KR20120075954A - Olefin polymerization catalyst composition and olefin polymerization process using the same - Google Patents

Abstract

PURPOSE: An olefin polymerization catalyst composition is provided to have excellent olefin polymerization activity, and to easily control molecular weight, molecular weight distribution, composition distribution of an olefin polymer or copolymer. CONSTITUTION: An olefin polymerization catalyst composition comprises an organic metal compound in chemical formula 1: (Cp')lM^1R^1_mR^2_n, and an organic transition metal compound in chemical formula 2: (4HInd)_2M^2X_2. In chemical formula 1, M^1 is atom from group 1, 2, 13, or 14, (Cp') is a cyclic hydrocarbon group having two or more conjugation double bonds. R^1 and R^2 is respectively C1-24hydrocarbon group, l is one or more, and is an integer lower than atomic value of M^1, m and n are respectively an integer from 0-2, and l+m+n is same with the atomic value of M^1.

Description

Olefin polymerization catalyst composition and olefin polymerization process using the same

The present invention relates to an olefin polymerization catalyst composition, and more particularly, to an olefin polymerization catalyst composition excellent in olefin polymerization activity and capable of easily adjusting the molecular weight, molecular weight distribution, and composition distribution of an olefin polymer or copolymer and an olefin using the same. It relates to a polymerization method.

Polyolefins, in particular ethylene polymers or ethylene / alpha-olefin copolymers, exhibit excellent properties in impact strength, transparency and the like. In order to prepare such an ethylene polymer, cyclopentadienyl, Indenyl, Cyclohepta dienyl, Fluorenyl, etc. which can control the molecular weight and stereoregularity of the polymer A metallocene catalyst system composed of an organometallic compound having a ligand of (generally, metallocene) and an activator such as aluminoxane is used (Germany Patent No. 3,007,725, US Patent No. 4,404,344, US Patent No. 4,874,880, USA). Patent 5,324,800, etc.). In addition, recently, a method of controlling the particle shape of a polymer by preparing a non-uniform solid catalyst by supporting a metallocene compound and an active agent on an inorganic carrier and applying the same to a slurry or a gas phase polymerization process has been used. 4,808,561 and Korean Patent Application No. 1998-44308. However, since the conventional metallocene catalyst is synthesized through a plurality of reaction processes under difficult reaction conditions, the production cost is high, and it is difficult to easily control the physical properties of the olefin polymer according to the needs of the user.

Accordingly, an object of the present invention is to provide an olefin polymerization catalyst composition having a simple production method and high catalytic activity.

Another object of the present invention is to provide an olefin polymerization catalyst composition capable of tailor-made olefin polymers of various properties by varying the catalyst properties and a method of polymerizing olefins using the same.

Another object of the present invention is to adjust the catalyst component and reaction conditions (temperature, time), and to easily control the molecular weight, molecular weight distribution and composition distribution of the olefin polymer or copolymer, and the olefin polymerization catalyst composition using the same. It is to provide a polymerization method.

In order to achieve the above object, the present invention is an organometallic compound represented by the formula (1); An organic transition metal compound represented by Formula 2; An organic transition metal compound represented by Formula 3 below; And it provides an olefin polymerization catalyst composition comprising aluminoxane.

(Cp ') _l M ¹ R ¹ _m R ² _n

In Formula 1, M ¹ is a group 1, 2, 12, 13, or 14 group element of the periodic table, and (Cp ') is a cyclic hydrocarbon group having 5 to 30 carbon atoms having two or more conjugated double bonds. , R ¹ and R ² are each independently a hydrocarbon group having 1 to 24 carbon atoms, l is 1 or more, an integer of less than or equal to the valence of M ¹ , m and n are each independently an integer of 0 to 2, l + m + n is equal to the valence of M ¹ .

(4HInd) ₂ M ² X ₂

[Formula 3] M ² X ₄

In Formulas 2 and 3, (4HInd) is a group having a tetrahydroindenyl nucleus, M ² is titanium (Ti), zirconium (Zr) or hafnium (Hf), and X is a halogen atom.

The present invention also provides a method for polymerizing olefins, which comprises polymerizing at least one olefin in the presence of the olefin polymerization catalyst composition.

The olefin polymerization catalyst composition according to the present invention can exhibit various properties by appropriately selecting and combining each component. Therefore, it is possible to customize the olefin polymer having a variety of properties, it is excellent commercial availability. In addition, the catalyst composition of the present invention can be prepared by a simple method, thereby reducing the catalyst preparation time and preparation step. In addition, the catalyst composition of the present invention exhibits not only high polymerization activity, but also exhibits a property that the polymerization activity remains constant, unlike the existing catalyst, in which the polymerization activity decreases with time of polymerization, and thus, the commercial productivity is excellent. In addition, the polymerization method of the olefin according to the present invention can easily control the molecular weight, molecular weight distribution and composition distribution of the olefin polymer or copolymer in a homogeneous phase (solution polymerization) or heterogeneous phase (gas phase or slurry polymerization).

Hereinafter, the present invention will be described in detail.

The olefin polymerization catalyst composition according to the present invention is an organometallic compound represented by the following formula (1); An organic transition metal compound represented by Formula 2, an organic transition metal compound represented by Formula 3 below; And aluminoxanes.

[Formula 1]

(Cp ') _l M ¹ R ¹ _m R ² _n

In Formula 1, M ¹ is a group 1, 2, 12, 13 or 14 group elements of the periodic table, for example, lithium (Li), sodium (Na), potassium (K), magnesium (Mg), Zinc (Zn), boron (B), aluminum (Al), gallium (Ga), indium (In), thallium (Thallium; Tl) and the like, preferably lithium (Li), sodium (Na), magnesium (Mg) Or aluminum (Al). (Cp ') is a cyclic hydrocarbon group having 5 to 30, preferably 5 to 13, carbon atoms having 2 or more, preferably 2 to 4, more preferably 2 or 3 conjugated double bonds. If necessary, it may be partially substituted with a substituent, for example, 1 to 6 substituents. Specific examples of the (Cp ') may include a substituted or unsubstituted cyclopentadienyl group, indenyl group, azulene group, fluorenyl group, and the like. The substituents may be the same or different from each other, alkyl, alkoxy, alkylsilyl, alkylsiloxy, alkylamino or haloalkyl having 1 to 20 carbon atoms, alkenyl or cycloalkyl having 3 to 20 carbon atoms, and 6 to 20 carbon atoms. Aryl, arylsilyl or aryloxy, arylalkyl or alkylaryl having 7 to 20 carbon atoms, a radical selected from the group consisting of halogen atoms and amino groups. R ¹ and R ² are each independently a hydrocarbon group having 1 to 24 carbon atoms, preferably 1 to 12 carbon atoms, for example, methyl, ethyl, propyl, isopropyl, butyl, t-butyl, isobutyl, pentyl Alkyl such as hexyl, octyl, cycloalkyl such as cyclopentyl, cyclohexyl, cycloheptyl, aryl such as phenyl, and arylalkyl such as benzyl. Further, l is 1 or more and an integer of more than ¹ atom of M, m and n are each independently an integer from 0 to 2, l + m + n is the same as that of M ¹ atoms.

[Formula 2]

(4HInd) ₂ M ² X ₂

In Formula 2, (4HInd) is a group having a tetrahydroindenyl nucleus, for example, a group having a 4,5,6,7-tetrahydroindenyl nucleus, M ² is titanium (Ti), zirconium (Zr ) Or hafnium (Hf), and X is a halogen atom, for example, fluorine, chlorine, bromine, iodine or the like. The 4HInd may be unsubstituted or have one or more substituents, for example, 1 to 11 substituents. The substituents may be the same or different from each other, alkyl, alkoxy, alkylsilyl, alkylsiloxy, alkylamino or haloalkyl having 1 to 20 carbon atoms, alkenyl or cycloalkyl having 3 to 20 carbon atoms, and 6 to 20 carbon atoms. Aryl, arylsilyl or aryloxy, arylalkyl or alkylaryl having 7 to 20 carbon atoms, a radical selected from the group consisting of halogen atoms and amino groups.

(3)

M ² X ₄

In Formula 3, M ² is titanium (Ti), zirconium (Zr) or hafnium (Hf), as defined in Formula 2, preferably the same as M ^{2 in} Formula 2, X is a halogen atom Fluorine, chlorine, bromine and iodine.

Non-limiting examples of the organometallic compound represented by the formula (1), cyclopentadienyl lithium, methyl cyclopentadienyl lithium, 1,2,3,4-tetramethyl cyclopentadienyl lithium, ethyl cyclopentadienyl Lithium, propyl cyclopentadienyl lithium, butyl cyclopentadienyl lithium, isobutyl cyclopentadienyl lithium, octadecyl cyclopentadienyl lithium, cyclopentyl cyclopentadienyl lithium, cyclohexyl cyclopentadienyl lithium, 1, 3-butylmethylcyclopentadienyllithium, indenylithium, 1-methylindenylithium, 2-methylindenylithium, 1-ethylindenylithium, 2-ethylindenylithium, 1-propylindenylithium, 2 -Propylindenylithium, 2-phenylindenylithium, 3-phenylindenylithium, fluorenyllithium, cyclopentadienylsodium, methylcyclopentadienylsodium, 1,2,3,4-tetramethylcyclopenta Dienylsodium, ethylcyclo Tadienyl sodium, propyl cyclopentadienyl sodium, butyl cyclopentadienyl sodium, isobutyl cyclopentadienyl sodium, octadecyl cyclopentadienyl sodium, cyclopentyl cyclopentadienyl sodium, cyclohexyl dicyclopentadien , 1,3-butylmethylcyclopentadienylsodium, indenyl sodium, 1-methyl indenyl sodium, 2-methyl indenyl sodium, 1-ethyl indenyl sodium, 2-ethyl indenyl sodium, 1-propyl indenyl Sodium, 2-propylinylsodium, 2-phenylindenylsodium, 3-phenylindenylsodium, fluorenylsodium, cyclopentadienylmagnesium methyl, cyclopentadienylmagnesium ethyl, cyclopentadienylmagnesium isobutyl, Cyclopentadienyl magnesium propyl, cyclopentadienyl magnesium heptyl, cyclopentadienyl magnesium octyl, methyl cyclopentadienyl magnesium methyl, methyl cyclopentadienyl magnesium Ethyl, methylcyclopentadienylmagnesium isobutyl, methylcyclopentadienylmagnesium propyl, methylcyclopentadienylmagnesium heptyl, methylcyclopentadienylmagnesium octyl, 1,2,3,4-tetramethylcyclopentadienylmagnesium Methyl, 1,2,3,4-tetramethylcyclopentadienylmagnesium ethyl, 1,2,3,4-tetramethylcyclopentadienylmagnesium isobutyl, 1,2,3,4-tetramethylcyclopentadier Neil magnesium propyl, 1,2,3,4-tetramethylcyclopentadienylmagnesium heptyl, 1,2,3,4-tetramethylcyclopentadienylmagnesium octyl, ethylcyclopentadienylmagnesium methyl, ethylcyclopentadidie Neil magnesium ethyl, ethyl cyclopentadienyl magnesium isobutyl, ethyl cyclopentadienyl magnesium propyl, ethyl cyclopentadienyl magnesium heptyl, ethyl cyclopentadienyl magnesium octyl, Propyl Cyclopentadienyl Magnesium Methyl, Propyl Cyclopentadienyl Magnesium Ethyl, Propyl Cyclopentadienyl Magnesium Isobutyl, Propyl Cyclopentadienyl Magnesium Propyl, Propyl Cyclopentadienyl Magnesium Heptyl, Propyl Cyclopentadienyl Methyl Cyclopentadienyl magnesium methyl, butyl cyclopentadienyl magnesium ethyl, butyl cyclopentadienyl magnesium isobutyl, butyl cyclopentadienyl magnesium propyl, butyl cyclopentadienyl magnesium heptyl, butyl oxy dimethyl dipentane Cyclopentadienyl magnesium methyl, isobutyl cyclopentadienyl magnesium ethyl, isobutyl cyclopentadienyl magnesium isobutyl, isobutyl cyclopentadienyl magnesium propyl, isobutyl cyclopentadienyl magnesium heptyl, isobutyl Butylcyclopentadienylmagnesium octyl, octadecylcyclopentadienylmagnesium methyl, octadecylcyclopentadienylmagnesium ethyl, octadecylcyclopentadienylmagnesium isobutyl, octadecylcyclopentadienylmagnesium propyl Neil magnesium heptyl, octadecyl cyclopentadienyl magnesium octyl, cyclopentyl cyclopentadienyl magnesium methyl, cyclopentyl cyclopentadienyl magnesium ethyl, cyclopentyl cyclopentadienyl magnesium isobutyl dimethyl isobutyl Cyclopentylcyclopentadienylmagnesium heptyl, cyclopentylcyclopentadienylmagnesium octyl, cyclohexylcyclopentadienylmagnesium methyl, cyclohexylcyclopentadienylmagnesium ethyl, cyclopentadiyl Neil magnesium isobutyl, cyclohexyl cyclopentadienyl magnesium propyl, cyclohexyl cyclopentadienyl magnesium heptyl, cyclohexyl cyclopentadienyl magnesium octyl, 1,3-butylmethylcyclopentadienyl magnesium, 1,3-butyl methyl, Methylcyclopentadienylmagnesium ethyl, 1,3-butylmethylcyclopentadienylmagnesium isobutyl, 1,3-butylmethylcyclopentadienylmagnesium propyl, 1,3-butylmethylcyclopentadienylmagnesium heptyl, 1, 3-butylmethylcyclopentadienylmagnesium octyl, bis (cyclopentadienyl) magnesium, bis (alkyl-cyclopentadienyl) magnesium, bis (indenyl) magnesium, bis (alkyl-indenyl) magnesium, indenylmagnesium Methyl, indenylmagnesium ethyl, indenylmagnesium isobutyl, indenylmagnesium propyl, indenylmagnesium heptyl, indenylmagnesium octyl, 2-methyl Denyl magnesium methyl, 2-methyl indenyl magnesium ethyl, 2-methyl indenyl magnesium isobutyl, 2-methyl indenyl magnesium propyl, 2-methyl indenyl magnesium heptyl, 2-methyl indenyl magnesium octyl, 3-methyl indenyl Magnesium Methyl, 3-methylindenylmagnesium ethyl, 3-methylindenylmagnesium isobutyl, 3-methylindenylmagnesium propyl, 3-methylindenylmagnesium heptyl, 3-methylindenylmagnesium octyl, 2-phenylindenylmagnesium Methyl, 2-phenyl indenyl magnesium ethyl, 2-phenyl indenyl magnesium isobutyl, 2-phenyl indenyl magnesium propyl, 2-phenyl indenyl magnesium heptyl, 2-phenyl indenyl magnesium octyl, 3-phenyl indenyl magnesium methyl , 3-phenyl indenyl magnesium ethyl, 3-phenyl indenyl magnesium isobutyl, 3-phenyl indenyl magnesium propyl, 3-phenyl indenyl magnesium heptyl, 3-phenyl indenyl magnesium octyl, fluorenyl magnesium methyl, fluore Neil Magnesium Ethyl, fluorenyl magnesium isobutyl, fluorenyl magnesium propyl, fluorenyl magnesium heptyl, fluorenyl magnesium octyl, cyclopentadienyl aluminum dimethyl, cyclopentadienyl aluminum diethyl, cyclopentadienyl aluminum diisobutyl , Cyclopentadienyl aluminum dipropyl, cyclopentadienyl aluminum diheptyl, cyclopentadienyl aluminum dioctyl, methyl cyclopentadienyl aluminum dimethyl, methyl cyclopentadienyl aluminum diethyl, methyl cyclopentadienyl aluminum diiso Butyl, methylcyclopentadienylaluminum dipropyl, methylcyclopentadienylaluminum diheptyl, methylcyclopentadienylaluminum dioctyl, 1,2,3,4-tetramethylcyclopentadienylaluminum dimethyl, 1,2, 3,4-tetramethylcyclopentadienylaluminum diethyl, 1,2,3,4-tetramethyl Iclopentadienyl aluminum diisobutyl, 1,2,3,4-tetramethylcyclopentadienylaluminum dipropyl, 1,2,3,4-tetramethylcyclopentadienylaluminum diheptyl, 1,2, 3,4-tetramethylcyclopentadienylaluminum dioctyl, ethylcyclopentadienylaluminum dimethyl, ethylcyclopentadienylaluminum diethyl, ethylcyclopentadienylaluminum diisobutyl, ethylcyclopentadienylaluminum dipropyl, Ethyl Cyclopentadienyl Aluminum Diheptyl, Ethyl Cyclopentadienyl Aluminum Dioctyl, Propylcyclopentadienyl Aluminum Dimethyl, Propylcyclopentadienyl Aluminum Diethyl, Propylcyclopentadienyl Aluminum Diisobutyl, Propylcyclopentadienyl Aluminum dipropyl, propylcyclopentadienylaluminum diheptyl, propylcyclopentadienylaluminum dioctyl, Butylcyclopentadienyl aluminum dimethyl, butylcyclopentadienyl aluminum diethyl, butylcyclopentadienyl aluminum diisobutyl, butyl cyclopentadienyl aluminum dipropyl, butyl cyclopentadienyl aluminum diheptyl, butyl cyclopentadienyl Aluminum Dioctyl, Isobutyl Cyclopentadienyl Aluminum Dimethyl, Isobutyl Cyclopentadienyl Aluminum Diethyl, Isobutyl Cyclopentadienyl Aluminum Diisobutyl, Isobutyl Cyclopentadienyl Aluminum Dipropyl, Isobutyl Cyclopentadienyl Aluminum Diheptyl, Isobutyl Cyclopentadienyl Aluminum Dioctyl, Octadecylcyclopentadienyl Aluminum Dimethyl, Cyclopentadienyl Aluminum Diethyl, Octadecylcyclopentadienyl Aluminum Diisobutyl, Octadecylcyclopentadienyl Aluminum Di Profile, octadecyl Cyclopentadienyl aluminum diheptyl, octadecylcyclopentadienyl aluminum dioctyl, cyclopentylcyclopentadienyl aluminum dimethyl, cyclopentylcyclopentadienyl aluminum diethyl, cyclopentylcyclo cyclopentadienyl aluminum diisobutyl, cyclopentadienyl Cyclopentadienyl aluminum dipropyl, cyclopentyl cyclopentadienyl aluminum diheptyl, cyclopentyl cyclopentadienyl aluminum dioctyl, cyclohexyl cyclopentadienyl aluminum dimethyl, cyclohexyl cyclopentadienyl aluminum diethyl, cyclohexyl Pentadienyl Aluminum Diisobutyl, Cyclohexyl Cyclopentadienyl Aluminum Dipropyl, Cyclohexyl Cyclopentadienyl Aluminum Diheptyl, Cyclohexyl Cyclopentadienyl Aluminum Dioctyl, 1,3-Butylmethylcyclopentadiene Neil aluminum dimethyl, 1,3-butylmethylcyclopentadienylaluminum diethyl, 1,3-butylmethylcyclopentadienylaluminum diisobutyl, 1,3-butylmethylcyclopentadienylaluminum dipropyl, 1,3 -Butylmethylcyclopentadienylaluminum diheptyl, 1,3-butylmethylcyclopentadienylaluminum dioctyl, indenylaluminum dimethyl, indenylaluminum diethyl, indenylaluminum diisobutyl, indenylaluminum dipropyl, Neil aluminum diheptyl, indenyl aluminum dioctyl, 2-methyl indenyl aluminum dimethyl, 2-methyl indenyl aluminum diethyl, 2-methyl indenyl aluminum diisobutyl, 2-methyl indenyl aluminum dipropyl, 2-methyl Indenyl aluminum diheptyl, 2-methyl indenyl aluminum dioctyl, 3-methyl indenyl aluminum dimethyl, 3-methyl indenyl aluminum diethyl, 3-methyl indenyl aluminum diisobutyl, 3-methyl indenyl aluminum dip Phil, 3-methylindenylaluminum diheptyl, 3-methylindenylaluminum dioctyl, 2-phenylindenylaluminum dimethyl, 2-phenylindenylaluminum diethyl, 2-phenylindenylaluminum diisobutyl, 2-phenyl Indenylaluminum dipropyl, 2-phenylindenylaluminum diheptyl, 2-phenylindenylaluminum dioctyl, 3-phenylindenylaluminum dimethyl, 3-phenylindenylaluminum diethyl, 3-phenylindenylaluminum diisobutyl , 3-phenylindenaluminum dipropyl, 3-phenylindenaluminum diheptyl, 3-phenylindenaluminum dioctyl, fluorenylaluminum dimethyl, fluorenylaluminum diethyl, fluorenylaluminum diisobutyl, flu Orenylaluminum dipropyl, fluorenylaluminum diheptyl, fluorenylaluminum dioctyl, bis (cyclopentadienyl) aluminum ethyl, bis (cyclopentadienyl) aluminum methyl, bis (methyl-cyclopentadienyl) al Medium ethyl, tris (cyclopentadienyl) aluminum, tris (methyl-cyclopentadienyl) aluminum, bis (indenyl) aluminum ethyl, bis (methyl-indenyl) aluminum ethyl, tris (indenyl) aluminum, tris ( Methyl-indenyl) aluminum etc. can be illustrated and these compounds can be used individually or in mixture of 2 or more types.

Non-limiting examples of the organic transition metal compound represented by the formula (2), bis (tetrahydro indenyl) zirconium diflurolide, bis (1-methyltetrahydro indenyl) zirconium diflurolide, bis (1- normal propyl) Tetrahydroindenyl) zirconium difluoride, bis (1-isopropyltetrahydroindenyl) zirconium diflurolide, bis (1-normalbutyltetrahydroindenyl) zirconium difluoride, bis (1-cyclopentyltetrahydro Indenyl) zirconium diflurolide, bis (1-cyclohexyl tetrahydroindenyl) zirconium diflurolide, bis (1,2-dimethyltetrahydroindenyl) zirconium diflurolide, bis (1-isobutyltetrahydroinde Nyl) zirconium diflurolide, bis (4-methyltetrahydroindenyl) zirconium diflurolide, bis (5-methyltetrahydroin Denyl) zirconium diflurolide, bis (4,5-dimethyltetrahydroindenyl) zirconium diflurolide, bis (5,7-dimethyltetrahydroindenyl) zirconium diflurolide, bis (4,5,6,7 Tetramethyltetrahydroindenyl) zirconium diflurolide, bis (2-methyltetrahydroindenyl) zirconium diflurolide, bis (2-normalpropyltetrahydroindenyl) zirconium diflurolide, bis (2-isopropyl Tetrahydroindenyl) zirconium difluoride, bis (2-normalbutyltetrahydroindenyl) zirconium diflurolide, bis (2-cyclopentyltetrahydroindenyl) zirconium diflurolide, bis (2-cyclohexyl tetrahydro Indenyl) zirconium diflurolide, bis (1,2-dimethyltetrahydroindenyl) zirconium diflurolide, bis (2-isobutyltetrahydroindenyl) zirconium Difluoride, Bis (tetrahydroindenyl) zirconium dichloride, Bis (1-methyltetrahydroindenyl) zirconium dichloride, Bis (1-normalpropyltetrahydroindenyl) zirconium dichloride, Bis (1-isopropyl Tetrahydroindenyl) zirconium dichloride, bis (1-normalbutyltetrahydroindenyl) zirconium dichloride, bis (1-cyclopentyltetrahydroindenyl) zirconium dichloride, bis (1-cyclohexyl tetrahydroindenyl) Zirconium dichloride, bis (1,2-dimethyltetrahydroindenyl) zirconium dichloride, bis (1-isobutyltetrahydroindenyl) zirconium dichloride, bis (4-methyltetrahydroindenyl) zirconium dichloride, bis (5-methyltetrahydroindenyl) zirconium dichloride, bis (4,5-dimethyltetrahydroindenyl) zirco Dichloride, bis (5,7-dimethyltetrahydroindenyl) zirconium dichloride, bis (4,5,6,7-tetramethyltetrahydroindenyl) zirconium dichloride, bis (2-methyltetrahydroindenyl) Zirconium dichloride, bis (2-normalpropyltetrahydroindenyl) zirconium dichloride, bis (2-isopropyltetrahydroindenyl) zirconium dichloride, bis (2-normalbutyltetrahydroindenyl) zirconium dichloride, bis (2-cyclopentyltetrahydroindenyl) zirconium dichloride, bis (2-cyclohexyl tetrahydroindenyl) zirconium dichloride, bis (1,2-dimethyltetrahydroindenyl) zirconium dichloride, bis (2-iso) Butyltetrahydroindenyl) zirconium dichloride, bis (tetrahydroindenyl) zirconium dibromide, bis (1-methyltetrahydro Nyl) zirconium dibromide, bis (1-normalpropyltetrahydroindenyl) zirconium dibromide, bis (1-isopropyltetrahydroindenyl) zirconium dibromide, bis (1-normalbutyltetrahydroindenyl) zirconium dibromide , Bis (1-cyclopentyltetrahydroindenyl) zirconium dibromide, bis (1-cyclohexyl tetrahydroindenyl) zirconium dibromide, bis (1,2-dimethyltetrahydroindenyl) zirconium dibromide, bis (1 Isobutyltetrahydroindenyl) zirconium dibromide, bis (4-methyltetrahydroindenyl) zirconium dibromide, bis (5-methyltetrahydroindenyl) zirconium dibromide, bis (4,5-dimethyltetrahydroinde Nil) zirconium dibromide, bis (5,7-dimethyltetrahydroindenyl) zirconium dibromide, bis (4,5,6,7-tetramethyl Tetrahydroindenyl) zirconium dibromide, bis (2-methyltetrahydroindenyl) zirconium dibromide, bis (2-normalpropyltetrahydroindenyl) zirconium dibromide, bis (2-isopropyltetrahydroindenyl) zirconium Dibromide, bis (2-normalbutyltetrahydroindenyl) zirconium dibromide, bis (2-cyclopentyltetrahydroindenyl) zirconium dibromide, bis (2-cyclohexyl tetrahydroindenyl) zirconium dibromide, bis ( 1,2-dimethyltetrahydroindenyl) zirconium dibromide, bis (2-isobutyltetrahydroindenyl) zirconium dibromide, bis (tetrahydroindenyl) zirconium diiodide, bis (1-methyltetrahydroindenyl ) Zirconium diiodide, bis (1-normalpropyltetrahydroindenyl) zirconium diiodide, non S (1-isopropyltetrahydroindenyl) zirconium diiodide, bis (1-normalbutyltetrahydroindenyl) zirconium diiodide, bis (1-cyclopentyltetrahydroindenyl) zirconium diiodide, bis ( 1-cyclohexyl tetrahydroindenyl) zirconium diiodide, bis (1,2-dimethyltetrahydroindenyl) zirconium diiodide, bis (1-isobutyltetrahydroindenyl) zirconium diiodide, bis (4 -Methyltetrahydroindenyl) zirconium diiodide, bis (5-methyltetrahydroindenyl) zirconium diiodide, bis (4,5-dimethyltetrahydroindenyl) zirconium diiodide, bis (5,7- Dimethyltetrahydroindenyl) zirconium diiodide, bis (4,5,6,7-tetramethyltetrahydroindenyl) zirconium diiodide, bis (2-methyltetrahi Rodenil) zirconium diiodide, bis (2-normalpropyltetrahydroindenyl) zirconium diiodide, bis (2-isopropyltetrahydroindenyl) zirconium diiodide, bis (2-normalbutyltetrahydroinde Nil) zirconium diiodide, bis (2-cyclopentyltetrahydroindenyl) zirconium diiodide, bis (2-cyclohexyl tetrahydroindenyl) zirconium diiodide, bis (1,2-dimethyltetrahydroindenyl ) Zirconium diiodide, bis (2-isobutyltetrahydroindenyl) zirconium diiodide, etc. can be illustrated, and these compounds can be used individually or in mixture of 2 or more types. In addition, the organic transition metal compound represented by Formula 2 is not limited to the examples given above, and includes an organic transition metal compound compound consisting of a ligand having another substituted or unsubstituted tetrahydroindenyl (4HInd) nucleus.

Non-limiting examples of the organic transition metal compound represented by Formula 3, titanium fluoride, titanium chloride, titanium bromide, titanium iodide, zirconium fluoride, zirconium chloride, zirconium bromide, zirconium iodide, hafnium fluoride , Hafnium chloride, hafnium bromide, hafnium iodide and the like can be exemplified. The compounds represented by Chemical Formulas 1 to 3 may be prepared according to known methods for preparing metallocene compounds, or may be easily obtained commercially.

The aluminoxanes included in the olefin polymerization catalyst composition according to the present invention are for removing the impurities and the function of the activator for the catalyst component, and may have a linear, cyclic or network structure. As said aluminoxane, the compound represented by following formula (4) can be used, For example, the linear aluminoxane represented by following formula (5), the cyclic aluminoxane represented by following formula (6), etc. can be used.

[Formula 4]

In Formula 4, R 'is a hydrocarbon radical having 1 to 10 carbon atoms, x is an integer of 1 to 70.

[Chemical Formula 5]

[Formula 6]

In Formulas 5 and 6, each R 'is independently a hydrocarbon radical, preferably a linear or branched alkyl radical having 1 to 10 carbon atoms, more preferably a majority of R' is a methyl group, and x is It is an integer of 1-50, Preferably it is 10-40, y is an integer of 3-50, Preferably it is 10-40.

In the present invention, a commercially available alkyl aluminoxane can be used as the aluminoxane. Non-limiting examples of the alkyl aluminoxane include methyl aluminoxane, ethyl aluminoxane, butyl aluminoxane, isobutyl aluminoxane, hexyl aluminoxane, octyl aluminoxane, decyl aluminoxane and the like. In addition, the aluminoxane is commercially available in various forms of a hydrocarbon solution, and among them, it is preferable to use an aromatic hydrocarbon solution aluminoxane, and more preferably to use an aluminoxane solution dissolved in toluene. The aluminoxanes may be used alone or in combination of one or more thereof. The alkyl aluminoxane may be prepared by a conventional method such as adding an appropriate amount of water to trialkylaluminum, or reacting a trialkylaluminum with a hydrocarbon compound or an inorganic hydrate salt containing water, and generally linear and cyclic alumina. Green acid is obtained in mixed form.

In the catalyst composition for olefin polymerization according to the present invention, the content of the organometallic compound represented by Formula 1 is 0.2 to 20 moles, preferably 0.5 to 1 mole of the total organic transition metal compound of Formulas 2 and 3. To 10 moles, and the content of the aluminoxane is included so that the aluminum of the aluminoxane is 1 to 100,000 moles, preferably 5 to 2,500 moles, more preferably 5 to 1,000 moles, and most preferably 10 to 500 moles. The molar ratio of the organic transition metal compound represented by Formula 2 to the organic transition metal compound represented by Formula 3 is 1: 0.8 to 1.2, preferably 0.9 to 1.1. Here, when the content of the organometallic compound represented by the formula (1) and the organic transition metal compound of the formula (2) and formula (3) is out of the range, there is a fear that the performance of the catalyst.

In the catalyst composition for olefin polymerization according to the present invention, the mixing of each component may be optionally performed without particular limitation. For example, four components (compounds) are mixed at the same time for 5 minutes to 24 hours, preferably 15 minutes to 16 hours, or the organometallic compound represented by Formula 1 and aluminoxane are 5 minutes to 10 hours, Preferably, the mixture is first mixed for 15 minutes to 4 hours, and then it is added to the reaction mixture of the organic transition metal compound represented by Formulas 2 and 3 and aluminoxane for 5 minutes to 24 hours, preferably 15 minutes to 16 hours. Can be mixed during. Mixing of the compounds is preferably carried out in the presence of an inert hydrocarbon solvent such as heptane, hexane, benzene, toluene, xylene, or mixtures thereof, in the absence of a solvent, usually under an inert atmosphere of nitrogen or argon. . The temperature of the mixing process is 0 to 150 ℃, preferably 10 to 90 ℃. The catalyst in a solution state uniformly dissolved in the hydrocarbon solvent or the like may be used as it is, or may be used in a solid powder state in which the solvent is removed. The catalyst in the solid powder state may precipitate a catalyst in a solution state and then precipitate the precipitate. It can also be prepared by a method of solidifying.

The catalyst composition for olefin polymerization according to the present invention is an organic or inorganic carrier supporting an organometallic compound represented by Formula 1, an organic transition metal compound represented by Formula 2, an organic transition metal compound represented by Formula 3, and aluminoxane ( Carrier may be further included. Thus, the catalyst composition according to the present invention may be present in the form of being supported on the carrier as well as in a homogeneous solution or in the form of insoluble particles of the carrier.

Examples of the method of contacting the catalyst composition according to the present invention to the carrier are as follows, but are not limited to the following methods. First, the organometallic compound represented by Formula 1; An organic transition metal compound represented by Formula 2; An organic transition metal compound represented by Formula 3; And a catalyst in solution prepared by mixing aluminoxane with a porous carrier (eg, a silica carrier having a pore size of 50 to 500 mm 3 and a pore volume of 0.1 to 5.0 cm 3 / g) to make a slurry. Next, an acoustic wave or vibration wave in the frequency range of 1 to 10,000 kHz is applied to the mixture in the slurry state for 1 to 6 hours at 0 ° C. to 120 ° C., so that the catalyst components are uniformly infiltrated deep into the micropores of the carrier. Next, the carrier in which the catalyst has penetrated is dried in a vacuum or in a nitrogen stream to prepare a catalyst in the form of a solid powder. The acoustic wave or vibration wave is preferably ultrasonic waves, more preferably using a frequency of 20 to 500 kHz. The supporting of the catalyst on the carrier may include adding the acoustic or vibration wave and then washing the supported catalyst using a hydrocarbon selected from the group consisting of pentane, hexane, heptane, isoparaffin, toluene, xylene and mixtures thereof. It may further include.

As the carrier, a porous inorganic material, an inorganic salt, an organic compound, etc. having fine pores and a large surface area can be used without limitation. The form of the inorganic carrier is not particularly limited as long as it can obtain a predetermined form in the process for preparing the supported catalyst. For example, the inorganic carrier may have a form of powder, particles, flakes, foils, fibers, or the like. Regardless of the form of the inorganic carrier, the maximum length of the inorganic carrier is 5 to 200 mu m, preferably 10 to 100 mu m, the surface area of the inorganic carrier is 50 to 1,000 m 2 / g, and the void volume is 0.05 to 5 cm 3. / g is preferred. In general, the inorganic carrier must undergo a water or hydroxy group removal process before use, which can be carried out by calcining the carrier to a temperature of 200 ℃ to 900 ℃ in an inert gas atmosphere such as air, nitrogen, argon. Non-limiting examples of the inorganic salt or inorganic carrier include silica, alumina, bauxite, zeolite, magnesium chloride (MgCl ₂ ), calcium chloride (CaCl ₂ ), magnesium oxide (MgO), zirconium oxide (ZrO ₂ ) Silica-magnesium oxide as titanium oxide (TiO ₂ ), boron oxide (B ₂ O ₃ ), calcium oxide (CaO), zinc oxide (ZnO), barium oxide (BaO), thorium oxide (ThO ₂ ) or mixtures thereof (SiO ₂ -MgO), silica-alumina (SiO ₂ -Al ₂ O ₃ ), silica-titanium oxide (SiO ₂ -TiO ₂ ), silica-vanadium pentoxide (SiO ₂ -V ₂ O ₅ ), silica-chromium oxide (SiO ₂ -CrO ₃ ), silica-titanium oxide-magnesium oxide (SiO ₂ -TiO ₂ -MgO), or compounds containing small amounts of carbonate, sulfate or nitrate in these compounds Non-limiting examples of the organic compound carrier may include starch, cyclodextrin, synthetic polymers, and the like. The solvent used when contacting the catalyst according to the present invention with the carrier is an aliphatic hydrocarbon solvent such as pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, benzene, monochlorobenzene, dichlorobenzene, trichloro Aromatic hydrocarbon solvents, such as robenzene and toluene, and halogenated aliphatic hydrocarbon solvents, such as dichloromethane, trichloromethane, dichloroethane, and trichloroethane, etc. can be used.

The present invention also provides a polymerization method of olefins, which comprises polymerizing at least one olefin in the presence of the olefin polymerization catalyst composition. The catalyst composition according to the present invention may be present in the form of an insoluble particle of a carrier or a carrier supported on an inorganic carrier (for example, silica, alumina, silica-alumina mixture, etc.) as well as a homogeneous solution. (Bulk Phase) or gas phase polymerization can be used. In addition, each polymerization reaction condition varies depending on the state of the catalyst used (uniform or heterogeneous phase (supported type)), the polymerization method (solution polymerization, slurry polymerization, gas phase polymerization), the desired polymerization result or the form of the polymer. Can be modified. The degree of modification thereof is apparent to those skilled in the art. When the polymerization is carried out in a liquid phase or a slurry phase, a solvent or olefin itself may be used as a medium. The solvent includes propane, butane, pentane, hexane, octane, decane, dodecane, cyclopentane, methylcyclopentane, cyclohexane, benzene, toluene, xylene, dichloromethane, chloroethane, 1,2-dichloroethane, chloro Benzene etc. can be illustrated and these solvent can also be mixed and used in fixed ratio.

The olefin polymerization catalyst composition according to the invention can be used not only for the homopolymerization of olefin monomers but also for the copolymerization of olefin monomers / comonomers. Preferred olefins for the polymerization or copolymerization include alpha-olefins, cyclic olefins, dienes, trienes, styrenes and the like. The alpha-olefins include aliphatic olefins having 2 to 12 carbon atoms, preferably 2 to 8 carbon atoms, specifically, ethylene, propylene, butene-1, pentene-1, 3-methylbutene-1, hexene-1, 4-methylpentene-1, 3-methylpentene-1, heptene-1, octene-1, decene-1 (decene-1), 4,4-dimethyl-1-pentene, 4,4-diethyl-1- Hexene, 3,4-dimethyl-1-hexene and the like can be exemplified. In addition, the alpha-olefins may be homopolymerized or two or more olefins may be alternating, random, or block copolymerized. Copolymerization of the alpha-olefins is copolymerization of ethylene and alpha-olefin having 3 to 12, preferably 3 to 8 carbon atoms (for example, ethylene and propylene, ethylene and butene-1, ethylene and hexene-1 and ethylene 4-methylpentene-1, ethylene and octene-1, etc.) and copolymerization of propylene with alpha-olefins of 4 to 12, preferably 4 to 8, carbon atoms (propylene and butene-1, propylene and 4-methylpentene-1 , Propylene and 4-methylbutene-1, propylene and hexene-1, propylene and octene-1). In the copolymerization of ethylene or propylene with other alpha-olefins, the amount of other alpha-olefins is 90 mol% or less of the total monomers, usually 40 mol% or less, preferably 30 mol% or less, more preferably in the case of ethylene copolymers. Is 20 mol% or less, in the case of the propylene copolymer, 1 to 90 mol%, preferably 5 to 90 mol%, more preferably 10 to 70 mol%.

As the cyclic olefins, cyclic olefins having 3 to 24 carbon atoms, preferably 3 to 18 carbon atoms, may be used. Specifically, cyclopentene, cyclobutene, cyclohexene, 3-methylcyclohexene, cyclooctene and tetra Cyclodecene, octacyclodecene, dicyclopentadiene, norbornene, 5-methyl-2-norbornene, 5-ethyl-2-norbornene, 5-isobutyl-2-norbornene, 5,6 -Dimethyl-2-norbornene, 5,5,6-trimethyl-2-norbornene, ethylene norbornene and the like can be exemplified. The cyclic olefins can be copolymerized with the alpha-olefins, wherein the amount of the cyclic olefin is 1 to 50 mol%, preferably 2 to 50 mol% with respect to the copolymer. In addition, the dienes and triene (polyene) is preferably a polyene having 4 to 26 carbon atoms having two or three double bonds, specifically 1,3-butadiene, 1,4-pentadiene, 1,4-hexa Dienes, 1,5-hexadiene, 1,9-decadiene, 2-methyl-1,3-butadiene and the like can be exemplified. Examples of the styrenes may include styrene or styrene substituted with an alkyl group having 1 to 10 carbon atoms, an alkoxy group or a halogenated alkyl group, a halogen group, an amine group, a silyl group, or the like.

In the polymerization or copolymerization of the olefin according to the present invention, the amount of the catalyst composition to be used is not particularly limited. Preferably, the concentration of the central metal of the organic transition metal compound represented by Chemical Formulas 2 and 3 in the reaction system to be polymerized is 10- ^{. 8} to 10 ¹ ㏖ / ℓ, and should preferably, less than 10 ^-7 to 10 ^-2 ㏖ / ℓ is more preferred. In the polymerization or copolymerization of the olefin according to the present invention, the polymerization temperature is not particularly limited because it may vary depending on the reaction material, reaction conditions, etc., but in the case of solution polymerization is 0 to 250 ℃, preferably 10 to 200 ℃, In the case of slurry or gas phase polymerization, it is 0-120 degreeC, Preferably it is 20-100 degreeC. In addition, the polymerization pressure is from atmospheric pressure to 500 kg / ㎠, preferably atmospheric pressure to 50 kg / ㎠, the polymerization can be carried out batchwise, semi-continuous or continuous. The polymerization can also be carried out in two or more steps with different reaction conditions, and the molecular weight of the final polymer can be controlled by varying the polymerization temperature or by injecting hydrogen into the reactor.

The olefin polymerization catalyst composition according to the present invention can be used not only for the main polymerization of the olefin monomer but also for the prepolymerization process. In the prepolymerization process, the olefin polymer or copolymer is preferably produced in 0.05 to 500 g, preferably 0.1 to 300 g, more preferably 0.2 to 100 g per 1 g of the olefin catalyst. Olefins usable in the prepolymerization process are ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1- C2-C20 alpha olefins, such as tetradecene, 3-methyl-1- butene, 3-methyl-1- pentene, etc. can be illustrated, It is preferable to use the same olefin as used for this polymerization. .

Hereinafter, the present invention will be described in more detail with reference to specific examples. The following examples are provided to illustrate the present invention, but the scope of the present invention is not limited by the following examples. In the following examples, the catalyst for olefin polymerization was prepared under Schlenk technique in which air and moisture were completely blocked, and purified dried nitrogen was used as the inert gas. The solvent was used after drying in the presence of sodium metal in an inert nitrogen atmosphere. Melt Index (MI) and High Load Melt Index (HLMI) of the polymer were measured according to ASTM D1238 and Density of the polymer according to ASTM D1505.

Example 1 Catalyst Preparation and Solution Polymerization of Ethylene

Under nitrogen atmosphere, 5.1 mg (0.018 mmol) of indenylaluminum diethyl (Ind-AlEt ₂ ), bis (tetrahydroindenyl) zirconium dichloride 2.4 mg (Mw: 401, 0.006 mmol), zirconium chloride (ZrCl) in a 500 ml flask ₄ ) 1.4 mg (0.006 mmol) and 10 ml of methylaluminoxane (MAO, Albemarle, 10% toluene solution) were mixed (Zr = 6.0 μmol, Al / Zr molar ratio = 2500) and stirred at 60 ° C. for 30 minutes, Catalyst solution was prepared.

A 1L stainless autoclave reactor equipped with a jacket capable of controlling the polymerization temperature by supplying external cooling water was sent once with isobutane and ethylene five times at about 85 ° C. to clean impurities in the reactor. After that, the temperature was lowered to room temperature. 300 mL of dried hexane and 1.0 mmol of triisobutylaluminum (TIBAL), an impurity remover, were added to the washed reactor at room temperature, and the temperature was raised to 70 ° C., and the catalyst solution was added directly to the reactor. Pressure) to increase the reactor pressure to the reaction pressure of 14 psig. After the polymerization was allowed to proceed for 1 hour, all the reaction gases were discharged and cooled to terminate the polymerization. A solution containing 5% by weight of hydrogen chloride (HCl) in 300 mL methanol was added to the reaction and stirred for about 2 hours to neutralize the MAO component and active catalyst component remaining in the polymer. The slurry containing the polymer was filtered and washed with 2 liters of water to obtain a polymer free of the hydrogen chloride component, and the obtained polymer was dried at 60 ° C. to give 60.5 g of the polymer. The polymerization activity of the catalyst was 9,967 g polymer / mol Zr. Time, the melt index (Melt Index: MI) of the prepared polymer was 0.18 g / 10 min, and the density was 0.9467 g / cm ³ .

Example 2 Preparation of Catalyst and Copolymerization of Ethylene / Hexene- 1

Under a nitrogen atmosphere, 318 mg of indenylaluminum diethyl (Ind-AlEt ₂ ), 124 mg of bis (tetrahydroindenyl) zirconium dichloride, 69 mg of zirconium chloride (ZrCl ₄ ) and methylaluminoxane (MAO, Albemarle, 10) in a 500 ml flask 50 ml of% toluene solution) was mixed and stirred at 60 ° C. for 30 minutes to prepare a catalyst solution. 10 g of silica calcined at 220 ° C. was added to the prepared catalyst solution, ultrasonic wave was applied for 90 minutes, and the supernatant was removed. The remaining solid particles were washed once with hexane, and then dried under vacuum to prepare a supported catalyst of free flowing solid powder.

A 1L stainless autoclave reactor equipped with a jacket capable of supplying external cooling water and controlling the polymerization temperature was sent once with isobutane and ethylene five times at about 110 ° C to wash impurities in the reactor, and then the temperature was 67 ° C. Lowered. 400 mL of isobutane and 1.0 mmol of triisobutylaluminum (TIBAL) as an impurity remover were added to the washed reactor, and stirred at 75 ° C., 100 mL of isobutane and 62 mg of the prepared supported catalyst were added to the reactor. Ethylene and 40 ml of 1-hexene were added to the reactor so that the ethylene partial pressure was 130 psig, and polymerization was performed for 3 hours while maintaining the reactor total pressure at 290 psig at 75 ° C. While the polymerization was in progress, the ethylene partial pressure was maintained at 130 psig, and the flow rate of additionally added ethylene was measured by a mass flow meter, and 10 wt% of 1-hexene was continuously added to the injected ethylene. After the polymerization was completed, unreacted 1-hexene and isobutane were discharged, and the reactor was opened to recover 348 g of free flowing polymer. During the 3 hours of polymerization, the polymerization rate was not lowered and remained steady. The polymerization activity of the catalyst was 1,850 g polymer / g.catalyst.time, and the melt index (Melt Index: MI) of the produced polymer was 1.16 g / 10 min and the density was 0.9297 g / cm ³ .

Example 3 Catalyst Preparation and Ethylene / Hexene- 1 Copolymerization

In a nitrogen atmosphere, 75 mg of indenyl lithium (Ind-Li), 124 mg of bis (tetrahydroindenyl) zirconium dichloride, 69 mg of zirconium chloride (ZrCl ₄ ) and methylaluminoxane (MAO, Albemarle, 10% toluene solution) in a 500 ml flask ) 50 ml were mixed and stirred at 60 ° C. for 90 minutes to prepare a catalyst solution. 10 g of silica calcined at 220 ° C. was added to the prepared catalyst solution, ultrasonic wave was applied for 90 minutes, and the supernatant was removed. The remaining solid particles were washed once with hexane, and then dried under vacuum to prepare a supported catalyst of free flowing solid powder. Except that 61 mg of the catalyst prepared in the catalyst preparation process was used, 327 g of polymer was obtained by polymerizing olefin in the same manner as in the polymerization method of Example 2 for 3 hours. During the 3 hours of polymerization, the polymerization rate was not lowered and remained steady. The polymerization activity of the catalyst was 1,737 g polymer / g.catalyst.time, and the melt index (Melt Index: MI) of the produced polymer was 1.14 g / 10 min and the density was 0.9308 g / cm ³ .

Example 4 Catalyst Preparation and Ethylene / Hexene- 1 Copolymerization

Under a nitrogen atmosphere, 323 mg of 2-methylindenaluminum diethyl (2-MeInd-AlEt ₂ ), 124 mg of bis (tetrahydroindenyl) zirconium dichloride, 69 mg of zirconium chloride (ZrCl ₄ ) and methylaluminoxane (MAO) in a 500 ml flask , Albemarle, 10% toluene solution) 50ml were mixed and stirred at 60 ° C. for 90 minutes to prepare a catalyst solution. 10 g of silica calcined at 220 ° C. was added to the prepared catalyst solution, ultrasonic wave was applied for 90 minutes, and the supernatant was removed. The remaining solid particles were washed once with hexane, and then dried under vacuum to prepare a supported catalyst of free flowing solid powder. Except that 60 mg of the catalyst prepared in the catalyst preparation process was used, 274 g of polymer was obtained by polymerizing olefin in the same manner as in the polymerization method of Example 2 for 3 hours. During the 3 hours of polymerization, the polymerization rate was not lowered and remained steady. The polymerization activity of the catalyst was 1,522 g polymer / g.catalyst.hours, and the melt index (Melt Index: MI) of the prepared polymer was 0.58 g / 10 min and the density was 0.9305 g / cm ³ .

Example 5 Catalyst Preparation and Ethylene / Hexene- 1 Copolymerization

Under a nitrogen atmosphere, 85 mg of 2-methylindenylithium (2-MeInd-Li), 124 mg of bis (tetrahydroindenyl) zirconium dichloride, 69 mg of zirconium chloride (ZrCl ₄ ) and methylaluminoxane (MAO, Albemarle) 50 ml of 10% toluene solution) was mixed and stirred at 60 ° C. for 90 minutes to prepare a catalyst solution. 10 g of silica calcined at 220 ° C. was added to the prepared catalyst solution, ultrasonic wave was applied for 90 minutes, and the supernatant was removed. The remaining solid particles were washed once with hexane, and then dried under vacuum to prepare a supported catalyst of free flowing solid powder. Except for using 61 mg of the catalyst prepared in the catalyst preparation process, olefin was polymerized for 3 hours in the same manner as in the polymerization method of Example 2 to obtain 294 g of a polymer. During the 3 hours of polymerization, the polymerization rate was not lowered and remained steady. The polymerization activity of the catalyst was 1,633 g polymer / g.catalyst.time, and the melt index (Melt Index: MI) of the produced polymer was 0.60 g / 10 min and the density was 0.9298 g / cm ³ .

Example 6 Preparation of Catalyst and Copolymerization of Ethylene / Hexene- 1

Under a nitrogen atmosphere, 111 mg of 1-normal butyl indenyl lithium (1-n-BuInd-Li), 124 mg of bis (tetrahydroindenyl) zirconium dichloride, 69 mg of zirconium chloride (ZrCl ₄ ) and methylaluminoxane (MAO) in a 500 ml flask , Albemarle, 10% toluene solution) 50ml were mixed and stirred at 60 ° C. for 90 minutes to prepare a catalyst solution. 10 g of silica calcined at 220 ° C. was added to the prepared catalyst solution, ultrasonic wave was applied for 90 minutes, and the supernatant was removed. The remaining solid particles were washed once with hexane, and then dried under vacuum to prepare a supported catalyst of free flowing solid powder. Except for using 61 mg of the catalyst prepared in the catalyst preparation process, olefin was polymerized for 3 hours in the same manner as in the polymerization method of Example 2 to obtain 205 g of a polymer. During the 3 hours of polymerization, the polymerization rate was not lowered and remained steady. The polymerization activity of the catalyst was 1,120 g polymer / g.catalyst.hours, and the melt index (Melt Index: MI) of the prepared polymer was 0.20 g / 10 min and the density was 0.9304 g / cm ³ .

Example 7 Catalyst Preparation and Ethylene / Hexene- 1 Copolymerization

Under a nitrogen atmosphere, in a 500 ml flask, 94 mg of 1-ethylindenylithium (1-EtInd-Li), 124 mg of bis (tetrahydroindenyl) zirconium dichloride, 69 mg of zirconium chloride (ZrCl ₄ ) and methylaluminoxane (MAO, Albemarle) 50 ml of 10% toluene solution) was mixed and stirred at 60 ° C. for 90 minutes to prepare a catalyst solution. 10 g of silica calcined at 220 ° C. was added to the prepared catalyst solution, ultrasonic wave was applied for 90 minutes, and the supernatant was removed. The remaining solid particles were washed once with hexane, and then dried under vacuum to prepare a supported catalyst of free flowing solid powder. Except that 60 mg of the catalyst prepared in the catalyst preparation process was used, 155 g of polymer was obtained by polymerizing olefin for 3 hours in the same manner as in the polymerization method of Example 2. During the 3 hours of polymerization, the polymerization rate was not lowered and remained steady. The polymerization activity of the catalyst was 861 g polymer / g catalyst. The melt index (Melt Index: MI) of the prepared polymer was 0.17 g / 10 min and the density was 0.9305 g / cm ³ .

Example 8 Preparation of Catalyst and Copolymerization of Ethylene / Hexene- 1

Under a nitrogen atmosphere, 280 mg of indenylaluminum diethyl (Ind-AlEt ₂ ), 124 mg of bis (tetrahydroindenyl) zirconium dichloride, 69 mg of zirconium chloride (ZrCl ₄ ) and methylaluminoxane (MAO, Albemarle, 10) in a 500 ml flask 50 ml of% toluene solution) was mixed and stirred at 80 ° C. for 60 minutes to prepare a catalyst solution. 10 g of silica calcined at 220 ° C. was added to the prepared catalyst solution, ultrasonic wave was applied for 90 minutes, and the supernatant was removed. The remaining solid particles were washed once with hexane, and then dried under vacuum to prepare a supported catalyst of free flowing solid powder. Except that 60 mg of the catalyst prepared in the catalyst preparation process was used, 335 g of polymer was obtained by polymerizing olefin in the same manner as in the polymerization method of Example 2 for 3 hours. During the 3 hours of polymerization, the polymerization rate was not lowered and remained steady. The polymerization activity of the catalyst was 1,861 g polymer / g. Catalyst. The melt index (Melt Index: MI) of the prepared polymer was 0.98 g / 10 min and the density was 0.9296 g / cm ³ .

Example 9 Catalyst Preparation and Ethylene / Hexene- 1 Copolymerization

Under a nitrogen atmosphere, 151 mg of tetramethylcyclopentadienyl lithium (Me ₄ CpLi), bis (tetrahydroindenyl) zirconium dichloride [(4HInd) ₂ ZrCl ₂ ] 124 mg, 69 mg zirconium chloride (ZrCl ₄ ) and methyl in a 500 ml flask 50 ml of aluminoxane (MAO, Albemarle, 10% toluene solution) was mixed and stirred at 90 ° C. for 60 minutes to prepare a catalyst solution. 10 g of silica calcined at 220 ° C. was added to the prepared catalyst solution, and the supernatant was removed after ultrasonic wave was applied for 1 hour. The remaining solid particles were washed once with hexane, and then dried under vacuum to prepare a supported catalyst of free flowing solid powder. Except that 60 mg of the catalyst prepared in the catalyst preparation process was used, olefin was polymerized in the same manner as in the polymerization method of Example 2 for 3 hours to obtain 210 g of a polymer. During the 3 hours of polymerization, the polymerization rate was not lowered and remained steady. The polymerization activity of the catalyst was 1,167 g polymer / g. Catalyst. Time, the melt index (Melt Index: MI) of the prepared polymer was 0.19 g / 10 min, and the density was 0.9271 g / cm ³ .

Comparative Example 1 Catalyst Preparation and Ethylene / Hexene- 1 Copolymerization

Under a nitrogen atmosphere, 10 ml of methylaluminoxane (MAO, Albemarle, 10% toluene solution) and 61 mg (0.2 mg mmol) of bis (cyclopentadienyl) zirconium dichloride (Cp ₂ ZrCl ₂ ) were mixed in a 500 ml flask at room temperature. The catalyst solution was prepared by stirring for 30 minutes. 2 g of silica calcined at 220 ° C. was added to the prepared catalyst solution, and the supernatant was removed after ultrasonic wave was applied for 1 hour. The remaining solid particles were washed once with hexane, and then dried under vacuum to prepare a supported catalyst of free flowing solid powder. Except that 60 mg of the catalyst prepared in the catalyst preparation process was used, olefin was polymerized for 60 minutes in the same manner as in the polymerization method of Example 2 to obtain 19 g of a polymer. The polymerization activity of the catalyst was very low, at 306 g polymer / g catalyst.

Comparative Example 2 Preparation of Catalyst and Copolymerization of Ethylene / Hexene- 1

In a nitrogen atmosphere, 11 ml of methylaluminoxane (MAO, Albemarle, 10% toluene solution) and 49 mg (0.21 mmol) of zirconium chloride (ZrCl ₄ ) were mixed in a 500 ml flask, and stirred at room temperature for 3 hours to prepare a catalyst solution. . 2 g of silica calcined at 220 ° C. was added to the prepared catalyst solution, and the supernatant was removed after ultrasonic wave was applied for 1 hour. The remaining solid particles were washed once with hexane, and then dried under vacuum to prepare a supported catalyst of free flowing solid powder. Except that 100 mg of the catalyst prepared in the catalyst preparation process was used, 8.6 g of the polymer was obtained by polymerizing olefin for 30 minutes in the same manner as in the polymerization method of Example 2. The polymerization activity of the catalyst was very low at 86 g polymer / g catalyst time.

From the above examples and comparative examples, the polymerization composition of the catalyst composition according to the present invention is excellent, in particular, by changing the type of the compound represented by the formula (1), (2) and (3), or the preparation conditions of the catalyst (the compound and alumina It can be seen that polymers having various melt indices (molecular weights) can be produced by changing the reaction time of noxic acid), polymerization conditions (temperature, etc.), and the like. Accordingly, the catalyst composition according to the present invention can be produced very simply, while having excellent polymerization activity, and also changing the components and mixing ratios of the constituent compounds, thereby preparing olefin polymers of various molecular weights and melt index (MI).

Claims (7)

An organometallic compound represented by Formula 1 below,
(Cp ') _l M ¹ R ¹ _m R ² _n
In Formula 1, M ¹ is a group 1, 2, 12, 13, or 14 group element of the periodic table, and (Cp ') is a cyclic hydrocarbon group having 5 to 30 carbon atoms having two or more conjugated double bonds. , R ¹ and R ² are each independently a hydrocarbon group having 1 to 24 carbon atoms, l is 1 or more, an integer of less than or equal to the valence of M ¹ , m and n are each independently an integer of 0 to 2, l + m + n is equal to the valence of M ¹ ;
An organic transition metal compound represented by Formula 2,
(4HInd) ₂ M ² X ₂
In Formula 2, (4HInd) is a group having a tetrahydroindenyl nucleus, M ² is titanium (Ti), zirconium (Zr) or hafnium (Hf), and X is a halogen atom;
An organic transition metal compound represented by Chemical Formula 3,
[Formula 3] M ² X ₄
In Formula 3, M ² is titanium (Ti), zirconium (Zr) or hafnium (Hf), and X is a halogen atom; And
An olefin polymerization catalyst composition comprising aluminoxane. The method of claim 1, wherein M ¹ is lithium (Li), sodium (Na), potassium (K), magnesium (Mg), zinc (Zn), boron (B), aluminum (Al), gallium (Ga), Indium (In) and thallium (Thallium; Tl), and (Cp ') is selected from the group consisting of a substituted or unsubstituted cyclopentadienyl group, indenyl group, azulene group, and fluorenyl group Will be, olefin polymerization catalyst composition. According to claim 1, wherein (Cp ') and (4HInd) is alkyl, alkoxy, alkylsilyl, alkylsiloxy, alkylamino or haloalkyl of 1 to 20 carbon atoms, alkenyl or cyclo of 3 to 20 carbon atoms The olefin polymerization catalyst composition which is substituted with a radical selected from the group consisting of alkyl, aryl, arylsilyl or aryloxy having 6 to 20 carbon atoms, arylalkyl or alkylaryl having 7 to 20 carbon atoms, a halogen atom and an amino group. The method of claim 1, wherein the amount of the organometallic compound represented by Formula 1 is 0.2 to 20 moles, and the content of the aluminoxane is about 1 mole of the total organic transition metal compound of Formula 2 and Formula 3 1 to 100,000 mol of aluminum is included, wherein the molar ratio of the organic transition metal compound represented by Formula 2: The organic transition metal compound represented by Formula 3 is 1: 0.8 to 1.2, olefin polymerization catalyst composition. The olefin according to claim 1, further comprising an organic metal compound represented by Formula 1, an organic transition metal compound represented by Formula 2, an organic transition metal compound represented by Formula 3, and an organic or inorganic carrier supporting aluminoxane. Polymerization catalyst composition. An organometallic compound represented by Formula 1 below,
(Cp ') _l M ¹ R ¹ _m R ² _n
In Formula 1, M ¹ is a group 1, 2, 12, 13, or 14 group element of the periodic table, and (Cp ') is a cyclic hydrocarbon group having 5 to 30 carbon atoms having two or more conjugated double bonds. , R ¹ and R ² are each independently a hydrocarbon group having 1 to 24 carbon atoms, l is 1 or more, an integer of less than or equal to the valence of M ¹ , m and n are each independently an integer of 0 to 2, l + m + n is equal to the valence of M ¹ ;
An organic transition metal compound represented by Formula 2,
(4HInd) ₂ M ² X ₂
In Formula 2, (4HInd) is a group having a tetrahydroindenyl nucleus, M ² is titanium (Ti), zirconium (Zr) or hafnium (Hf), and X is a halogen atom;
An organic transition metal compound represented by Chemical Formula 3,
[Formula 3] M ² X ₄
In Formula 3, M ² is titanium (Ti), zirconium (Zr) or hafnium (Hf), and X is a halogen atom; And
A method of polymerizing olefins comprising polymerizing at least one olefin in the presence of an olefin polymerization catalyst composition comprising aluminoxane. The method for polymerizing olefins according to claim 6, wherein the polymerization reaction is liquid phase, slurry phase, bulk phase or gas phase polymerization.