KR20160067509A - Supported hybrid catalyst and method for preparing olefin polymer using the same - Google Patents

Abstract

According to the present invention, a supported hybrid catalyst and a preparation method of an olefin polymer using the same are provided. The supported hybrid catalyst can exhibit high activity in olefin polymerization reaction, and can simply prepare an olefin polymer having high molecular weight and desired physical properties. According to an embodiment of the present invention, the supported hybrid catalyst comprises: a first transition metal compound represented by chemical formula 1; a second transition metal compound represented by a chemical formula of [Cp1(R11)_u][Cp2(R12)_v]M2X3X4; and a carrier to which the first transition metal compound and the second transition metal compound are supported.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hybrid supported catalyst and a method for producing the olefin polymer using the hybrid supported catalyst,

The present invention relates to a hybrid supported catalyst and a process for producing an olefin polymer using the same.

Olefin polymerization catalyst systems can be classified into Ziegler-Natta and metallocene catalyst systems, both of which have been developed for their respective characteristics. Since the Ziegler-Natta catalyst has been widely applied to commercial processes since its invention in the 1950's, it is characterized by a broad molecular weight distribution of the polymer because it is a multisite catalyst having a plurality of active sites mixed therein. The composition of the comonomer There is a problem that the desired physical properties can not be secured because the distribution is not uniform.

On the other hand, the metallocene catalyst is composed of a combination of a main catalyst mainly composed of a transition metal compound and a cocatalyst, which is an organometallic compound mainly composed of aluminum. Such a catalyst is a single site catalyst as a homogeneous complex catalyst, , And has a characteristic that a molecular weight distribution is narrow according to a single active point property and a polymer having uniform composition distribution of a comonomer is obtained.

However, a polymer polymerized by using a metallocene catalyst has a narrow molecular weight distribution, and when applied to some products, there is a problem that the productivity is lowered due to the influence of extrusion loads and the like.

To solve this problem, there has been proposed a method of controlling the molecular weight distribution of a polymer by carrying two different metallocene catalyst precursors together with an activator on a carrier and polymerizing the polymer using the precursor. However, existing catalysts have limitations in simultaneously realizing two kinds of catalytic properties, and metallocene compounds are liberated from the supported catalyst, which causes fouling of the reactor.

An object of the present invention is to provide a hybrid supported catalyst which is excellent in polymerization activity and can easily produce an olefin polymer of desired physical properties.

The present invention also provides a process for producing an olefin polymer using the hybrid supported catalyst.

According to an embodiment of the present invention, a first transition metal compound represented by the following general formula (1); A second transition metal compound represented by the following formula (2); And a carrier on which the first and second transition metal compounds are supported.

[Chemical Formula 1]

(2)

[Cp ₁ (R ₁₁ ) _u ] [Cp ₂ (R ₁₂ ) _v ] M ₂ X ₃ X ₄

In the above Formulas 1 and 2,

C ₁ is any one of the ligands represented by the following formulas (3) to (6)

(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

R ₁ to R ₆ are the same or different from each other and are each independently any one of hydrogen, hydrocarbyl group having 1 to 30 carbon atoms and hydrocarbyloxy group having 1 to 30 carbon atoms,

Z is -O-, -S-, -NR ₇ - or -PR ₇ - and,

R ₇ is any one of hydrogen, a hydrocarbyl group having 1 to 20 carbon atoms, a hydrocarbyl (oxy) silyl group having 1 to 20 carbon atoms, and a silylhydrocarbyl group having 1 to 20 carbon atoms,

M &_lt; _{1 >} and M < ₂ &_gt; are the same or different from each other and each independently Ti, Zr or Hf,

X ₁ to X ₄ are the same or different from each other and each independently represents a halogen, a nitro group, an amido group, a phospho group, a phosphide group, a hydrocarbyl group having 1 to 30 carbon atoms, a hydrocarbyloxy group having 1 to 30 carbon atoms, A hydrocarbyl oxyhydrocarbyl group having 2 to 30 carbon atoms, -SiH ₃ , a hydrocarbyl (oxy) silyl group having 1 to 30 carbon atoms, a sulfonate group having 1 to 30 carbon atoms, and a sulfone group having 1 to 30 carbon atoms,

또는

이며, T is an alkylene group having 1 to 5 carbon atoms,

or

Lt;

T ₁ is C, Si, Ge, Sn or Pb,

Y ₁ and Y ₂ are the same or different from each other and each independently represents hydrogen, a hydrocarbyl group having 1 to 30 carbon atoms, a hydrocarbyloxy group having 1 to 30 carbon atoms, a hydrocarbyl oxyhydrocarbyl group having 2 to 30 carbon atoms, -SiH ₃ , a hydrocarbyl (oxy) silyl group having 1 to 30 carbon atoms, a hydrocarbyl group having 1 to 30 carbon atoms substituted with halogen, and -NR ₉ R ₁₀ ,

R ₉ and R ₁₀ are each independently any one of hydrogen and a hydrocarbyl group having 1 to 30 carbon atoms or may be linked to each other to form an aliphatic or aromatic ring,

Cp ₁ and Cp ₂ are the same or different and are each independently any one of a cyclopentadienyl group, an indenyl group, a 4,5,6,7-tetrahydro-1-indenyl group and a fluorenyl group,

R ₁₁ and R ₁₂ are the same or different from each other and each independently represents hydrogen, a hydrocarbyl group having 1 to 30 carbon atoms, a hydrocarbyloxy group having 1 to 30 carbon atoms, a hydrocarbyl oxyhydrocarbyl group having 2 to 30 carbon atoms, -SiH ₃ , a hydrocarbyl (oxy) silyl group having 1 to 30 carbon atoms and a halogen-substituted hydrocarbyl group having 1 to 30 carbon atoms,

u and v are each independently an integer of 0 to 5;

Specifically, the hybrid supported catalyst is a catalyst in which R ₁ to R ₄ in formulas (3) to (6) are the same as or different from each other, and are each independently any one of hydrogen and a hydrocarbyl group having 1 to 10 carbon atoms, and R ₅ and R ₆ Or a hydrocarbyl group having from 1 to 10 carbon atoms, which are different from each other, and each independently represents a first transition metal compound.

The hybrid supported catalyst may include a first transition metal compound wherein Z is -NR ₇ - and R ₇ is any one of hydrocarbyl groups having 1 to 10 carbon atoms.

이고, 상기 T₁이 C 또는 Si이며, Y₁ 및 Y₂가 서로 동일하거나 상이하고 각각 독립적으로 탄소수 1 내지 30의 하이드로카빌기, 탄소수 1 내지 30의 하이드로카빌옥시기 및 탄소수 2 내지 30의 하이드로카빌옥시하이드로카빌기 중 어느 하나인 제 1 전이 금속 화합물을 포함할 수 있다. The hybrid supported catalyst has a T

, T ₁ is C or Si, Y ₁ and Y ₂ are the same or different from each other, and each independently represents a hydrocarbyl group having 1 to 30 carbon atoms, a hydrocarbyloxy group having 1 to 30 carbon atoms and a hydrocarbyl group having 2 to 30 carbon atoms And a first transition metal compound that is any one of a carbyloxyhydrocarbyl group.

The hybrid supported catalyst may include a first transition metal compound wherein X ₁ and X ₂ are the same or different from each other and each independently any one of halogens.

The first transition metal compound may be any one of compounds represented by the following formulas (7) to (10).

(7)

[Chemical Formula 8]

[Chemical Formula 9]

[Chemical formula 10]

In the general formulas (7) to (10), R ₁ to R ₄ are the same as or different from each other, and are each independently any one of hydrogen and a hydrocarbyl group having 1 to 10 carbon atoms,

R ₅ to R ₇ are the same as or different from each other, and are each independently any one of hydrocarbyl groups having 1 to 10 carbon atoms,

M ₁ is Ti, Zr or Hf,

X < _{1 >} and X < ₂ > are the same or different from each other and are each independently any one of halogen,

T ₁ is C or Si,

Y ₁ and Y ₂ are the same or different from each other and are each independently any one of a hydrocarbyl group having 1 to 30 carbon atoms, a hydrocarbyloxy group having 1 to 30 carbon atoms and a hydrocarbyl oxyhydrocarbyl group having 2 to 30 carbon atoms.

The hybrid supported catalyst may include a second transition metal compound in which Cp ₁ and Cp ₂ are cyclopentadienyl groups.

Wherein R ₁₁ and R ₁₂ are the same or different and each independently represents hydrogen, a hydrocarbyl group having 1 to 10 carbon atoms, a hydrocarbyloxy group having 1 to 10 carbon atoms, and a hydrocarbyl oxyhydrocarbon having 2 to 20 carbon atoms, And a second transition metal compound that is either a carbyl group.

The hybrid supported catalyst may include a second transition metal compound wherein X ₃ and X ₄ are the same or different from each other and each independently any one of halogens.

The hybrid supported catalyst may include a first transition metal compound and a second transition metal compound in a molar ratio of 1: 0.5 to 1: 5.

And, the carrier may be silica, alumina, magnesia, or a mixture thereof.

The hybrid supported catalyst may further include at least one cocatalyst selected from the group consisting of compounds represented by the following formulas (11) to (13).

(11)

R ₂₀ - [Al (R ₁₉ ) -O] _n -R ₂₁

Wherein R ₁₉ , R ₂₀ and R ₂₁ are each independently any one of hydrogen, halogen, hydrocarbyl group having 1 to 20 carbon atoms and hydrocarbyl group having 1 to 20 carbon atoms substituted with halogen,

n is an integer of 2 or more,

[Chemical Formula 12]

D (R _{22) 3}

In Formula 12,

D is aluminum or boron,

R ₂₂ is each independently any one selected from the group consisting of halogen, a hydrocarbyl group having 1 to 20 carbon atoms, a hydrocarbyloxy group having 1 to 20 carbon atoms, and a hydrocarbyl group having 1 to 20 carbon atoms substituted with halogen,

[Chemical Formula 13]

^{[LH] + [W (A} ) 4] - or ^{[L] + [W (A} ) 4] -

In Formula 13,

L is a neutral or cationic Lewis base, H is a hydrogen atom,

W is a Group 13 element, A is independently a hydrocarbyl group having 1 to 20 carbon atoms; A hydrocarbyloxy group having 1 to 20 carbon atoms; And substituents in which at least one hydrogen atom of these substituents is substituted with at least one substituent selected from halogen, a hydrocarbyloxy group having 1 to 20 carbon atoms and a hydrocarbyl (oxy) silyl group having 1 to 20 carbon atoms.

According to another embodiment of the present invention, there is provided a process for producing an olefin polymer comprising the step of polymerizing an olefin monomer in the presence of the hybrid supported catalyst.

The olefin monomers that can be used in the above process are ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, Dodecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-aidocene, norbornene, norbornadiene, ethylidenenorbornene, phenyl norbornene, vinyl norbornene, dicyclopentadiene, Butadiene, butadiene, 1,5-pentadiene, 1,6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene and 3-chloromethylstyrene.

In particular, the above production method can produce an olefin polymer having a molecular weight distribution of 3.5 to 5.0 using a hybrid supported catalyst comprising the first and second transition metal compounds having the above-described specific structures. In addition, the olefin polymer having a weight average molecular weight of 100,000 to 800,000 g / mol can be prepared using the hybrid supported catalyst.

According to the present invention, there is provided a hybrid supported catalyst capable of easily producing an olefin polymer having high molecular weight and desired physical properties as well as exhibiting high activity in olefin polymerization, and a process for producing an olefin polymer using the hybrid supported catalyst Can be provided.

Hereinafter, a hybrid supported catalyst according to a specific embodiment of the present invention and a method for producing an olefin polymer using the same will be described.

According to an embodiment of the present invention, a first transition metal compound represented by the following general formula (1); A second transition metal compound represented by the following formula (2); And a carrier on which the first and second transition metal compounds are supported.

[Chemical Formula 1]

(2)

[Cp ₁ (R ₁₁ ) _u ] [Cp ₂ (R ₁₂ ) _v ] M ₂ X ₃ X ₄

In the above Formulas 1 and 2,

C ₁ is any one of the ligands represented by the following formulas (3) to (6)

(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

R ₁ to R ₆ are the same or different from each other and are each independently any one of hydrogen, hydrocarbyl group having 1 to 30 carbon atoms and hydrocarbyloxy group having 1 to 30 carbon atoms,

Z is -O-, -S-, -NR ₇ - or -PR ₇ - and,

R ₇ is any one of hydrogen, a hydrocarbyl group having 1 to 20 carbon atoms, a hydrocarbyl (oxy) silyl group having 1 to 20 carbon atoms, and a silylhydrocarbyl group having 1 to 20 carbon atoms,

M ₁ and M ₂ are the same or different and are each independently Ti, Zr or Hf,

X ₁ to X ₄ are the same or different and each independently represents a halogen, a nitro group, an amido group, a phospho group, a phosphide group, a hydrocarbyl group having 1 to 30 carbon atoms, a hydrocarbyloxy group having 1 to 30 carbon atoms, A hydrocarbyl oxyhydrocarbyl group having 2 to 30 carbon atoms, -SiH ₃ , a hydrocarbyl (oxy) silyl group having 1 to 30 carbon atoms, a sulfonate group having 1 to 30 carbon atoms, and a sulfone group having 1 to 30 carbon atoms,

또는

이고,T is an alkylene group having 1 to 5 carbon atoms,

or

ego,

T ₁ is C, Si, Ge, Sn or Pb,

Y ₁ and Y ₂ are the same or different from each other and each independently represent hydrogen, a hydrocarbyl group having 1 to 30 carbon atoms, a hydrocarbyloxy group having 1 to 30 carbon atoms, a hydrocarbyl oxyhydrocarbyl group having 2 to 30 carbon atoms, -SiH ₃ , a hydrocarbyl (oxy) silyl group having 1 to 30 carbon atoms, a hydrocarbyl group having 1 to 30 carbon atoms substituted with halogen, and -NR ₉ R ₁₀ ,

R ₉ and R ₁₀ are each independently selected from the group consisting of hydrogen and a hydrocarbyl group having 1 to 30 carbon atoms or bonded to each other to form an aliphatic or aromatic ring,

Cp < _{1 >} and Cp < ₂ > are the same or different from each other and each independently represents any one of a cyclopentadienyl group, an indenyl group, a 4,5,6,7-tetrahydro-1-indenyl group and a fluorenyl group Lt;

R ₁₁ and R ₁₂ are the same or different from each other and each independently represents hydrogen, a hydrocarbyl group having 1 to 30 carbon atoms, a hydrocarbyloxy group having 1 to 30 carbon atoms, a hydrocarbyl oxyhydrocarbyl group having 2 to 30 carbon atoms, -SiH ₃ , a hydrocarbyl (oxy) silyl group having 1 to 30 carbon atoms and a halogen-substituted hydrocarbyl group having 1 to 30 carbon atoms,

u and v are each independently an integer of 0 to 5;

Unless defined otherwise herein, the following terms may be defined as follows.

The hydrocarbyl group is a monovalent functional group having a hydrogen atom removed from a hydrocarbon and is an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an aralkyl group, an aralkenyl group, an aralkynyl group, an alkylaryl group, an alkenylaryl group, Aryl group, and the like. The hydrocarbyl group having 1 to 30 carbon atoms may be a hydrocarbyl group having 1 to 20 carbon atoms or 1 to 10 carbon atoms. Specific examples of the hydrocarbyl group having 1 to 30 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, , an n-heptyl group, a cyclohexyl group, and other straight, branched or cyclic alkyl groups; Or an aryl group such as a phenyl group, a naphthyl group, or an anthracenyl group.

The hydrocarbyloxy group is a functional group in which the hydrocarbyl group is bonded to oxygen. Specifically, the hydrocarbyloxy group having 1 to 30 carbon atoms may be a hydrocarbyloxy group having 1 to 20 carbon atoms or 1 to 10 carbon atoms. More specifically, the hydrocarbyloxy group having 1 to 30 carbon atoms is preferably a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, a n-butoxy group, an iso-butoxy group, , an n-hexoxy group, an n-heptoxy group, a cycloheptoxy group, and other straight-chain, branched-chain or cyclic alkoxy groups; Or an aryloxy group such as a phenoxy group or a naphthalenoxy group.

The hydrocarbyloxyhydrocarbyl group is a functional group in which at least one hydrogen of the hydrocarbyl group is substituted with at least one hydrocarbyloxy group. Specifically, the hydrocarbyl oxyhydrocarbyl group having 2 to 30 carbon atoms may be a hydrocarbyl oxyhydrocarbyl group having 2 to 20 carbon atoms or 2 to 15 carbon atoms. More specifically, the hydrocarbyloxyhydrocarbyl group having 2 to 30 carbon atoms is preferably a methoxymethyl group, a methoxyethyl group, an ethoxymethyl group, an isopropoxymethyl group, an isopropoxyethyl group, an iso-propoxyhexyl group, A tert-butoxyethyl group, a tert-butoxyhexyl group, or a phenoxyhexyl group.

Hydrocarbyl (oxy) group is a silyl functional group is substituted with one to three of the hydrogen -SiH ₃ group one to three dihydro car invoke or hydrocarbyl oxy. Specifically, the hydrocarbyl (oxy) silyl group having 1 to 30 carbon atoms may be a hydrocarbyl (oxy) silyl group having 1 to 20 carbon atoms, 1 to 15 carbon atoms, 1 to 10 carbon atoms, or 1 to 5 carbon atoms. More specifically, the hydrocarbyl (oxy) silyl group having 1 to 30 carbon atoms is an alkyl group such as a methylsilyl group, a dimethylsilyl group, a trimethylsilyl group, a dimethylethylsilyl group, a diethylmethylsilyl group and a dimethylpropylsilyl group Silyl group; Alkoxysilyl groups such as a methoxysilyl group, a dimethoxysilyl group, a trimethoxysilyl group, and a dimethoxyethoxysilyl group; An alkoxyalkylsilyl group such as a methoxydimethylsilyl group, a diethoxymethylsilyl group, and a dimethoxypropylsilyl group.

The silylhydrocarbyl group having 1 to 20 carbon atoms is a functional group in which at least one hydrogen atom of the hydrocarbyl group is substituted with a silyl group. The silyl group may be -SiH ₃ or a hydrocarbyl (oxy) silyl group. Specifically, the silyl hydrocarbyl group having 1 to 20 carbon atoms may be a silyl hydrocarbyl group having 1 to 15 carbon atoms or 1 to 10 carbon atoms. More specifically, the silyl hydrocarbyl group having 1 to 20 carbon atoms may be -CH ₂ -SiH ₃ , a methylsilylmethyl group, a dimethylethoxysilylpropyl group, or the like.

The halogen may be fluorine (F), chlorine (Cl), bromine (Br) or iodine (I).

The sulfonate group may have the structure of -O-SO ₂ -R ^a , wherein R ^a may be a hydrocarbyl group having 1 to 30 carbon atoms. Specifically, the sulfonate group having 1 to 30 carbon atoms may be a methane sulfonate group, a phenyl sulfonate group, or the like.

The sulfone group having 1 to 30 carbon atoms has the structure of -R ^{b '} -SO ₂ -R ^{b "} wherein R ^b' and R ^{b "} are the same or different and each independently is any one of hydrocarbyl groups having 1 to 30 carbon atoms . Specifically, the sulfone group having 1 to 30 carbon atoms may be a methylsulfonylmethyl group, a methylsulfonylpropyl group, a methylsulfonylbutyl group, or a phenylsulfonylpropyl group.

The alkylene group is a divalent functional group in which two hydrogen atoms are removed from an alkane. Specifically, the alkylene group having 1 to 5 carbon atoms may be a methylene group, an ethylene group, a propylene group, a butylene group or a pentylene group.

In the present specification, two adjacent substituents connected to each other to form an aliphatic or aromatic ring means that two atoms of the substituent (s) and a valence (atom) to which the two substituents are bonded are linked to form a ring do. Specifically, -NR ₉ R ₁₀ is R ₉ and R ₁₀ are connected to each other in the example forming the aliphatic ring may be mentioned piperidinyl (piperidinyl) group, the R ₉ and R ₁₀ of -NR ₉ R ₁₀ Examples of an aromatic ring formed by linking with each other include a pyrrolyl group and the like.

The above-mentioned substituents may optionally be substituted with a hydroxyl group, a hydroxyl group, halogen; Hydrocarbyl group; Hydrocarbyloxy group; A hydrocarbyl group or hydrocarbyloxy group containing at least one heteroatom of the group 14 to 16 heteroatoms; -SiH _3; A hydrocarbyl (oxy) silyl group; Force popularity; Phosphide group; Sulfonate groups; And a sulfone group.

The first transition metal compound represented by Formula 1 includes an aromatic ring compound containing thiophene as a different ligand and a base compound containing Group 14 or Group 15 atoms, , And M ₁ (X ₁ ) (X ₂ ) exists between the different ligands. The first transition metal compound having such a specific structure has excellent support stability, exhibits high activity in the polymerization of olefin, and can provide an olefin polymer having a high molecular weight.

Specifically, the C ₁ ligand in the structure of the first transition metal compound represented by the formula (1) may affect, for example, the olefin polymerization activity and the copolymerization characteristics of the olefin.

Particularly, as a ligand of C ₁ , R ₁ to R ₄ in formulas (3) to (6) are any one of hydrogen and a hydrocarbyl group having 1 to 10 carbon atoms, and R ₅ and R ₆ are any of hydrocarbyl groups having 1 to 10 carbon atoms The first transition metal compound of formula (1) comprising one ligand can provide a catalyst exhibiting very high activity and high comonomer conversion in the olefin polymerization process.

In the structure of the first transition metal compound represented by the formula (1), the Z ligand may affect, for example, the olefin polymerization activity.

In particular, when Z in the general formula (1) is -NR ₇ -, and R ₇ is any one of hydrocarbyl groups having 1 to 10 carbon atoms, it is possible to provide a catalyst exhibiting very high activity in olefin polymerization.

의 구조를 가질 수 있으며, 여기서 T₁은 C 또는 Si이고, Y₁ 및 Y₂는 서로 동일하거나 상이하며 각각 독립적으로 탄소수 1 내지 30의 하이드로카빌기, 탄소수 1 내지 30의 하이드로카빌옥시기 및 탄소수 2 내지 30의 하이드로카빌옥시하이드로카빌기 중 어느 하나일 수 있다. The ligand of C < ₁ &_gt; and the ligand of Z may be crosslinked by -T- to exhibit excellent support stability. For this effect, the -T-

Wherein T ₁ is C or Si, Y ₁ and Y ₂ are the same as or different from each other, and each independently represents a hydrocarbyl group having 1 to 30 carbon atoms, a hydrocarbyloxy group having 1 to 30 carbon atoms, And from 2 to 30 hydrocarbyl oxyhydrocarbyl groups.

On the other hand, M ₁ (X ₁ ) (X ₂ ) exists between the crosslinked cyclopentadienyl ligand and the tetrahydroindenyl ligand, and M ₁ (X ₁ ) (X ₂ ) is influenced by the storage stability of the metal complex Lt; / RTI >

In order to more effectively ensure this effect, a transition metal compound wherein X ₁ and X ₂ are each independently any one of halogens can be used.

As a first example, compounds represented by the following formulas (7) to (10) can be exemplified as the first transition metal compound for exhibiting superior activity in olefin polymerization and for providing a high molecular weight olefin polymer.

(7)

[Chemical Formula 8]

[Chemical Formula 9]

[Chemical formula 10]

In the general formulas (7) to (10), R ₁ to R ₄ are the same as or different from each other, and are each independently any one of hydrogen and a hydrocarbyl group having 1 to 10 carbon atoms,

R ₅ to R ₇ are the same as or different from each other, and are each independently any one of hydrocarbyl groups having 1 to 10 carbon atoms,

M ₁ is Ti, Zr or Hf,

X < _{1 >} and X < ₂ > are the same or different from each other and are each independently any one of halogen,

T ₁ is C or Si,

Y ₁ and Y ₂ are the same or different from each other and are each independently any one of a hydrocarbyl group having 1 to 30 carbon atoms, a hydrocarbyloxy group having 1 to 30 carbon atoms and a hydrocarbyl oxyhydrocarbyl group having 2 to 30 carbon atoms.

The first transition metal compound represented by the general formula (1) can be synthesized by applying known reactions, and a more detailed synthesis method can be referred to the examples.

Unlike the first transition metal compound, when the second transition metal compound represented by the general formula (2) is activated by an appropriate method and used as a catalyst for olefin polymerization, an olefin polymer having a low molecular weight can be provided. Therefore, the hybrid supported catalyst comprising the first and second transition metal compounds can provide an olefin polymer having a broad molecular weight distribution.

Specifically, Cp ₁ and Cp ₂ in formula (2) may be a cyclopentadienyl group. The second transition metal compound wherein Cp ₁ and Cp ₂ are cyclopentadienyl groups and the cyclopentadienyl group is not bridged exhibits a low copolymerization to alpha-olefins during olefin polymerization, and low molecular weight olefins Predominantly produces a polymer. Therefore, when such a second transition metal compound is mixed and supported on the same carrier as the first transition metal compound of formula (1), the molecular weight distribution of the olefin polymer, the distribution of the monomer copolymerized in the olefin polymer chain and the copolymerization characteristics of the olefin can be easily The physical properties of the desired olefin polymer can be more easily realized.

The Cp ₁ may be substituted by 1 to 5 R ₁₁ , and the Cp ₂ may be substituted with 1 to 5 R ₁₂ . In Formula 2, when u is an integer of 2 or more, a plurality of R < ₁₁ > may be the same as or different from each other. When v is an integer of 2 or more in the general formula (2), a plurality of R < ₁₂ > may be the same or different from each other.

Each of R ₁₁ and R ₁₂ may independently be any one of hydrogen, a hydrocarbyl group having 1 to 10 carbon atoms, a hydrocarbyloxy group having 1 to 10 carbon atoms, and a hydrocarbyl oxyhydrocarbyl group having 2 to 20 carbon atoms. The second transition metal compound in which R < ₁₁ > and R < ₁₂ > each have a substituent as described above may have excellent support stability.

X ₃ and X ₄ in the general formula (2) may be the same or different from each other and each independently halogen. The second transition metal compound in which X ₃ and X ₄ have a substituent as described above can be easily substituted with an alkyl group by reaction with a cocatalyst alkylmetal or methylaluminoxane. Further, by the subsequent alkyl abstraction, the second transition metal compound forms an ionic intermediate with the cocatalyst to provide a cationic form which is an active species of the olefin polymerization reaction more easily have.

As a second example, as a second transition metal compound for providing an olefin polymer having a broad molecular weight distribution in combination with the first transition metal compound, the following compounds can be exemplified.

The first and second transition metal compounds may be combined in an appropriate amount depending on the physical properties of the olefin polymer to be produced. As an example, to provide a broad molecular weight distribution and high molecular weight olefin polymer, the first and second transition metal compounds may be used in a molar ratio of 1: 0.5 to 1: 5. Accordingly, the molecular weight distribution of the olefin polymer, the distribution of the copolymerized monomers in the polymer chain, and the copolymerization characteristics of the olefin can be easily controlled, thereby achieving the desired physical properties more easily.

As the carrier, a carrier containing a hydroxyl group or a siloxane group on its surface can be used. Specifically, as the carrier, a carrier containing a hydroxyl group or a siloxane group having high reactivity by removing moisture on the surface by drying at a high temperature may be used. More specifically, examples of the carrier include silica, alumina, magnesia, and mixtures thereof. The carrier may be one which has been dried at elevated temperatures and these may typically comprise oxides, carbonates, sulphates and nitrate components such as Na ₂ O, K ₂ CO ₃ , BaSO ₄ and Mg (NO ₃ ) ₂ .

The hybrid supported catalyst may further include a cocatalyst to activate transition metal compounds which are catalyst precursors. As the cocatalyst, those conventionally used in the technical field to which the present invention belongs can be applied without particular limitation. As a non-limiting example, the cocatalyst may be at least one compound selected from the group consisting of compounds represented by the following formulas (11) to (13).

(11)

R ₂₀ - [Al (R ₁₉ ) -O] _n -R ₂₁

Wherein R ₁₉ , R ₂₀ and R ₂₁ are each independently any one of hydrogen, halogen, hydrocarbyl group having 1 to 20 carbon atoms and hydrocarbyl group having 1 to 20 carbon atoms substituted with halogen,

n is an integer of 2 or more,

[Chemical Formula 12]

D (R _{22) 3}

In Formula 12,

D is aluminum or boron,

R ₂₂ is each independently any one selected from the group consisting of halogen, a hydrocarbyl group having 1 to 20 carbon atoms, a hydrocarbyloxy group having 1 to 20 carbon atoms, and a hydrocarbyl group having 1 to 20 carbon atoms substituted with halogen,

[Chemical Formula 13]

^{[LH] + [W (A} ) 4] - or ^{[L] + [W (A} ) 4] -

In Formula 13,

L is a neutral or cationic Lewis base, H is a hydrogen atom,

W is a Group 13 element, A is independently a hydrocarbyl group having 1 to 20 carbon atoms; A hydrocarbyloxy group having 1 to 20 carbon atoms; And substituents in which at least one hydrogen atom of these substituents is substituted with at least one substituent selected from halogen, a hydrocarbyloxy group having 1 to 20 carbon atoms and a hydrocarbyl (oxy) silyl group having 1 to 20 carbon atoms.

Non-limiting examples of the compound represented by the formula (11) include methyl aluminoxane, ethyl aluminoxane, iso-butyl aluminoxane, and tert-butyl aluminoxane. Non-limiting examples of the compound represented by the formula (12) include trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, tripropyl aluminum, tributyl aluminum, dimethyl chloro aluminum, triisopropyl aluminum, tri- , Tricyclopentyl aluminum, tripentyl aluminum, triisopentyl aluminum, trihexyl aluminum, trioctyl aluminum, ethyl dimethyl aluminum, methyl diethyl aluminum, triphenyl aluminum, tri-p-tolyl aluminum, dimethyl aluminum methoxide or dimethyl aluminum Ethoxide and the like. Non-limiting examples of the compound represented by the formula (13) include trimethylammonium tetrakis (pentafluorophenyl) borate, triethylammonium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (Pentafluorophenyl) borate, N, N-dimethylanilinium n-butyltris (pentafluorophenyl) borate, N, N-dimethylanilinium benzyltris (pentafluorophenyl) (4- (t-butyldimethylsilyl) -2,3,5,6-tetrafluorophenyl) borate, N, N-dimethylanilinium tetrakis (4- (triisopropylsilyl) N, N-dimethyl anilinium pentafluorophenoxy tris (pentafluorophenyl) borate, N, N-dimethyl-2,4,6-trimethylanilinium Tetrakis (pentafluorophenyl) borate, trimethylammonium tetrakis (2,3,4,6-tetra (Pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (2,3,4,6-tetrafluorophenyl) borate, hexadecyldimethylammonium tetrakis N-dodecyl anilinium tetrakis (pentafluorophenyl) borate or methyldi (dodecyl) ammonium tetrakis (pentafluorophenyl) borate.

Such hybrid supported catalysts can be produced, for example, by carrying a promoter on a support and supporting the catalyst precursor, first and second transition metal compounds, on the catalyst support carrier.

Specifically, in the step of supporting the carrier on the carrier, the carrier which is dried at a high temperature and the cocatalyst may be mixed and stirred at a temperature of about 20 to 120 ° C to prepare a cocatalyst-carrying carrier.

In the step of supporting the catalyst precursor on the catalyst supporting carrier, a first transition metal compound is added to the catalyst supporting carrier, the mixture is stirred at a temperature of about 20 to 120 ° C, a second transition metal compound is added, And then it is stirred at a temperature of about 20 to 120 DEG C to prepare a hybrid supported catalyst.

In the step of supporting the catalyst precursor on the catalyst supporting carrier, the catalyst precursor may be added to the catalyst supporting carrier, followed by stirring, and then the co-catalyst may be further added to prepare the hybrid supported catalyst.

The content of the carrier, co-catalyst, co-catalyst supporting carrier, first and second transition metal compounds used for using the hybrid supported catalyst may be appropriately controlled depending on the physical properties or effects of the desired hybrid supported catalyst.

As the reaction solvent in the preparation of the hybrid supported catalyst, hydrocarbon solvents such as pentane, hexane, heptane and the like, or aromatic solvents such as benzene, toluene and the like may be used.

As a specific method for producing the hybrid supported catalyst, the following examples can be referred to. However, the manufacturing method of the hybrid supported catalyst is not limited to the description described in the present specification, and the manufacturing method may further employ a step that is conventionally employed in the technical field of the present invention, (S) may typically be altered by alterable step (s).

According to another embodiment of the present invention, there is provided a process for producing an olefin polymer comprising the step of polymerizing an olefin monomer in the presence of the hybrid supported catalyst.

As described above, the hybrid supported catalyst is a catalyst in which a first and a second transition metal compound of a specific structure are combined and supported on a carrier, and has a broad molecular weight distribution as compared with a polyolefin polymerized using a conventional metallocene catalyst, It provides an olefin polymer having a high molecular weight, exhibits higher activity in the polymerization of the olefin monomer, and can improve the copolymerization property of ethylene.

Examples of olefin monomers polymerizable with the hybrid supported catalyst include ethylene, alpha-olefins, cyclic olefins and the like. Dioene olefin monomers or triene olefin monomers having two or more double bonds can also be polymerized. Specific examples of the monomer include ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, Butene, dicyclopentadiene, 1,4-butadiene, 1,4-butadiene, 1,3-butadiene, 1,3-butadiene, Pentadiene, 1,6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene, 3-chloromethylstyrene and the like. These two or more monomers may be mixed and copolymerized. When the olefin polymer is a copolymer of ethylene and another comonomer, the comonomer is at least one comonomer selected from the group consisting of propylene, 1-butene, 1-hexene, 4-methyl- .

Various polymerization processes known as polymerization of olefin monomers such as a continuous solution polymerization process, a bulk polymerization process, a suspension polymerization process, a slurry polymerization process, or an emulsion polymerization process can be employed for the polymerization reaction of the olefin monomer.

Specifically, the polymerization reaction may be carried out at a temperature of about 50 to 110 DEG C or about 60 to 100 DEG C and a pressure of about 1 to 100 kgf / cm ² or about 1 to 50 kgf / cm ² .

In addition, in the above polymerization reaction, the hybrid supported catalyst may be used in a state of being dissolved or diluted in a solvent such as pentane, hexane, heptane, nonane, decane, toluene, benzene, dichloromethane, chlorobenzene and the like. At this time, by treating the solvent with a small amount of alkylaluminum or the like, a small amount of water or air that can adversely affect the catalyst can be removed in advance.

The olefin polymer prepared by the above-mentioned method can be produced by using the hybrid supported catalyst described above and thus can have a broad molecular weight distribution and a high molecular weight. For example, the olefin polymer may have a broad molecular weight distribution ranging from 3.5 to 5.0. In addition, the olefin polymer may have a weight average molecular weight of 100,000 to 800,000 g / mol.

BRIEF DESCRIPTION OF THE DRAWINGS The above and other objects, features and advantages of the present invention will be more apparent from the following detailed description taken in conjunction with the accompanying drawings, in which: FIG. However, this is provided as an example of the invention, and the scope of the invention is not limited thereto in any sense.

Manufacturing example  1: Preparation of transition metal compounds

(1) Preparation of ligand A

A solution of 1-benzothiophene was prepared by dissolving 4.0 g (30 mmol) of 1-benzothiophene in THF. Then, 14 mL (36 mmol, 2.5 M in hexane) of n-BuLi solution and 1.3 g (15 mmol) of CuCN were added to the 1-benzothiophene solution.

Subsequently, 3.6 g (30 mmol) of tigloyl chloride was slowly added to the solution at -80 DEG C, and the resulting solution was stirred at room temperature for about 10 hours.

Thereafter, 10% HCl was poured into the solution to quench the reaction, and the organic layer was separated with dichloromethane to obtain (2E) -1- (1-benzothiazol-2-yl) -2- Methyl-2-butene-1-one.

¹ H NMR (CDCl ₃ ): 7.85-7.82 (m, 2H), 7.75 (m, 1H), 7.44-7.34 (m, 2H), 6.68 , 3H)

(22 mmol) of the (2E) -1- (1-benzothiene-2-yl) -2-methyl-2-buten-1-one prepared above in 5 ml of chlorobenzene was vigorously stirred 34 mL of sulfuric acid was slowly added to the solution. Then, the solution was stirred at room temperature for about 1 hour. Then, ice water was poured into the solution, and the organic layer was separated with an ether solvent to obtain a yellow solid, 1,2-dimethyl-1,2-dihydro-3H-benzo [b] cyclopenta [d] thiophene- 4.5 g (91% yield) was obtained.

¹ H NMR (CDCl ₃ ): 7.95-7.91 (m, 2H), 7.51-7.45 (m, 2H), 3.20 , 3H)

To a solution of 2.0 g (9.2 mmol) of 1,2-dimethyl-1,2-dihydro-3H-benzo [b] cyclopenta [d] thiophen-3-one dissolved in a mixed solvent of 20 mL of THF and 10 mL of methanol It was added to the NaBH ₄ 570mg (15mmol) at 0 ℃. Then, the solution was stirred at room temperature for about 2 hours. Then, HCl was added to the solution to adjust the pH to 1, and an organic layer was separated with an ether solvent to obtain an alcohol intermediate.

The alcohol intermediate was dissolved in toluene to prepare a solution. Then, 190 mg (1.0 mmol) of p-toluenesulfonic acid was added to the solution, and the mixture was refluxed for about 10 minutes. The resulting reaction mixture was separated by column chromatography to obtain 1.8 g (9.0 mmol, 98 mmol) of l, 2-dimethyl-3H-benzo [b] cyclopenta [d] thiophene % yield).

_{^{1 H NMR (CDCl 3):}} 7.81 (d, 1H), 7.70 (d, 1H), 7.33 (t, 1H), 7.19 (t, 1H), 6.46 (s, 1H), 3.35 (q, 1H), 2.14 (s, 3 H), 1.14 (d, 3 H)

(2) Preparation of ligand B

(60 mmol) of (6-tert-butoxyhexyl) dichloro (methyl) silane and 40 mL of an ether solvent were added to a 250 mL schlenk flask different from the above flask, Butylamine solution and (6-tert-butoxyhexyl) dichloro (methyl) silane solution were prepared, respectively. Then, the t-butylamine solution was cooled to -78 ° C, and a solution of (6-tert-butoxyhexyl) dichloro (methyl) silane was slowly poured into the cooled solution and stirred at room temperature for about 2 hours Respectively. The resultant white suspension was filtered to obtain an ivory colorless solution of 1- (6- (tert-butoxy) hexyl) -N- (tert-butyl) -1-chloro-1-methylsilanamine B).

¹ H NMR (CDCl ₃ ): 3.29 (t, 2H), 1.52-1.29 (m, 10H), 1.20 (s, 9H)

(3) Crosslinking of ligands A and B

1.7 g (8.6 mmol) of 1,2-dimethyl-3H-benzo [b] cyclopenta [d] thiophene (ligand A) was added to a 250 mL schlenk flask and 30 mL of THF was added to prepare a ligand A solution. After cooling the ligand A solution to -78 ° C, 3.6 mL (9.1 mmol, 2.5 M in hexane) of n-BuLi solution was added to the ligand A solution, which was stirred overnight at room temperature to give a purple-brown solution . The solvent of the purple-brown solution was replaced with toluene, and a solution of 39 mg (0.43 mmol) of CuCN dispersed in 2 mL of THF was added to this solution to prepare Solution A.

Meanwhile, a solution B prepared by injecting 1- (6- (tert-butoxy) hexyl) -N- (tert-butyl) -1-chloro-1-methylsilanamine (ligand B) and toluene into a 250 mL schlenk flask And cooled to -78 deg. The solution A prepared before the cooled solution B was slowly injected. And the mixture of solutions A and B was stirred at room temperature overnight. The resultant solid was removed by filtration to obtain a viscous liquid 1- (6- (tert-butoxy) hexyl) -N- (tert-butyl) -1- 4.2 g (> 99% yield) of 3H-benzo [b] cyclopenta [d] thiophene-3-yl) -1-methylsilanamine (crosslinked product of ligands A and B).

In order to confirm the structure of the crosslinked product of the ligands A and B, the crosslinked product was lithiated at room temperature, and a 1H-NMR spectrum was obtained using a sample dissolved in a small amount of pyridine-D5 and CDCl ₃ .

¹ H NMR (pyridine-D5 and _{CDCl 3): 7.81 (d,} 1H), 7.67 (d, 1H), 7.82-7.08 (m, 2H), 3.59 (t, 2H), 3.15 (s, 6H), 2.23 (S, 9H), 1.91 (s, 9H), 1.68 (s, 3H)

(4) Preparation of transition metal compounds

To a 250 mL schlenk flask was added 1- (6- (tert-butoxy) hexyl) -N- (tert-butyl) -1- (1,2- 4.2 g (8.6 mmol) of 3-yl) -1-methylsilanamine (the crosslinking product of ligands A and B) were placed, and 14 mL of toluene and 1.7 mL of n-hexane were injected into the flask to dissolve the crosslinking product. After cooling the solution to -78 ° C, 7.3 mL (18 mmol, 2.5 M in hexane) of n-BuLi solution was injected into the cooled solution. Then, the solution was stirred at room temperature for about 12 hours. Then, 5.3 mL (38 mmol) of trimethylamine was added to the solution, and the solution was stirred at about 40 째 C for about 3 hours to prepare Solution C.

Meanwhile, 2.3 g (8.6 mmol) of TiCl ₄ (THF) ₂ and 10 mL of toluene were added to a separately prepared 250 mL schlenk flask to prepare a solution D in which TiCl ₄ (THF) ₂ was dispersed in toluene. The solution C prepared before the solution D was slowly poured at -78 캜, and the mixture of the solutions C and D was stirred at room temperature for about 12 hours. Thereafter, the solution was depressurized to remove the solvent, and the obtained solute was dissolved in toluene. The solids not dissolved in toluene were removed by filtration and the solvent was removed from the filtered solution to obtain 4.2 g (83% yield) of a transition metal compound in the form of a brown solid.

_{H NMR (CDCl 3): 8.01} (d, 1H), 7.73 (d, 1H), 7.45-7.40 (m, 2H), 3.33 (t, 2H), 2.71 (s, 3H), 2.33 (d, 3H) , 1.18 (s, 9H), 1.80-0.79 (m, 10H), 0.79 (d, 3H)

Manufacturing example  2: Preparation of transition metal compound

A transition metal compound of the following structure was prepared in the same manner as in Production Example 1, except that (1) 6-phenyl-1-benzothiophene was used instead of 1-benzothiophene in the preparation of ligand A of Production Example 1.

Example  1: Preparation of hybrid supported catalyst and preparation of olefin polymer using the same

(1) Preparation of hybrid supported catalyst

Silica (SP 952 from Grace Davison) was dehydrated and dried for about 12 hours at a temperature of 600 캜 and a vacuum state.

50 mL of toluene was placed in a glass reactor and 10 g of the dried silica was added thereto to disperse the silica at a temperature of about 40 캜. Subsequently, 61 mL of a methylaluminoxane (MAO) solution (10 wt% in toluene) was added to the reactor, the mixture was stirred at about 200 rpm for about 12 hours while raising the temperature of the glass reactor to about 60 DEG C, .

On the other hand, a solution of the first transition metal compound was prepared by dissolving 0.1 mmol of the transition metal compound prepared in Preparation Example 1 in toluene.

Then, the temperature of the reactor containing the co-catalyst supporting carrier was lowered to about 40 占 폚, the solution of the first transition metal compound prepared was put into the reactor, and the mixture was stirred for about 2 hours.

Then, 0.1 mmol of bis (n-butylcyclopentadienyl) -zirconium dichloride as a second transition metal compound was added to the reactor, and the mixture was stirred for about 2 hours.

Then, when the reaction was completed, stirring was stopped and the toluene layer was separated from the reaction product. Subsequently, the remaining reaction product was depressurized at about 40 ° C to remove toluene remaining in the reaction product to obtain a hybrid supported catalyst.

(2) Production of olefin polymer

For the preparation of the olefin polymer, a 600 mL metal alloy reactor equipped with a mechanical stirrer and capable of temperature control and for high pressure reaction was prepared.

Meanwhile, the hybrid supported catalyst prepared in (1) of Example 1 was quantified in a dry box and placed in a 50 mL glass bottle, and then the inlet of the glass bottle was sealed with a rubber diaphragm.

Then, 400 mL of hexane containing 1.0 mmol of triethylaluminum and the previously prepared hybrid supported catalyst were introduced into the 600 mL metal alloy reactor without air contact. Then, the temperature of the reactor was raised to about 80 DEG C, and ethylene was injected into the reactor to polymerize ethylene for about 1 hour. At this time, the ethylene gas was continuously injected so that the pressure of the reactor was maintained at about 30 kgf / cm ² .

Thereafter, when ethylene was polymerized to the desired level, stirring of the reactor was stopped, and unreacted ethylene gas was removed by evacuation. Then, the solvent was removed from the reaction product, and the obtained solid was dried in a vacuum oven at about 80 캜 for about 4 hours to obtain an ethylene homopolymer.

Example  2: Preparation of hybrid supported catalyst and preparation of olefin polymer using the same

A mixed supported catalyst was prepared in the same manner as in Example 1 except that the content of the transition metal compound of Preparation Example 1 was adjusted to 0.06 mmol in Example 1 and the same procedure as in Example 1 was conducted using the hybrid supported catalyst Ethylene homopolymer was obtained.

Example  3: Preparation of hybrid supported catalyst and preparation of olefin polymer using the same

After adding the second transition metal compound in Example 2 and stirring for about 2 hours, 0.15 mmol of N, N-dimethylanilinium tetrakis (pentafluorophenyl) -borate was further added to the reactor to obtain about The mixed supported catalyst was prepared in the same manner as in Example 2, except that the mixture was stirred at a temperature of 40 DEG C for about 2 hours. An ethylene homopolymer was prepared in the same manner as in Example 1 using the mixed supported catalyst.

Example  4: Preparation of hybrid supported catalyst and preparation of olefin polymer using the same

A mixed supported catalyst was prepared in the same manner as in Example 1, except that the transition metal compound prepared in Preparation Example 2 was used as the first transition metal compound in Example 1, An ethylene homopolymer was obtained in the same manner.

Comparative Example  1: Preparation of hybrid supported catalyst and preparation of olefin polymer using the same

Except that t-butoxyhexylmethylsilyl (Nt-butylamido) (2,3,4,5-tetramethylcyclopentadienyl) -titanium dichloride was used instead of the first transition metal compound in Example 1 , A hybrid supported catalyst was prepared in the same manner as in Example 1, and an ethylene homopolymer was obtained in the same manner as in Example 1 using the hybrid supported catalyst.

Test Example

The mass of the ethylene homopolymer prepared in Examples 1 to 4 and Comparative Example 1 was measured and the amount of the polymer obtained was divided by the amount of the catalyst used to calculate the activity of the catalyst used in each of the Examples and Comparative Examples The results are shown in Table 1 below.

The weight average molecular weight (Mw) and the molecular weight distribution (PDI) of the polymer prepared in each of the examples and comparative examples were determined by GPC analysis, and the results are shown in Table 1 below.

Further, after the polymer was dropped vertically into a 100 mL bulk density meter, the bulk density (BD) was calculated by weighing the filled polymer, and these values are shown in Table 1 below.

Active [kg PE / g SiO ₂ ] Weight average molecular weight Molecular weight distribution BD [g / mL] Example 1 16.9 694,000 g / mol 4.6 0.36 Example 2 11.4 573,000 g / mol 4.4 0.39 Example 3 18.9 425,000 g / mol 3.9 0.34 Example 4 15.5 628,000 g / mol 4.1 0.37 Comparative Example 1 10.6 394,000 g / mol 3.4 0.37

Referring to Table 1, it is possible to provide a hybrid supported catalyst having high activity compared to Comparative Example 1 by employing a specific combination of catalyst precursors in Examples 1 to 4, It is confirmed that an olefin polymer having a molecular weight distribution can be provided.

Claims (15)

A first transition metal compound represented by the following formula (1);
A second transition metal compound represented by the following formula (2); And
A hybrid supported catalyst comprising a carrier on which the first and second transition metal compounds are supported;
[Chemical Formula 1]

(2)
[Cp ₁ (R ₁₁ ) _u ] [Cp ₂ (R ₁₂ ) _v ] M ₂ X ₃ X ₄
In the above Formulas 1 and 2,
C ₁ is any one of the ligands represented by the following formulas (3) to (6)
(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

R ₁ to R ₆ are the same or different from each other and are each independently any one of hydrogen, hydrocarbyl group having 1 to 30 carbon atoms and hydrocarbyloxy group having 1 to 30 carbon atoms,
Z is -O-, -S-, -NR ₇ - or -PR ₇ - and,
R ₇ is any one of hydrogen, a hydrocarbyl group having 1 to 20 carbon atoms, a hydrocarbyl (oxy) silyl group having 1 to 20 carbon atoms, and a silylhydrocarbyl group having 1 to 20 carbon atoms,
M ₁ and M ₂ are the same or different and are each independently Ti, Zr or Hf,
X ₁ to X ₄ are the same or different and each independently represents a halogen, a nitro group, an amido group, a phospho group, a phosphide group, a hydrocarbyl group having 1 to 30 carbon atoms, a hydrocarbyloxy group having 1 to 30 carbon atoms, A hydrocarbyl oxyhydrocarbyl group having 2 to 30 carbon atoms, -SiH ₃ , a hydrocarbyl (oxy) silyl group having 1 to 30 carbon atoms, a sulfonate group having 1 to 30 carbon atoms, and a sulfone group having 1 to 30 carbon atoms,
T is an alkylene group having 1 to 5 carbon atoms,

or

ego,
T ₁ is C, Si, Ge, Sn or Pb,
Y ₁ and Y ₂ are the same or different from each other and each independently represent hydrogen, a hydrocarbyl group having 1 to 30 carbon atoms, a hydrocarbyloxy group having 1 to 30 carbon atoms, a hydrocarbyl oxyhydrocarbyl group having 2 to 30 carbon atoms, -SiH ₃ , a hydrocarbyl (oxy) silyl group having 1 to 30 carbon atoms, a hydrocarbyl group having 1 to 30 carbon atoms substituted with halogen, and -NR ₉ R ₁₀ ,
R ₉ and R ₁₀ are each independently selected from the group consisting of hydrogen and a hydrocarbyl group having 1 to 30 carbon atoms or bonded to each other to form an aliphatic or aromatic ring,
Cp ₁ and Cp ₂ are the same or different and are each independently any one of a cyclopentadienyl group, an indenyl group, a 4,5,6,7-tetrahydro-1-indenyl group and a fluorenyl group,
R ₁₁ and R ₁₂ are the same or different from each other and each independently represents hydrogen, a hydrocarbyl group having 1 to 30 carbon atoms, a hydrocarbyloxy group having 1 to 30 carbon atoms, a hydrocarbyl oxyhydrocarbyl group having 2 to 30 carbon atoms, -SiH ₃ , a hydrocarbyl (oxy) silyl group having 1 to 30 carbon atoms and a halogen-substituted hydrocarbyl group having 1 to 30 carbon atoms,
u and v are each independently an integer of 0 to 5;
The compound according to claim 1, wherein R ₁ to R ₄ in the formulas (3) to (6) are the same as or different from each other and are each independently any one selected from the group consisting of hydrogen and a hydrocarbyl group having 1 to 10 carbon atoms, and R ₅ and R _6, And each independently a hydrocarbyl group having 1 to 10 carbon atoms.
The hybrid supported catalyst according to claim 1, wherein Z is -NR ₇ -, and R ₇ is a hydrocarbyl group having 1 to 10 carbon atoms.
2. The compound according to claim 1, wherein T is

, T ₁ is C or Si, Y ₁ and Y ₂ are the same or different from each other, and each independently represents a hydrocarbyl group having 1 to 30 carbon atoms, a hydrocarbyloxy group having 1 to 30 carbon atoms and a hydrocarbyl group having 2 to 30 carbon atoms And a first transition metal compound which is any one of a covalent hydrocarbyl group and a carbyloxyhydrocarbyl group.
The hybrid supported catalyst according to claim 1, wherein X ₁ and X ₂ are the same or different and each independently is a halogen.
The hybrid supported catalyst according to claim 1, wherein the first transition metal compound is any one of compounds represented by the following formulas (7) to (10):
(7)

[Chemical Formula 8]

[Chemical Formula 9]

[Chemical formula 10]

In the general formulas (7) to (10), R ₁ to R ₄ are the same as or different from each other, and are each independently any one of hydrogen and a hydrocarbyl group having 1 to 10 carbon atoms,
R ₅ to R ₇ are the same as or different from each other, and are each independently any one of hydrocarbyl groups having 1 to 10 carbon atoms,
M ₁ is Ti, Zr or Hf,
X < _{1 >} and X < ₂ > are the same or different from each other and are each independently any one of halogen,
T ₁ is C or Si,
Y ₁ and Y ₂ are the same or different from each other and are each independently any one of a hydrocarbyl group having 1 to 30 carbon atoms, a hydrocarbyloxy group having 1 to 30 carbon atoms and a hydrocarbyl oxyhydrocarbyl group having 2 to 30 carbon atoms.
The hybrid supported catalyst according to claim 1, wherein Cp ₁ and Cp ₂ comprise a second transition metal compound which is a cyclopentadienyl group.
The process of claim 1, wherein R ₁₁ and R ₁₂ are the same or different and each independently represents hydrogen, a hydrocarbyl group having 1 to 10 carbon atoms, a hydrocarbyloxy group having 1 to 10 carbon atoms and hydrocarbyloxy having 2 to 20 carbon atoms And a second transition metal compound which is one of hydrocarbyl groups.
The hybrid supported catalyst according to claim 1, wherein the first transition metal compound and the second transition metal compound are contained in a molar ratio of 1: 0.5 to 1: 5.
The hybrid supported catalyst according to claim 1, wherein the carrier is silica, alumina, magnesia or a mixture thereof.
The hybrid supported catalyst according to claim 1, further comprising at least one cocatalyst selected from the group consisting of compounds represented by the following Chemical Formulas 11 to 13:
(11)
R ₂₀ - [Al (R ₁₉ ) -O] _n -R ₂₁
Wherein R ₁₉ , R ₂₀ and R ₂₁ are each independently any one of hydrogen, halogen, hydrocarbyl group having 1 to 20 carbon atoms and hydrocarbyl group having 1 to 20 carbon atoms substituted with halogen,
n is an integer of 2 or more,
[Chemical Formula 12]
D (R _{22) 3}
In Formula 12,
D is aluminum or boron,
R ₂₂ is each independently any one selected from the group consisting of halogen, a hydrocarbyl group having 1 to 20 carbon atoms, a hydrocarbyloxy group having 1 to 20 carbon atoms, and a hydrocarbyl group having 1 to 20 carbon atoms substituted with halogen,
[Chemical Formula 13]
^{[LH] + [W (A} ) 4] - or ^{[L] + [W (A} ) 4] -
In Formula 13,
L is a neutral or cationic Lewis base, H is a hydrogen atom,
W is a Group 13 element, A is independently a hydrocarbyl group having 1 to 20 carbon atoms; A hydrocarbyloxy group having 1 to 20 carbon atoms; And substituents in which at least one hydrogen atom of these substituents is substituted with at least one substituent selected from halogen, a hydrocarbyloxy group having 1 to 20 carbon atoms and a hydrocarbyl (oxy) silyl group having 1 to 20 carbon atoms.
A process for producing an olefin polymer comprising the step of polymerizing an olefin monomer in the presence of the hybrid supported catalyst of claim 1.
13. The method of claim 12 wherein the olefin monomer is selected from the group consisting of ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, Dodecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-aidocene, norbornene, norbornadiene, ethylidenenorbornene, phenyl norbornene, vinyl norbornene, dicyclopentadiene, A process for producing an olefin polymer comprising at least one member selected from the group consisting of butadiene, 1,5-pentadiene, 1,6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene and 3-chloromethylstyrene.
13. The process for producing an olefin polymer according to claim 12, which produces an olefin polymer having a molecular weight distribution of 3.5 to 5.0.
The process for producing an olefin polymer according to claim 12, which produces an olefin polymer having a weight average molecular weight of 100,000 to 800,000 g / mol.