KR101720843B1 - Manufacturing method of ethylene polymers and ethylene polymers manufactured therefrom - Google Patents

Abstract

The present invention relates to a process for preparing an ethylene polymer by polymerizing ethylene alone or with ethylene and a monomer in the presence of a catalyst containing a specific metallocene-based transition metal compound as a main catalyst compound.

Description

TECHNICAL FIELD [0001] The present invention relates to an ethylene polymer and an ethylene polymer produced by the method. [0002]

The present invention relates to a process for the production of ethylene polymers with ethylene alone or with ethylene and monomers and to ethylene polymers prepared by this process.

Conventionally, a Ziegler-Natta catalyst system composed of a main catalyst component of a titanium or vanadium compound and a cocatalyst component of an alkylaluminum compound was used for preparing an ethylene homopolymer or a copolymer of ethylene and a monomer. However, although the Ziegler-Natta catalyst system exhibits high activity in the production of ethylene polymer, it is difficult to obtain a polymer having a specific molecular weight distribution due to a non-uniform catalytic activity point, and in particular, the copolymer composition of ethylene and monomer has a disadvantage in that the composition distribution is not uniform .

To improve this, a metallocene catalyst system having a compound containing a Group 4 transition metal of the periodic table as a main catalyst component has been developed. Such a metallocene catalyst system can produce a polymer having a narrow molecular weight distribution and uniform composition distribution as compared with the case of using a Ziegler-Natta catalyst system because the catalyst active sites are uniform.

However, there is a problem that it is difficult to obtain a polymer having a high molecular weight by the metallocene catalyst system. In particular, when applied to a solution polymerization method carried out at a high temperature of 140 ° C or higher, there is a limit to the production of a high molecular weight polymer having a weight-average molecular weight of 100,000 (Mw) or more because the polymerization activity rapidly decreases and the β-hydrogen elimination reaction predominates.

Korean Patent Publication No. 2010-0126650

It is an object of the present invention to provide a process for producing an ethylene polymer having a specific molecular weight distribution and a high molecular weight in order to solve the above problems.

It is also an object of the present invention to provide an ethylene polymer produced by the above production method.

In order to achieve the above object, the present invention provides a process for producing ethylene, comprising polymerizing ethylene alone or ethylene and a monomer in the presence of a catalyst,

(A) a main catalyst compound represented by the following general formula (I); And (B) at least one cocatalyst compound selected from the group consisting of compounds represented by the following formulas (III-1) and (III-2).

(I)

In the formula (I)

M is a Group 3 to 10 element in the periodic table,

X is C ₁ ~ C ₂₀ alkyl group, C ₃ ~ C ₂₀ cycloalkyl group, C ₁ ~ C ₂₀ alkylsilyl group, C ₁ ~ C ₂₀ alkylsilyl group, C ₆ ~ C ₂₀ aryl group, C ₆ ~ of an alkoxy group of C ₂₀ aryl group, C ₆ ~ C ₂₀ alkylaryl group, C ₆ ~ C ₂₀ aryl silyl group, C ₆ ~ C ₂₀ silyl aryl group, C ₁ ~ C ₂₀ of the, C ₁ ~ C ₂₀ An aryloxy group of C ₆ to C ₂₀ , a halogen group, and an amine group,

n is determined by the oxidation number of the central metal, is an integer of 1 to 5,

Cp ¹ and Cp ² each independently represent a ligand having a cyclopentadienyl skeleton, and has at least one substituent selected from the group consisting of the following formulas (II-1) and (II-2)

[Formula II-1]

[Formula II-2]

In the above formula (II-1) and (II-2)

Z is an element of group 15 or group 16 of the periodic table,

R is selected from the group consisting of hydrogen, a C ₁ to C ₂₀ alkyl group, a C ₃ to C ₂₀ cycloalkyl group, a C ₁ to C ₂₀ alkylsilyl group, a C ₁ to C ₂₀ silylalkyl group, a C ₆ to C ₂₀ aryl group, a C ₆ ~ C ₂₀ aryl group, selected from the group consisting of a silyl aryl of C ₆ ~ C ₂₀ alkylaryl group, C ₆ ~ C ₂₀ aryl silyl group and C ₆ ~ C ₂₀ of,

m is an integer of 1 or 2 determined depending on the kind of Z,

p is an integer of 1 to 5,

Other substituents bonded to CP ¹ and CP ² in addition to the substituents represented by the above general formulas II-1 and II-2, and other substituents bonded to carbon atoms in the phenyl ring not bonded to ZR _m in the general formulas II-1 and II- the other substituents being coupled are each independently hydrogen, C ₁ ~ C ₂₀ alkyl group, C ₃ ~ C ₂₀ cycloalkyl group, C ₁ ~ C ₂₀ alkylsilyl group, C ₁ ~ silyl group of C _20, C ₁ ~ C of _A C ₆ to C ₂₀ arylalkyl group, a C ₆ to C ₂₀ arylalkyl group, a C ₆ to C ₂₀ alkylaryl group, a C ₆ to C ₂₀ arylsilyl group, a C ₆ to C ₂₀ silyl An aryl group and a halogen group, and adjacent substituents may be bonded to each other to form a ring.

[Formula (III-1)

In the above formula (III-1)

R ¹ is a C ₁ -C ₁₀ alkyl group,

q is an integer of 1 to 70;

[Formula (III-2)

In the above formula (III-2)

R ^2, R ³ and R ⁴ are the same or different, each independently represent a C ₁ ~ C ₁₀ alkyl group, is selected from an alkoxy group, and the group consisting of a halogen, C ₁ ~ C ₁₀ of the, at this time, R ^2, R ^3, and at least one of R ⁴ is an alkyl group of C ₁ ~ C _10.

The present invention also provides an ethylene polymer produced by the above production method.

The ethylene polymer of the present invention can be defined as a polymer in which ethylene is contained in the molecular structure. At this time, the polymer is a concept including a copolymer such as a random copolymer, a block copolymer and the like.

The present invention relates to a process for polymerizing ethylene alone or in combination with ethylene and a monomer in the presence of a catalyst comprising the main catalyst compound represented by the above formula (I) and a promoter compound of any one of the above-mentioned formula (III-1) , An ethylene polymer having a specific molecular weight distribution and a high molecular weight can be provided.

Hereinafter, the present invention will be described.

1. Process for the production of ethylene polymers

The process for producing an ethylene polymer of the present invention comprises polymerizing ethylene alone or ethylene and a monomer in the presence of a specific metallocene catalyst different from the conventional metallocene catalyst. The specific metallocene catalyst includes the main catalyst compound (A) and the cocatalyst compound (B), which will be described in detail as follows.

The main catalyst compound (A) contained in the catalyst of the present invention is represented by the following general formula (I).

(I)

In the formula (I)

M is a Group 3 to 10 element in the periodic table,

X is C ₁ ~ C ₂₀ alkyl group, C ₃ ~ C ₂₀ cycloalkyl group, C ₁ ~ C ₂₀ alkylsilyl group, C ₁ ~ C ₂₀ alkylsilyl group, C ₆ ~ C ₂₀ aryl group, C ₆ ~ of an alkoxy group of C ₂₀ aryl group, C ₆ ~ C ₂₀ alkylaryl group, C ₆ ~ C ₂₀ aryl silyl group, C ₆ ~ C ₂₀ silyl aryl group, C ₁ ~ C ₂₀ of the, C ₁ ~ C ₂₀ An aryloxy group of C ₆ to C ₂₀ , a halogen group, and an amine group,

n is determined by the oxidation number of the central metal, is an integer of 1 to 5,

Cp ¹ and Cp ² each independently represent a ligand having a cyclopentadienyl skeleton, and has at least one substituent selected from the group consisting of the following formulas (II-1) and (II-2)

[Formula II-1]

[Formula II-2]

In the above formula (II-1) and (II-2)

Z is an element of group 15 or group 16 of the periodic table,

R is selected from the group consisting of hydrogen, a C ₁ to C ₂₀ alkyl group, a C ₃ to C ₂₀ cycloalkyl group, a C ₁ to C ₂₀ alkylsilyl group, a C ₁ to C ₂₀ silylalkyl group, a C ₆ to C ₂₀ aryl group, a C ₆ ~ C ₂₀ aryl group, selected from the group consisting of a silyl aryl of C ₆ ~ C ₂₀ alkylaryl group, C ₆ ~ C ₂₀ aryl silyl group and C ₆ ~ C ₂₀ of,

m is an integer of 1 or 2 determined depending on the kind of Z,

p is an integer of 1 to 5,

Other substituents bonded to CP ¹ and CP ² in addition to the substituents represented by the above general formulas II-1 and II-2, and other substituents bonded to carbon atoms in the phenyl ring not bonded to ZR _m in the general formulas II-1 and II- the other substituents being coupled are each independently hydrogen, C ₁ ~ C ₂₀ alkyl group, C ₃ ~ C ₂₀ cycloalkyl group, C ₁ ~ C ₂₀ alkylsilyl group, C ₁ ~ silyl group of C _20, C ₁ ~ C of _A C ₆ to C ₂₀ arylalkyl group, a C ₆ to C ₂₀ arylalkyl group, a C ₆ to C ₂₀ alkylaryl group, a C ₆ to C ₂₀ arylsilyl group, a C ₆ to C ₂₀ silyl An aryl group and a halogen group, and adjacent substituents may be bonded to each other to form a ring.

The main catalyst compound (A) represented by the formula (I) is a compound having at least one substituent selected from the group consisting of the formula (II-1) and the formula (II-2) bonded to Cp ¹ and / or Cp ² , So that the interaction can be smoothly performed. As a result, the catalyst of the present invention exhibits high activity. According to the production of an ethylene polymer using such a catalyst, the present invention can produce an ethylene polymer having a specific molecular weight distribution and a high molecular weight.

In consideration of the physical properties of the ethylene polymer of the present invention, it is preferable that M in the main catalyst compound (A) represented by the above formula (I) is zirconium (Zr), titanium (Ti), or hafnium (Hf). Also, it is preferable that Cp ¹ and Cp ² are each independently a cyclopentadienyl group, an indenyl group, or a fluorenyl group.

In the main catalyst compound (A) represented by the above formula (I), a C ₁ to C ₂₀ alkyl group, a C ₃ to C ₂₀ cycloalkyl group, a C ₁ to C ₂₀ alkylsilyl group and a C ₁ to C ₂₀ alkyl group Examples of the silylalkyl group having 1 to ₂₀ carbon atoms include, but are not limited to, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, A heptyl group, an octyl group, a nonyl group, a decyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, A cyclohexyl group, a cyclohexyl group, a cyclooctyl group, a decahydronaphthalyl group, a methylsilyl group, a dimethylsilyl group, a trimethylsilyl group, an ethylsilyl group, a diethylsilyl group, A triethylsilyl group, a propylsilyl group, a dipropylsilyl group, a tripropylsilyl group, a butylsilyl (Bu) silyl group, a tributylsilyl group, a (methylsilyl) methyl group, a (dimethylsilyl) methyl group, a (trimethylsilyl) group, a dibutylsilyl group, (Ethylsilyl) methyl group, (diethylsilyl) methyl group, (triethylsilyl) methyl group, (ethylsilyl) methyl group, (Methylsilyl) ethyl group, (dimethylsilyl) ethyl group, and (trimethylsilyl) ethyl group, and the like.

Of a C ₆ ~ C ₂₀ included in the definition of the X-aryl group, C ₆ ~ C ₂₀ aryl group, C ₆ ~ C ₂₀ alkylaryl group, C ₆ ~ C ₂₀ aryl silyl group, and a C ₆ ~ C ₂₀ of the Examples of the silylaryl group include, but are not limited to, a phenyl group, a biphenyl group, a terphenyl group, a naphtyl group, a fluorenyl group, a benzyl group, A phenyl group, a phenylethyl group, a phenylpropyl group, a methylphenyl group, a dimethylphenyl group, a trimethylphenyl group, an ethylphenyl group, a diethylphenyl group, A triethylphenyl group, a propylphenyl group, a dipropylphenyl group, a tripropylphenyl group, a phenylsilyl group, a methylphenylsilyl group, a dimethylphenylsilyl group, Methylphenylsilyl group, triphenylsilyl group, ethylphenylsilyl group, (methylphenylsilyl) group, (Methylphenyl) silyl group, (ethylphenyl) silyl group, trifluoromethylphenylsilyl group, (methylsilyl) phenyl group, (dimethylsilyl) (Trimethylsilyl) phenyl group, (ethylsilyl) phenyl group (diethylsilyl) phenyl group, (triethylsilyl) phenyl group, (Butylsilyl) phenyl group, (butylsilyl) phenyl group, a (propylsilyl) phenyl group, a dipropylsilylphenyl group, (Dibutylsilyl) phenyl group, and the like.

Examples of the C ₁ - C ₂₀ alkoxy group and the C ₁ - C ₂₀ alkylsiloxy group included in the definition of X include, but are not limited to, a methoxy group, an ethoxy group, a propoxy group A butoxy group, a pentoxy group, a hexyloxy group, a methylsiloxy group, and a dimethylsiloxy group. A trimethylsiloxy group, an ethylsiloxy group, a diethylsiloxy group, a triethylsiloxy group, and the like.

Examples of the C ₆ -C ₂₀ aryloxy group included in the definition of X are not particularly limited,

A phenoxy group, a naphthoxy group, a methylphenoxy group, a dimethylphenoxy group, a trimethylphenoxy group, an ethylphenoxy group, a diethylphenoxy group, A diethylphenoxy group, a triethylphenoxy group, a propylphenoxy group, a dipropylphenoxy group and a tripropylphenoxy group.

Examples of the halogen group included in the definition of X include, but not limited to, a fluoro group, a chloro group, a bromo group, and an iodo group,

Examples of the amine group included in the definition of X include, but not limited to, a dimethylamine group, a diethylamine group, a dipropylamine group, a dibutylamine group, a diphenylamine group Diphenylamine group, and dibenzylamine group.

In these examples, X is a group selected from the group consisting of a methyl group, an ethyl group, a propyl group, a phenoxy group, a naphthoxy group, a methylphenoxy group, a dimethylphenoxy group, ), A trimethylphenoxy group, an ethylphenoxy group, a diethylphenoxy group, a triethylphenoxy group, a propylphenoxy group, a dipropylphenoxy group ( Tripropylphenoxy group, tripropylphenoxy group, chloro group, bromo group, dimethylamine group, diethylamine group, dipropylamine group, dibutyl A dibutylamine group, a diphenylamine group, or a dibenzylamine group.

In consideration of the physical properties of the ethylene polymer of the present invention, Z in the substituent represented by the above general formulas (II-1) and (II-2) is preferably selected from the group consisting of nitrogen (N), phosphorus (P), arsenic (As) S), or selenium (Se).

The formula Ⅱ-1) and (Ⅱ-2 substituent a C alkyl group of ₁ ~ C ₂₀ included in the definition of R in represented by, C ₃ ~ C ₂₀ cycloalkyl group, C ₁ ~ C ₂₀ alkyl silyl group, and a C ₁ Examples of the C ₂₀ silylalkyl group include, but are not limited to, methyl, ethyl, propyl, butyl, pentyl, hexyl, A heptyl group, an octyl group, a nonyl group, a decyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, A Cyclooctyl group, a decahydronaphthalyl group, a methylsilyl group, a dimethylsilyl group, a trimethylsilyl group, an ethylsilyl group, a diethylsilyl group (e.g., Diethylsilyl group, triethylsilyl group, propylsilyl group, dipropylsilyl group, tripropylsilyl group, (Dimethylsilyl) methyl group, (trimethylsilyl) methyl group, (trimethylsilyl) methyl group, and the like. Examples of the alkyl group include a methyl group, an ethyl group, a butyl group, a butyl group, a butyl group, a dibutyl group, a tributylsilyl group, Triethylsilyl) methyl group, (ethylsilyl) methyl group, (diethylsilyl) methyl group, (triethylsilyl) methyl group, (Methylsilyl) ethyl group, (dimethylsilyl) ethyl group, and (trimethylsilyl) ethyl group (trimethylsilyl) ethyl group.

Of a C ₆ ~ C ₂₀ included in the definition of R an aryl group, a C ₆ ~ C ₂₀ aryl group, C ₆ ~ C ₂₀ alkylaryl group, C ₆ ~ C ₂₀ aryl silyl group, and a C ₆ ~ C ₂₀ of the Examples of the silylaryl group include, but are not limited to, a phenyl group, a biphenyl group, a terphenyl group, a naphtyl group, a fluorenyl group, a benzyl group, A phenyl group, a phenylethyl group, a phenylpropyl group, a methylphenyl group, a dimethylphenyl group, a trimethylphenyl group, an ethylphenyl group, a diethylphenyl group, A triethylphenyl group, a propylphenyl group, a dipropylphenyl group, a tripropylphenyl group, a phenylsilyl group, a methylphenylsilyl group, a dimethylphenylsilyl group, Methylphenylsilyl group, triphenylsilyl group, ethylphenylsilyl group, (methylphenylsilyl) group, (Methylphenyl) silyl group, (ethylphenyl) silyl group, trifluoromethylphenylsilyl group, (methylsilyl) phenyl group, (dimethylsilyl) (Trimethylsilyl) phenyl group, (ethylsilyl) phenyl group (diethylsilyl) phenyl group, (triethylsilyl) phenyl group, Ethylsilyl) phenyl group, a (propylsilyl) phenyl group, a dipropylsilylphenyl group, a butylsilylphenyl group, a dibutylsilylphenyl group, ((Dibutylsilyl) phenyl) group and the like.

Other substituents bonded to CP ¹ and CP ² in addition to the substituents represented by the above general formulas II-1 and II-2, and other substituents bonded to carbon atoms in the phenyl ring not bonded to ZR _m in the general formulas II-1 and II- alkyl group of C ₁ ~ C ₂₀ included in the definition of other substituents bonded, C ₃ ~ C ₂₀ cycloalkyl group, C ₁ ~ C ₂₀ alkylsilyl group, C ₁ ~ silyl alkyl group and a C ₁ ~ C ₂₀ of the C ₂₀ Examples of the haloalkyl group include but are not limited to a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, A cyclopentyl group, a cyclohexyl group, a cyclohexyl group, a cyclohexyl group, a cyclohexyl group, a cyclohexyl group, a cyclohexyl group, a cyclohexyl group, a cyclohexyl group, A cyclohexyl group, a cyclohexyl group, a cyclohexyl group, a cyclohexyl group, a cyclohexyl group, a cyclohexyl group, a cyclohexyl group, a cyclohexyl group, a cyclohexyl group, ethylsilyl group, ethylsilyl group, ethylsilyl group, diethylsilyl group, triethylsilyl group, propylsilyl group, dipropylsilyl group, tripropylsilyl group, Butylsilyl group, dibutylsilyl group, tributylsilyl group, (methylsilyl) methyl group, (dimethylsilyl) methyl group, (dimethylsilyl) methyl group, (Trimethylsilyl) methyl group, (ethylsilyl) methyl group, (diethylsilyl) methyl group, (triethylsilyl) methyl group, (Methylsilyl) ethyl group, (dimethylsilyl) ethyl group, (trimethylsilyl) ethyl group, a trifluoromethyl group (methylsilyl) ethyl group, , Trichloromethyl group, and the like,

Other substituents bonded to CP ¹ and CP ² in addition to the substituents represented by the formulas II-1 and II-2, and other substituents bonded to carbon atoms in the phenyl ring not bonded to ZR _m in the above formulas II-1 and II- an aryl group of C ₆ ~ C ₂₀ included in the definition of the other substituents, C ₆ ~ C ₂₀ aryl group, C ₆ ~ alkylaryl group of C _20, C ₆ ~ C ₂₀ aryl silyl group, and a C ₆ ~ C silyl examples of the aryl group of ₂₀ is not specifically restricted, phenyl (phenyl) group, biphenyl (biphenyl) group, a terphenyl (terphenyl) group, a naphthyl (naphtyl) group, a fluorenyl group (fluorenyl) group, benzyl ( A benzyl group, a phenylethyl group, a phenylpropyl group, a methylphenyl group, a dimethylphenyl group, a trimethylphenyl group, an ethylphenyl group, a diethylphenyl group, A triethylphenyl group, a propylphenyl group, a dipropylphenyl group, a tripropylphenyl group, Tripropylsilyl group, triphenylsilyl group, triphenylsilyl group, triphenylsilyl group, triphenylsilyl group, triphenylsilyl group, diphenylsilyl group, triphenylsilyl group, triphenylsilyl group, triphenylsilyl group, triphenylsilyl group, triphenylsilyl group, triphenylsilyl group, triphenylsilyl group, triphenylsilyl group, triphenylsilyl group, Ethylphenylsilyl group, a (methylphenyl) silyl group, an (ethylphenyl) silyl group, a trifluoromethylphenylsilyl group, a (methylsilyl) phenyl group (Dimethylsilyl) phenyl group, (trimethylsilyl) phenyl group, (ethylsilyl) phenyl group (diethylsilyl) phenyl (diethylsilyl) phenyl group, (Triethylsilyl) phenyl group, a propylsilyl phenyl group, a dipropylsilyl phenyl group, a butylsilyl phenyl group, a triethylsilyl phenyl group, , A dibutylsilyl phenyl group, and the like.

Other substituents bonded to CP ¹ and CP ² in addition to the substituents represented by the formulas II-1 and II-2, and other substituents bonded to carbon atoms in the phenyl ring not bonded to ZR _m in the above formulas II-1 and II- Examples of the halogen group included in the definition of other substituents include, but are not limited to, a fluoro group, a chloro group, a bromo group, and an iodo group.

The promoter compound (B) contained in the catalyst of the present invention is composed of at least one compound selected from the group consisting of compounds represented by the following formulas (III-1) and (III-2).

[Formula (III-1)

In the above formula (III-1)

R ¹ is a C ₁ -C ₁₀ alkyl group,

q is an integer of 1 to 70;

[Formula (III-2)

In the above formula (III-2)

R ^2, R ³ and R ⁴ are the same or different, each independently represent a C ₁ ~ C ₁₀ alkyl group, is selected from an alkoxy group, and the group consisting of a halogen, C ₁ ~ C ₁₀ of the, at this time, R ^2, R ^3, and at least one of R ⁴ is an alkyl group of C ₁ ~ C _10.

Considering the physical properties of the ethylene polymer of the present invention, the compound represented by the above formula (III-1) may be selected from the group consisting of methylaluminoxane, ethylaluminoxane, butylaluminoxane, hexylaluminoxane, Octylaluminoxane, or decylaluminoxane is preferable.

The compound represented by the above formula (III-2) can be synthesized by reacting a compound represented by the formula (III-2) with a compound selected from the group consisting of trimethylaluminum, triethylaluminum, tributylaluminum, trihexylaluminum, trioctylaluminum and tridecylaluminum ), Dimethylaluminum methoxide, diethylaluminum methoxide, dibutylaluminum methoxide, dimethylaluminum chloride, diethylaluminum chloride, dibutyl (meth) acrylate, But are not limited to, dibutylaluminum chloride, methylaluminum dimethoxide, ethylaluminum dimethoxide, butylaluminum dimethoxide, methylaluminum dichloride, ethylaluminium That the dichloride (Ethylaluminum dichloride), or butyl aluminum dichloride (Butylaluminum dichloride) is preferred.

In addition, the catalyst of the present invention may further comprise a carrier for supporting the main catalyst compound (A) and the co-catalyst compound (B). The carrier is not particularly limited as long as it is a porous organic / inorganic compound having a pore on the surface or inside thereof, but is not limited to silica, alumina, magnesium chloride, calcium chloride, borocite, zeolite, magnesium oxide, zirconium oxide, Titanium oxide, boron trioxide, calcium oxide, zinc oxide, barium oxide, thorium oxide, and combinations thereof. Specifically, examples of the porous organic compound Starch, Cyclodextrin, or may be made of composite Polymer like, Examples of the composite _{SiO 2 -MgO, SiO 2 -Al 2} O 3, SiO 2 -TiO 2, SiO 2 -V ₂ O ₅ , SiO ₂ -Cr ₂ O ₃ , or SiO ₂ -TiO ₂ -MgO.

As a method for preparing the catalyst of the present invention by supporting the main catalyst compound (A) and the promoter compound (B) on such a support, there is a method in which the main catalyst compound (A) is directly supported on a dehydrated support How to; A method in which the carrier is pretreated with the promoter compound (B) and then supported by the main catalyst compound (A); Carrying the main catalyst compound (A) on the carrier and then post-treating it with the co-catalyst compound (B); And a method of reacting the main catalyst compound (A) with the co-catalyst compound (B), followed by adding a carrier.

A solvent is used to carry the main catalyst compound (A) and / or the promoter compound (B) to the carrier. Examples of the solvent include pentane, hexane, heptane, Aliphatic hydrocarbon solvents such as octane, nonane, decane, undecane, and dodecane; Aromatic hydrocarbon solvents such as benzene, monochlorobenzene, dichlorobenzene, trichlorobenzene and toluene; and aromatic hydrocarbon solvents such as benzene, monochlorobenzene, dichlorobenzene, trichlorobenzene and toluene; Halogenated aliphatic hydrocarbon solvents such as dichloromethane, trichloromethane, dichloroethane, and trichloroethane; Or a mixture thereof.

The temperature at which the main catalyst compound (A) and the co-catalyst compound (B) are supported on the carrier may be -20 to 120 캜, preferably 0 to 100 캜, considering the efficiency of the supporting step.

The mixing ratio of the main catalyst compound (A) and the co-catalyst compound (B) contained in the catalyst of the present invention is not particularly limited, but from the viewpoint of catalyst activity and production efficiency (economy) The catalyst compound (B) is preferably mixed in a weight ratio of 1:10 to 10,000, more preferably 1:10 to 1,000, and further preferably 1:50 to 500.

The ethylene polymer of the present invention is obtained by polymerizing ethylene alone or by polymerizing ethylene and a monomer. The monomer to be used is not particularly limited, but C ₂ to C ₂₀ α-olefin (α-olefin), C It is preferably at least one member selected from the group consisting of ₄ to ₂₀ C diolefins, C ₃ to C ₂₀ cycloolefins, C ₃ to C ₂₀ cyclodiolefins and styrene.

Examples of the C ₂ -C ₂₀ -olefins include, but are not limited to, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, In fact,

Examples of the C ₄ -C ₂₀ diolefins include, but are not limited to, 1,3-butadiene, 1,4-pentadiene, , 3-butadiene (2-Methyl-1,3-butadiene), and the like.

Examples of the C ₃ -C ₂₀ cycloolefin or the C ₃ -C ₂₀ cyclodiolefin include, but are not limited to, cyclopentene, cyclohexene, cyclopentadiene, Cyclopentadiene, cyclohexadiene, norbonene, or methyl-2-norbornene.

The styrene may be styrene in which the hydrogen of the benzene ring of styrene is substituted with a C ₁ -C ₁₀ alkyl group, a C ₁ -C ₁₀ alkoxy group, a halogen group, an amine group, a silyl group, a halogenated alkyl group or the like have.

Meanwhile, the polymerization for producing the ethylene polymer of the present invention can be carried out in a liquid phase, a gas phase, a bulk phase, and a slurry phase. In the case where an ethylene polymer is polymerized in a liquid phase or a slurry phase, an organic solvent may be used as a medium, or ethylene or a monomer itself may be used as a medium.

Examples of the organic solvent used for the medium include, but are not limited to, butane, isobutane, pentane, hexane, cyclohexane, heptane, octane, ), Nonane, decane, undecane, dodecane, and the like; Aromatic hydrocarbon solvents such as benzene, monochlorobenzene, dichlorobenzene, trichlorobenzene, and toluene; aromatic hydrocarbon solvents such as benzene, monochlorobenzene, dichlorobenzene, trichlorobenzene, and toluene; And halogenated aliphatic hydrocarbon solvents such as dichloromethane, trichloromethane, dichloroethane, and trichloroethane, and the like.

The polymerization temperature for producing the ethylene polymer of the present invention is not particularly limited, but is preferably 0 to 200 캜, more preferably 20 to 100 캜. The polymerization pressure is not particularly limited, but is preferably 1 to 100 bar, more preferably 5 to 60 bar. The polymerization reaction may be carried out in a batch type, a semi-continuous type, or a continuous type.

2. Ethylene polymer

The present invention provides the ethylene polymer produced by the above production method. The ethylene polymer of the present invention exhibits a specific molecular weight distribution and can have a high molecular weight as prepared by the above production method.

More specifically, the ethylene polymer of the present invention is a molecular weight distribution (Mw / Mn) 3.4 to 7, and a weight average molecular weight (M _W) of 30,000 to 3,000,000.

Since the ethylene polymer of the present invention has a specific molecular weight distribution and a high molecular weight and is excellent in moldability, a product (molded article) having excellent physical properties can be produced with high efficiency.

Conventionally, the ethylene polymer prepared by applying the metallocene catalyst system has a narrow molecular weight distribution, and a product having good physical properties can be produced. However, since the ethylene polymer having a narrow molecular weight distribution has poor moldability, the production efficiency of the product is not high.

However, since the ethylene polymer of the present invention is produced by the above production method, the molecular weight distribution can be efficiently controlled, resulting in a broad molecular weight distribution rather than a narrow molecular weight distribution. In this case, a high molecular weight The molecular weight distribution is widened in the direction in which the content is widened. Therefore, when a product is produced from the ethylene polymer of the present invention, a product having excellent physical properties can be produced with high efficiency.

Hereinafter, the present invention will be described concretely through synthesis examples and polymerization examples. However, the following synthesis examples and polymerization examples are merely illustrative of one embodiment of the present invention, and the scope of the present invention is limited by the following synthesis examples and polymerization examples It is not.

[Preparation of main catalyst compound]

All synthesis reactions proceeded in an inert atmosphere such as nitrogen or argon, using the standard Schlenk technique and the glove box technique.

Tetrahydrofuran (Tetahydrofuran, THF), toluene (Toluene), normal hexane (n -Hexane), diethyl ether (Diethyl Ether), the solvent is Sigma Aldrich Corporation grade anhydrous methylene chloride _{(Methylene Chloride, CH 2 Cl 2} ) ( Anhydrous Grade) was purchased and passed through an activated alumina column to remove moisture, and then stored on activated molecular sieve (Molecular Sieve 5A, Yakuri Pure Chemicals Co.).

Further ethanol (Ethanol), normal pentane (n -Pentane), ethyl acetate (Ethyl acetate), normal butyl lithium (n -Butyllithium (2.5 M Solution in n -Hexane)), methyl lithium (Methyllithium (1.6 M solution in Diethyl ether ), 4-methoxyphenylmagnesium bromide (0.5 M solution in THF), 4-bromo-4'-methoxybiphenyl, 4-bromo - N, N - dimethylaniline (4-Bromo- N, N -dimethylaniline ), 4- bromo-thioanisole (4-Bromothioanisole), ammonium chloride (ammonium chloride), anhydrous magnesium sulfate (magnesium sulfate, anhydrous), para - toluenesulfonic acid monohydrate (para -Toluenesulfonic acid monohydrate (p -TsOH · H 2 O)) was used without purification purchased from Sigma-Aldrich Corporation.

In addition, tetrachlorobis (tetrahydrofuran) zirconium (Tetrachlorobis (tetr

_{ahydrofuran) zirconium, ZrCl 4 · 2C} 4 H 8 O) was used without purification purchased from Strem Company, 3,4-dimethyl-hour post-penta-2-enone (3,4-Dimethylcyclopent-2-enone , 3, 4-Me ₂ -C ₅ H ₄ O) were synthesized and used by methods known in the art.

[Analysis method]

¹ H NMR and ¹³ C NMR were measured at room temperature using a Bruker Avance 400 Spectrometer and the chemical shifts of the NMR spectra were determined by chemical shifts ( ¹ H NMR (CDCl ₃ )) as indicated by deuterated chloroform 7.24 ppm in the case of ¹³ C NMR, and 77.0 ppm in ¹³ C NMR). At this time, the deuterated chloroform (CDCl ₃ ) was purchased from Cambridge Isotope Laboratories and dried on the activated molecular sieve (Molecular Sieve 5A, Yakuri Pure Chemicals Co.).

All elemental analyzes were also performed using EA 1110-FISION (CE Instruments).

[Synthesis Example 1] Synthesis of bis- [1- ( p -Dimethylaminophenyl) -3,4-dimethylcyclopentadienyl] zirconium dichloride (Bis- [1- ( p -Dimethylaminophenyl) -3,4-dimethylcyclopentadienyl] zirconium dichloride, [1- ( p -Me ₂ NC ₆ H ₄ ) -3,4-Me ₂ C ₅ H ₂ ] ₂ ZrCl ₂ ) Synthesis of

[Synthesis Example 1-1] 1- ( p -Dimethylaminophenyl) -3,4-dimethylcyclopentadiene (1- ( p -Dimethylaminophenyl) -3,4-dimethylcyclopentadiene, ( p -Me ₂ NC ₆ H ₄ ) -3,4-Me ₂ C ₅ H ₃ ) Synthesis of

4-Bromo- N , N -dimethylaniline (4.00 g, 20 mmol) was dissolved in 50 mL of diethyl ether and 1 equivalent of n-butyllithium (8.0 mL) was added at 0 ° C. After stirring at room temperature for 2 hours, 20 mL of a tetrahydrofuran solution in which 1 equivalent of 3,4-dimethylcyclopent-2-enone (2.20 g, 20 mmol) was dissolved at -78 ° C was added dropwise It was slowly raised to room temperature and stirred overnight. Then, an appropriate amount of a saturated aqueous solution of ammonium chloride was added to the obtained orange colored solution, and the reaction was terminated. Then, only the organic solution layer was extracted with diethyl ether (50 mL), collected, dried over anhydrous magnesium sulfate, and filtered. The filtered solution was then stripped of solvent in a rotary evaporator to give a yellow oil. The oil was dissolved in methylene chloride (30 mL), para-toluenesulfonic acid hydrate (ca. 0.1 g) was added thereto, and the mixture was stirred at room temperature for one hour to obtain an ivory solid. The solvent was evaporated on a rotary evaporator and then precipitated with 30 mL of n-hexane and filtered using a glass filter. The filtered solids were rinsed with ethanol (30 mL), diethyl ether (30 mL) and n-pentane (30 mL) and dried in vacuo to give 1- ( p- dimethylaminophenyl) -3,4-dimethylcyclopentadiene 63% yield.

The ¹ H NMR results of the 1- ( p -dimethylaminophenyl) -3,4-dimethylcyclopentadiene are as follows.

^{1 H NMR (400.13 MHz, CDCl} 3): d 7.33 (d, 2H), 6.69 (d, 2H), 6.45 (s, 1H), 3.21 (s, 2H), 2.93 (s, 6H), 1.94 (s , ≪ / RTI > 3H), 1.86 (s, 3H).

[Synthesis Example 1-2] Synthesis of bis [1- ( p -Dimethylaminophenyl) -3,4-dimethylcyclopentadienyl] zirconium dichloride (Bis- [1- ( p -Dimethylaminophenyl) -3,4-dimethylcyclopentadienyl] zirconium dichloride, [1- ( p -Me ₂ NC ₆ H ₄ ) -3,4-Me ₂ C ₅ H ₂ ] ₂ ZrCl ₂ ) Synthesis of

1- ( p -Dimethylaminophenyl) -3,4-dimethylcyclopentadiene (1.280 g, 6.0 mmol) synthesized in [Synthesis Example 1-1] was dissolved in 30 mL of diethyl ether, Was added 1 equivalent of n-butyllithium (2.4 mL). The reactor was warmed to room temperature and stirred for 4 hours. The solvent was evaporated and the obtained white lithium salt was mixed with half as much tetrachlorobis (tetrahydrofuran) zirconium (1.132 g, 3 mmol) and dissolved in toluene (50 mL) at -78 ° C. The mixed solution was slowly warmed to room temperature and stirred while heating to 60 ° C overnight. Lithium chloride (LiCl), which is a byproduct of the reaction, was then removed by filtration through Celite and the solvent was evaporated. The residue was washed with n-hexane and dried to obtain 0.968 g of bis [1- ( p- dimethylaminophenyl) -3,4-dimethylcyclopentadienyl] zirconium dichloride was obtained in a yield of 55%.

The ¹ H of the bis [1- ( p -dimethylaminophenyl) -3,4-dimethylcyclopentadienyl] zirconium dichloride The results of NMR are as follows.

¹ H NMR (400.13 MHz, CDCl ₃ ): d 7.34 (d, 4H), 6.77 (d, 4H), 6.14 (s, 4H), 2.99 (s, 12H), 1.77 (s, 12H).

[Synthesis Example 2] Synthesis of bis- [1- ( p -Methoxyphenyl) -3,4-dimethylcyclopentadienyl] zirconium dichloride (Bis- [1- ( p -methoxyphenyl) -3,4-dimethylcyclopentadienyl] zirconium dichloride, [1- ( p -MeOC ₆ H ₄ ) -3,4-Me ₂ C ₅ H ₂ ] ₂ ZrCl ₂ ) Synthesis of

[Synthesis Example 2-1] 1- ( p -Methoxyphenyl) -3,4-dimethylcyclopentadiene (1- ( p -methoxyphenyl) -3,4-dimethylcyclopentadiene, ( p -MeOC ₆ H ₄ ) -3,4-Me ₂ C ₅ H ₃ ) Synthesis of

After dissolving 3,4-dimethylcyclopenta-2-enone (2.20 g, 20 mmol) in tetrahydrofuran (20 mL), 1 equivalent of 4-methoxyphenylmagnesium bromide (20 mmol) He added. The reaction solution was warmed to room temperature and stirred overnight. Thereafter, an appropriate amount of an aqueous ammonium chloride solution saturated with an orange solution was added to terminate the reaction. Then, the organic layer was extracted with diethyl ether (50 mL), collected by drying over anhydrous magnesium sulfate, and filtered. The filtered solution was poured into a rotary evaporator and the solvent was removed to give an orange oil. The oil was dissolved again in methylene chloride (30 mL), paratoluenesulfonic acid hydrate (ca. 0.1 g) was added, and the mixture was stirred at room temperature for one hour. The solution was appropriately removed with a rotary evaporator, then dissolved again in ethanol and recrystallized to obtain 1- ( p -methoxyphenyl) -3,4-dimethylcyclopentadiene in 47% yield (2.20 g).

¹ H NMR results confirming the synthesis of 1- ( p -methoxyphenyl) -3,4-dimethylcyclopentadiene are as follows.

^{1 H NMR (400.13 MHz, CDCl} 3): d 7.36 (d, 2H), 6.81 (d, 2H), 6.50 (s, 1H), 3.79 (s, 3H), 3.22 (s, 2H), 1.95 (s , ≪ / RTI > 3H), 1.87 (s, 3H).

[Synthesis Example 2-2] Synthesis of bis - [1- ( p -Methoxyphenyl) -3,4-dimethylcyclopentadienyl] zirconium dichloride (Bis- [1- ( p -methoxyphenyl) -3,4-dimethylcyclopentadienyl] zirconium dichloride, [1- ( p -MeOC ₆ H ₄ ) -3,4-Me ₂ C ₅ H ₂ ] ₂ ZrCl ₂ ) Synthesis of

Except that the 1- ( p -methoxyphenyl) -3,4-dimethylcyclopentadiene synthesized in [Synthesis Example 2-1] (1.202 g, 6.0 mmol) was used in place of [Synthesis Example 1-2 ], 0.891 g (53% yield) of bis- [1- ( p -methoxyphenyl) -3,4-dimethylcyclopentadienyl] zirconium dichloride as a light yellow solid was obtained.

¹ H of the bis - [1- ( p -methoxyphenyl) -3,4-dimethylcyclopentadienyl] zirconium dichloride The NMR results are as follows.

¹ H NMR (400.13 MHz, CDCl ₃ ): d 7.38 (d, 4H), 6.96 (d, 4H), 6.16 (s, 4H), 3.85 (s, 6H), 1.78

[Synthesis Example 3] Synthesis of bis- [1- ( p - methylthiophenyl) -3,4-dimethylcyclopentadienyl] zirconium dichloride (Bis- [1- ( p -methylthiophenyl) -3,4-dimethylcyclopentadienyl] zirconium dichloride, [1- ( p -MeSC ₆ H ₄ ) -3,4-Me ₂ C ₅ H ₂ ] ₂ ZrCl ₂ ) Synthesis of

[Synthesis Example 3-1] 1- ( p -Methylthiophenyl) -3,4-dimethylcyclopentadiene (1- ( p -Methylthiophenyl) -3,4-dimethylcyclopentadiene, ( p -MeSC ₆ H ₄ ) -3,4-Me ₂ C ₅ H ₃ ) Synthesis of

Except that 4-bromothioanisole (4.33 g, 20 mmol) was used instead of 4-bromo- N , N -dimethylaniline used in [Synthesis Example 1-1] 1] to obtain 1- ( p -methylthiophenyl) -3,4-dimethylcyclopentadiene as a pale yellow solid in a yield of 39% (1.69 g).

The ¹ H NMR results of the 1- ( p -methylthiophenyl) -3,4-dimethylcyclopentadiene are as follows.

^{1 H NMR (400.13 MHz, CDCl} 3): d 7.34 (d, 2H), 7.17 (d, 2H), 6.61 (s, 1H), 3.22 (s, 2H), 2.46 (s, 3H), 1.96 (s , ≪ / RTI > 3H), 1.87 (s, 3H).

[Synthesis Example 3-2] Synthesis of bis - [1- ( p - methylthiophenyl) -3,4-dimethylcyclopentadienyl] zirconium dichloride (Bis- [1- ( p methylthiophenyl-3,4-dimethylcyclopentadienyl] zirconium dichloride, [1- ( p -MeSC ₆ H ₄ ) -3,4-Me ₂ C ₅ H ₂ ] ₂ ZrCl ₂ ) Synthesis of

The [Synthesis Example 1-1] Synthesis of 1-in (p - dimethylaminophenyl) -3,4-dimethyl-cyclopentadiene instead of the [Synthesis Example 3-1] Synthesis of 1-in (p - methylthiophenyl) -3,4-dimethylcyclopentadiene (1.298 g, 6.0 mmol) was used in the same manner as in [Synthesis Example 1-2] above to give a yellow solid of bis- [1- ( p -methylthiophenyl ) -3,4-dimethylcyclopentadienyl] zirconium dichloride was obtained in a yield of 51% (0.907 g).

The ¹ H of the bis - [1- ( p -methylthiophenyl) -3,4-dimethylcyclopentadienyl] zirconium dichloride The NMR results are as follows.

¹ H NMR (400.13 MHz, CDCl ₃ ): d 7.35 (d, 4H), 7.30 (d, 4H), 6.20 (s, 4H), 2.51 (s, 6H), 1.79

[Synthesis Example 4] Synthesis of bis- [1- ( p -Methoxybiphenyl) -3,4-dimethylcyclopentadienyl] zirconium dichloride (Bis- [1- ( p -methoxybiphenyl) -3,4-dimethylcyclopentadienyl] zirconium dichloride, [1- ( p -MeO C ₆ H ₄ C ₆ H ₄ ) -3,4-Me ₂ C ₅ H ₂ ] ₂ ZrCl ₂ ) Synthesis of

[Synthesis Example 4-1] 1- ( p -Methoxyphenyl) -3,4-dimethylcyclopentadiene (1- ( p -methoxyphenyl) -3,4-dimethylcyclopentadiene, ( p -MeOC ₆ H ₄ C ₆ H ₄ ) -3,4-Me ₂ C ₅ H ₃ ) Synthesis of

4-Bromo-4'-methoxybiphenyl (2.631 g, 10 mmol) was dissolved in 50 mL of diethyl ether, followed by the addition of 1 equivalent of n-butyllithium (4.0 mL) at 0 ° C. After the temperature was raised to room temperature and stirred for 2 hours, 20 mL of a tetrahydrofuran solution obtained by lowering the temperature to -78 ° C and dissolving 1 equivalent of 3,4-dimethylcyclopent-2-enone (1.10 g, 10 mmol) After the dropwise addition, the temperature was slowly raised to room temperature and stirred overnight. Then, an appropriate amount of a saturated aqueous solution of ammonium chloride was added to the obtained orange colored solution, and the reaction was terminated. Then, only the organic solution layer was extracted with diethyl ether (50 mL), collected, dried over anhydrous magnesium sulfate, and filtered. The filtered solution was poured into a rotary evaporator and the solvent was removed to give a yellow oil. The oil was dissolved in methylene chloride (30 mL), para-toluenesulfonic acid hydrate (ca. 0.1 g) was added thereto, and the mixture was stirred at room temperature for one hour to obtain an ivory solid. The solvent was evaporated on a rotary evaporator, and then 30 mL of ethanol was poured into the obtained solid and filtered using a glass filter. Subsequently, the resultant was washed with diethyl ether (10 mL) and n-pentane (10 mL), and dried under vacuum to obtain 1- ( p -methoxybiphenyl) -3,4-dimethylcyclopentadiene in 55% yield.

The ¹ H NMR results of the 1- ( p -methoxybiphenyl) -3,4-dimethylcyclopentadiene are as follows.

^{1 H NMR (400.13 MHz, CDCl} 3): d 7.52 (dd, 2H), 7.47 (s, 4H), 6.95 (dd, 2H), 6.68 (s, 1H), 3.83 (s, 3H), 3.29 (s , 2H), 1.98 (s, 3H), 1.90 (s, 3H).

[Synthesis Example 4-2] Synthesis of bis - [1- ( p -Methoxybiphenyl) -3,4-dimethylcyclopentadienyl] zirconium dichloride (Bis- [1- ( p -methoxybiphenyl) -3,4-dimethylcyclopentadienyl] zirconium dichloride, [1- ( p -MeOC ₆ H ₄ C ₆ H ₄ ) -3,4-Me ₂ C ₅ H ₂ ] ₂ ZrCl ₂ ) Synthesis of

[0154] The 1- (p-dimethylaminophenyl) -3,4-dimethylcyclopentadiene synthesized in [Synthesis Example 1-1] Instead of Synthesis Example 1-2] was repeated except for using 1- ( p -methoxybiphenyl) -3,4-dimethylcyclopentadiene (0.829 g, 3.0 mmol) synthesized in [Synthesis Example 4-1] To obtain a yellow solid of bis- [1- ( p -methoxybiphenyl) -3,4-dimethylcyclopentadienyl] zirconium dichloride in a yield of 60%.

The ¹ H of the bis- [1- ( p -methoxybiphenyl) -3,4-dimethylcyclopentadienyl] zirconium dichloride The NMR results are as follows.

¹ H NMR (400.13 MHz, CDCl ₃ ): d 7.64 (d, 4H), 7.58 (d, 4H), 7.51 , ≪ / RTI > 6H), 1.80 (s, 12H).

[Preparation of supported catalyst]

All synthesis reactions proceeded in an inert atmosphere such as nitrogen or argon, using the standard Schlenk technique and the glove box technique.

Toluene was purchased from Sigma-Aldrich and then dried using an activated molecular sieve (Molecular Sieve, 4A), or an activated alumina layer, followed by further drying. MAO (methylaluminoxane) was purchased from Albemarle Corporation using 10% toluene solution (HS-MAO-10%), and Silica used Grace's XPO2410 without further processing.

In addition, bis (indenyl) zirconium dichloride and racemic-ethylene bis (tetrahydroindenyl) zirconium dichloride, which were used in the preparation of the comparative supported catalyst, Purchased from Chemtura Organometallics GmbH and used without purification.

[Supported Catalyst Preparation Example 1]

(0.059 g) and Silica (1.0 g) synthesized in Synthesis Example 1 were put in a 250 mL round bottom flask and taken out of the glove box. Then, 10 mL of toluene was added to the flask containing the compound, Methylaluminoxane (MAO) (5.3 mL) was added slowly at room temperature, followed by stirring for 1 hour. 10 mL of toluene was added to the flask containing the silica, the silica temperature in the slurry state was lowered to 0 ° C, and the mixed reaction solution of the compound and methylaluminoxane was slowly added. After stirring for 1 hour, the temperature was raised to 70 占 폚 and further reacted for 6 hours. After the reaction was completed, the stirring was stopped, and the toluene layer was separated and removed. Then, the solution was washed with n-hexane, and then vacuum was applied to remove all the toluene to prepare a pale-brown free flowing powder supported catalyst.

[Supported Catalyst Preparation Example 2]

A supported catalyst was prepared under the same conditions as in the above-mentioned Supported Catalyst Preparation Example 1, except that the compound (0.056 g) synthesized in [Synthesis Example 2] was used instead of the compound synthesized in [Synthesis Example 1].

[Supported Catalyst Preparation Example 3]

A supported catalyst was prepared under the same conditions as in the above-mentioned Supported Catalyst Preparation Example 1, except that the compound (0.059 g) synthesized in [Synthesis Example 3] was used instead of the compound synthesized in [Synthesis Example 1].

[Supported Catalyst Preparation Example 4]

A supported catalyst was prepared under the same conditions as in the above-mentioned Supported Catalyst Preparation Example 1, except that the compound (0.071 g) synthesized in [Synthesis Example 4] was used in place of the compound synthesized in [Synthesis Example 1].

[Supported Catalyst Comparative Production Example 1]

A supported catalyst was prepared under the same conditions as in the above-mentioned Supported Catalyst Preparation Example 1, except that bis (indenyl) zirconium dichloride (0.039 g) was used instead of the compound synthesized in [Synthesis Example 1].

[Supported Catalyst Comparative Production Example 2]

A supported catalyst was prepared under the same conditions as in the above-mentioned Supported Catalyst Preparation Example 1 except that Racemic-ethylene bis (tetrahydroindenyl) zirconium dichloride (0.043 g) was used instead of the compound synthesized in [Synthesis Example 1] .

[Polymerization Preparation]

All the polymerization proceeded under constant ethylene pressure after injection of the required amount of solvent, catalyst, ethylene and monomers, etc. in an autoclave completely blocked with outside air. Anhydrous grade toluene and n-hexane used in the polymerization were purchased from Sigma-Aldrich and then further dried by passing through an activated molecular sieve (4A) or an activated alumina layer , 1.0 M triisobutylaluminum solution was purchased from Sigma-Aldrich and used as is.

[Polymerization Example 1] Using a non-supported catalyst

The inside of a stainless steel autoclave having an internal capacity of 2 L was completely replaced with nitrogen and then 1 L of n-hexane was maintained while maintaining nitrogen purging. Then, 0.58 g of methylaluminoxane ( Al standard 10 mmol) was added in toluene solution, and then toluene solution (2.0 mL, 5.0 mmol of Zr) in which the compound synthesized in Synthesis Example 1 was dissolved was added. After that, the temperature was raised to 65 deg. C, ethylene gas was introduced at a pressure of 7 bar, and the polymerization reaction was carried out for 1 hour while maintaining the temperature at 70 deg. When the polymerization reaction was completed, the supply of ethylene was stopped, the reactor temperature was cooled to 20 DEG C, and unreacted ethylene was vented to the outside of the reactor. The remaining compound and methylaluminoxane were deactivated by the addition of 20 mL of acidified ethanol. Thereafter, the reaction product was filtered, the solid component was separated, and dried under vacuum at 80 캜 to obtain an ethylene polymer (polyethylene).

[Polymerization Example 2]

An ethylene polymer (polyethylene) was prepared under the same conditions as in Polymerization Example 1, except that the compound synthesized in [Synthesis Example 2] was used instead of the compound synthesized in [Synthesis Example 1].

[Polymerization Example 3]

An ethylene polymer (polyethylene) was prepared under the same conditions as in polymerization example 1, except that the compound synthesized in [Synthesis Example 3] was used instead of the compound synthesized in [Synthesis Example 1].

[Polymerization Example 4]

An ethylene polymer (polyethylene) was prepared under the same conditions as in Polymerization Example 1, except that the compound synthesized in [Synthesis Example 4] was used instead of the compound synthesized in [Synthesis Example 1].

[Polymerization Example 5] Using a supported catalyst

The inside of the stainless steel reactor was replaced with nitrogen, and 1L of normal hexane was charged. Then, 2mmol of triisobutylaluminum was added thereto and 50mg of the supported catalyst prepared in the above-mentioned supported catalyst preparation example 1 was injected in order. Thereafter, when the temperature was raised to 70 ° C, ethylene gas was introduced at a pressure of 7 bar and the polymerization reaction was conducted for 1 hour while maintaining the temperature at 70 ° C. Upon completion of the polymerization reaction, the supply of ethylene was stopped, the reactor temperature was cooled to 20 DEG C, and unreacted ethylene was vented to the outside of the reactor. The remaining supported catalyst and triisobutylaluminum were deactivated by the addition of 20 mL of acidified ethanol. Thereafter, the reaction product was filtered, the solid component was separated, and dried under vacuum at 80 캜 to obtain an ethylene polymer (polyethylene).

[Polymerization Example 6]

An ethylene polymer (polyethylene) was prepared under the same conditions as in Polymerization Example 5, except that the supported catalyst prepared in Supported Catalyst Preparation Example 2 was used instead of the supported catalyst prepared in Supported Catalyst Preparation Example 1.

[Polymerization Example 7]

An ethylene polymer (polyethylene) was prepared under the same conditions as in Polymerization Example 5, except that the supported catalyst prepared in Supported Catalyst Preparation Example 3 was used instead of the supported catalyst prepared in Supported Catalyst Preparation Example 1.

[Polymerization Example 8]

An ethylene polymer (polyethylene) was prepared under the same conditions as in Polymerization Example 5, except that the supported catalyst prepared in Supported Catalyst Preparation Example 4 was used in place of the supported catalyst prepared in Supported Catalyst Preparation Example 1.

[Polymerization Example 9]

An ethylene polymer (ethylene-1-butene copolymer) was prepared under the same conditions as in Polymerization Example 5 except that 10 mL of 1-butene was added together with triisobutylaluminum.

[Polymerization Example 10]

An ethylene polymer (ethylene-1-hexene copolymer) was prepared under the same conditions as in Polymerization Example 5, except that 10 mL of 1-hexene was added together with triisobutylaluminum.

[Polymerization Example 11]

Except that the supported catalyst prepared in Supported Catalyst Preparation Example 4 was used in place of the supported catalyst prepared in Supported Catalyst Preparation Example 1 and 10 mL of 1-hexene was added together with triisobutylaluminum, to give Polymerization Example 5 (Ethylene-1-hexene copolymer) was prepared under the same conditions as in Example 1.

[Polymerization Example 12]

An ethylene polymer (ethylene-1-octene copolymer) was prepared under the same conditions as in Polymerization Example 5 except that 10 mL of 1-octene was added together with triisobutylaluminum.

[Polymerization Comparative Example 1]

An ethylene polymer (polyethylene) was prepared under the same conditions as in Polymerization Example 1, except that bis (indenyl) zirconium dichloride was used instead of the compound synthesized in [Synthesis Example 1].

[Polymerization Comparative Example 2]

Supported Catalyst An ethylene polymer (polyethylene) was prepared under the same conditions as in Polymerization Example 5, except that the supported catalyst prepared in Comparative Preparation Example 1 was used in place of the supported catalyst prepared in Production Example 1.

[Polymerization Comparative Example 3]

Supported Catalyst An ethylene polymer (ethylene-1-hexene copolymer) was produced under the same conditions as in Polymerization Example 10, except that the supported catalyst prepared in Comparative Preparation Example 1 was used in place of the supported catalyst prepared in Production Example 1 Respectively.

[Polymerization Comparative Example 4]

Supported Catalyst An ethylene polymer (ethylene-1-hexene copolymer) was produced under the same conditions as in Polymerization Example 10, except that the supported catalyst prepared in Comparative Preparation Example 2 was used in place of the supported catalyst prepared in Production Example 1 Respectively.

[Experimental Example]

The weight average molecular weight and molecular weight distribution of the polymerized ethylene polymer were measured by GPC (Gel Permeation Chromatography, PL-GPC220) method. The melting point was measured by DSC (Differential Scanning Calorimetry, TA Instruments) Table 1 shows the results.

Monomer Weight average molecular weight (x 10 ⁴ ) Molecular weight distribution (Mw / Mn) Tm Polymerization Example 1 - 279 5.27 137.8 Polymerization Example 2 - 200 4.02 137.9 Polymerization Example 3 - 98 4.20 135.7 Polymerization Example 4 - 120 5.14 136.4 Polymerization Example 5 - 134 3.84 135.8 Polymerization Example 6 - 126 3.72 135.3 Polymerization Example 7 - 67 4.25 135.1 Polymerization Example 8 - 97 4.09 135.1 Polymerization Example 9 1-butene 65 3.50 127.8 Polymerization Example 10 1-hexene 62 3.46 127.8 Polymerization Example 11 1-hexene 40 3.50 125.4 Polymerization Example 12 1-octene 38 3.81 123.3 Comparative Example 1 - 43 3.04 139.1 Comparative Example 2 - 30 2.50 135.0 Comparative Example 3 1-hexene 27 2.78 128.2 Comparative Example 4 1-hexene 30 3.18 124.0

Referring to Table 1, it was found that the ethylene polymer produced by the production method of the present invention had a molecular weight distribution within a specific range within a range of 3.4 to 7 in molecular weight distribution. In addition, the ethylene polymers prepared by the process of the invention it was found even with a high weight-average molecular weight (M _W).

Claims (9)

(A) a main catalyst compound represented by the following formula (I);
(B-1) a promoter compound represented by the following formula (III-1);
(B-2) a promoter compound represented by the following formula (III-2); And
(C) a step of polymerizing ethylene alone or ethylene and a monomer in the presence of the carrier carrying the main catalyst compound (A) and the co-catalyst compound (B-1) Lt; RTI ID = 0.0 > 3.4 < / RTI >
(I)

(I)
M is zirconium (Zr), titanium (Ti) or hafnium (Hf)
X is a halogen group,
n is determined by the oxidation number of the central metal, is an integer of 2,
Cp ¹ and Cp ² are each independently a cyclopentadienyl group and have at least one substituent selected from the group consisting of the following formulas (II-1) and (II-2)
[Formula II-1]

[Formula II-2]

In the above formula (II-1) and (II-2)
Z is nitrogen (N), oxygen (O) or sulfur (S)
R is a C ₁ to C ₂₀ alkyl group,
m is an integer of 1 or 2 determined depending on the kind of Z,
p is an integer of 1,
A substituent bonded to CP ¹ and CP ² in addition to the substituent represented by the above formulas II-1 and II-2, and a substituent bonded to the carbon atom in the phenyl ring not bonded to ZR _m in the above formulas II-1 and II- Are each independently hydrogen.
[Formula (III-1)

(In the above formula (III-1)
R ¹ is a C ₁ -C ₁₀ alkyl group,
and q is an integer of 1 to 70.)
[Formula (III-2)

(In the above formula (III-2)
R ² , R ³ and R ⁴ are the same or different and are each independently a C ₁ to C ₁₀ alkyl group.) delete delete delete The method according to claim 1,
The carrier is selected from the group consisting of silica, alumina, magnesium chloride, calcium chloride, bauxite, zeolite, magnesium oxide, zirconium oxide, titanium oxide, boron trioxide, calcium oxide, zinc oxide, barium oxide, thorium oxide, ≪ / RTI > The method according to claim 1,
The monomers of C ₂ ~ C ₂₀ α- olefin _{(α-Olefin), C 4} ~ C 20 of diolefins _{(Diolefin), C 3 ~ C} 20 cycloolefin _{(Cycloolefin), C 3 ~ C} 20 of the cycloalkyl-di Olefin (Cyclodiolefin), and styrene. 7. An ethylene polymer produced by the production method of any one of claims 1, 5, and 6. 8. The method of claim 7,
And a molecular weight distribution (Mw / Mn) of 3.4 to 6.5. 8. The method of claim 7,
An ethylene polymer is 30,000 to 3,000,000 weight average molecular weight (M _W).