KR20170114056A - metallocene supported catalyst for polymerization of olefin, its preparation method and production method of a polyolefin using the same - Google Patents

Abstract

The present invention relates to a metallocene supported catalyst for olefin polymerization, a process for producing the metallocene supported catalyst, and a process for producing a polyolefin using the metallocene supported catalyst, wherein the metallocene supported catalyst for olefin polymerization of the present invention comprises a transition metal compound and a cocatalyst It is possible to easily produce various polyolefins having physical properties required to have high activity and stable apparent density when carrying out olefin polymerization.

Description

TECHNICAL FIELD The present invention relates to a metallocene supported catalyst for olefin polymerization, a process for producing the metallocene supported catalyst, and a process for producing a polyolefin using the metallocene supported catalyst,

The present invention relates to a metallocene supported catalyst for olefin polymerization, a process for producing the metallocene supported catalyst, and a process for producing a polyolefin using the same.

The Ziegler-Natta catalyst widely used in conventional commercial processes is characterized by a wide molecular weight distribution of the produced polymer due to a multi-site catalyst, and the composition distribution of the comonomer is not uniform, thus limiting the desired properties.

The metallocene catalysts developed to remedy these problems have a narrow molecular weight distribution of the polymer produced by a single active site catalyst having one kind of active site, and the molecular weight, stereoregularity, and crystallinity The reactivity of the comonomer can be greatly controlled.

Such a metallocene catalyst system is composed of a combination of a main catalyst mainly composed of a transition metal compound centered on a Group 4 metal and a cocatalyst comprising an organometallic compound mainly composed of a Group 13 metal such as aluminum. A polymer such as polyolefin having a narrow molecular weight distribution can be produced according to the single active site characteristic of the metallocene catalyst system.

The metallocene catalyst can not be used in the form of the organometallic compound itself as a homogeneous catalyst in gas phase, slurry or polymerization, and immobilization is indispensable. Carrierization is a disadvantage of the processes such as homogeneous metallocene catalyst slurry, agglomerate, fouling, sheeting, and plugging phenomenon of the produced polymer when the catalyst is added to the gas phase polymerization process And to prevent the reduction of the apparent density of the resulting polyolefin.

That is, studies have been made on the support of a metallocene catalyst in order to reduce the irregularity of the particle shape of the produced polyolefin polymer, suppress the decrease of the apparent density of the polyolefin, and solve the disadvantages of the process, and silica, alumina, A metallocene supported catalyst is prepared by supporting a metallocene alone or a metallocene and a cocatalyst on various porous inorganic substances or organic substances such as chloride and chloride, and applying the catalyst to a slurry or a gas phase polymerization process using the metallocene supported catalyst, and polymerizing the polyolefin .

For example, Korean Patent Laid-Open Publication No. 1999-0071655 discloses a method for synthesizing a metallocene supported catalyst by surface-treating silica using a boron-based organometallic compound instead of an aluminum organometallic compound and introducing metallocene thereto .

On the other hand, the molecular weight and the molecular weight distribution of polyolefin are important factors in determining the flow and mechanical properties affecting the processability of the polymer.

Particularly, in the case of polyethylene, quality, resistance and resistance to environmental stress are very important.

Therefore, there is still a need for a catalyst for olefin polymerization which can easily control the required molecular weight and molecular weight distribution, and can solve the above-mentioned problems of activity and process.

Korean Patent Publication No. 1999-0071655

Accordingly, the present invention provides a metallocene supported catalyst for olefin polymerization and a method for producing the metallocene supported catalyst, wherein the catalyst activity is increased during the olefin polymerization and the problems in the process are remarkably improved.

The present invention also provides a method for polymerizing a polyolefin using the supported metallocene catalyst for olefin polymerization of the present invention.

The present invention provides a metallocene supported catalyst for olefin polymerization capable of easily producing an olefin polymer having high catalytic activity and having desired physical properties, wherein the metallocene supported catalyst for olefin polymerization of the present invention has the following structural formula 1 and a cocatalyst supported on an inorganic or organic porous support surface-modified with a transition metal precursor represented by the following formula (2).

[Chemical Formula 1]

M ₁ (R) ₄

[In the above formula (1)

M ₁ is a Group 4 transition metal on the periodic table;

R is (C1-C20) alkoxy.]

(2)

Cp'L ¹ ML ² _n

[Formula 2]

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, (C6-C30) aryl group, (C1-C20) alkyl substituted or (C6-C30) aryl substituted silyl group, Substituted or (C6-C20) aryl-substituted siloxy group, (C1-C20) alkyl-substituted or (C6-C30) aryl-substituted phosphine group;

n is an integer of 1 or 2;

Wherein Cp 'and L ¹ are not connected to each other or may be connected to silicon or (C 1 -C 4) alkenylene, and the fused Cp' and L ¹ include cyclopentadienyl rings or cyclopentadienyl rings of Cp ' The ring may further be substituted with a (C1-C20) alkyl group, a (C6-C30) aryl group, a (C2-C20) alkenyl group or a (C6-

Preferably, M ₁ in Formula 1 according to an embodiment of the present invention may be Ti, Zr, or Hf.

Specifically, the transition metal precursor represented by Formula 1 according to an embodiment of the present invention may be one selected from the group consisting of titanium tetrabutoxide (Ti (OCH ₂ CH ₂ CH ₂ CH ₄ ) ₄ ), titanium tetraisopropoxide tetraisopropoxide, Ti [OCH (CH ₃ ) ₂ ] ₄ ) or titanium (IV) tetraethoxide.

The transition metal precursor according to an embodiment of the present invention may be used in an amount of 10 to 30 parts by weight based on 100 parts by weight of the inorganic or organic porous carrier.

Preferably, the inorganic or organic porous carrier according to an embodiment of the present invention is any one selected from the group consisting of silica, alumina, magnesium chloride, magnesium oxide, mineral clay, kaolin, talc, mica, montyrilonite, polysiloxane- Or two or more.

Preferably, in the transition metal compound represented by Formula 2 according to an embodiment of the present invention, M is Ti, Zr, or Hf;

The above Cp 'is at least one selected from the group consisting of cyclopentadienyl, methylcyclopentadienyl, dimethylcyclopentadienyl, tetramethylcyclopentadienyl, pentamethylcyclopentadienyl, butylcyclopentadienyl, sec -butylcyclopentadienyl, tert -Butylmethylcyclopentadienyl, trimethylsilylcyclopentadienyl, indenyl, methylindenyl, ethylindenyl, isopropylindenyl, fluorenyl, methylfuranyl, dimethylflorenyl, ethylflorenyl, And may be specifically represented by the following formula (3).

(3)

(3)

X ¹ and X ² are each independently selected from the group consisting of a halogen atom, (C 1 -C 20) alkyl group, (C 6 -C 30) aryl (C 1 -C 20) alkyl group, (C 3 -C 20) cycloalkyl group, Substituted or unsubstituted C6-C30 aryloxy group, (C6-C30) aryl group, (C1-C20) alkyl substituted or (C6- (C1-C20) alkyl substituted or (C6-C20) aryl substituted siloxy group, (C1-C20) alkyl substituted or (C6-C30) aryl substituted phosphine group;

R ¹ and R ² are independently of each other a (C1-C20) alkyl group, (C6-C30) aryl group, (C2-C20) alkenyl group or (C6-C30) aryl (C1-C20) alkyl group;

a and b are independently 0 or an integer of 1 to 5, and when a and b are 2 or more, R ¹ and R ² may be the same or different.

Preferably, the cocatalyst according to an embodiment of the present invention may be an alkylaluminoxane cocatalyst, an organoaluminum cocatalyst or a boron compound cocatalyst, or a mixture thereof. More preferably, the alkylaluminoxane cocatalyst is methylaluminoxane, Ethyl aluminoxane, propyl aluminoxane, butyl aluminoxane and isobutyl aluminoxane, and the organic alkyl aluminum cocatalyst may be one or two or more selected from trimethyl aluminum, triethyl aluminum and diisobutyl aluminum chloride, And the boron compound co-catalyst is selected from tris (pentafluorophenyl) borane, N, N-dimethylanilium tetrakispentafluorophenyl borate, and triphenylmethylninium tetrapentafixifluoroborate One or two or more.

The ratio of the transition metal compound of Formula 2 to the alkylaluminoxane co-catalyst according to one embodiment of the present invention may be 1: 0.01 to 1: 1000, based on the molar ratio of transition metal: aluminum.

The present invention also provides a process for preparing a metallocene supported catalyst for olefin polymerization, which comprises the steps of: a) preparing a metallocene supported catalyst for olefin polymerization, comprising the steps of: a) Preparing an inorganic or organic porous carrier; b) adding a cocatalyst to the surface-modified inorganic or organic porous carrier to prepare a surface-modified inorganic or organic porous carrier carrying the cocatalyst; And c) preparing a supported catalyst by adding a Group 4 transition metal compound represented by the following formula (2) to the surface-modified mucilage or organic porous carrier carrying the cocatalyst of step b).

The present invention also provides a process for producing a polyolefin using the supported metallocene catalyst for olefin polymerization according to the present invention.

The process for producing a polyolefin of the present invention uses a metallocene supported catalyst for olefin polymerization of the present invention having high activity and high selectivity to solve the problems of process such as fouling, sheeting, plugging and the like The polyolefin can be efficiently produced with high catalytic activity while being improved.

Preferably, the polyolefin according to one embodiment of the present invention may be a homopolymer or a copolymer of an alpha olefin, and more specifically, the alpha olefin may be ethylene, propylene, 1-butene, 1-pentene, -Decene, 1-dodecene, 4-methyl-1-pentene, 3-methyl-1-pentene and 3-methyl-1-butene.

The metallocene supported catalyst for olefin polymerization, in which the transition metal compound and the promoter are supported on an inorganic or organic porous support surface-modified with the transition metal precursor of the present invention, maintains a high catalytic activity during olefin polymerization to maintain the apparent density stably The polyolefin can be obtained in high yield.

The metallocene supported catalyst for olefin polymerization of the present invention has high activity and high selectivity in the polymerization of olefins, so that a polyolefin having physical properties required for various applications can be easily produced.

Therefore, the process for producing a polyolefin of the present invention is very efficient and economical to easily produce a polyolefin having various physical properties by an improved process by using the metallocene supported catalyst for olefin polymerization of the present invention having high activity and high selectivity .

The present invention provides a metallocene supported catalyst for olefin polymerization having high activity, wherein the metallocene supported catalyst for olefin polymerization of the present invention comprises an inorganic or organic porous carrier surface-modified with a transition metal precursor represented by the following formula And a cocatalyst supported on the transition metal compound represented by the following formula (2).

[Chemical Formula 1]

M ₁ (R) ₄

(In the formula 1,

M ₁ is a Group 4 transition metal on the periodic table;

R is (C1-C20) alkoxy.)

(2)

Cp'L ¹ ML ² _n

(2)

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, (C6-C30) aryl group, (C1-C20) alkyl substituted or (C6-C30) aryl substituted silyl group, Substituted or (C6-C20) aryl-substituted siloxy group, (C1-C20) alkyl-substituted or (C6-C30) aryl-substituted phosphine group;

n is an integer of 1 or 2;

Wherein Cp 'and L ¹ are not connected to each other or may be connected to silicon or (C 1 -C 4) alkenylene, and the fused Cp' and L ¹ include cyclopentadienyl rings or cyclopentadienyl rings of Cp ' The ring may be further substituted with a (C1-C20) alkyl group, a (C6-C30) aryl group, a (C2-C20) alkenyl group or a (C6-C30) aryl (C1-

The metallocene supported catalyst for olefin polymerization of the present invention has high activity and can easily produce a polyolefin. By using a metallocene supported catalyst, disadvantages such as fouling, sheeting, and tube clogging can be improved .

That is, the metallocene supported catalyst for olefin polymerization according to the present invention is an inorganic or organic porous support having a hydroxy group on the pore surface and having been surface-modified with a transition metal precursor represented by the above formula (1) The polyolefin can be easily produced at a high yield because it has a high activity compared to the conventional supported catalyst in olefin polymerization using the transition metal compound represented by Formula 2 and the cocatalyst supported thereon.

Further, the metallocene supported catalyst for olefin polymerization of the present invention has excellent catalytic activity during olefin polymerization and has an excellent apparent density of polyolefin, and thus can be easily applied to a slurry or a gas phase process to obtain a desired polyolefin .

In the formula 1 according to an embodiment of the present invention, M ₁ may be any of the Group 4 transition metals, preferably Ti, Zr, or Hf, and more preferably Ti or Zr Specifically, titanium tetrabutoxide (Ti (OCH ₂ CH ₂ CH ₂ CH ₄ ) ₄ ), titanium tetraisopropoxide (Ti [OCH (CH ₃ ) ₂ ] _4, or titanium tetra Titanium (IV) tetraethoxide), and may preferably be titanium tetrabutoxide or titanium tetraisopropoxide.

The transition metal precursor represented by Formula 1 according to an embodiment of the present invention may be used in an amount of 10 to 30 parts by weight based on 100 parts by weight of the inorganic or organic porous support and may be used in an amount of 15 to 25 parts by weight , So that the total weight of the surface-modified inorganic or organic porous carrier may include 2 to 3% by weight, preferably 1.5 to 2.5% by weight of transition metal.

The inorganic or organic porous support according to an embodiment of the present invention may have inorganic or organic pores, and they must have pores and surface area capable of supporting a transition metal precursor, a transition metal compound, and a cocatalyst. The surfaces of these carriers may have functional groups having hydrophobic properties, or they may be surface-treated with various silane compounds, aluminum compounds or halogen compounds. The inorganic porous carrier may be any carrier that is conventionally used to support a transition metal compound such as silica, alumina, magnesium chloride, or magnesium oxide, and may be a mesoporous material, such as MCM-41, MCM-48, SBA-15 , Preferably 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, and montmorillonite may also be used as porous inorganic supports. As the porous organic carrier, a polysiloxane-based polymer compound, polystyrene gel, beads, or the like can be used. Such a carrier may be used in its original state or may be heat-treated at a temperature within a range from 100 to 1000 ^° C. to control the amount of a hydrophobic functional group or the like in the pore surface of the carrier.

The transition metal compound represented by Formula 2 according to an embodiment of the present invention is preferably M, Ti, Zr, or Hf in Formula 2;

The above Cp 'is at least one selected from the group consisting of cyclopentadienyl, methylcyclopentadienyl, dimethylcyclopentadienyl, tetramethylcyclopentadienyl, pentamethylcyclopentadienyl, butylcyclopentadienyl, sec -butylcyclopentadienyl, tert -Butylmethylcyclopentadienyl, trimethylsilylcyclopentadienyl, indenyl, methylindenyl, ethylindenyl, isopropylindenyl, fluorenyl, methylfuranyl, dimethylflorenyl, ethylflorenyl, Neal, and specifically

M is Ti, Zr or Hf;

Cp 'is a cyclopentadiene capable of η ⁵ -binding with the central metal;

L ¹ is cyclopentadiene;

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, (C6-C30) aryl group, (C1-C20) alkyl substituted or (C6-C30) aryl substituted silyl group, Substituted or (C6-C20) aryl-substituted siloxy group, (C1-C20) alkyl-substituted or (C6-C30) aryl-substituted phosphine group;

n is an integer of 1 or 2;

The Cp 'and L ¹ are not connected to each other, wherein Cp' is and the fused ring containing a cyclopentadienyl ring or the cyclopentadienyl ring of L ¹ (C1-C20) alkyl, (C6-C30) aryl (C2-C20) alkenyl group or (C6-C30) aryl (C1-C20) alkyl group.

Preferably, Formula 2 according to an embodiment of the present invention may be represented by Formula 3 below.

(3)

(3)

X ¹ and X ² are each independently selected from the group consisting of a halogen atom, (C 1 -C 20) alkyl group, (C 6 -C 30) aryl (C 1 -C 20) alkyl group, (C 3 -C 20) cycloalkyl group, Substituted or unsubstituted C6-C30 aryloxy group, (C6-C30) aryl group, (C1-C20) alkyl substituted or (C6- (C1-C20) alkyl substituted or (C6-C20) aryl substituted siloxy group, (C1-C20) alkyl substituted or (C6-C30) aryl substituted phosphine group;

R ¹ and R ² are independently of each other a (C1-C20) alkyl group, (C6-C30) aryl group, (C2-C20) alkenyl group or (C6-C30) aryl (C1-C20) alkyl group;

a and b are independently 0 or an integer of 1 to 5, and when a and b are 2 or more, R ¹¹ and R ¹² may be the same or different.

The transition metal compound of Formula 2 according to an embodiment of the present invention may be selected from the following, but is not limited thereto.

 Zirconium dichloride, bis (cyclopentadienyl) zirconium dichloride, bis (methylcyclopentadienyl) zirconium dichloride, bis (normal butylcyclopentadienyl) zirconium dichloride, bis (cyclopentylcyclopentadienyl) zirconium dichloride, bis (Cyclohexylated chloropentadienyl) zirconium dichloride, bis (1,3-dimethylcyclopentadienyl) zirconium dichloride,

Zirconium dichloride, bis (indenyl) zirconium dichloride, bis (fluorenyl) zirconium dichloride, bis (isobutylcyclopentadienyl) zirconium dichloride, bis 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- (Cyclopentadienyl) zirconium dichloride, diphenylsilyl (cyclopentadienyl) (fluorenyl) zirconium dichloride, (cyclopentylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride , (1-methyl-3-cyclopentylcyclopentadienyl) zirconium dichloride, (1-ethyl-3-cyclopentylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride, (Cyclopentadienyl) zirconium dichloride, (cyclopentylcyclopentadienyl) (cyclomethylcyclopentadienyl) zirconium dichloride, (1-methyl-3-cyclopentadienyl) (Pentamethylcyclopentadienyl) zirconium dichloride, (1-ethyl-3-cyclopentylcyclopentadienyl) (pentamethylcyclopentadienyl) zirconium dichloride, (1-butyl- (Cyclopentylcyclopentadienyl) zirconium dichloride, (cyclohexylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride, (1-methyl-3-cyclohexenylcyclopentadienyl) Pentadienyl) (pentamethylcyclopentadiene < RTI ID = 0.0 > Zirconium dichloride, (1-ethyl-3-cyclohexenylcyclopentadienyl) (pentamethylcyclopentadienyl) zirconium dichloride, (1-butyl-3-cyclohexylcyclopentadienyl) Zirconium dichloride, (cyclopentadienyl) zirconium dichloride, (cyclohexylmethylcyclopentadienyl) zirconium dichloride, (cycloheptylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride, (Pentamethylcyclopentadienyl) zirconium dichloride, (1-ethyl-3-cycloheptylcyclopentadienyl) (pentamethylcyclopentadienyl) zirconium dichloride, (1-butyl-3-cycloheptylcyclopentadienyl) (pentamethylcyclopentadienyl) zirconium dichloride, (cyclohexylethylenecyclopentadienyl) (cyclopentadienyl) zirconium dichloride

The substituents comprising the "alkyl", "alkoxy" and other "alkyl" moieties described in the present invention include both straight-chain or branched forms and include 1 to 20 carbon atoms, preferably 1 to 10, more preferably 1 Lt; / RTI > to 7 carbon atoms.

The term " aryl " in the present invention means an organic radical derived from an aromatic hydrocarbon by the removal of one hydrogen, and may be a single or fused ring containing 4 to 7, preferably 5 or 6 ring atoms, A ring system, and a form in which a plurality of aryls are connected by a single bond. Specific examples include, but are not limited to, phenyl, naphthyl, biphenyl, anthryl, indenyl, fluorenyl, and the like.

The term " alkenyl ", alone or as part of another group described herein, means a straight, branched or cyclic hydrocarbon radical containing from 2 to 20 carbon atoms and at least one carbon to carbon double bond. More preferred alkenyl radicals are lower alkenyl radicals having 2 to about 10 carbon atoms. The most preferred lower alkenyl radical is a radical having from 2 to about 7 carbon atoms. The alkenyl group may also be substituted at any available point of attachment. Examples of alkenyl radicals include ethenyl, propenyl, allyl, propenyl, butenyl, and 4-methylbutenyl. The terms alkenyl and lower alkenyl include cis and trans orientation, or alternatively, radicals having an E and Z orientation.

&Quot; Cycloalkyl ", as used herein, refers to a non-aromatic monocyclic or multicyclic ring system having from 3 to 20 carbon atoms, including, but not limited to cyclopropyl, cyclobutyl , Cyclopentyl, and cyclohexyl. Examples of polycyclic cycloalkyl groups include perhydronaphthyl, perhydroindenyl, and the like; Branched polycyclic cycloalkyl groups include adamantyl and norbornyl and the like.

The transition metal compound according to an embodiment of the present invention may be used in an amount of 1 to 10 parts by weight, preferably 1 to 7 parts by weight, based on 100 parts by weight of the surface-modified inorganic or organic porous support.

The cocatalyst to be supported on the surface-modified inorganic or organic porous carrier according to an embodiment of the present invention may be one or a mixture of two or more selected from an alkylaluminoxane cocatalyst, an organoalkyl aluminum cocatalyst and a boron compound cocatalyst.

The alkylaluminoxane according to one embodiment of the present invention may be mainly alkylaluminoxane represented by the following formula (4).

[Chemical Formula 4]

(-Al (R ⁴ ) -O-) _m

(Wherein R ⁴ is a (C 1 -C 20) alkyl group, and m is an integer of 5 or more.)

In formula (4), R ⁴ may preferably be a methyl group or an isobutyl group, and specific examples thereof include methyl aluminoxane, ethyl aluminoxane, propyl aluminoxane, butyl aluminoxane, and isobutyl aluminoxane.

The organic alkyl aluminum promoter may be represented by the formula (5).

[Chemical Formula 5]

_{^{(R 5) r Al (E}} ) 3 -r

(Wherein R ⁵ is a (C 1 -C 8) alkyl group, E is a hydrogen atom or a halogen atom, and r is an integer of 1 to 3.)

Specific examples of the organic alkyl aluminum co-catalyst according to an embodiment of the present invention include trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, tributylaluminum, triisobutylaluminum, triisorenylaluminum and the like. Dialkylaluminum chloride including dialkyl aluminum chloride, dimethyl aluminum chloride, diethyl aluminum chloride, dipropyl aluminum chloride, diisobutyl aluminum chloride, dihexyl aluminum chloride, methyl aluminum dichloride, ethyl aluminum dichloride, propyl aluminum Chloride, isobutylaluminum chloride, and the like, preferably trialkylaluminum chloride or triisobutylaluminium chloride.

The boron compound cocatalyst according to an embodiment of the present invention may be selected from the compounds represented by the following formulas (6) to (8).

[Chemical Formula 6]

B (R < ⁶ >) ₃

(7)

[R ⁷ ] ⁺ [B (R ⁶ ) ₄ ] ^-

[Chemical Formula 8]

[(R ⁸ ) _q ZH] ⁺ [B (R ⁶ ) ₄ ] ^-

(6) to (8), B is a boron atom, R ⁶ is a phenyl group or a (C1-C4) alkyl group optionally substituted with a fluorine atom or a fluorine atom, R ⁷ is a cyclic (C 5 -C ⁷ ) aromatic cation or an alkyl substituted cation such as triphenylmethyl cation, Z is nitrogen or phosphorous, R ⁸ is a (C 1 -C 4) alkyl radical Or an anilinium radical substituted with two (C1-C4) 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 (3,5-bistrifluoromethylphenyl) borate, tetrakis (2,2,4-trifluorophenyl) borate, phenylbis (pentafluorophenyl) borate or tetrakis Lt; / RTI >

The cocatalyst according to an embodiment of the present invention may be used in an amount of 500 to 700 parts by weight based on 100 parts by weight of the surface-modified inorganic or organic porous carrier, and therefore, the cocatalyst may be used in an amount of 8 to 30 wt% based on the total weight of the metallocene supported catalyst for olefin polymerization %, Preferably 20 to 25% by weight.

The ratio of the transition metal compound of Formula 2 to the alkylaluminoxane co-catalyst or the alkyl organoaluminum co-catalyst according to one embodiment of the present invention may be from 1: 0.01 to 1: 1000 based on the molar ratio of the transition metal: aluminum Lt; RTI ID = 0.0 > 1: 1 < / RTI >

In the case of the boron compound promoter, the ratio of the transition metal compound of Formula 2 to the co-catalyst of the boron compound may be 1: 0.01 to 1: 100, preferably 1: 0.1 to 1:20 in terms of the molar ratio of transition metal: Lt; / RTI >

When the boron compound promoter and the promoter containing aluminum are used together as the promoter, the molar ratio of the boron compound promoter to the promoter containing aluminum is suitably 1: 0.1 to 1: 100 on the basis of boron: aluminum, and 1: To 1:20.

The present invention also provides a process for preparing a metallocene supported catalyst for olefin polymerization according to the present invention, which comprises the steps of: a) reacting a transition metal precursor Preparing an inorganic or organic porous carrier surface-modified with an inorganic or organic carrier; b) adding a cocatalyst to the surface-modified inorganic or organic porous carrier to prepare a surface-modified mucilage or organic porous carrier carrying the cocatalyst; And c) preparing a supported catalyst by adding a Group 4 transition metal compound represented by Formula 2 to a surface-modified inorganic or organic porous carrier carrying a cocatalyst.

The method for producing the metallocene supported catalyst for olefin polymerization of the present invention will be described in detail by way of example, but is not limited thereto.

In the method for producing metallocene supported catalyst for olefin polymerization according to the present invention, the inorganic or organic porous support surface-modified with the precursor of step a) is added to a solution in which an inorganic or organic porous support is dehydrated and dried under vacuum, The surface-modified inorganic or organic porous carrier can be prepared.

The produced surface-modified inorganic or organic porous carrier can be produced by carrying out calcination and then carrying a transition metal and a cocatalyst represented by the above formula (2) in an aliphatic or aromatic hydrocarbon solvent.

First, the surface-modified inorganic or organic porous carrier may be dispersed in an aliphatic or aromatic hydrocarbon solvent to obtain a slurry, followed by supporting the co-catalyst, and then the transition metal compound may be supported.

At this time, the residual co-catalyst remaining after being not supported can be removed by using a solvent, and then a transition metal compound can be added and carried.

The present invention also provides a process for producing a polyolefin using the supported metallocene catalyst for olefin polymerization of the present invention.

The polyolefin according to one embodiment of the present invention may be a homopolymer or copolymer of an alpha olefin.

Examples of possible olefinic monomers that can be employed in the process for producing a polyolefin according to an embodiment of the present invention include ethylene, alpha olefins, cycloolefins, etc. Diene monomers, triene, styrene and cyclic olefins are also possible .

Examples of specific monomers include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, Butene, styrene, para-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.

The metallocene-supported catalyst for olefin polymerization of the present invention can be used for polymerization of one olefin monomer or two or more of these monomers, and the olefin monomer is polymerized in a slurry or gas phase of an organic solvent such as hexane do. The metallocene supported catalyst for olefin polymerization 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, octane, and the like.

The metallocene supported catalyst for olefin polymerization of the present invention can be applied not only to gas phase, slurry, and liquid phase polymerization processes but also to both batch type and continuous type polymerization processes, but is more preferable for slurry and gas phase reaction.

As an example of the olefin polymerization method using the metallocene supported catalyst for olefin polymerization of the present invention, a batch slurry polymerization process will be described as follows.

First, at high temperature, the high-pressure reactor is vacuumed to remove water and air and then replaced with ethylene to make the inside of the reactor to be an ethylene environment. Then, a solvent is introduced into the reactor, and an organic alkyl aluminum promoter as a scavenger or an alkyl Aluminoxane co-catalyst is added. After the temperature is raised to the polymerization temperature, the metallocene supported catalyst for olefin polymerization of the present invention is added. 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 a polymer which is passed through a tube filled with molecular sieve 5A and activated alumina and bubbled with high purity nitrogen to remove moisture, oxygen and other catalyst poisons. The polymerization temperature is -50 to 200 ^{° C} C, and 50 to 100 ^o C are suitable. Polymerization pressure can be from 1 to 50 atm, preferably from 5 to 30 atm.

Hereinafter, the present invention will be described with reference to specific examples and comparative examples, but the following examples do not limit the claims of the present invention.

The metallocene supported catalyst for olefin polymerization according to the present invention and the polyolefin prepared using the supported metallocene catalyst were carried out as follows.

1) the metal content in the supported catalyst

The metal content was measured by ICP analysis.

2) 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 ^o 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]

Surface modified Carrier  Produce

Silica (XPO-2402, manufactured by Grace Davison) was dehydrated and dried at 100 占 폚 under 1 atm for 4 hours. 50 g of Toluene was added to 5 g of the dried silica, and the mixture was stirred at room temperature for 30 minutes. 0.9 g of titanium tetraisopropoxide (Ti (i-PrO) ₄ ) was slowly added thereto at -20 ° C. After completion of the addition, the mixture was stirred at room temperature for 1 hour. After the completion of the reaction, the unreacted titanium compound was washed with hexane (twice with 60 g each). After washing, the reaction mixture was removed under reduced pressure, and silica modified with titanium tetraisopropoxide was obtained. The silica was calcined at 400 ° C for 4 hours under a nitrogen atmosphere to finally obtain 5.7 g of surface-modified silica.

For olefin polymerization Metallocene Of the supported catalyst  Produce

5 g of the surface-modified silica prepared above was added to a 250 ml flask, and 50 g of toluene was stirred as a solvent at room temperature for 30 minutes. While stirring, 35 g of 10 wt% methylaluminoxane (MAO) was added slowly over 30 minutes. Methylaluminoxane was added thereto, followed by stirring at 110 DEG C for 2 hours. And washed twice with 60 g of toluene to remove unreacted aluminum compounds. After washing, 50 g of toluene was added thereto again, and the mixture was stirred at room temperature for 30 minutes. 0.2 g of the following transition metal compound (A1, Bis (1-butyl-3-methylcyclopentadienyl) zirconium dichloride) was dissolved in 20 mL of toluene and slowly added thereto, followed by stirring at 70 DEG C for 2 hours. After the reaction was completed, the unreacted transition metal compound was washed with toluene (2 x 60 g portions). And then washed twice with the same amount of hexane as the toluene again. After the solvent was removed from the reaction mixture under reduced pressure, a supported metallocene catalyst for olefin polymerization was prepared. The Zr content of the prepared metallocene supported catalyst for olefin polymerization was measured in terms of the amount of the catalyst added to the supported catalyst to show that all of the transition metal compounds were supported thereon. For more accurate analysis, the toluene solution was collected and the ICP analysis was performed. As a result, Al was detected in several ppm and Zr was not detected. It can be clearly seen that all of the transition metal compounds were supported thereon.

[Transition metal compound, A1]

Metallocene The supported catalyst  Ethylene polymerization using

The 2L high pressure reactor was vacuum purged for 30 minutes. After 30 minutes, vacuum / ethylene substitution was carried out five times to make the inside of the reactor an ethylene environment. Purified hexane (Molecular Sieve < RTI ID = 0.0 > 4A, 13X column), and 3 mL of triethyl aluminum (TEAL, 1M hexane solution) for water removal was injected. The mixture was stirred at 200 rpm and the reactor was heated to 70 캜. Then, 30 mg of the metallocene supported catalyst for olefin polymerization prepared above was charged through a sample vessel connected to the reactor. After the temperature of the reactor was raised to 80 ° C, ethylene was fed into the reactor at a constant temperature, and the internal pressure was kept constant at 22 rpm (400 rpm). After one hour, residual ethylene was discharged to terminate the polymerization. The remaining suspension was filtered and dried to obtain 110 g (BD 0.39 g / ml 3) of a polyethylene powder. No deposits or agglomerates were found in the reactor walls and inside, and the activity and apparent density of the catalysts are shown in Table 1 below.

[Comparative Example 1]

In the same manner as in Example 1 except that silica (XPO-2402 manufactured by Grace Davison) was dehydrated and dried at 100 ° C under 1 atmospheric pressure for 4 hours instead of the silica surface-modified with titanium tetraisopropoxide in Example 1 To obtain 110 g of a polyethylene powder. Adhesion or agglomerates were found somewhat in the reactor wall and inside, and the activity and bulk density of the catalyst at the time of polymerization are shown in Table 1 below.

Supported catalyst Activity of the catalyst
(g-PE / g-cat) Bulk density
(g / ml) Comparative Example 1
(SiO2 / MAO / A1) 2800 0.37 Example
(SiO2-Ti / MAO / A1) 3700 0.39

* Polymerization conditions: Hexane 1 L / TEAL 3 ml / Catalyst 30 mg / Ethylene 22 bar

As shown in Table 1, the metallocene supported catalyst for olefin polymerization according to Example 1 of the present invention, which was prepared using a carrier surface-modified with a transition metal precursor, was a supported catalyst prepared by using a carrier not surface- The olefin polymer can be produced in a high yield with a very high catalytic activity as compared with Comparative Example 1 using the catalyst.

Claims (14)

A metallocene supported catalyst for olefin polymerization comprising an inorganic or organic porous support surface-modified with a transition metal precursor represented by the following general formula (1), and a cobalt-containing transition metal compound represented by the following general formula (2)
[Chemical Formula 1]
M ₁ (R) ₄
[In the above formula (1)
M ₁ is a Group 4 transition metal on the periodic table;
R is (C1-C20) alkoxy.]
(2)
Cp'L ¹ ML ² _n
[Formula 2]
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, (C6-C30) aryl group, (C1-C20) alkyl substituted or (C6-C30) aryl substituted silyl group, Substituted or (C6-C20) aryl-substituted siloxy group, (C1-C20) alkyl-substituted or (C6-C30) aryl-substituted phosphine group;
n is an integer of 1 or 2;
The Cp 'and the L ¹ may not be connected to each other or may be connected to silicon or (C 1 -C 4) alkenylene, and the fused Cp' and L ¹ groups may include a cyclopentadienyl ring or a cyclopentadienyl ring, The ring may further be substituted with a (C1-C20) alkyl group, a (C6-C30) aryl group, a (C2-C20) alkenyl group or a (C6- The method according to claim 1,
The metallocene supported catalyst for olefin polymerization according to claim 1, wherein M ₁ is Ti, Zr or Hf. 3. The method of claim 2,
The transition metal precursor is titanium tetrabutoxide _{(titanium tetrabutoxide, Ti (OCH 2} CH 2 CH 2 CH 3) 4), titanium tetraisopropoxide (titanium tetraisopropoxide, Ti [OCH ( CH 3) 2] 4) , or titanium Supported on a metallocene catalyst for the polymerization of olefins such as titanium (IV) tetraethoxide. The method according to claim 1,
Wherein the transition metal precursor is used in an amount of 10 to 30 parts by weight based on 100 parts by weight of the inorganic or organic porous carrier. The method according to claim 1,
Wherein the inorganic or organic porous carrier is at least one selected from the group consisting of silica, alumina, magnesium chloride, magnesium oxide, mineral clay, kaolin, talc, mica, montyrilonite, polysiloxane- Supported catalyst. The method according to claim 1,
In Formula 2, M is Ti, Zr or Hf;
The above Cp 'is at least one selected from the group consisting of cyclopentadienyl, methylcyclopentadienyl, dimethylcyclopentadienyl, tetramethylcyclopentadienyl, pentamethylcyclopentadienyl, butylcyclopentadienyl, sec -butylcyclopentadienyl, tert -Butylmethylcyclopentadienyl, trimethylsilylcyclopentadienyl, indenyl, methylindenyl, ethylindenyl, isopropylindenyl, fluorenyl, methylfuranyl, dimethylflorenyl, ethylflorenyl, Supported Metallocene Catalyst for Polymerization of. The method according to claim 6,
Wherein the metallocene supported catalyst for olefin polymerization is represented by the following general formula (3).
(3)

(3)
X ¹ and X ² are each independently selected from the group consisting of a halogen atom, (C 1 -C 20) alkyl group, (C 6 -C 30) aryl (C 1 -C 20) alkyl group, (C 3 -C 20) cycloalkyl group, Substituted or unsubstituted C6-C30 aryloxy group, (C6-C30) aryl group, (C1-C20) alkyl substituted or (C6- (C1-C20) alkyl substituted or (C6-C20) aryl substituted siloxy group, (C1-C20) alkyl substituted or (C6-C30) aryl substituted phosphine group;
R ¹ and R ² are independently of each other a (C1-C20) alkyl group, (C6-C30) aryl group, (C2-C20) alkenyl group or (C6-C30) aryl (C1-C20) alkyl group;
a and b are independently 0 or an integer of 1 to 5, and when a and b are 2 or more, R ¹¹ and R ¹² may be the same or different. The method according to claim 1,
Wherein the promoter is a metallocene supported catalyst for olefin polymerization, wherein the promoter is an alkylaluminoxane promoter, an organoalkyl aluminum promoter, a boron compound promoter, or a mixture thereof. 9. The method of claim 8,
Wherein the alkylaluminoxane promoter is one or two or more selected from methyl aluminoxane, ethyl aluminoxane, propyl aluminoxane, butyl aluminoxane and isobutyl aluminoxane;
Wherein the organic alkyl aluminum co-catalyst is one or two or more selected from trimethylaluminum, triethylaluminum and diisobutylaluminum chloride;
Wherein the boron compound promoter is one or two selected from tris (pentafluorophenyl) borane, N, N-dimethylanilinium tetrakispentafluorophenyl borate, and triphenylmethylninium tetrapentafisulfuroborate Supported metallocene catalyst composition for olefin polymerization. 9. The method of claim 8,
Wherein the ratio of the transition metal compound of Formula 2 to the aluminoxane co-catalyst is in the range of 1: 0.01 to 1: 1000 based on the molar ratio of transition metal: aluminum. a) preparing an inorganic or organic porous support surface-modified with a transition metal precursor represented by the following formula (1);
b) adding a cocatalyst to the surface-modified inorganic or organic porous carrier to prepare a surface-modified inorganic or organic porous carrier carrying the cocatalyst; And
c) preparing a supported catalyst by adding a Group 4 transition metal compound represented by the following formula (2) to a surface-modified inorganic or organic porous carrier carrying a cocatalyst to prepare a supported catalyst for olefin polymerization; Way.
[Chemical Formula 1]
M ₁ (R) ₄
[In the above formula (1)
M ₁ is a Group 4 transition metal on the periodic table;
R is (C1-C20) alkoxy.]
(2)
Cp'L ¹ ML ² _n
[Formula 2]
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, (C6-C30) aryl group, (C1-C20) alkyl substituted or (C6-C30) aryl substituted silyl group, Substituted or (C6-C20) aryl-substituted siloxy group, (C1-C20) alkyl-substituted or (C6-C30) aryl-substituted phosphine group;
n is an integer of 1 or 2;
Wherein Cp 'and L ¹ are not connected to each other or may be connected to silicon or (C 1 -C 4) alkenylene, and the fused Cp' and L ¹ include cyclopentadienyl rings or cyclopentadienyl rings of Cp ' The ring may further be substituted with a (C1-C20) alkyl group, a (C6-C30) aryl group, a (C2-C20) alkenyl group or a (C6- A process for producing a polyolefin using the metallocene supported catalyst for olefin polymerization according to any one of claims 1 to 10. 13. The method of claim 12,
Wherein the polyolefin is a homopolymer or copolymer of alpha olefins. 14. The method of claim 13,
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.