zirconium dimethyl (ethylene-b is (indenyl) zirconium dimethyl, Et (ind) ₂ ZrCl ₂ ), dimethylsilyl-bis (indenyl) zirconium dichloride, dimethylsilyl-bis (indenyl) zirconium dimethylsilyl -bis (indenyl) zirconium dimethyl, dimethylsilyl-bis (indenyl) titanium dichloride, dimethylsilyl-bis (indenyl) titanium dimethyl ), Dimethylsilyl-bis (indenyl) hafnium dichloride, dimethylsilyl-bis (indenyl) hafnium dimethyl, ethylenebis (indenyl) Ethylenebis (indenyl) titanium dichloride, ethylenebis (indenyl) titanium dimethyl, ethylenebis (indenyl) hafnium dichloride, ethylenebis (Indenyl) Hafnium Methylene (ethylenebis (indenyl) hafnium dimethyl), bis (pentamethyl cyclopentadienyl) zirconium dichloride (bis (pentamethyl cyclopentadienyl) zirconium dichloride), bis (pentamethyl cyclopentadienyl) zirconium dimethyl (bis (pentamethyl cyclopentadienyl) zirconium dimethyl), bis (pentamethylcyclopentadienyl) titanium dichloride (bis (pentamethylcyclopentadienyl) titanium dichloride), bis (pentamethylcyclopentadienyl) titanium dimethyl (bis (pentamethylcyclopentadienyl) titanium dimethyl), bis (pentamethylcyclopenta Dienyl) hafnium dichloride (bis (pentamethylcyclopentadienyl) hafnium dichoride), bis (pentamethylcyclopentadienyl) hafnium dimethyl (bis (pentamethylcyclopentadienyl) hafnium dimethyl), bis (indenyl) zirconium dichloride (bis (indenyl) zirconium dichloride ), Bis (indenyl) zirconium dimethyl (bis (indenyl) zirconium dimethyl), bis (dimethylcyclopentadienyl) zirconium di Lide (bis (dimethylcyclopentadienyl) zirconium dichloride), bis (dimethylcyclopentadienyl) zirconium dimethyl (bis (dimethylcyclopentadienyl) zirconium dimethyl), isopropylidene (cyclopentadienyl) (fluorenyl) zirconium dichloride (isopropylidene (isopropylidene) cyclopentadienyl (fluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (fluorenyl) zirconium dimethyl (isopropylidene (cyclopentadienyl) (fluorenyl) zirconium dimethyl), dimethyldimethyl (cyclopentadienyl) (fluorenyl) Zirconium dichloride (dimethylsilyl (cyclopentadienyl) (fluorenyl) zirconium dichloride), dimethylsilyl (cyclopentadienyl) fluorenyl) zirconium (dimethylsilyl (cyclopentadienyl) (fluorenyl) zirconium dimethyl), (t-butylamido) dimethyl (tetra methyl -η ⁵⁵ - cyclopentadienyl) silane titanium entities, dichloride ((tert-butylamido) dimethyl ( tetramethyl-η 5 -cyclopentadienyl) silanetitanium dichloride), (t- butylamido ) Dimethyl (tetramethyl -η ⁵ - cyclopentadienyl) silane titanium dimethyl (tert-butylamido) dimethyl (tetramethyl -η 5 -cyclopentadienyl) silanetitanium dimethyl), (t- butylamido) dimethyl (tetramethyl -η ⁵ - cyclopentadienyl) silane zirconium dichloride ((tert-butylamido) dimethyl ( tetramethyl-η 5 -cyclopentadienyl) silanezirconium dichloride) or (t- butylamido) dimethyl (tetramethyl -η ⁵ - cyclopentadienyl) silane zirconium (Tert-butylamido) dimethyl (tetramethyl-η ⁵ -cyclopentadienyl) silanezirconium dimethyl).

(3) promoter

As the promoter, an aluminum compound having a central element of aluminum or a boron anionic compound having a center element of boron is used. The aluminum compound has an aluminoxane type (AIR _i Xj _, i + j = 3, R = alkyl group, X Halogen group), preferably methylaluminoxane (MAO), modified methylaluminoxane (MMAO), ethylaluminoxane, n-butylaluminoxane or isobutylaluminoxane or trialkylaluminum series are used, and boron anion is used. Type compounds include tris (pentafluorophenyl) borane, trityl tetrakis (pentafuoropheny) borate, N, N-dimethylanilium tetrakis (penta) Fluorophenyl) borate (N, N-dimethylanilium tetrakis (pentafluorophenyl) borate) is used.

(4) solvent

As a solvent, an organic solvent capable of dissolving a metallocene catalyst and a cocatalyst and being liquid supported in the pores of the carrier, preferably toluene, xylene, hexane, heptane, pentane, Isopar ^tm (C ₈ ~ C ₁₀ saturated hydrocarbon mixture) ), 1,2,4-trilolobenzene (1,2,4-trichlorobenzene), diphenyl ether, triphenylphosphine, biphenyl, biphenyl, chlorobenzenenitrile ), Chlorobenzophenone, nitrobenzene, decahydronaphthalene, diphenyl-2-ethylhexylphosphate, butylbenzylphthalate, glycerol tributylate gryceroltributylate, tetraethyleneglycol, polyethyleneglycol, triphenylphosphate, dimethylsulfoxide, methylenediphenyl-4,4'-diisocyanate Methylenediphenyl-4,4'-diisocyanate, benzene, chloroform, pyridine, tetrachloroethane, isobutyl isobutylate, isoamylether , Propyleneglycol, phenylether, or the like, or a mixed solvent in which two or three electric solvents are mixed is used.

The quantitative ratio of each component depends on the volume of the carrier pores used and the solubility of the metallocene catalyst and the promoter in the solvent, so that the solution can be supported in the pores by the maximum volume of the carrier pores used.

In general, the weight ratio of each component is 1 to 10000 _% by weight of the metallocene catalyst _, preferably 10 to 1000 _% by weight of the metallocene catalyst _, 1 to 100000 _{% by} weight of the central element of the promoter and 10 to 1000 _{% by} weight of the solvent _, Preferably it is 50-500 weight _% .

In addition, the weight ratio of the metallocene catalyst and the promoter is 1 to 100000 _{% by} weight of the central element of the promoter relative to the metal of the metallocene catalyst, preferably 10 to 10000 _% by weight of aluminum when the aluminum compound is used as the promoter. .

The manufacturing method of the metallocene liquid supported catalyst of the present invention will be described as follows. All processes for preparing the liquid supported catalyst are carried out in an inertgar atmosphere such as nitrogen.

First step; Preparation of Carriers

As the carrier, the organic or inorganic substance described above may be used as it is, or in the case of the inorganic substance, the carrier may be surface treated to reduce the influence of OH groups on the surface and increase the hydrophobicity of the carrier. That is, the organic compound having a functional group and a hydrophobic functional group, such as chlorine or alkoxide group, which can react with the OH group of the carrier in an organic solvent such as toluene, hexane, heptane, and the like After the reaction for 0.5 to 24 hours and washed with at least 5 times using an organic solvent and dried to obtain a surface-treated carrier.

The surface-treated carrier or the surface-treated carrier is dried in a vacuum or inert gas at 50 to 600 ° C. for 1 to 100 hours to remove moisture present in the pores and OH groups present on the surface of the carrier by dehydration. The temperature and time depends on the type of carrier.

Second process; Preparation of Metallocene Liquid Support Catalyst

The above-described metallocene catalyst and the co-catalyst are dissolved in a solvent by stirring for 0.5 to 10 hours at a boiling point of 0 ° C. or more and below the boiling point of the solvent, wherein the solvent is a single organic solvent or an organic solvent having 2 or more solvents according to polymerization conditions and purposes. Three mixed solvents are used.

The volume of the solution used is 10 to 100 _% of the pore volume of the carrier to be used, and the amount and quantitative ratio of the catalyst and the promoter depend on the solubility of each component in the solvent.

In general, the amount of the metallocene catalyst, the promoter and the solvent is such that the weight ratio of each component is 1 to 10000 _{% by} weight of the metal of the metallocene catalyst _, preferably 10 to 1000 _{% by} weight _{, and} 1 to 1 central element of the promoter. 100000 _{% by} weight and solvent 10-1000 _{% by} weight, preferably 50-500 _{% by} weight, the weight ratio of the metallocene catalyst and the promoter is 1-100000 _{% by} weight of the central element of the promoter relative to the metal of the metallocene catalyst, Preferably, when using an aluminum compound as a promoter, it is used so that the aluminum is 10 to 10000 _% by weight.

The solution obtained in the above is injected into the reactor into which the carrier obtained in the above step is put, and the solution is supported in the pores of the carrier by using a shaker or agitator at about -50 ° C to 100 ° C for 0.1 to 24 hours. To prepare a metallocene liquid supported catalyst, the temperature depends on the solvent used.

In order to better disperse the solution in the carrier, a post-treatment may be performed on the liquid supported catalyst prepared in the former.

In the case of a liquid supported catalyst prepared by using a single solvent, the temperature of the liquid supported catalyst prepared in the electric process is lowered below the freezing point of the solvent used to solidify the solvent in the pores, and preferably to a temperature higher than the melting point. After raising to 0 to 100 ° C and stirring to prepare a post-treated metallocene liquid supported catalyst. In the case of a liquid supported catalyst prepared by using a mixed solvent in which a highly volatile solvent and a weak solvent are mixed, the temperature of the liquid supported catalyst prepared in the electrical process is lowered between the volatile solvent and the freezing point of the weak solvent, and the vacuum or After 0.5 to 10 hours of treatment with an inert gas to remove the highly volatile solvent, the temperature is raised to above the melting point of the weakly volatile solvent, and stirred to prepare a post-treated metallocene liquid supported catalyst.

The metallocene liquid supported catalyst prepared in electricity is stored at a low temperature in a nitrogen atmosphere, and the inductively coupled plasma (ICP) analysis of the metallocene liquid supported catalyst prepared in electricity is conventional in the art. It is carried out by the method.

Olefin, preferably ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 3-methyl-1-pentene, 4-methyl-1 using the metallocene liquid supported catalyst of the present invention Conduct a slurry or gas phase synthesis reaction of pentene styrene and its derivatives, diene compounds or cyclic olefins or mixtures of two or three of these monomers.

Slurry phase synthesis is carried out by adding an organic solvent, preferably toluene, xylene, hexane, heptane or Isopar, a metallocene liquid supported catalyst prepared previously, and methylaluminoxane (MAO) to a high pressure reactor, and olefin at -50 to 200 ° C. It is carried out at about 2 to 20 atmospheres.

In addition, a process of completing the reaction by adding hydrogen in order to control the molecular weight of the prepared polymer may be added.

Gas phase synthesis is carried out in a high-pressure reactor with a metallocene liquid support catalyst prepared in the past and a medium which improves the contact between the gas phase and the solid phase, preferably sodium chloride or polystyrene beads, if a laboratory scale is applied, and then methylaluminoxane. The olefin was charged with 2 to 20 atm and then run at -50 to 200 ° C.

Polyethylene, polypropylene, syndiotactic polystyrene, a-olefin copolymer, etc. are produced by the electric synthesis reaction. The measurement of the activity of the metallocene liquid support catalyst, the volume average diameter of the prepared polymer, and the size distribution of the particles in the preparation of the electric polymer are performed by conventional methods in the art.

The particle size of the polymer suitable for the commercial process is 70 to 350㎛, the narrower the particle size distribution is more convenient for commercial use.

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

These examples are only for illustrating the present invention, and it will be apparent to those skilled in the art that the scope of the present invention is not limited to these examples according to the gist of the present invention.

[Example 1]; Preparation of Metallocene Liquid Support Catalyst and Polymerization Using Electrocatalyst (1)

[Example 2]; Preparation of Metallocene Liquid Support Catalyst

Silica 948 (Grace, USA) was dried for 12 hours at 500 ° C. in a nitrogen atmosphere, 2.03 g of dried silica 948 was added to a round bottom flask equipped with 100 ml of stopcock, followed by Cp ₂ ZrCl ₂ (Aldrich Co., USA) 25mg and MMAO-4 (Arzo Co., USA) 7.6mmol-A1 was dissolved in 3.8ml of toluene by stirring at 45 ° C for 1 hour, and then stirred at 25 ° C for 4 hours. To prepare a catalyst. As a result of ICP analysis of the catalyst prepared in the above, it was found that Zr was 7.4 μmol and Al was 1.64 mmol per 1 g of the catalyst.

[Example 1-2]; Slurry Phase Polymerization (A)

300 ml of toluene, 0.5 g of a previously prepared catalyst and 4 mmol of MAO (Arzo Co., USA) were added to a 1 liter high-pressure reactor, and polymerization was carried out at 50 ° C. for 8 minutes at 8 atmospheres of ethylene. At this time, the catalyst was placed in a glass ampoule and mounted in a reactor. The reaction was started by breaking the glass ampoule with a stirrer. After 60 minutes, 600 ml of ethanol mixed with hydrochloric acid was added to complete the reaction. The prepared polymer was washed with ethanol. After drying in vacuo to prepare about 50g of polyethylene.

At this time, the activity of the catalyst was 1690 kg-PE / (mol-Zr · atm · hr), and it was found that the catalyst had high activity.

In addition, the volume average diameter of the polyethylene particles is 935㎛, and the particle size distribution is shown in FIG. 1. As a result, the polyethylene is a spherical shape suitable for a commercial process, and the particle size and a narrow range of particles suitable for a commercial industry. It can be seen that it has a size distribution.

[Example 1-3]; Slurry Phase Polymerization (B)

About 90 g of polyethylene was prepared in the same manner as in Example 1, except that the polymerization was carried out at 80 ° C., wherein the activity of the catalyst was 3040 kg-PE / (mol-Zr · atm · hr). It was found to have activity.

[Example 2]; Preparation of Metallocene Liquid Supported Catalyst and Polymerization Using Electrocatalyst (Ⅱ)

Example 2-1; Preparation of Metallocene Liquid Support Catalyst

Silica 948 was dried at 500 ° C. for 12 hours in a nitrogen atmosphere, and 2.5 g of dried silica 948 was added to a round bottom flask equipped with 100 ml of stopcock, followed by Et (ind) ₂ ZrCl ₂ (Witco Co., Germany). 20.6mg and MAO 5mmol-Al were injected into a mixed solvent of 2.5 ml of toluene and 2 ml of xylene for 1 hour at 45 ° C for dissolution. The solution was stirred at 50 ° C for 1 hour, and then the temperature was lowered to -60 ° C. The catalyst was prepared by treating under vacuum for 1 hour 30 minutes and then raising the temperature to 25 ° C. and stirring for 30 minutes.

As a result of ICP analysis of the catalyst prepared in the above, it was found that Zr was 2.98 µm and Al was 849 µm per 1 g of the catalyst.

[Example 2-2]; Slurry Phase Polymerization

About 145 g of polypropylene was prepared in the same manner as in Example 1-2, except that 300 ml of toluene, 0.4 g of a catalyst prepared in advance and 4 mmol of MAO were added thereto, and the polymerization reaction was carried out at 50 ° C. at 8 atmospheres of propylene for 120 minutes. It was found that the activity of the catalyst was 16880 kg-PP / (mol-Zr · atm · hr) and the catalyst had a high activity. In addition, the volume average diameter of the electric polypropylene particles was 300 μm, and the size distribution of the particles was shown in FIG. 2. As a result, the electric polyethylene was spherical and suitable for commercial processes. It can be seen that it has a particle size distribution.

Example 2-3; Gas phase polymerization

In a 1 liter high-pressure reactor, 0.8 g of a catalyst prepared in electricity and supported in a glass ampoule and 40 g of NaCl dehydrated at about 500 ° C. were added, followed by vacuum cleaning of the reactor and then 1 ml of MAO (2 mmol) as a scavenger. -Al) was injected, propylene was charged with 9.2 atmospheres, and the glass ampoule was broken with a stirrer to carry out a polymerization reaction at 50 ° C. for 300 minutes to prepare about 13.5 g of polypropylene, wherein the activity of the catalyst was 309 kg-. It was found that the PP (mol-Zr. Atm.hr) catalyst had a high activity.

In addition, the volume average diameter of the electric polypropylene particles was 90 μm, and the size distribution of the particles was shown in FIG. 3, and as a result, the electric polyethylene was spherical and suitable for commercial processes. It can be seen that it has a particle size distribution.

[Example 3]; Preparation of Metallocene Liquid Supported Catalyst and Polymerization Using Electrocatalyst (III)

Example 3-1; Preparation of Metallocene Liquid Support Catalyst

Silica 948 was dried at 500 ° C. for 12 hours in a nitrogen atmosphere. 2.5 g of dried silica 948 was added to a round-bottomed flask equipped with 100 ml of sawtopcock, followed by 25 mg of Cp ₂ ZrCl ₂ and 3.6 mmol of MAO toluene. Inject a solution of 1.8 ml and 2 ml of xylene mixed solvent by stirring at 45 ° C. for 1 hour, and after stirring sufficiently at 50 ° C. for 1 hour, the temperature was lowered to -60 ° C. and vacuumed for 1 hour. The catalyst was prepared by raising the temperature to 25 ° C. and stirring for 30 minutes. As a result of ICP analysis of the catalyst prepared in the above, it was found that Zr was 14.98 μmol and Al was 1.3 mmol supported on 1 g of the catalyst.

Example 3-2; Gas phase polymerization

About 22.8 g of polyethylene was prepared in the same manner as in Example 2-3, except that 6 g of the catalyst prepared in the above was added, ethylene was charged with 12 atm, and the polymerization was carried out at 70 ° C. for 120 minutes. In this case, the activity of the catalyst was 123kg-PE / (mol-Zr · atm · hr), and the catalyst was found to have high activity. In addition, the volume average diameter of the electrical polyethylene particles is 110㎛, the size distribution of the polymer particles is shown in Figure 4, as a result, the electrical polyethylene is a spherical shape suitable for commercial processes, the particle size and a narrow range suitable for commercial processes It can be seen that it has a particle size distribution.

[Example 4]; Preparation of Metallocene Liquid Supported Catalyst and Polymerization Using Electrocatalyst (Ⅳ)

[Example 4-1]; Preparation of Metallocene Liquid Support Catalyst

2.03 g of dried silica 948 was added, and then a solution of 70 mg of Et (ind) ₂ ZrCl ₂ and 7.6 mmol-Al of MAO was stirred in 3.8 ml of toluene by stirring at 25 ° C. for 2 hours, and 3 hours at 25 ° C. A catalyst was prepared in the same manner as in Example 1-1 except for stirring.

As a result of ICP analysis of the catalyst prepared in the above, it was found that Zr was 8.33 μmol and Al was 534 μm per 1 g of the catalyst.

[Example 4-2]; Gas phase polymerization

About 9.6 g of polypropylene was added in the same manner as in Example 2-3, except that 0.5 g of the catalyst prepared above was charged, propylene was charged with 9.2 atm, and polymerization was carried out at 50 ° C. for 120 minutes. It was found that the activity of the catalyst was 129 kg-PP / (mol-Zr · atm · hr) and the catalyst had a high activity. The volume average diameter of the particles was 140 μm, and the size distribution of the particles was shown in FIG. 5. As a result, the electrical polyethylene was a spherical shape suitable for a commercial process, and a particle size and a narrow range of particle size distribution suitable for a commercial process. It can be seen that.

[Example 5]; Preparation of Metallocene Liquid Supported Catalyst and Polymerization Using Electrocatalyst (Ⅴ)

Example 5-1; Preparation of Metallocene Liquid Support Catalyst

MCM-41 (synthesized by known method; see WO91 / 11390 (1991) was dried for 12 h at 500 ° C. in a nitrogen atmosphere and dried in a round bottom flask with 100 ml stopcock MCM-41 2.0 2 g of Et (ind) ₂ ZrCl ₂ and MAO 5 mmol-Al were dissolved in 4.5 ml of toluene at 45 ° C. for 1 hour, and then dissolved at 50 ° C. for 1 hour. The catalyst was prepared by lowering the temperature to -60 ° C, vacuuming for 1 hour, raising the temperature to 25 ° C, and stirring for 30 minutes.

As a result of ICP analysis of the catalyst prepared in the former, it was found that Zr was loaded to 2.51 μm and 1023 μm of Al per 1 g of the catalyst.

Example 5-2; Slurry Phase Polymerization

About 170 g of polypropylene was prepared in the same manner as in Example 1-2, except that 300 ml of toluene, 0.4 g of a catalyst prepared in advance and 4 mmol of MAO were added thereto, and the polymerization reaction was carried out at 50 ° C. at 8 atmospheres of propylene for 120 minutes. It was found that the activity of the catalyst was 10582 kg-PP (mol-Zr · atm · hr) and the catalyst had a high activity.

Example 5-3; Weather polymerization

About 25 g of polypropylene was prepared in the same manner as in Example 2-3, except that 0.5 g of the catalyst prepared in the above was added, wherein the activity of the catalyst was 1082 kg-PP / (mol-Zr · atm · hr) It can be seen that the catalyst has a high activity.

[Example 6]; Preparation of Metallocene Liquid Supported Catalyst and Polymerization Using Electrocatalyst (Ⅵ)

Example 6-1; Preparation of Metallocene Liquid Support Catalyst

MCM-41 was dried for 12 hours at 500 ° C. in a nitrogen atmosphere, and 2.0 g of dried MCM-41 was added to a round bottom flask equipped with 100 ml of stopcock, followed by (t-butylamide) dimethyl (tetramethyl-). η ⁵ - injection the solution was cyclopentadienyl) silane titanium di stirred for one hour chloride 25mg and 5mmol MAO-Al in toluene at 45 ℃ 4.5ml by dissolving, and the mixture was stirred at 50 ℃ for one hour to produce a catalyst .

As a result of ICP analysis of the catalyst prepared in the former, it was found that 3.51 μm of Ti and 1023 μm of Al were supported per 1 g of the catalyst.

Example 6-2; Slurry Phase Polymerization

About 95 g of polyethylene was prepared in the same manner as in Example 1-2, except that 300 ml of Isopar, 0.4 g of the catalyst prepared before, and 4 mmol of MAO were added, and the polymerization was carried out at 150 ° C. for 10 minutes at 10 atmospheres of ethylene. In this case, the activity of the catalyst was 6770kg-PE / mol-Zr.atm.hr).

[Example 7]; Preparation of Metallocene Liquid Support Catalyst and Polymerization Using Electrocatalyst

Example-1; Preparation of Metallocene Liquid Support Catalyst

MCM-41 was dried for 12 hours at 500 ° C. in a nitrogen atmosphere, and 2.0 g of dried MCM-41 was added to a round bottom flask equipped with 100 ml of stopcock, followed by (t-butylamide) dimethyl (tetramethyl-). η ⁵ - cyclopentadienyl) silane titanium dichloride and 25mg N, N- dimethylanilinium cerium tetrakis (pentafluorophenyl) injecting the solution obtained by dissolving the mixture was stirred for 1 hour at 45 ℃ borate 15mg in 4.5ml of toluene and The catalyst was prepared by sufficiently stirring for 1 hour at 50 ° C.

As a result of ICP analysis of the catalyst prepared in the former, it was found that 3.51 μm of Ti was loaded per 1 g of the catalyst.

Example 7-2; Slurry Phase Polymerization

About 87 g of polyethylene was prepared in the same manner as in Example 1-2, except that 300 ml of Isopar, 0.4 g of the catalyst prepared before, and 4 mmol of MAO were added, and the polymerization was carried out at 150 ° C. for 10 minutes at 10 atmospheres of ethylene. It was found that the activity of the catalyst was 6196 kg-PE / (mol-Zr · atm · hr) and the catalyst had high activity.

Example 7-3; Weather polymerization

Except for adding 0.5 g of the catalyst prepared in the previous, about 31 g of polyethylene was prepared in the same manner as in Example 3-2, wherein the activity of the catalyst was 736 kg-PE (mol-Zr atm · hr). It can be seen that has a high activity.

[Example 8]; Preparation of Metallocene Liquid Support Catalyst and Polymerization Using Electrocatalyst

[Example 8-1]; Preparation of Metallocene Liquid Support Catalyst

The crosslinked polystyrene resin (Rohm and Haas, Germany) was dried under vacuum at 100 ° C. for 24 hours, and 2.1 g of dried polystyrene resin was added to a round bottom flask equipped with 100 ml of stopcock, followed by Cp ₂ ZrCl ₂ 25.0 A solution in which mg and MMAO-47.0mmol-Al was dissolved in 3.5 ml of toluene was stirred for 1 hour at 40 ° C., and then stirred at 50 ° C. for 1 hour to prepare a catalyst.

As a result of ICP analysis of the catalyst prepared in the former, it was found that Zr per gram was loaded with 6.9 μmol.

[Example 8-2]; Slurry Phase Polymerization

About 23 g of polyethylene was prepared in the same manner as in Example 1-2, except that 300 ml of toluene, 0.4 g of a catalyst prepared in advance, and 4 mmol of MAO were added to carry out the polymerization reaction at 50 ° C. at 10 atmospheres of ethylene for 60 minutes. It was found that the activity of the catalyst was 832kg-PE / (mol-Zr · atm · hr) and the catalyst had a high activity.

[Example 9]; Preparation of Metallocene Liquid Support Catalyst and Polymerization Using Electrocatalyst

Example 9-1; Preparation of Metallocene Liquid Support Catalyst

2.1 g of silica 948 was reacted with 2.5 mg of Me ₂ SiCl ₂ in toluene at 50 ° C., washed 5 times with toluene, and then dried at 25 ° C. in vacuum for 1 hour to obtain a surface-treated carrier.

Then, silica 948 obtained from the electrical process was added to a round bottom flask equipped with 100 ml stopcock, and 25.0 mg of Cp ₂ ZrCl ₂ and MMAO-47.0 mmol-Al were stirred in 3.5 ml of toluene at 40 ° C. for 1 hour. The dissolved solution was injected, and then stirred at 50 ° C. for 1 hour to prepare a catalyst.

As a result of ICP analysis of the catalyst prepared in the above, it was found that Zr per 7.g of the catalyst was supported by 7.26 μmol.

Example 9-2; Slurry Phase Polymerization

About 55 g of polyethylene was prepared in the same manner as in Example 1-2, except that 300 ml of toluene, 0.5 g of a catalyst prepared previously, and 4 mmol of MAO were added thereto, and the polymerization reaction was carried out at 50 ° C. at 8 atmospheres of ethylene for 60 minutes. It was found that the activity of the catalyst was 1894 kg-PE / (mol-Zr · atm · hr) and the catalyst had a high activity.

As described and demonstrated in detail above, the present invention provides a method for conveniently preparing a metallocene liquid supported catalyst and an electrocatalyst in which a solution in which a metallocene catalyst and a promoter are dissolved is supported in a liquid phase in pores of a carrier. .

Since the metallocene liquid support catalyst of the present invention has a very high activity of the polymerization reaction, it is used in the polymerization reaction of ethylene or propylene and is applied to synthesize polyethylene or polypropylene.

According to the method for producing a metallocene liquid catalyst supported according to the present invention, it is possible to greatly reduce the amount of the cocatalyst used in the polymerization and to easily synthesize the liquid catalyst supported, thereby maintaining a low catalyst production price. In addition, the polymer prepared by using the metallocene liquid supported catalyst of the present invention has a spherical shape suitable for a commercial process, and has a particle size, a particle size distribution, and a bulk density suitable for a commercial process.

Claims (9)

A solution in which a metallocene catalyst and a cocatalyst, a boron-based anionic compound, is dissolved in a solvent is supported in the pores of an inorganic carrier with or without pores surface-treated with an organic compound having a hydrophobic functional group. Metallocene liquid supported catalyst. The metallocene liquid catalyst according to claim 1, wherein the organic compound is a silane compound. [Claim 2] The metallocene catalyst according to claim 1, wherein the metallocene catalyst is a compound of formula (I); R ¹ _m (C _p R ² _n ) (C _p R ² _n ) MR ³ ₂ (n, m = integer) (I) wherein C _p R ² _n is a cyclopentene group or a sirlofen with a substituent Ten groups; R _n ² is a C ₄ to C ₁₀ cyclic compound having or without a substituent; R ¹ is a carbon, silicon or germanium compound covalently bonded to C _p R _n ² ; R ³ is a hydrogen, halogen, amine or alkyl group; And M is a Group 4, 5, 6 transition metal or a lanthanide metal. The metallocene liquid catalyst according to claim 1, wherein the metallocene catalyst is a compound of the following general formula (II); [R ¹ _m (C _p R ² _n ) (C _p R ² _n ) MR ³ R ⁴ ] ⁺ R ^5- (n, m = integer) (II) wherein C _p R ² _n is a cyclopentene group or A cyclopentene group having a substituent; R _n ² is a C ₄ to C ₁₀ cyclic compound having or without a substituent; R ¹ is a carbon, silicon or germanium compound covalently bonded to C _p R _n ² ; R ³ is a hydrogen, halogen, amine or alkyl group; R ⁴ is a hydrogen, halogen, amine or alkyl group; R ^5- is a counter anion that stabilizes the cationic metal; And M is a Group 4, 5, 6 transition metal or a lanthanide metal. The metallocene liquid catalyst according to claim 1, wherein the metallocene catalyst is a compound represented by the following general formula (III); R ¹ _m (C _p R ² _n ) LR ³ _n MR ⁴ ₂ (n, m = integer) (III) wherein C _p R ² _n is a cyclopentene group or a cyclopentene group having a substituent; R _n ² is a C ₄ to C ₁₀ cyclic compound having or without a substituent; R ¹ is a carbon, silicon or germanium compound covalently bonded to C _p R _n ² ; R ³ is a hydrogen, halogen, amine or alkyl group; R ⁴ is a hydrogen, halogen, amine or alkyl group; L is an amine, alkyl or alkoxy group; And M is a Group 4, 5, 6 transition metal or a lanthanide metal. (i) drying the carrier to remove water present in the pores and OH groups present on the carrier surface; and (ii) a solution in which the metallocene catalyst and the co-catalyst dissolved in a solvent are dried in an electrical process. A method of producing a metallocene liquid supported catalyst, comprising the step of injecting into a reactor into which is injected, and carrying a solution in the pores of a carrier. 7. The metallocene liquid support according to claim 6, wherein the carrier reacts the inorganic material having pores with an organic compound having a functional group and a hydrophobic functional group capable of reacting with an OH group of an inorganic solvent in an organic solvent, followed by washing and drying. Method for preparing a catalyst. The method of claim 6, wherein the solvent is a single organic solvent, and the temperature of the prepared metallocene liquid supported catalyst is lowered below the freezing point of the solvent used to solidify the solvent in the pores, and then the temperature is raised above the melting point and stirred. Method for producing a metallocene liquid supported catalyst, characterized in that. The solvent of claim 6, wherein the solvent is a mixed solvent in which a highly volatile solvent and a weak solvent are mixed, and the temperature of the prepared metallocene liquid supported catalyst is lowered between the freezing point of the highly volatile solvent and the weak solvent, and the highly volatile solvent is added. Removing and then raising the temperature to above the melting point of the weakly volatile solvent and stirring the metallocene liquid supported catalyst.