KR20210065312A - Catalyst for polyolefin polymerization and preparation method thereof - Google Patents

Abstract

The present invention is to provide a catalyst for polymerization of polyolefin having high activity and improved flowability by increasing the amount of a metallocene compound supported. According to the present invention, provided is the catalyst for polymerization of the polyolefin comprising two or more kinds of carriers having different average particle diameters, two or more kinds of metallocene compounds and an antistatic agent.

Description

Catalyst for polyolefin polymerization and method for preparing the same {CATALYST FOR POLYOLEFIN POLYMERIZATION AND PREPARATION METHOD THEREOF}

The present invention relates to a catalyst for polyolefin polymerization and a method for preparing the same.

In the case of a high-density polyethylene product, since a small amount of comonomer is added during polymerization, there is a problem of low productivity compared to a low-density polyethylene product. In order to solve this problem, a catalyst having a high activity has been required, and it is known that a catalyst having a high activity can be prepared by increasing the amount of an active material supported on a carrier.

There is a method of chemically modifying the carrier as a method for increasing the amount of the active material supported on the carrier, but in this case, the catalyst manufacturing process is complicated. Alternatively, a carrier having a small size may be used, but in this case, the flowability of the catalyst is reduced, thereby causing a fouling phenomenon during the reaction. From this point of view, if a carrier having a large size is used, the flow property is improved and the fouling phenomenon can be improved, but the amount of the active material that can be supported is reduced, so there is a limit in increasing the activity.

As another method, when the active material is input to the maximum in order to exhibit the maximum activity of the carrier, the active material is not fully supported on the carrier, thereby causing a fouling phenomenon in the reactor. In addition, since a heterogeneous catalyst and a homogeneous catalyst exist together, the characteristics of the polyolefin expressed by each catalyst may be different, and thus non-uniform polyolefin may be produced.

In particular, in the case of a metallocene co-supported catalyst supporting two or more metallocene compounds, if the active material is not fully supported on the carrier, the metallocene compound is supported differently in the finally synthesized catalyst, so molecular weight and molecular weight distribution There is a disadvantage in that it is difficult to control the mechanical properties because polyolefins having different polyolefins are prepared.

Korean Patent Publication No. 10-2014-0146994

It is an object of the present invention to provide a catalyst for polymerization of polyolefin having improved flowability as well as high activity by increasing the amount of metallocene compound supported.

Another object of the present invention is to provide a catalyst capable of producing a polyolefin having a constant molecular weight and molecular weight distribution under the same reaction conditions.

According to an embodiment of the present invention, two or more kinds of carriers having different average particle diameters; two or more metallocene compounds; and an antistatic agent, wherein the antistatic agent provides a catalyst for polyolefin polymerization comprising at least one functional group selected from the group consisting of an acid group, an ester group, an amine group, an amide group, a hydroxyl group, and an ether group.

According to another embodiment of the present invention, comprising the steps of supporting two or more types of metallocene compounds on two or more types of carriers having different average particle diameters, and reacting the carrier on which the metallocene compound is supported and an antistatic agent, Antistatic agent is an acid group, an ester group, an amine group, an amide group, a hydroxyl group, and a method for preparing a catalyst for polyolefin polymerization comprising at least one functional group selected from the group consisting of an ether group is provided.

According to the present invention, by supporting the metallocene compound on two or more types of carriers having different average particle diameters, the supported amount of the metallocene compound can be increased, and a catalyst for polyolefin polymerization with high activity and improved flowability can be prepared. can

In addition, according to the present invention, a catalyst with high reproducibility can be prepared by uniformly supporting a metallocene compound on a carrier under the same reaction conditions, and polyolefin having a constant molecular weight and molecular weight distribution can be prepared under the catalyst.

Hereinafter, preferred embodiments of the present invention will be described. However, the embodiment of the present invention may be modified in various other forms, and the scope of the present invention is not limited to the embodiments described below.

The present invention provides a catalyst for polymerization of polyolefin having excellent catalytic activity and flowability as well as excellent reproducibility, including two or more types of carriers having different average particle diameters, two or more types of metallocene compounds and an antistatic agent.

In one embodiment, the carrier serves as a support for supporting the metallocene compound. The carrier is a porous inorganic oxide, and may be a material obtained from a metal oxide containing a metal atom of Group 2, 3, 4, 5, 13 or 14, for example, silica, alumina, silica- It may be an alumina mixture, titanium oxide, zeolite, or the like. The most preferred carrier may be at least one selected from the group consisting of silica, alumina, and silica-alumina.

The carrier may have an average particle diameter of 10 to 200 μm, preferably 20 to 80 μm. If the average particle diameter is less than 10㎛, the flowability of the catalyst is lowered, which may cause a fouling phenomenon in the reactor. can decrease.

In addition, the carrier may have ^{a surface area of 100 to 700 m 2} /g, a total pore volume of 0.1 to 5.0 cc/g, and an average pore size of 50 to 500 Å, preferably a surface area ^{of 200 to 500 m 2 /g,} It may be a mixture of porous inorganic oxides having a total pore volume of 1.0 to 3.0 cc/g and an average pore size of 80 to 400 Å.

In one embodiment, the carrier having the largest average particle diameter among the carriers may be included in an amount of 50 to 90% by weight, and when the content of the carrier having the largest average particle diameter is less than 50% by weight, the flowability of the catalyst is reduced, and 90% by weight of the carrier is When it exceeds, the supported amount of the metallocene compound decreases, which is not preferable in terms of catalytic activity.

Also, in an embodiment, the average particle diameter ratio of the carrier having the smallest average particle diameter to the carrier having the largest average particle diameter among the carriers may be 1.5 to 3. Within the above range, the supported amount of the metallocene compound can be maximized, and a catalyst with improved flowability can be prepared.

In one embodiment, the metallocene compound is supported on a carrier to exhibit catalytic activity, and the metallocene compound is not particularly limited, but is at least two or more selected from the group consisting of compounds represented by the following Chemical Formula 1, or At least two or more selected from the group consisting of compounds represented by 2, or at least one or more selected from the group consisting of compounds represented by Formula 1 and at least one or more selected from the group consisting of compounds represented by Formula 2 Can be a combination and, preferably, may be a combination of at least one or more selected from the group consisting of compounds represented by Chemical Formula 1 and at least one selected from the group consisting of compounds represented by Chemical Formula 2.

In Formula 1 and Formula 2,

M ¹ and M ² are each independently selected from the group consisting of elements from groups 3 to 10 on the periodic table,

X ¹ and X ² are each independently a halogen group, an amine group, (C ₁ -C ₂₀ )alkyl group, (C ₃ -C ₂₀ )cycloalkyl group, (C ₁ -C ₂₀ )alkylsilyl group, silyl (C ₁ -C ₂₀ )alkyl group, (C ₆ -C ₂₀ )aryl group, (C ₆ -C ₂₀ )aryl (C ₁ -C ₂₀ )alkyl group, (C ₁ -C ₂₀ )alkyl (C ₆ -C ₂₀ )aryl group , (C ₆ -C ₂₀ )arylsilyl group, silyl (C ₆ -C ₂₀ )aryl group, (C ₁ -C ₂₀ )alkoxy group, (C ₁ -C ₂₀ )alkylsiloxy group and (C ₆ -C _{20 )} ) is selected from the group consisting of an aryloxy group,

Ar ¹ , Ar ² , Ar ³ and Ar ⁴ are the same as or different from each other, and are each independently a ligand having a cyclopentadienyl skeleton,

B is a component that does not directly coordinate with the transition metal M ^{2 and connects the ligands Ar 3} and Ar ⁴ , and is a group consisting of carbon (C), silicon (Si), germanium (Ge), nitrogen (N) and phosphorus (P). containing an element selected from

L is hydrogen, (C ₁ -C ₂₀ )alkyl group, (C ₃ -C ₂₀ )cycloalkyl group, (C ₁ -C ₂₀ )alkylsilyl group, silyl (C ₁ -C ₂₀ )alkyl group, (C ₆ -C _{20 )} ) aryl group, (C ₆ -C ₂₀ )aryl (C ₁ -C ₂₀ )alkyl group, (C ₁ -C ₂₀ )alkyl (C ₆ -C ₂₀ )aryl group, (C ₆ -C ₂₀ )arylsilyl group and Silyl (C ₆ -C ₂₀ ) It is selected from the group consisting of an aryl group,

n is an integer from 1 to 5,

m is an integer from 1 to 5,

p is 1 or 2.

As used herein, the term “alkyl” refers to a monovalent straight-chain or branched saturated hydrocarbon radical composed only of carbon and hydrogen atoms, and examples of such alkyl radicals include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t- butyl, pentyl, hexyl, octyl, dodecyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, and the like.

In addition, as used herein, the term "alkenyl" refers to a straight-chain or branched hydrocarbon radical containing one or more carbon-carbon double bonds, and includes ethenyl, propenyl, butenyl, pentenyl, and the like, However, the present invention is not limited thereto.

In addition, the term "alkynyl" as used in the present invention refers to a straight-chain or branched hydrocarbon radical containing at least one carbon-carbon triple bond, and methynyl, ethynyl, propynyl, butynyl, pentynyl, hexy nyl, heptynyl, octynyl, and the like.

In addition, the term "aryl" described in the present invention is an organic radical derived from an aromatic hydrocarbon by removal of one hydrogen, and includes a single or fused ring system. Specific examples include, but are not limited to, phenyl, naphthyl, biphenyl, anthryl, fluorenyl, phenanthryl, triphenylenyl, pyrenyl, peryleneyl, chrysenyl, naphthacenyl, fluoranthenyl, and the like.

In addition, the term "alkylaryl" as used in the present invention refers to an organic group in which one or more hydrogens of the aryl group are substituted with an alkyl group, methylphenyl, ethylphenyl, n-propylphenyl, iso-propylphenyl, n-butylphenyl, iso-butylphenyl, tert-butylphenyl, and the like.

In addition, the term "arylalkyl" described in the present invention refers to an organic group in which one or more hydrogens of the alkyl group are substituted by an aryl group, and includes, but is not limited to, phenylpropyl, phenylhexyl, and the like.

In addition, the term "amido" described in the present invention refers to an amino group (-NH ₂ ) bonded to a carbonyl group (C=O), and “alkylamido” is an alkyl group in which at least one hydrogen in _{-NH 2 of the amido group is} means an organic group substituted with, "arylamido" means an organic group _{in which at least one hydrogen is substituted with an aryl group in -NH 2} of the amido group, an alkyl group in the alkylamido group, and an aryl group in the arylamido group It may be the same as the examples of the above-described alkyl group and aryl group, but is not limited thereto.

In addition, the term "alkylidene" as used in the present invention refers to a divalent aliphatic hydrocarbon group in which two hydrogen atoms have been removed from the same carbon atom of the alkyl group, and ethylidene, propylidene, isopropylidene, butylidene, pentylidene and the like.

In addition, the term "acetal" described in the present invention refers to an organic group formed by the bond between alcohol and aldehyde, that is, a substituent having two ether (-OR) bonds on one carbon, methoxymethoxy, 1-meth ethoxy, 1-methoxypropyloxy, 1-methoxybutyloxy, 1-ethoxyethoxy, 1-ethoxypropyloxy, 1-ethoxybutyloxy, 1-(n-butoxy)ethoxy, 1-(iso-butoxy)ethoxy, 1-(sec-butoxy)ethoxy, 1-(tert-butoxy)ethoxy, 1-(cyclohexyloxy)ethoxy, 1-methoxy -1-methylmethoxy, 1-methoxy-1-methylethoxy, and the like.

In addition, the term "ether" described in the present invention is an organic group having at least one ether bond (-O-), 2-methoxyethyl, 2-ethoxyethyl, 2-butoxyethyl, 2-phenoxyethyl , 2- (2-methoxyethoxy) ethyl, 3-methoxypropyl, 3-butoxypropyl, 3-phenoxypropyl, 2-methoxy-1-methylethyl, 2-methoxy-2-methylethyl , 2-methoxyethyl, 2-ethoxyethyl, 2-butoxyethyl, 2-phenoxyethyl, and the like.

In addition, the term "silyl" described in the present invention refers to a -SiH ₃ radical derived from silane, and at least one of the hydrogen atoms in the silyl group may be substituted with various organic groups such as alkyl and halogen, and specifically as trimethylsilyl, triethylsilyl, t-butyldimethylsilyl, vinyldimethylsilyl, propyldimethylsilyl, triphenylsilyl, diphenylsilyl, phenylsilyl, trimethoxysilyl, methyldimeroxysilyl, ethyldiethoxysilyl, triethoxysilyl, vinyldimethoxysilyl, triphenoxysilyl, and the like.

In addition, as used herein, the term “alkoxy” refers to an —O-alkyl radical, where “alkyl” is as defined above. Examples of such alkoxy radicals include, but are not limited to, methoxy, ethoxy, isopropoxy, butoxy, isobutoxy, t-butoxy, and the like.

In addition, the term "halogen" as used herein means a fluorine, chlorine, bromine or iodine atom.

In addition, the term "C _n " described in the present invention means that the number of carbon atoms is n.

In one embodiment, specific examples of the compound represented by Formula 1 include bis(1-butyl-3-methylcyclopentadienyl)zirconium dichloride, bis(cyclopentadienyl)zirconium dichloride, bis(methylcyclopentadiene). nyl)zirconium dichloride, bis(ethylcyclopentadienyl)zirconium dichloride, bis(1,3-dimethylcyclopentadienyl)zirconium dichloride, bis(tetramethylcyclopentadienyl)zirconium dichloride, bis(iso propylcyclopentadienyl)zirconium dichloride, bis(pentamethylcyclopentadienyl)zirconium dichloride, bis(n-butylcyclopentadienyl)zirconium dichloride, bis(isobutylcyclopentadienyl)zirconium dichloride, Bis(t-butylcyclopentadienyl)zirconium dichloride, bis(indenyl)zirconium dichloride, bis(2-methylindenyl)zirconium dichloride, bis(4,5,6,7-tetrahydro-1- and indenyl)zirconium dichloride, bis(cyclopentadienyl)titanium dichloride, bis(cyclopentadienyl)hafnium dichloride, and bis(n-butylcyclopentadienyl)hafnium dichloride.

Specific examples of the compound represented by Formula 2 in one embodiment, rac-ethylenebis(1-indenyl)zirconium dichloride, rac-ethylenebis(1-indenyl)hafnium dichloride, rac-ethylenebis(1-indenyl) Tetrahydro-indenyl)zirconium dichloride, rac-ethylenebis(1-tetrahydro-indenyl)hafnium dichloride, rac-dimethylsilanediylbis(2-methyl-tetrahydrobenzindenyl)zirconium dichloride, rac -Dimethylsilanediylbis(2-methyl-tetrahydrobenzindenyl)hafnium dichloride, rac-diphenylsilanediylbis(2-methyl-tetrahydrobenzindenyl)zirconium dichloride, rac-diphenylsilanedi Ilbis(2-methyl-tetrahydrobenzindenyl)hafnium dichloride, rac-dimethylsilanediylbis(2-methyl-4,5-benzindenyl)zirconium dichloride, rac-dimethylsilanediylbis(2 -Methyl-4,5-benzindenyl) hafnium dichloride, rac-diphenylsilanediylbis(2-methyl-4,5-benzindenyl)zirconium dichloride, rac-diphenylsilanediylbis(2 -Methyl-4,5-benzindenyl)hafnium dichloride, rac-dimethylsilanediylbis(2-methyl-5,6-cyclopentadienylindenyl)zirconium dichloride, rac-dimethylsilanediylbis(2-methyl-5,6-cyclopentadienylindenyl) 2-methyl-5,6-cyclopentadienylindenyl)hafnium dichloride, rac-diphenylsilanediylbis(2-methyl-5,6-cyclopentadienylindenyl)zirconium dichloride, rac-di Phenylsilanediylbis(2-methyl-5,6-cyclopentadienylindenyl)hafnium dichloride, id, rac-dimethylsilylbis(2-methyl-4-phenylindenyl)zirconium dichloride, rac- Dimethylsilylbis(2-methyl-4-phenylindenyl)hafnium dichloride, rac-diphenylsilylbis(2-methyl-4-phenylindenyl)zirconium dichloride, rac-diphenylsilylbis(2-methyl- 4-phenylindenyl)hafnium dichloride, iso-propylidene (cyclopentadienyl) (9-fluorenyl) zirconium dichloride, iso-propylidene (cyclopentadienyl) (9-fluorenyl) hafnium di Chloride, diphenylmethylidene (cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylidene (cyclopentadienyl) (9-fluorenyl) hafnium Dichloride, iso-propylidene (3-methylcyclopentadienyl) (9-fluorenyl) zirconium dichloride, iso-propylidene (3-methylcyclopentadienyl) (9-fluorenyl) hafnium dichloride , Diphenylmethylidene (3-methylcyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylidene (3-methylcyclopentadienyl) (9-fluorenyl) hafnium dichloride, di Phenylsilyl (cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylsilyl (cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylidene (cyclopentadienyl) ( 2,7-di-tert-butylfluoren-9-yl)zirconium dichloride, diphenylmethylidene(cyclopentadienyl)(2,7-di-tert-butylfluoren-9-yl)hafnium dichloride , Diphenylmethylidene (3-tert-butylcyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl) zirconium dichloride, diphenylmethylidene (3-tert-butylcyclopentadie nyl) (2,7-di-tert-butylfluoren-9-yl) hafnium dichloride, diphenylmethylidene (3-tert-butyl-5-methylcyclopentadienyl) (2,7-di-tert) -Butylfluoren-9-yl)zirconium dichloride, diphenylmethylidene (3-tert-butyl-5-methylcyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl)hafnium Dichloride, 1,2-ethylenebis(9-fluorenyl)zirconium dichloride, 1,2-ethylenebis(9-fluorenyl)hafnium dichloride, rac-[1,2-bis(9-fluorenyl) nyl)-1-phenyl-ethane]zirconium dichloride, rac-[1,2-bis(9-fluorenyl)-1-phenyl-ethane]hafnium dichloride, [1-(9-fluorenyl)- 2-(5,6-Cyclopenta-2-methyl-1-indenyl)-ethane]zirconium dichloride, [1-(9-fluorenyl)-2-(5,6-cyclopenta-2-methyl) -1-indenyl)-ethane]hafnium dichloride, [4-(fluorenyl)-4,6,6-trimethyl-2-phenyl-tetrahydropentaren]zirconium dichloride, [4-(fluorenyl) )-4,6,6-trimethyl-2-phenyl-tetrahydropentaren]hafnium dichloride, iso-propylidene (2-phenyl-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, iso- Profilely Den (2-phenyl-cyclopentadienyl) (9-fluorenyl) hafnium dichloride, diphenylmethylidene (2-phenyl-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethyl Liden (2-phenyl-cyclopentadienyl) (9-fluorenyl) hafnium dichloride, isopropylidene (2-phenyl-cyclopentadienyl) (2,7-di-tert-butylfluorene-9- yl) zirconium dichloride, isopropylidene (2-phenyl-cyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl) hafnium dichloride, diphenylmethylidene (2-phenyl-cyclo Pentadienyl) (2,7-di-tert-butylfluoren-9-yl) zirconium dichloride, diphenylmethylidene (2-phenyl-cyclopentadienyl) (2,7-di-tert-butylfluorenyl) Oren-9-yl) hafnium dichloride, [4- (fluorenyl) -4,6,6-trimethyl-2- (p-tolyl) -tetrahydropentaren] zirconium dichloride, [4- (fluorene) nyl)-4,6,6-trimethyl-2-(p-tolyl)-tetrahydropentaene]hafnium dichloride, [isopropylidene-(2-(p-tolyl)-cyclopentadienyl)-(9 -fluorenyl)]zirconium dichloride, [isopropylidene-(2-(p-tolyl)-cyclopentadienyl)-(9-fluorenyl)]hafnium dichloride, [4-(fluorenyl) -4,6,6-trimethyl-2-(m-tolyl)-tetrahydropentaene]zirconium dichloride, [4-(fluorenyl)-4,6,6-trimethyl-2-(m-tolyl) -tetrahydropentaren] hafnium dichloride, [isopropylidene (2- (m-tolyl) -cyclopentadienyl) - (9-fluorenyl)] zirconium dichloride, [isopropylidene (2- (m -Tolyl)-cyclopentadienyl)-(9-fluorenyl)]hafnium dichloride, [diphenylmethylidene(2-(m-tolyl)-cyclopentadienyl)-(9-fluorenyl)] Zirconium dichloride, [diphenylmethylidene(2-(m-tolyl)-cyclopentadienyl)-(9-fluorenyl)]hafnium dichloride, [isopropylidene(2-(m-tolyl)-cyclo Pentadienyl) (2,7-di-tert-butylfluoren-9-yl)] zirconium dichloride, [isopropylidene (2- (m-tolyl) -cyclopentadienyl) (2,7-di -tert-butylfluoren-9-yl)]hafnium dichloride, [diphenylmethylidene (2-(m-Tolyl)-cyclopentadienyl)(2,7-di-tert-butylfluoren-9-yl)]zirconium dichloride, [diphenylmethylidene(2-(m-tolyl)- Cyclopentadienyl)(2,7-di-tert-butylfluoren-9-yl)]hafnium dichloride, [4-(fluorenyl)-4,6,6-trimethyl-2-(o-tolyl) )-tetrahydropentaren]zirconium dichloride, [4-(fluorenyl)-4,6,6-trimethyl-2-(o-tolyl)-tetrahydropentaren]hafnium dichloride, [isopropylidene ( 2-(o-tolyl)-cyclopentadienyl)(9-fluorenyl)]zirconium dichloride, [isopropylidene(2-(o-tolyl)-cyclopentadienyl)(9-fluorenyl) ] hafnium dichloride, [4- (fluorenyl) -4,6,6-trimethyl-2- (2,3-dimethylphenyl) -tetrahydropentaren] zirconium dichloride, [4- (fluorenyl) -4,6,6-trimethyl-2-(2,3-dimethylphenyl)-tetrahydropentaene]hafnium dichloride, [4-(fluorenyl)-4,6,6-trimethyl-2-(2) ,4-Dimethylphenyl)-tetrahydropentaren]zirconium dichloride, [4-(fluorenyl)-4,6,6-trimethyl-2-(2,4-dimethylphenyl)-tetrahydropentaren]zirconium Dichloride, [Isopropylidene(2-(2,3-dimethylphenyl)-cyclopentadienyl)(9-fluorenyl)]zirconium dichloride, [isopropylidene(2-(2,3-dimethylphenyl) )-Cyclopentadienyl)(9-fluorenyl)]hafnium dichloride, [isopropylidene(2-(2,4-dimethylphenyl)-cyclopentadienyl)(9-fluorenyl)]zirconium di Chloride, [Isopropylidene(2-(2,3-dimethylphenyl)-cyclopentadienyl)(9-fluorenyl)]hafnium dichloride, [diphenylmethylidene(2-(2,3-dimethylphenyl) )-Cyclopentadienyl)(9-fluorenyl)]zirconium dichloride, [diphenylmethylidene(2-(2,3-dimethylphenyl)-cyclopentadienyl)(9-fluorenyl)]hafnium Dichloride, [diphenylmethylidene(2-(2,4-dimethylphenyl)-cyclopentadienyl)(9-fluorenyl)]zirconium dichloride, [diphenylmethylidene(2-(2,4- Dimethylphenyl)-cyclopentadienyl)(9-fluorenyl)]hafnium dichloride, [iso Propylene (2- (2,3-dimethylphenyl) -cyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl)] zirconium dichloride, [isopropylidene (2- (2 ,3-Dimethylphenyl)-cyclopentadienyl)(2,7-di-tert-butylfluoren-9-yl)]hafnium dichloride, [isopropylidene (2-(2,4-dimethylphenyl)- Cyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl)] zirconium dichloride, [isopropylidene (2- (2,4-dimethylphenyl) -cyclopentadienyl) (2 ,7-di-tert-butylfluoren-9-yl)]hafnium dichloride, [diphenylmethylidene(2-(2,3-dimethylphenyl)-cyclopentadienyl)(2,7-di-tert) -Butylfluoren-9-yl)]zirconium dichloride, [diphenylmethylidene(2-(2,3-dimethylphenyl)-cyclopentadienyl)(2,7-di-tert-butylfluorene-9) -yl)]hafnium dichloride, [diphenylmethylidene(2-(2,4-dimethylphenyl)-cyclopentadienyl)(2,7-di-tert-butylfluoren-9-yl)]zirconium di Chloride, [diphenylmethylidene(2-(2,4-dimethyl phenyl)-cyclopentadienyl)(2,7-di-tert-butylfluoren-9-yl)]hafnium dichloride, [4-( Fluorenyl)-4,6,6-trimethyl-2-(2,6-dimethylphenyl)-tetrahydropentaene]zirconium dichloride, [4-(fluorenyl)-4,6,6-trimethyl- 2-(2,6-Dimethylphenyl)-tetrahydropentaene]hafnium dichloride, [4-(fluorenyl)-4,6,6-trimethyl-2-(3,5-dimethylphenyl)-tetrahydro Pentarene] zirconium dichloride, [4- (fluorenyl) -4,6,6-trimethyl-2- (3,5-dimethylphenyl) -tetrahydropentaren] hafnium dichloride, [4- (fluorene) nyl)-4,6,6-trimethyl-2-tetramethylphenyl-tetrahydropentaene]zirconium dichloride, [4-(fluorenyl)-4,6,6-trimethyl-2-tetramethylphenyl-tetrahydropentane Ren] hafnium dichloride, [4- (fluorenyl) -4,6,6-trimethyl-2- (2,4-dimethoxyphenyl) -tetrahydropentaren] zirconium dichloride, [4- (fluorene) nyl)-4,6,6-trimethyl-2-(2,4-dimethoxyphenyl)-tetrahydropentaren]hafnium dichloride; [4-(fluorenyl)-4,6,6-trimethyl-2-(3,5-dimethoxyphenyl)-tetrahydropentaren]zirconium dichloride, [4-(fluorenyl)-4,6 ,6-trimethyl-2-(3,5-dimethoxyphenyl)-tetrahydropentaene]hafnium dichloride, [4-(fluorenyl)-4,6,6-trimethyl-2-(chlorophenyl)- Tetrahydropentaren] zirconium dichloride, [4- (fluorenyl) -4,6,6-trimethyl-2- (chlorophenyl) -tetrahydropentaren] hafnium dichloride, [4- (fluorenyl) -4,6,6-trimethyl-2-(fluorophenyl)-tetrahydropentaene]zirconium dichloride, [4-(fluorenyl)-4,6,6-trimethyl-2-(fluorophenyl) -tetrahydropentaren] hafnium dichloride, [4- (fluorenyl) -4,6,6-trimethyl-2- (difluorophenyl) -tetrahydropentaren] zirconium dichloride, [4- (flu Orenyl)-4,6,6-trimethyl-2-(difluorophenyl)-tetrahydropentaene]hafnium dichloride, [4-(fluorenyl)-4,6,6-trimethyl-2- (Pentafluorophenyl)-tetrahydropentaren]zirconium dichloride, [4-(fluorenyl)-4,6,6-trimethyl-2-(difluorophenyl)-tetrahydropentaren]hafnium dichloride , [4- (fluorenyl) -4,6,6-trimethyl-2- (tert-butyl-phenyl) -tetrahydropentaene] hafnium dichloride, [4- (fluorenyl) -4,6, 6-trimethyl-2-(3,5-trifluoromethyl-phenyl)-tetrahydropentaene]zirconium dichloride, [4-(fluorenyl)-4,6,6-trimethyl-2-(3, 5-Trifluoromethyl-phenyl)-tetrahydropentaene]hafnium dichloride, [4-(fluorenyl)-4,6,6-trimethyl-2-(3,5-di-tert-butylphenyl) tetrahydropentaren] zirconium dichloride, [4- (fluorenyl) -4,6,6-trimethyl-2- (3,5-di-tert-butylphenyl) tetrahydropentaene] hafnium dichloride, [ 4-(fluorenyl)-4,6,6-trimethyl-2-(biphenyl)-tetrahydropentaene]zirconium dichloride, [4-(fluorenyl)-4,6,6-trimethyl-2 -(biphenyl)-tetrahydropentaene]hafnium dichloride, [4- (fluorenyl)-4,6,6-trimethyl-2-naphthyl-tetrahydropentaren]zirconium dichloride, [4-(fluorenyl)-4,6,6-trimethyl-2-naphthyl- Tetrahydropentaren] hafnium dichloride, [4- (fluorenyl) -4,6,6-trimethyl-2- (3,5-diphenyl-phenyl) -tetrahydropentaene] zirconium dichloride, [4 -(Fluorenyl)-4,6,6-trimethyl-2-(3,5-diphenyl-phenyl)-tetrahydropentaene]hafnium dichloride, isopropylidene (2-tetramethylphenyl-cyclopentadienyl) ) (9-fluorenyl) zirconium dichloride, isopropylidene (2- (2,6-dimethylphenyl) -cyclopentadienyl) (9-fluorenyl) zirconium dichloride, isopropylidene (2- ( 3,5-Dimethylphenyl)-cyclopentadienyl)(9-fluorenyl)zirconium dichloride, isopropylidene(2-(2,4-dimethoxyphenyl)-cyclopentadienyl)(9-fluorene Nyl) zirconium dichloride, isopropylidene (2- (3,5-dimethoxyphenyl) -cyclopentadienyl) (9-fluorenyl) zirconium dichloride, isopropylidene (2- (2,3-dimethy Toxyphenyl) -cyclopentadienyl) (9-fluorenyl) zirconium dichloride, isopropylidene (2- (2,6-dimethoxyphenyl) -cyclopentadienyl) (9-fluorenyl) zirconium di Chloride, isopropylidene (2- (chlorophenyl) -cyclopentadienyl) (9-fluorenyl) zirconium dichloride, isopropylidene (2- (dichlorophenyl) -cyclopentadienyl) (9-fluorene Nyl) zirconium dichloride, isopropylidene (2- (trichlorophenyl) -cyclopentadienyl) (9-fluorenyl) zirconium dichloride, isopropylidene (2- (fluorophenyl) -cyclopentadienyl) ) (9-fluorenyl) zirconium dichloride, isopropylidene (2- (difluorophenyl) -cyclopentadienyl) (9-fluorenyl) zirconium dichloride, isopropylidene (2- (pentafluoro Rophenyl)-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, isopropylidene (2- (3,5-trifluoromethyl-phenyl) -cyclopentadienyl) (9-fluorenyl) ) zirconium dichloride, isopropylidene (2- (tert-butylphenyl) -cyclopentadienyl) (9-fluorenyl) zirconium dichloro Ride, isopropylidene (2- (3,5-di-tert-butylphenyl) -cyclopentadienyl) (9-fluorenyl) zirconium dichloride, isopropylidene (2- (biphenyl) -cyclopenta Dienyl) (9-fluorenyl) zirconium dichloride, isopropylidene (2- (3,5-diphenyl-phenyl) -cyclopentadienyl) (9-fluorenyl) zirconium dichloride, isopropylidene (2-naphthyl-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylidene (2-tetramethylphenyl-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenyl Methylidene(2-(2,6-dimethylphenyl)-cyclopentadienyl)(9-fluorenyl)zirconium dichloride, diphenylmethylidene(2-(3,5-dimethylphenyl)-cyclopentadienyl ) (9-fluorenyl) zirconium dichloride, diphenylmethylidene (2- (2,4-dimethoxyphenyl) -cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylidene ( 2-(3,5-dimethoxyphenyl)-cyclopentadienyl)(9-fluorenyl)zirconium dichloride, diphenylmethylidene (2-(2,3-dimethoxyphenyl)-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylidene (2- (2,6-dimethoxyphenyl) -cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylidene (2 - (chlorophenyl) -cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylidene (2- (dichlorophenyl) -cyclopentadienyl) (9-fluorenyl) zirconium dichloride, Diphenylmethylidene (2- (trichlorophenyl) -cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylidene (2- (fluorophenyl) -cyclopentadienyl) (9- Fluorenyl) zirconium dichloride, diphenylmethylidene (2- (difluorophenyl) -cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylidene (2- (pentafluorophenyl) )-Cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylidene (2- (3,5-trifluoromethyl-phenyl) -cyclopentadienyl) (9-fluorenyl) Zirconium dichloride, diphenylmethylidene (2- (tert-butylphenyl) -cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethyl Den(2-(3,5-di-tert-butylphenyl)-cyclopentadienyl)(9-fluorenyl)zirconium dichloride, diphenylmethylidene(2-(biphenyl)-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylidene (2- (3,5-diphenyl-phenyl) -cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylidene ( 2-Naphthyl-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, isopropylidene (2-tetramethylphenyl-cyclopentadienyl) (2,7-di-tert-butylfluorene-9- yl) hafnium dichloride, isopropylidene (2-(2,6-dimethylphenyl)-cyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl) hafnium dichloride, isopropylidene (2-(3,5-Dimethylphenyl)-cyclopentadienyl)(2,7-di-tert-butylfluoren-9-yl)hafnium dichloride, isopropylidene (2-(2,4-dimethy Toxyphenyl)-cyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl) hafnium dichloride, isopropylidene (2- (3,5-dimethoxyphenyl) -cyclopentadienyl) ) (2,7-di-tert-butylfluoren-9-yl) hafnium dichloride, isopropylidene (2- (2,3-dimethoxyphenyl) -cyclopentadienyl) (2,7-di- Tert-butylfluoren-9-yl) hafnium dichloride, isopropylidene (2-(2,6-dimethoxyphenyl)-cyclopentadienyl) (2,7-di-tert-butylfluorene-9- yl) hafnium dichloride, isopropylidene (2- (chlorophenyl) -cyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl) hafnium dichloride, isopropylidene (2- ( Dichlorophenyl) -cyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl) hafnium dichloride, isopropylidene (2- (trichlorophenyl) -cyclopentadienyl) (2, 7-di-tert-butylfluoren-9-yl)hafnium dichloride, isopropylidene (2-(fluorophenyl)-cyclopentadienyl) (2,7-di-tert-butylfluorene-9- yl) hafnium dichloride, isopropylidene (2- (difluorophenyl) -cyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl) hafnium dichloride, isopropylidene (2 -(Pentafluorophenyl)-cyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl) half nium dichloride, isopropylidene (2- (3,5-trifluoromethyl-phenyl) -cyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl) hafnium dichloride, iso Propylene (2- (tert-butylphenyl) -cyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl) hafnium dichloride, isopropylidene (2- (3,5-di -tert-butylphenyl)-cyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl) hafnium dichloride, isopropylidene (2- (biphenyl) -cyclopentadienyl) ( 2,7-di-tert-butylfluoren-9-yl)hafnium dichloride, isopropylidene (2-(3,5-diphenyl-phenyl)-cyclopentadienyl) (2,7-di-tert) -Butylfluoren-9-yl) hafnium dichloride, isopropylidene (2-naphthyl-cyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl) hafnium dichloride, diphenyl Methylidene (2-tetramethylphenyl-cyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl) hafnium dichloride, diphenylmethylidene (2- (2,6-dimethyl phenyl) - Cyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl) hafnium dichloride, diphenylmethylidene (2- (3,5-dimethylphenyl) -cyclopentadienyl) (2, 7-di-tert-butylfluoren-9-yl) hafnium dichloride, diphenylmethylidene (2-(2,4-dimethoxyphenyl)-cyclopentadienyl) (2,7-di-tert-butyl) Fluoren-9-yl) hafnium dichloride, diphenylmethylidene (2- (3,5-dimethoxyphenyl) -cyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl) Hafnium dichloride, diphenylmethylidene (2- (2,3-dimethoxyphenyl) -cyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl) hafnium dichloride, diphenylmethyl Liden (2- (2,6-dimethoxyphenyl) -cyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl) hafnium dichloride, diphenylmethylidene (2- (chlorophenyl) )-Cyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl) hafnium dichloride, diphenylmethylidene (2- (dichlorophenyl) -cyclopentadienyl) (2,7- Di-tert-butylfluoren-9-yl) hafnium dichloride, diphenylmethylidene (2- (trichlorophenyl) -cyclopentadienyl) (2,7-di-tert-butyl Fluoren-9-yl) hafnium dichloride, diphenylmethylidene (2- (fluorophenyl) -cyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl) hafnium dichloride, Diphenylmethylidene (2- (difluorophenyl) -cyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl) hafnium dichloride, diphenylmethylidene (2- (pentafluoro Rophenyl) -cyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl) hafnium dichloride, diphenylmethylidene (2- (3,5-trifluoromethyl-phenyl) - Cyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl) hafnium dichloride, diphenylmethylidene (2- (tert-butylphenyl) -cyclopentadienyl) (2,7- Di-tert-butylfluoren-9-yl)hafnium dichloride, diphenylmethylidene (2-(3,5-di-tert-butylphenyl)-cyclopentadienyl) (2,7-di-tert- Butylfluoren-9-yl)hafnium dichloride, diphenylmethylidene (2-(biphenyl)-cyclopentadienyl)(2,7-di-tert-butylfluoren-9-yl)hafnium dichloride; Diphenylmethylidene (2- (3,5-diphenyl-phenyl) -cyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl) hafnium dichloride, diphenylmethylidene (2 -naphthyl-cyclopentadienyl)(2,7-di-tert-butylfluoren-9-yl)hafnium dichloride etc. are mentioned.

Preferably, as the metallocene compound, bis(indenyl)zirconium dichloride and rac-ethylenebis(1-indenyl)zirconium dichloride may be selected and used.

In an embodiment, when the reaction conditions are the same, the two or more metallocene compounds may be supported on each of the two or more kinds of carriers in the same ratio. For example, when two types of metallocene compounds are supported on two types of carriers, the first metallocene compound and the second metallocene compound are supported on a carrier having a small average particle diameter in a ratio of 1:1; The first metallocene compound and the second metallocene compound may be supported on a carrier having a large average particle diameter in a ratio of 1:1.

At this time, the supporting reaction may be carried out at 20 to 120° C., preferably at 50 to 100° C., for 30 minutes to 4 hours, preferably for 2 hours to 3 hours.

When preparing the catalyst, the reaction solvent includes an aliphatic hydrocarbon solvent such as hexane and pentane, an aromatic hydrocarbon solvent such as toluene and benzene, a hydrocarbon solvent substituted with a chlorine atom such as dichloromethane, an ether solvent such as diethyl ether and tetrahydrofuran, Most organic solvents such as acetone and ethyl acetate may be used, and toluene and hexane may be preferably used, but the present invention is not limited thereto.

In addition, in one embodiment, the catalyst may further include a cocatalyst compound, wherein the cocatalyst compound is a compound including a unit represented by the following Chemical Formula 3, a compound represented by the following Chemical Formula 4, and a compound represented by the following Chemical Formula 5 It may be at least one selected from the group consisting of.

In Formula 3,

q is an integer greater than or equal to 2,

Al is aluminum,

O is oxygen,

Ra is halogen; Or a halogen-substituted or unsubstituted (C ₁ -C ₂₀ )hydrocarbyl group,

In Formula 4,

Q is aluminum or boron,

Rb are the same as or different from each other, and each independently halogen; Or a halogen-substituted or unsubstituted (C ₁ -C ₂₀ )hydrocarbyl group,

In Formula 5,

[W] ⁺ is a cationic Lewis acid; or a cationic Lewis acid to which a hydrogen atom is bound,

Z is a group 13 element,

Rc is the same as or different from each other, and each independently halogen, (C ₁ -C _{20 ) A (C 6} -C ₂₀ )aryl substituted with one or two or more substituents selected from the group consisting of a hydrocarbyl group, an alkoxy group and a phenoxy group. group; halogen, (C ₁ -C _{20 ) A (C 1} -C ₂₀ )alkyl group substituted with one or two or more substituents selected from the group consisting of a hydrocarbyl group, an alkoxy group and a phenoxy group.

The promoter compound is included in the catalyst together with the transition metal compound represented by Formula 1 or Formula 2 to activate the transition metal compound. Specifically, in order for the transition metal compound to become an active catalyst component used for olefin polymerization, a ligand in the transition metal compound is extracted ^{to cationize the central metal (M 1} or M ² ) while cationizing a counterion having weak binding force, that is, an anion. The compound including the unit represented by Formula 3, the compound represented by Formula 4, and the compound represented by Formula 5, which can act as a cocatalyst, act together as a cocatalyst.

The 'unit' represented by Formula 3 is a structure in which q structures in [ ] are connected in the compound, and if the unit represented by Formula 3 is included, other structures in the compound are not particularly limited, and repeating Formula 3 The unit may be a cluster type, such as a globular compound, connected to each other.

The compound including the unit represented by the formula (3) is not particularly limited, and is preferably an alkylaluminoxane. Non-limiting examples include methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, butylaluminoxane, hexylaluminoxane, octylaluminoxane, decylaluminoxane, and the like. Considering the activity of the transition metal compound, methylaluminoxane may be preferably used.

In addition, the compound represented by Formula 4 is not particularly limited as an alkyl metal compound, and non-limiting examples thereof include trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, dimethylchloroaluminum, and triiso. Propyl aluminum, tri-s-butylaluminum, tricyclopentylaluminum, tripentylaluminum, triisopentylaluminum, trihexylaluminum, trioctylaluminum, ethyldimethylaluminum, methyldiethylaluminum, triphenylaluminum, tri-p-tolyl aluminum, dimethyl aluminum methoxide, dimethyl aluminum ethoxide, trimethyl boron, triethyl boron, triisobutyl boron, tripropyl boron, tributyl boron, and the like. Considering the activity of the transition metal compound, one or more selected from the group consisting of trimethylaluminum, triethylaluminum and triisobutylaluminum may be preferably used.

When considering the activity of the transition metal compound, the compound represented by Formula 5 is a ^{dimethylanilinium cation when [W] +} is a cationic Lewis acid to which a hydrogen atom is bonded, and [W] ⁺ is a cationic Lewis acid, [ (C ₆ H ₅ ) ₃ C] ⁺ , and [Z(Rc) ₄ ] ^- is [B(C ₆ F ₅ ) ₄ ] ^- , which may be preferably used.

The compound represented by Formula 5 is not particularly limited, but ^{non-limiting examples of the case where [W] +} is a cationic Lewis acid to which a hydrogen atom is bonded include triphenylcarbenium borate, trimethylammonium tetraphenylborate, methyldioctadecylammonium tetraphenyl Borate, triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tri(n-butyl)ammonium tetraphenylborate, methyltetradecyclooctadecylammonium tetraphenylborate, N,N-dimethylaninium tetraphenylborate, N ,N-diethylaninium tetraphenylborate, N,N-dimethyl (2,4,6-trimethylaninium)tetraphenylborate, trimethylammonium tetrakis(pentafluorophenyl)borate, methylditetradecylammonium tetrakis (Pentaphenyl)borate, methyldioctadecylammonium tetrakis(pentafluorophenyl)borate, triethylammonium tetrakis(pentafluorophenyl)borate, tripropylammonium tetrakis(pentafluorophenyl)borate, tri(n -Butyl)ammonium tetrakis(pentafluorophenyl)borate, tri(sec-butyl)ammonium tetrakis(pentafluorophenyl)borate, N,N-dimethylaninium tetrakis(pentafluorophenyl)borate, N ,N-diethylaninium tetrakis(pentafluorophenyl)borate, N,N-dimethyl(2,4,6-trimethylaninium)tetrakis(pentafluorophenyl)borate, trimethylammonium tetrakis(2, 3,4,6-tetrafluorophenyl)borate, triethylammonium tetrakis(2,3,4,6-tetrafluorophenyl)borate, tripropylammonium tetrakis(2,3,4,6-tetrafluoro Rophenyl)borate, tri(n-butyl)ammonium tetrakis(2,3,4,6-tetrafluorophenyl)borate, dimethyl(t-butyl)ammonium tetrakis(2,3,4,6-tetrafluoro Rophenyl) borate, N,N-dimethylaninium tetrakis (2,3,4,6-tetrafluorophenyl) borate, N,N-diethylanilium tetrakis (2,3,4,6-tetra) Fluorophenyl)borate, N,N-dimethyl-(2,4,6-trimethylaninium)tetrakis-(2,3,4,6-tetrafluorophenyl)borate, dioctadecylammonium tetrakis(pentadecylammonium) Fluorophenyl) borate, ditetradecylammonium tetra Lakis (pentafluorophenyl) borate, dicyclohexylammonium tetrakis (pentafluorophenyl) borate, triphenylphosphonium tetrakis (pentafluorophenyl) borate, methyldioctadecylphosphonium tetrakis (pentafluorophenyl) ) borate, tri(2,6-dimethylphenyl)phosphonium tetrakis(pentafluorophenyl)borate, methyldi(octadecyl)ammonium tetrakis(pentafluorophenyl)borate, methyldi(tetradecyl)-ammonium tetra kiss (pentafluorophenyl) borate, triethyl tetrakis (pentafluorophenyl) borate, and the like.

The promoter compound may be included in a molar ratio of 10 to 200 with respect to the content of the metallocene compound. When the molar ratio of the promoter is less than 10, the amount of the transition metal compound supported on the carrier is small, and when the molar ratio exceeds 200, the transition metal compound reacts with the promoter present in the solvent layer, which is not preferable.

In one embodiment, the antistatic agent is a material added to improve the flowability of the catalyst, and may be added after the reaction between the carrier and the metallocene compound is completed or after the reaction between the carrier, the metallocene compound and the cocatalyst is completed. . The antistatic agent may be reacted with the carrier at room temperature for 30 minutes to 4 hours, preferably 30 minutes to 1 hour.

In one embodiment, the antistatic agent includes at least one polar functional group selected from the group consisting of an acid group, an ester group, an amine group, an amide group, a hydroxyl group, and an ether group, but is not particularly limited, for example, including an amine group An antistatic agent may be used.

In one embodiment, the catalyst may include 0.1 to 100,000 molar equivalents of the antistatic agent based on the total number of moles of the metallocene compound, and preferably 0.1 to 1,000 molar equivalents of the antistatic agent. If the content of the antistatic agent is less than 0.1 molar equivalent, the antistatic effect hardly appears, and if it exceeds 100,000 molar equivalent, it is not preferable because it may cause deterioration in activity.

According to another aspect of the present invention, polyolefin may be prepared by polymerizing an olefin monomer in the presence of a catalyst for polyolefin polymerization including a carrier, a metallocene compound, and an antistatic agent. The polymerization reaction of polyolefin may be carried out in a gas phase, liquid phase or slurry phase, and preferably, polymerization in a gas phase using a gas phase polymerization machine. In addition, each polymerization reaction condition may be variously modified depending on the polymerization method, the desired polymerization result, or the type of polymer.

The prepared polyolefin may have a bimodal or multimodal molecular weight distribution depending on the transition metal compound contained in the catalyst. In more detail, when two types of transition metal compounds are used, a polyolefin having a bimodal molecular weight distribution can be prepared, for example, 50 to 90% by weight of a polyolefin having a specific molecular weight less than a specific molecular weight based on the total weight of the polyolefin and a specific A polyolefin containing 10 to 50% by weight of a polyolefin having a molecular weight or higher may be prepared.

In addition, the prepared polyolefin may have a density of 0.925 to 0.950 g/cm ³ , a molecular weight distribution of 2.0 to 20.0, and a melt flow index (MI _2.16 ) of 0.01 to 10 g/10 min.

In addition, since the catalyst according to an embodiment of the present invention has the same composition under the same reaction conditions, a polyolefin having a constant molecular weight and molecular weight distribution can be prepared regardless of a polyolefin polymerization reaction time point. Thereby, the stability of the polyolefin polymerization process is improved and a uniform polyolefin can be produced.

Example

Hereinafter, embodiments of the present invention will be described in detail. The following examples are only for the understanding of the present invention, but do not limit the present invention.

[Example 1]

1. Reaction conditions

(1) Catalyst synthesis reaction conditions

Toluene was purchased from Sigma-Aldrich as Anhydrous Grade, and then passed through an activated molecular sieve (Molecular Sieve, 4A) or activated alumina layer to further dry it before use. MAO (methylaluminoxane, Methylaluminoxane) was purchased from Albemarle's 10% toluene solution (HS-MAO-10%), and for silica, Grace's product was used without further treatment.

In addition, rac-ethylenebis(indenyl) zirconium dichloride used in Examples was purchased from Chemtura Organometallics GmbH and used without purification. Bisindenyl zirconium dichloride (Bis(indenyl)zirconium dichloride) was purchased from S-PCI and used without purification. 1-Hexene was purchased from Sigma-Aldrich and used.

(2) polymerization reaction conditions

The polymerization reaction was carried out while maintaining a constant ethylene pressure after injecting required amounts of solvent, catalyst, activator, ethylene and comonomer in an autoclave reactor completely blocked from outside air. Normal hexane solvent and comonomer used for polymerization were purchased from Sigma-Aldrich in anhydrous grade, and then passed through an activated molecular sieve (4A) or activated alumina layer to further It was used after removing moisture, and 1.0M triethylaluminum solution was purchased from Sigma-Aldrich and used without further treatment.

2. Catalyst Synthesis

(a) In a glove box, 69.1 mg of rac-ethylenebis(indenyl) zirconium dichloride and 64.7 mg of bisindenyl zirconium dichloride were dissolved in a metallocene compound. It was put in a round bottom flask, taken out of the glove box, and dissolved by adding 10 mL of toluene.

(b) Mix 50㎛ silica and 30㎛ silica in a glove box at a weight ratio of 70:30 (silica mixture 5.0g), put it in a round bottom flask, take it out of the glove box, and add 15mL of toluene to make a slurry After stirring for 10 minutes, 2.029 g of MAO solution (10 wt% solution in toluene) at 10° C. was slowly added. While stirring again, the temperature was raised to 70 °C, reacted for 4 hours more, and the temperature was lowered to room temperature.

(c) (a) was slowly added to (b) to react, and the temperature was raised to 80° C. while stirring to further react for 1 hour. When the reaction time was completed, the temperature was lowered, the stirring was stopped, the toluene layer was separated and removed, and then toluene and hexane were additionally added to wash the unreacted material. In this step, Innospec's STATSAFE 6000 as an antistatic agent was added in an amount of 1000 molar equivalents compared to the metallocene compound and reacted for 30 minutes. After the solid slurry was well settled, the supernatant was poured out, and the solid slurry was vacuum dried to obtain a supported catalyst in the form of a fluidized powder.

3. Polyethylene Polymerization

After replacing the inside of the stainless steel reactor with nitrogen, 1 L of normal hexane was filled, and 0.4 mmol of triethylaluminum was added, and 100 mg of the synthesized supported catalyst was injected.

By introducing ethylene gas at a pressure of 1 bar, a pre-polymerization reaction was performed for 5 minutes while maintaining a temperature of 25°C. After 15 mL of comonomer (1-hexene) was added in a nitrogen atmosphere, the temperature was raised to 75°C. When the temperature was reached, ethylene gas was introduced at a pressure of 8 bar to carry out a polymerization reaction for 1 hour. When the polymerization reaction was completed, the ethylene supply was stopped, the reactor temperature was cooled to 20° C., and unreacted ethylene was vented to the outside of the reactor. A polyethylene polymer was prepared by filtering the reactant to separate it into a solid component, and then drying it under vacuum at a temperature of 80°C.

[Example 2]

A catalyst was synthesized in the same manner as in Example 1, and a polyethylene polymer was prepared in the same manner as in Example 1, except that 50 μm silica and 30 μm silica were added in a weight ratio of 50:50 in the step 2. catalyst synthesis of Example 1.

[Comparative Example 1]

A catalyst was synthesized in the same manner as in Example 1, and a polyethylene polymer was prepared, except that 50 μm silica was added alone in the catalyst synthesis step of Example 1.

[Comparative Example 2]

A catalyst was synthesized in the same manner as in Example 1, and a polyethylene polymer was prepared, except that 30 μm silica was added alone in the catalyst synthesis step of Example 1.

[Comparative Example 3]

A catalyst was synthesized in the same manner as in Example 1, except that an antistatic agent was not added in the 2. catalyst synthesis step of Example 1 to prepare a polyethylene polymer.

[Experimental example]

The catalysts and polyethylene synthesized in Examples and Comparative Examples were evaluated according to the following items 1 to 4, and the results are shown in Table 1.

1. Supernatant Metal Content

The toluene layer separated after completion of the reaction during the preparation of the supported catalyst is referred to as a supernatant, and the metal content of the supernatant was analyzed for inorganic elements of the supernatant using XRF (Rigaku's ZSX Primus II).

2. Catalytic activity

It is a value converted by measuring the weight of the produced polyethylene compared to the catalyst added during polyethylene polymerization.

3. Bulk Density (BD)

Using the Bulk Density Tester, pour the sample powder into the container at a constant speed and use the volume of the container and the weight of the polyethylene powder to indicate the weight of the filled powder in g per ml of the volume of the container.

4. Weight average molecular weight (M _W )

Polymer Laboratories Ltd (UK)'s PL GPC-220 and a GPC system consisting of a Differential Viscometer (M210R) was applied to the measurement result at 160 ℃.

Example 1 Example 2 Comparative Example 1 Comparative Example 2 Comparative Example 3 silica
weight ratio 50㎛ (wt%) 70 50 100 0 70 30㎛ (wt%) 30 50 0 100 30 Compared to metallocene compounds
Antistatic agent content (molar equivalent) 1000 1000 1000 1000 0 supernatant
metal content Al (wt%) 0.0018 0.0017 0.1036 0.0017 0.0025 Zr (wt%) 0.0001 0.0001 0.0005 0.0000 0.0001 catalyst
characteristic activation
(kg-PE/g-cat) 2.1 1.7 1.3 1.8 1.7 Apparent density
(g/ml) 0.35 0.35 0.37 0.30 0.30 polymer
characteristic High Mw
(g/mol) 292,875 288,855 292,244 211,533 257,001 High Mw
(%) 49.9 49.9 47.2 47.7 45.4 Low Mw (g/mol) 143,600 142,392 143,357 104,958 104,308 Low Mw
(%) 50.1 50.1 52.8 52.3 54.6

Table 1 shows the results of synthesizing the catalyst and polyethylene using the same amount of silica in Examples 1-2 and Comparative Examples 1-3.

As in Examples 1 and 2, when two types of carriers (50 μm, 30 μm) having different average particle diameters are mixed and used, the Al and Zr metal content of the supernatant is low, so the amount of unsupported metallocene compound is small, It can be seen that a catalyst with high activity was synthesized from However, in Comparative Example 1, a large amount of unsupported metallocene compounds were generated using only a carrier having an average particle diameter of 50 μm, and thus, the catalytic activity was also low.

In addition, in the case of Examples 1 and 2, an apparent density of 0.35 g/ml was shown, but in Comparative Example 2 using only a carrier having an average particle diameter of 30 μm and Comparative Example 3 without an antistatic agent, an apparent density of 0.30 g/ml was shown. As the apparent density is higher, it means that a large amount of catalyst is present in a certain volume, and it can be seen that the catalysts prepared in Examples 1 and 2 have improved flow properties.

5. Catalyst synthesis reproducibility evaluation

The experiment was performed twice in the same manner as in Example 1, and the characteristics of the synthesized catalyst and polymer were evaluated by performing the experiment twice in the same manner as in Comparative Example 1.

Example 1 Comparative Example 1 1 time Episode 2 1 time Episode 2 silica
weight ratio 50㎛ (wt%) 70 70 100 100 30㎛ (wt%) 30 30 0 0 Compared to metallocene compounds
Antistatic agent content (molar equivalent) 1000 1000 1000 1000 Supernatant metal content Al (wt%) 0.0018 0.0017 0.1036 0.0238 Zr (wt%) 0.0001 0.0001 0.0005 0.0002 catalyst
characteristic activation
(kg-PE/g-cat) 2.1 2.0 1.3 1.7 Apparent density
(g/ml) 0.35 0.35 0.37 0.36 polymer
characteristic High Mw
(g/mol) 292,875 288,855 292,244 201,738 High Mw
(%) 49.9 50.1 47.2 6.3 Low Mw (g/mol) 143,600 142,392 143,357 51,116 Low Mw
(%) 50.1 49.9 52.8 93.7

As in Example 1, when two types of carriers having different average particle diameters were used, it was confirmed that a polymer having a constant ratio of the polymer domain (more than 200,000 g/mol) and the low molecular domain (less than 200,000 g/mol) was prepared under the same reaction conditions. .

On the other hand, in the case of Comparative Example 1 using only one type of carrier, it can be seen that there is a significant difference in the ratio of the polymer region and the low molecular region according to the experiment even if the reaction conditions are the same.

From the above results, as in the present invention, by using two or more types of carriers having different average particle diameters, a polymer having a constant ratio of a high molecular domain and a low molecular domain can be obtained, and a polymer having a uniform molecular weight distribution can be manufactured.

Claims (8)

two or more types of carriers having different average particle diameters;
two or more metallocene compounds; and
containing an antistatic agent;
The antistatic agent is a catalyst for polyolefin polymerization comprising at least one functional group selected from the group consisting of an acid group, an ester group, an amine group, an amide group, a hydroxyl group and an ether group.
According to claim 1,
The catalyst for polyolefin polymerization, characterized in that the average particle diameter of each of the carriers is 10 to 200㎛.
According to claim 1,
The catalyst for polyolefin polymerization, characterized in that the ratio of the average particle diameter of the carrier having the smallest average particle diameter to the carrier having the largest average particle diameter among the carriers is 1.5 to 3.
According to claim 1,
The catalyst for polyolefin polymerization, characterized in that the content of the carrier having the largest average particle diameter among the carriers is 50 to 90 wt%.
According to claim 1,
The content of the antistatic agent is a catalyst for polyolefin polymerization, characterized in that 0.1 to 100,000 molar equivalents based on the total number of moles of the metallocene compound.
According to claim 1,
The metallocene compound is a catalyst for polyolefin polymerization, characterized in that at least two compounds selected from the group consisting of a compound represented by the following formula (1) and a compound represented by the following formula (2):

[Formula 1]

[Formula 2]

(In Formula 1 and Formula 2,
M ¹ and M ² are each independently selected from the group consisting of elements from groups 3 to 10 on the periodic table,
X ¹ and X ² are each independently a halogen group, an amine group, (C ₁ -C ₂₀ )alkyl group, (C ₃ -C ₂₀ )cycloalkyl group, (C ₁ -C ₂₀ )alkylsilyl group, silyl (C ₁ -C ₂₀ )alkyl group, (C ₆ -C ₂₀ )aryl group, (C ₆ -C ₂₀ )aryl (C ₁ -C ₂₀ )alkyl group, (C ₁ -C ₂₀ )alkyl (C ₆ -C ₂₀ )aryl group , (C ₆ -C ₂₀ )arylsilyl group, silyl (C ₆ -C ₂₀ )aryl group, (C ₁ -C ₂₀ )alkoxy group, (C ₁ -C ₂₀ )alkylsiloxy group and (C ₆ -C _{20 )} ) is selected from the group consisting of an aryloxy group,
Ar ¹ , Ar ² , Ar ³ and Ar ⁴ are the same as or different from each other, and are each independently a ligand having a cyclopentadienyl skeleton,
B is a component that does not directly coordinate with the transition metal M ^{2 and connects the ligands Ar 3} and Ar ⁴ , and is a group consisting of carbon (C), silicon (Si), germanium (Ge), nitrogen (N) and phosphorus (P). containing an element selected from
L is hydrogen, (C ₁ -C ₂₀ )alkyl group, (C ₃ -C ₂₀ )cycloalkyl group, (C ₁ -C ₂₀ )alkylsilyl group, silyl (C ₁ -C ₂₀ )alkyl group, (C ₆ -C _{20 )} ) aryl group, (C ₆ -C ₂₀ )aryl (C ₁ -C ₂₀ )alkyl group, (C ₁ -C ₂₀ )alkyl (C ₆ -C ₂₀ )aryl group, (C ₆ -C ₂₀ )arylsilyl group and Silyl (C ₆ -C ₂₀ ) It is selected from the group consisting of an aryl group,
n is an integer from 1 to 5,
m is an integer from 1 to 5,
p is 1 or 2).
According to claim 1,
The catalyst for polyolefin polymerization further comprises one or two or more compounds selected from the group consisting of a compound represented by the following formula (3), a compound represented by the following formula (4), and a compound represented by the following formula (5) A catalyst for polyolefin polymerization comprising:

[Formula 3]

(In Formula 3,
q is an integer greater than or equal to 2,
Al is aluminum,
O is oxygen,
Ra is halogen; Or halogen-substituted or unsubstituted (C ₁ -C ₂₀ ) A hydrocarbyl group),
[Formula 4]

(In Formula 4,
Q is aluminum or boron,
Rb are the same as or different from each other, and each independently halogen; Or halogen-substituted or unsubstituted (C ₁ -C ₂₀ ) A hydrocarbyl group),
[Formula 5]

(In Formula 5,
[W] ⁺ is a cationic Lewis acid; or a cationic Lewis acid to which a hydrogen atom is bound,
Z is a group 13 element,
Rc is the same as or different from each other, and each independently halogen, (C ₁ -C _{20 ) A (C 6} -C ₂₀ )aryl substituted with one or two or more substituents selected from the group consisting of a hydrocarbyl group, an alkoxy group and a phenoxy group. group; halogen, (C ₁ -C _{20 ) A (C 1} -C ₂₀ )alkyl group substituted with one or two or more substituents selected from the group consisting of a hydrocarbyl group, an alkoxy group and a phenoxy group).
Supporting two or more kinds of metallocene compounds on two or more kinds of carriers having different average particle diameters;
Mixing the carrier on which the metallocene compound is supported and the antistatic agent
including,
The antistatic agent comprises at least one functional group selected from the group consisting of an acid group, an ester group, an amine group, an amide group, a hydroxyl group and an ether group.