KR101715259B1 - Novel metallocene catalyst compositions and process for preparing polyolefines - Google Patents

Abstract

The present invention relates to a supported metallocene catalyst composition and a process for preparing an olefin polymer using the metallocene supported catalyst composition. The metallocene supported catalyst composition according to the present invention is characterized in that a Group 4 transition metal compound is reacted with aryl boronic acid and alkyl aluminoxane The metallocene supported catalyst composition according to the present invention is characterized in that the metallocene supported catalyst composition according to the present invention is prepared by contacting a metallocene supported catalyst composition according to the present invention with an inorganic or organic porous carrier, The catalytic activity of the slurry and the gaseous olefin compound is greatly increased during the polymerization reaction.

Description

TECHNICAL FIELD [0001] The present invention relates to a novel metallocene supported catalyst composition and a process for preparing the same,

The present invention relates to a metallocene supported catalyst composition, a process for preparing the olefin polymer using the same, and an olefin polymer produced therefrom.

The olefin polymerization catalyst can be classified into a Ziegler-Natta heterogeneous catalyst and a single active site metallocene catalyst. The metallocene catalysts of the present invention were disclosed by Kaminsky in 1980 and have been used to produce various polyolefin products Has been developed. The metallocene catalyst is formed by a combination of a main catalyst mainly composed of a transition metal compound and an organometallic compound promoter mainly composed of aluminum or boron. The metallocene catalyst is a homogeneous, single-site catalyst. The molecular weight distribution and chemical compositional distribution of the polyolefin produced are very narrow and homogeneous. Depending on the ligand structure of the metallocene catalyst, stereoregularity, comonomer, The responsiveness and the hydrogen responsiveness can be freely controlled, and the physical properties of the polyolefin associated therewith can be greatly improved as compared with the Ziegler-Natta catalyst.

Immobilization is indispensable for the use of such metallocene catalysts in slurry or gaseous olefin polymerization processes. This is due to the fact that when the homogeneous metallocene catalyst is added to the slurry and the gas phase polymerization process, there is a problem in the process such as agglomerate, fouling, sheeting and plugging of the produced polymer And the shape of the polyolefin polymer particle is very irregular, and the product density is low and the production of the product is impossible.

In order to solve these various problems, researches have been carried out on the support, and a metallocene supported catalyst is supported on a porous inorganic or organic material such as silica, alumina, magnesium dichloride or the like by metallocene alone or metallocene and cocatalyst. A method of polymerizing a polyolefin has been developed.

As a conventional method for supporting a metallocene catalyst, a method in which an aluminum compound, that is, trimethylaluminum, triethylaluminum, or the like, is added to the unfired silica and then the metallocene is supported thereon (U.S. Patent Nos. 4937217 and 4912075 , No. 4935397), a method of surface-treating fired silica with methylaluminoxane or surface-treating silica containing water with alkylaluminum and then introducing metallocene to prepare a supported metallocene catalyst (U.S. Patent No. 4808561 No. 4912075, No. 4904631), and the like are known. Also, a method of synthesizing a supported metallocene catalyst by surface-treating silica with a boron-based organometallic compound instead of an aluminum organometallic compound and introducing metallocene (U.S. Patent No. 6087293), a method of replacing aluminum or a boron-based organometallic compound A method of preparing a supported metallocene catalyst by treating the surface of silica with an organic compound and contacting the metallocene (U.S. Patent No. 5643847, No. 5972823) is known, and other metallocene catalysts (Japanese Patent Application No. 10-1999-0023575 and Korean Patent No. 10-0536181) are known in which a covalent bond is formed and attached to a silica surface through a chemical reaction.

However, when the metallocene supported catalyst is prepared by the above methods, the catalyst component can not be uniformly supported in the pores, the catalyst preparation time is long, and the activity of the catalyst is low. In addition, since aluminoxane is not uniformly present in the pores, it may cause problems such as reduction in activity and hot spot in the reactor. In the slurry polymerization process, the catalyst component in the metallocene supported catalyst dissolves and polymerized polymer particles may cause fouling or tube clogging. In order to solve these problems, there are disadvantages in that the metallocene supported catalyst prepared through the above-described conjugation bonding has a high production cost of the catalyst and low activity of the prepared catalyst due to the manufacturing method over several stages.

Accordingly, an object of the present invention is to provide a metallocene supported catalyst for olefin polymerization by a boron method capable of introducing a boron group having a higher electronegativity than aluminum in order to overcome problems such as reduction in activity and hot spot in a reactor It is also an object of the present invention to provide a method for producing a variety of polyolefin products exhibiting high activity and process operation stability in a slurry or gaseous olefin polymerization process having a single reactor or multiple reactors, The present invention also provides a metallocene supported catalyst which can greatly overcome the process problems such as fouling, sheeting and plugging during the polymerization reaction of the slurry and the gaseous olefin compound For the purpose of the invention.

In order to achieve the above object, the present invention provides a process for producing a metallocene catalyst by contacting a reaction product of an arylboronic acid and an alkylaluminoxane with an inorganic or organic porous carrier to treat the surface of the carrier and the inner surface of the pore, Characterized in that the supported metallocene supported catalyst composition is characterized in that it provides a supported catalyst composition and that the metallocene supported catalyst composition is used to polymerize an olefin monomer or an olefin based and olefin comonomer thereof to provide an olefin polymer.

Hereinafter, the features of the present invention will be described in detail.

The metallocene supported catalyst composition for olefin polymerization according to the present invention is characterized in that a metallocene supported metallocene catalyst composition (A) is supported on an inorganic or organic porous carrier treated with a reactant (B) of arylboronic acid and alkylaluminoxane, .

[Chemical Formula 1]

Cp'L ¹ ML ² _n

[In the above formula (1)

M is a Group 4 transition metal on the Periodic Table;

Cp 'is a fused ring comprising a cyclopentadiene or cyclopentadienyl ring which is capable of η ⁵ -binding to a central metal;

L ¹ is an anionic ligand containing a fused ring or (C1-C20) hydrocarbon substituent comprising a cyclopentadiene, cyclopentadienyl ring and an O, N or P atom; ; L ² represents a halogen atom, a (C 1 -C 20) alkyl group, a (C 6 -C 30) aryl (C 6 -C 20) alkyl group, a (C 3 -C 20) cycloalkyl group, , A (C6-C30) aryl group, -SiR ^a R ^b R ^c , -NR ^d R ^e , -OSiR ^f R ^g R ^h or -PR ⁱ R ^j ; R ^a to R ^j are independently of each other a (C1-C20) alkyl group or a (C6-C30) aryl group;

n is an integer of 1 or 2;

The Cp 'and L ¹ may not be connected to each other or may be connected to each other by a silicon or (C 1 -C 4) alkenylene bond, and the cyclopentadienyl ring or cyclopentadienyl fused ring of Cp' and L ¹ may be (C 1 -C 20) alkyl group, (C 3 -C 20) cycloalkyl group, (C 6 -C 30) aryl group, (C 2 -C 20) alkenyl group or Can be.]

That is, in the metallocene supported catalyst composition according to the present invention, the carrier on which the metallocene catalyst represented by Formula 1 is supported comprises a porous inorganic or organic carrier having a hydroxy group on the carrier pore surface, The carrier having a hydroxy group on its surface can be obtained by sufficiently treating the reaction product (B) of arylboronic acid and alkylaluminoxane and physically and chemically surface-treating the inner and outer surfaces of the carrier pores.

The arylboronic acid used in the present invention is represented by the formula (2).

(2)

Ar-B (OH) ₂

In the above formula (2), Ar is a (C6-C30) aryl group, and the aryl group of Ar may be further substituted with at least one selected from the group consisting of a (C1-C20) alkyl group and a (C1-C20) alkoxy group. ]

Wherein Ar is a phenyl group, a naphthyl group or a fluorenyl group, and the phenyl, naphthyl and fluorenyl groups of Ar are substituted with at least one substituent selected from a (C1-C10) alkyl group and a (C1-C10) alkoxy group, Can be further substituted. More specifically, Ar is selected from the following structures.

The alkylaluminoxane used in the present invention is represented by the general formula (3).

(3)

(-Al (R ¹ ) -O-) _m

[Wherein R ¹ is a (C ¹ -C 20) alkyl group and m is an integer of 5 to 20].

Wherein R ¹ is methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl or t-butyl and more specifically methyl aluminoxane (MAO) MMAO), ethylaluminoxane, propylaluminoxane, butylaluminoxane, isobutylaluminoxane, and the like.

The inorganic or organic porous carrier treated with the reaction product of the arylboronic acid and the alkylaluminoxane may be an inorganic or organic material having pores. The inorganic or organic porous carrier may be a porous material having a pore capable of supporting metallocene and a reaction product of arylboronic acid and alkylaluminoxane, . The surfaces of these carriers may have functional groups having hydrophobic properties, or they may be surface-treated with various silane compounds, aluminum compounds and halogen compounds. Typical inorganic carriers include silica, alumina, magnesium chloride, magnesium oxide, and other carriers that have been used to support metallocene catalysts. In addition, mesoporous materials such as MCM-41, MCM-48, SBA -15, and they have a surface area of 100 m ² / g or more and a pore volume of 0.1 cc / g or more. Clay compounds such as mineral clay, kaolin, talc, mica, montmorillonite and the like can also be used as carriers. As the organic carrier, a substance such as a polysiloxane-based polymer compound, polystyrene gel or beads can be employed. These carrier compounds may be used in their original state or may be heat-treated at a temperature of 100 to 1000 ° C. to control the amount of hydrophobic functional groups and the like in the pore surface of the carrier.

Examples of the metallocene or nonmetallocene catalyst that can be used in the present invention are as follows and are not necessarily limited thereto.

The aryl boronic acid and an alkyl aluminoxane reaction product with an inorganic or a transition metal of the formula (1) is supported on the organic porous carrier Cp 'is a central metal and η ⁵ treated with the-cyclopentadienyl or capable of binding to the cyclopentadienyl The fused ring containing the ring is preferably a cyclic ring selected from the group consisting of cyclopentadienyl, methylcyclopentadienyl, dimethylcyclopentadienyl, tetramethylcyclopentadienyl, pentamethylcyclopentadienyl, butyl cyclopentadienyl, sec -butyl cyclopentadienyl Ethyl, propyl, isopropyl, n-butyl, tert -butylmethylcyclopentadienyl, trimethylsilylcyclopentadienyl, indenyl, methylindenyl, ethylindenyl, isopropylindenyl, fluorenyl, methylfluorenyl, dimethylfluorenyl, Fluorenyl, isopropylfluorenyl, and specific examples of the compound of formula (1) include bis (cyclopentadienyl) zirconium dichloride Bis (cyclopentadienyl) zirconium dichloride, bis (cyclopentylcyclopentadienyl) zirconium dichloride, bis (cyclopentadienyl) zirconium dichloride, bis (cyclopentadienyl) zirconium dichloride, bis ) Zirconium dichloride, bis (1,3-dimethylcyclopentadienyl) zirconium dichloride, bis (i-butylcyclopentadienyl) zirconium dichloride, bis (indenyl) zirconium dichloride, bis (fluorenyl) zirconium Bis (4,5,6,7-tetrahydro-1-indenyl) zirconium dichloride, ethylene-bis (indenyl) zirconium dichloride, ethylene- [bis (Indenyl) zirconium dichloride, isopropyl (cyclopentadienyl) (fluorenyl) zirconium dichloride, dimethylsilyl-bis (indenyl) zirconium dichloride, diphenylsilyl- Zirco (Cyclopentadienyl) (fluorenyl) zirconium dichloride, diphenylsilyl (cyclopentadienyl) (fluorenyl) zirconium dichloride, (cyclopentylcyclopentadienyl) (cyclopentadienyl) (1-methyl-3-cyclopentylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride, (1-ethyl-3-cyclopentylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride, Zirconium dichloride, (1-butyl-3-cyclopentylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride, (cyclopentylcyclopentadienyl) (cyclomethylcyclopentadienyl) zirconium dichloride, -Methyl-3-cyclopentylcyclopentadienyl) (pentamethylcyclopentadienyl) zirconium dichloride, (1-ethyl-3-cyclopentylcyclopentadienyl) (pentamethylcyclopentadienyl) zirconium dichloride, ( 1-butyl-3-cyclopentylcyclopentadienyl) (pentamethylcyclopentadienyl) zirconium dichloride, (cyclohexylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride, (Pentamethylcyclopentadienyl) zirconium dichloride, (1-ethyl-3-cyclohexylcyclopentadienyl) (pentamethylcyclopentadienyl) zirconium dichloride, (1-ethyl- (Cyclopentadienyl) zirconium dichloride, (cyclohexylcyclopentadienyl) zirconium dichloride, (cyclohexylmethylenecyclopentadienyl) (cyclopentadienyl) zirconium dichloride, (cyclohexylcyclopentadienyl) Dienyl) (cyclopentadienyl) zirconium dichloride, (1-methyl-3-cycloheptylcyclopentadienyl) (pentamethylcyclopentadienyl) zirconium dichloride, (1-ethyl-3-cycloheptylcyclopenta Dienyl) (pentamethylcyclo Zirconium dichloride, (1-butyl-3-cycloheptylcyclopentadienyl) (pentamethylcyclopentadienyl) zirconium dichloride, (cyclohexylethylenecyclopentadienyl) (cyclopentadienyl) zirconium dichloride, Zirconium dichloride and the like are exemplified, and metallocene compounds and nonmetallocene compounds in which the center metal includes titanium and a hafnium transition metal are also usable.

In the case of the metallocene supported catalyst composition according to the present invention, the supported metallocene or nonmetallocene organometallic catalyst (transition metal compound of the formula (I)) supported on the surface-treated carrier with the reaction product of arylboronic acid and alkylaluminoxane In the case of a metallocene or non-metallocene organometallic catalyst, in the range of 0.01 to 20 wt% based on the supported metallocene catalyst (based on the final supported catalyst including carrier, reaction product of arylboronic acid and alkylaluminoxane, and organometallic catalyst) Is suitably 0.1 to 10% by weight.

The metallocene supported catalyst composition according to the present invention may further comprise an organoaluminum promoter or boron compound promoter, or a mixture thereof.

 The organoaluminum co-catalyst used in the present invention includes the alkyl aluminum compound represented by the formula (4).

[Chemical Formula 4]

(R ⁵ ) _r Al (E) _3-r

[Wherein, in Formula 4, R ⁵ is a (C 1 -C 20) alkyl group; E is a hydrogen atom or a halogen atom, and r is an integer of 1 to 3.]

Examples of the alkyl aluminum compound which can be used include trialkyl aluminum including trimethyl aluminum, triethyl aluminum, tripropyl aluminum, triisopropyl aluminum, tributyl aluminum, triisobutyl aluminum, triisoorenyl aluminum and the like, dimethyl aluminum chloride Dialkylaluminum chloride including diethylaluminum chloride, dipropylaluminum chloride, diisobutylaluminum chloride, dihexylaluminum chloride, methylaluminum dichloride, ethylaluminum dichloride, propylaluminum chloride, isobutylaluminum chloride and the like And the like, and preferably trialkylaluminum chloride and triisobutylaluminum chloride.

The boron compound which can be used as a promoter in the present invention can be selected from the compounds represented by the following formulas (5) to (7).

[Chemical Formula 5]

B (R ² ) ₃

[Chemical Formula 6]

[R ³ ] ⁺ [B (R ² ) ₄ ] ^-

(7)

[(R ⁴ ) _q ZH] ⁺ [B (R ² ) ₄ ] ^-

[In the formulas (5) to (7), B is a boron atom; R ² is phenyl and the phenyl is optionally substituted with one to three substituents selected from the group consisting of a fluorine atom, (C 1 -C 4) alkyl optionally substituted by fluorine atom, or (C 1 -C 4) alkoxy optionally substituted by fluorine atom Lt; / RTI > may be further substituted with a substituent; R ³ is a (C 5 -C 7) cycloalkyl radical, a (C 6 -C 20) aryl radical or a (C 6 -C 20) alkyl radical or a (C 6 -C 20) Lt; / RTI > is a triphenylmethyl radical; Z is nitrogen or phosphorus; R ⁴ is a (C ₁ -C ₄ ) alkyl radical or an anilinium radical substituted with two (C ₁ -C ₄ ) alkyl groups together with the nitrogen atom; q is an integer of 2 or 3.]

Preferable examples of the boron compound promoter include tris (pentafluorophenyl) borane, tris (2,3,5,6-tetrafluorophenyl) borane, tris (2,3,4,5-tetrafluoro (2,3,4-trifluorophenyl) borane, phenylbis (pentafluorophenyl) borane, tetrakis (triphenylphosphine) borane, (Pentafluorophenyl) borate, tetrakis (2,3,5,6-tetrafluorophenyl) borate, tetrakis (2,3,4,5-tetrafluorophenyl) borate, tetrakis , 5-tetrafluorophenyl) borate, tetrakis (2,2,4-trifluorophenyl) borate, phenylbis (pentafluorophenyl) borate, tetrakis (3,5-bistrifluoromethylphenyl) , N, N-dimethylanilium tetrakis pentafluorophenyl borate, and triphenylmethylnium tetrapentafixfluoroborate.

Also, in the case of an aluminum-based co-catalyst such as an alkyl aluminum compound to be added and a boron-based co-catalyst, 0.01 to 0.01 based on a metallocene-supported catalyst (final supported catalyst) supported in a carrier surface-treated with a reaction product of arylboronic acid and alkylaluminoxane To 50% by weight, and more preferably 0.1 to 30% by weight.

When the transition metal compound represented by the general formula (1) is dissolved in an organic solvent such as an aluminum-based co-catalyst such as an organoaluminum compound and carried on a carrier surface-treated with a reaction product of an arylboronic acid and an alkylaluminoxane, The molar ratio of the two components of the catalyst is suitably from 1: 1 to 1: 1000, particularly preferably from 1:10 to 1: 1000, based on the molar ratio of the transition metal M: aluminum atom.

When the boron compound is used as a cocatalyst, the molar ratio of the transition metal compound represented by the general formula (1) to the cocatalyst of the boron compound is suitably in the range of 1: 0.01 to 1: 100, particularly 1: 0.1 to 1: : 20 is preferable. The molar ratio of the boron compound promoter to the aluminum compound is preferably 1: 0.1 to 1: 100, more preferably 1: 1 to 1:20, based on boron: aluminum.

 The present invention features a process for preparing an olefin polymer using the above metallocene supported catalyst composition for olefin polymerization, wherein the olefin polymer comprises a homopolymer or copolymer of an alpha olefin.

Examples of possible olefinic monomers that can be employed in the production process according to the present invention include ethylene, alpha olefins, cycloolefins, and diene monomers, triene, styrene, and cyclic olefins.

Examples of such monomers include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, Butene, styrene, alpha-methylstyrene, allylbenzene, divinylbenzene, vinylcyclohexane, vinylcycloheptane, vinylcyclohexane, 1,3-butadiene, 1,4-pentadiene, 1,4-hexadiene and cyclopentadiene, and these monomers may be used singly or in combination of two or more kinds of monomers such as cyclopentene, cycloheptene, norbornene, tetracyclododecene, isoprene, Or more.

Hereinafter, a method for preparing the supported metallocene catalyst composition according to the present invention will be described.

In the present invention, an inorganic or organic porous carrier treated with a reaction product of an arylboronic acid and an alkylaluminoxane on which a Group 4 transition metal compound is supported can be prepared from the following method.

An inorganic or organic porous carrier and an arylboronic acid are mixed and stirred in an organic solvent such as toluene, and alkylaluminoxane is slowly injected into the mixture. In this case, the molar ratio of boron to aluminum is suitably in the range of 1:10 to 1: 1000, preferably 1: 500 to 1:20. After the mixture is stirred at room temperature for 2 hours, the metallocene of formula (1) is slowly dissolved in an organic solvent such as toluene. The molar ratio of the metallocene to the alkylaluminoxane is preferably 1: 1 to 1: 100.

 Subsequently, to remove the unreacted metallocene, unreacted arylboronic acid and alkylaluminoxane, an organic solvent such as toluene is used for washing three times or more, followed by drying with vacuum or nitrogen gas, and finally ionic Thereby obtaining a metallocene catalyst supported on the compound surface-treated carrier.

The transition metal content in the supported catalyst made by the above method was analyzed to be 0.05 to 1.5 wt%.

The metallocene supported catalyst supported on the carrier treated with the reaction product of arylboronic acid and alkylaluminoxane thus obtained can be subjected to multi-polymerization using one kind of olefin monomer or two or more kinds of monomers, and the olefin monomer can be polymerized with an organic solvent such as hexane The polymerization reaction is carried out in a slurry or gas phase. The catalyst according to the present invention is dispersed in a reaction solvent in the absence of water. The polymerization reaction solvent is generally an aliphatic hydrocarbon or a mixture thereof. Examples thereof include propane, isobutane, isopentane, hexane, heptane, to be.

The metallocene supported catalyst of the present invention is applicable not only to the gas phase, slurry, and liquid phase polymerization processes but also to both the batch and continuous polymerization processes, but is most suitable for slurry and gas phase reaction.

The batch slurry polymerization process as an example of the polyolefin polymerization process using the supported catalyst according to the present invention will now be described.

First, the high-pressure reactor is vacuumed to remove water and air, and then the solvent is introduced into the reactor. After the temperature is raised to the polymerization temperature, alkyl aluminum or MAO is added as a scavenger, and the metallocene supported catalyst . Then, olefins such as ethylene are introduced, and hydrogen is injected as necessary when olefins are added. When the required polymerization time is reached, the addition of olefins is stopped, the unreacted olefin and solvent are removed, and the reactor is opened to obtain a solid polymer.

The polymerization solvent used is passed through a tube filled with molecular sieve 5A and activated alumina and bubbled with high purity nitrogen to sufficiently remove water, oxygen and other catalyst poisons. The polymerization temperature is -50 to 200 ° C Lt; 0 > C and 50 < 0 > C to 100 < 0 > C. The polymerization pressure is 1 to 50 atm, preferably 5 to 30 atm.

The metallocene supported catalyst supported on an inorganic or organic porous support surface treated with a reaction product of arylboronic acid and alkylaluminoxane containing boron having a large electronegativity according to the present invention can be prepared by a conventional method The bulk density of the prepared polymer was also good. Thus, there is a very economical and useful advantage in producing metallocene polyolefins in commercial slurry or gas phase processes.

Hereinafter, the present invention will be described by way of Comparative Examples and Examples, but the present invention is not limited by the following Examples.

The metallocene supported catalyst and the polymer polymer analysis according to the present invention were carried out as follows.

1) the metal content in the supported catalyst

The metal content was measured by ICP analysis.

2) Melt index

It was measured according to ASTM D 2839.

3) Melting point analysis

Using Dupont DSC2910 was measured at 2 ^nd heating condition to 20 ℃ / min. Rate under cant atmosphere.

4) Molecular weight and molecular weight distribution

TOHO Company Column TSK Guard Column HHR (S) + TSK-Gel The PL GPC210 (manufactured by Polymer Laboratories) equipped with GMHHR H (S) was measured at 160 ° C at a rate of 1 ml / min. 1,2,3-trichlorobenzene was used as the solvent, and the molecular weight was corrected by the standard sample PS1_A, B (Mw = 580 to 7,500,000).

[Example 1]

1. Preparation of Catalyst Supported with Metallocene on Surface-Treated Silica with Reaction Products of 2-Methoxyphenylboronic Acid and Methyl Aluminoxane

¹ g of silica XPO-2412 (Grace, USA, surface area 460 m ² / g, average pore diameter 12.8 nm) and 9.1 mg (0.06 mmol) of 2-methoxyphenylboronic acid were introduced into a round bottom flask equipped with a stopcock After 30 mL of toluene was mixed, 8 mmol-Al of MAO (aluminum content: 4.6 wt%, Albermale Co.) in the toluene solution was slowly added at room temperature and stirred for 2 hours. (N-BuCp) ₂ ZrCl ₂ was dissolved in 10 mL of toluene in a round bottom flask equipped with another stopcock, and the mixture was slowly added thereto, followed by stirring for 30 minutes. The above mixed solution was transferred to a flask containing the prepared silica and agitated at 50 DEG C for 1 hour. Stirring was stopped, the silica was settled, the upper layer solution was taken out, 50 mL of toluene was added, and the mixture was stirred for 10 minutes. The same procedure was repeated three times. Thereafter, the toluene present in the flask was removed by vacuum for 1 hour to obtain 1.10 g of a catalyst carrying the final metallocene compound.

2. Ethylene slurry polymerization

1.5 liters of hexane was added to a 2 liter high-pressure reactor which had been washed in a high-temperature vacuum, the temperature was raised to 70 ° C., 0.4 mmol-Al of TEAL was added for scavenger and cocatalyst function, and the metallocene 20 mg of the supported catalyst was fed into the reactor with a hexane slurry. The ethylene pressure was adjusted so that the total pressure in the reactor was 7 atm, saturated ethylene gas was introduced, and the ethylene polymerization reaction was started by rotating the stirrer. The total polymerization reaction time was 60 minutes and the temperature was maintained at 80 ° C. After completion of the reaction, the prepared polymer was washed with ethanol and dried in vacuo to obtain 60 g of polymer.

[Comparative Example 1]

1. Manufacture of metallocene supported catalyst

1 g of silica XPO-2412 was added to a round bottom flask equipped with a stopcock. MAO 3 mmol-Al and (n-BuCp) ₂ ZrCl ₂ 0.35 mmol in toluene solution were added to another round bottom flask equipped with a stopcock and stirred again for 30 minutes. The above mixed solution was transferred to a flask containing the prepared silica and agitated at 50 DEG C for 1 hour. After the stirring was stopped, the toluene present in the flask was removed by vacuum for 1 hour to obtain 0.98 g of a catalyst carrying the final metallocene compound.

2. Ethylene slurry polymerization

Using the supported catalyst prepared in the above step, a polymerization reaction was carried out according to the polymerization method of ethylene slurry in 2 of [Example 1] to obtain 11 g of a polymer.

The results of the above experiments show that the metallocene supported catalyst supported on the silica XPO-2412 surface-treated with a boron-containing aryl boronic acid and alkylaluminoxane, which is a core technology of the present invention, Compared to the conventional method of carrying out the catalyst (Comparative Example 1), the catalytic activity showed an excellent activity of 4 times or more, and the apparent density of the prepared polymer was 0.30 g / cc.

Claims (13)

(A) represented by the following formula (1) is supported on an inorganic or organic porous carrier treated with a reactant (B) of an arylboronic acid represented by the following formula (2) and an alkylaluminoxane represented by the following formula Supported metallocene catalyst composition.
[Chemical Formula 1]
Cp'L ¹ ML ² _n
[In the above formula (1)
M is a Group 4 transition metal on the Periodic Table;
Cp 'is a fused ring comprising a cyclopentadiene or cyclopentadienyl ring which is capable of η ⁵ -binding to a central metal;
L ¹ is a fused ring containing a cyclopentadiene or cyclopentadienyl ring; L ² represents a halogen atom, a (C 1 -C 20) alkyl group, a (C 6 -C 30) aryl (C 6 -C 20) alkyl group, a (C 3 -C 20) cycloalkyl group, , A (C6-C30) aryl group, -SiR ^a R ^b R ^c , -NR ^d R ^e , -OSiR ^f R ^g R ^h or -PR ⁱ R ^j ; R ^a to R ^j are independently of each other a (C1-C20) alkyl group or a (C6-C30) aryl group;
n is an integer of 1 or 2;
The Cp 'and L ¹ may not be connected to each other or may be connected to each other by a silicon or (C 1 -C 4) alkenylene bond, and the cyclopentadienyl ring or cyclopentadienyl fused ring of Cp' and L ¹ may be (C 1 -C 20) alkyl group, (C 3 -C 20) cycloalkyl group, (C 6 -C 30) aryl group, (C 2 -C 20) alkenyl group or Can be.]

(2)
Ar-B (OH) ₂
In the above formula (2), Ar is a (C6-C30) aryl group, and the aryl group of Ar may be further substituted with at least one selected from the group consisting of a (C1-C20) alkyl group and a (C1-C20) alkoxy group. ]

(3)
(-Al (R ¹ ) -O-) _m
[Wherein R ¹ is a (C ¹ -C 20) alkyl group and m is an integer of 5 to 20].
The method according to claim 1,
Wherein Ar is a phenyl group, a naphthyl group or a fluorenyl group, and the phenyl, naphthyl and fluorenyl groups of Ar are substituted with at least one substituent selected from a (C1-C10) alkyl group and a (C1-C10) alkoxy group, Further substituted; The metallocene supported catalyst composition for olefin polymerization according to claim 3, wherein R ¹ is methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl or t-butyl.
3. The method of claim 2,
Wherein Ar is selected from the following structures.

The method according to claim 1,
The metallocene supported catalyst composition for olefin polymerization according to claim 1, wherein the Group 4 transition metal compound (A) is contained in an amount of 0.01 to 20% by weight based on the total weight of the metallocene supported catalyst composition for olefin polymerization.
The method according to claim 1,
Wherein the reaction ratio of the arylboronic acid of Formula 2 to the alkylaluminoxane of Formula 3 is 1:10 to 1: 1000 based on the molar ratio of boron to aluminum.
The method according to claim 1,
Wherein the metallocene supported catalyst composition for olefin polymerization further comprises at least one selected from the group consisting of an organoalkyl aluminum promoter represented by the following general formula (4) and a boron compound promoter represented by the following general formulas (5) to (7) Supported catalyst composition.
[Chemical Formula 4]
(R ⁵ ) _r Al (E) _3-r
[Wherein, in Formula 4, R ⁵ is a (C 1 -C 20) alkyl group; E is a hydrogen atom or a halogen atom, and r is an integer of 1 to 3.]
[Chemical Formula 5]
B (R ² ) ₃
[Chemical Formula 6]
[R ³ ] ⁺ [B (R ² ) ₄ ] ^-
(7)
[(R ⁴ ) _q ZH] ⁺ [B (R ² ) ₄ ] ^-
[In the formulas (5) to (7), B is a boron atom; R ² is phenyl and the phenyl is optionally substituted with one to three substituents selected from the group consisting of a fluorine atom, (C 1 -C 4) alkyl optionally substituted by fluorine atom, or (C 1 -C 4) alkoxy optionally substituted by fluorine atom Lt; / RTI > may be further substituted with a substituent; R ³ is a (C5-C7) cycloalkyl radical, a (C6-C20) aryl radical or a (C1-C20) alkyl (C6-C20) aryl radical or a (C6-C30) aryl (C1-C20) alkyl radical; Z is nitrogen or phosphorus; R ⁴ is a (C ₁ -C ₄ ) alkyl radical or an anilinium radical substituted with two (C ₁ -C ₄ ) alkyl groups together with the nitrogen atom; q is an integer of 2 or 3.]
The method according to claim 6,
The organic alkyl aluminum co-catalyst includes trialkylaluminum including trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, tributylaluminum, triisobutylaluminum, triisoorilylaluminum and the like, dimethylaluminum chloride, diethyl At least one member selected from the group consisting of aluminum chloride, dipropylaluminum chloride, diisobutylaluminum chloride, dialkylaluminum chloride including dihexylaluminum chloride, methylaluminum dichloride, ethylaluminum dichloride, propylaluminum chloride and isobutylaluminum chloride ego;
The boron compound promoter may be at least one selected from the group consisting of tris (pentafluorophenyl) borane, tris (2,3,5,6-tetrafluorophenyl) borane, tris (2,3,4,5-tetrafluorophenyl) (Pentafluorophenyl) borane, tetrakis (pentafluorophenyl) borane, tris (3,4,5-trifluorophenyl) Tetrakis (2,3,5,6-tetrafluorophenyl) borate, tetrakis (2,3,4,5-tetrafluorophenyl) borate, tetrakis (3,4,5- (3,5-bistrifluoromethylphenyl) borate, tetrakis (2,2,4-trifluorophenyl) borate, phenylbis (pentafluorophenyl) N-dimethylanilinium tetrakispentafluorophenylborate, and triphenylmethyllithium tetrapentafluoroborate. It is also possible to use at least one compound selected from the group consisting of A metallocene for olefin polymerization of metallocene supported catalyst composition.
The method according to claim 1,
The Group 4 transition metal compound (A) may be at least one selected from the group consisting of bis (cyclopentadienyl) zirconium dichloride, bis (methylcyclopentadienyl) zirconium dichloride, bis (normal butylcyclopentadienyl) zirconium dichloride, bis (Cyclopentadienyl) zirconium dichloride, bis (cyclopentadienyl) zirconium dichloride, bis (1,3-dimethylcyclopentadienyl) zirconium dichloride, bis (isobutylcyclopentadienyl) zirconium di Zirconium dichloride, bis (indenyl) zirconium dichloride, bis (indenyl) zirconium dichloride, bis (4,5,6,7-tetrahydro- Bis (indenyl) zirconium dichloride, diphenylsilyl-bis (diphenylsilyl) bis (diphenylsilyl) bis (Cyclopentadienyl) (cyclopentadienyl) (fluorenyl) zirconium dichloride, dimethylsilyl (cyclopentadienyl) (fluorenyl) zirconium dichloride, diphenylsilyl Zirconium dichloride, (cyclopentadienyl) zirconium dichloride, (1-methyl-3-cyclopentylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride, (1- Cyclopentylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride, (1-butyl-3-cyclopentylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride, (cyclopentylcyclopentane) Dienyl) (cyclomethylcyclopentadienyl) zirconium dichloride, (1-methyl-3-cyclopentylcyclopentadienyl) (pentamethylcyclopentadienyl) zirconium dichloride, (1-ethyl- (Pentamethylcyclopentadienyl) zirconium dichloride, (1-butyl-3-cyclopentylcyclopentadienyl) (pentamethylcyclopentadienyl) zirconium dichloride, (cyclohexylcyclopentadienyl) (Cyclopentadienyl) zirconium dichloride, (1-methyl-3-cyclohexylcyclopentadienyl) (pentamethylcyclopentadienyl) zirconium dichloride, (1-ethyl- (Pentamethylcyclopentadienyl) zirconium dichloride, (1-butyl-3-cyclohexylcyclopentadienyl) (pentamethylcyclopentadienyl) zirconium dichloride, (cyclohexylmethylenecyclopentane (Cyclopentadienyl) zirconium dichloride, (cycloheptylcyclopentadienyl) zirconium dichloride, (1-methyl-3-cycloheptylcyclopentadienyl) (pentamethylcyclopentane) Dienyl) zirconium (1-ethyl-3-cycloheptylcyclopentadienyl) (pentamethylcyclopentadienyl) zirconium dichloride, (1-butyl-3-cycloheptylcyclopentadienyl) (pentamethylcyclopentadienyl (Cyclopentadienyl) zirconium dichloride and (cyclohexylethylenecyclopentadienyl) (cyclopentadienyl) zirconium dichloride. The metallocene supported catalyst composition for olefin polymerization according to claim 1,
The method according to claim 1,
Wherein the inorganic or organic porous carrier is selected from silica, alumina, magnesium chloride, magnesium oxide, mineral clay, kaolin, talc, mica, montyrilonite, polysiloxane polymeric compounds and polystyrene, or mixtures thereof. ≪ / RTI >
A process for producing an olefin polymer using the metallocene supported catalyst composition for olefin polymerization according to any one of claims 1 to 9.
11. The method of claim 10,
Wherein the olefin polymer is a homopolymer or copolymer of an alpha olefin.
12. The method of claim 11,
The alpha olefins may be selected from the group consisting of ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, Methyl-1-butene, or mixtures thereof. ≪ Desc / Clms Page number 13 >
An olefin polymer produced using the metallocene supported catalyst composition for olefin polymerization according to any one of claims 1 to 9.