KR20170073385A - Polyolefin having excellent processibility - Google Patents

Abstract

The present invention relates to a polyolefin having excellent environmental stress cracking resistance and processability, as it has a large molecular weight, a broad molecular weight distribution and a high long chain side branch content. According to the polyolefin of the present invention, it is excellent in workability and stability and can be suitably used as a food container, a bottle cap or the like.

Description

[0001] Polyolefin having excellent processibility [

The present invention relates to a polyolefin having excellent processability.

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.

Against this backdrop, there is a continuing need to produce better products with a balance between physical and processability, and further improvements are needed.

In order to solve the problems of the prior art, the present invention aims to provide a polyolefin having excellent processability and improved mechanical properties.

Accordingly,

A first transition metal compound represented by the following formula (1);

A second transition metal compound represented by the following formula (2); And

Wherein the polyolefin is produced by polymerizing an olefin-based monomer in the presence of 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,

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 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;

Industrial Applicability According to the present invention, it is possible to provide a polyolefin resin having excellent ultrafine molecular weight, broad molecular weight distribution, high side chain side chain content, high environmental stress cracking property and melt flow rate ratio, A polyolefin can be provided.

In the present invention, the terms first, second, etc. are used to describe various components, and the terms are used only for the purpose of distinguishing one component from another.

Moreover, the terminology used herein is for the purpose of describing exemplary embodiments only and is not intended to be limiting of the present invention. The singular expressions include plural expressions unless the context clearly dictates otherwise. In this specification, the terms "comprising," "comprising," or "having ", and the like are intended to specify the presence of stated features, But do not preclude the presence or addition of one or more other features, integers, steps, components, or combinations thereof.

While the invention is susceptible to various modifications and alternative forms, specific embodiments thereof are shown by way of example in the drawings and will herein be described in detail. It should be understood, however, that the invention is not intended to be limited to the particular forms disclosed, but includes all modifications, equivalents, and alternatives falling within the spirit and scope of the invention.

Hereinafter, a polyolefin according to a specific embodiment of the present invention will be described.

The polyolefin according to one embodiment of the present invention comprises 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 supported on the first and second transition metal compounds, in the presence of a hybrid supported catalyst.

[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.

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 olefin polymerization, and can provide a polyolefin 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, the first transition metal compound for providing a polyolefin having a higher molecular weight and exhibiting better activity in the case of olefin polymerization can be exemplified by the 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 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 formula (2) is activated by an appropriate method and used as a catalyst for the olefin polymerization reaction, a low molecular weight polyolefin can be provided. Therefore, the hybrid supported catalyst comprising the first and second transition metal compounds can provide a polyolefin 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 in which Cp ₁ and Cp ₂ are cyclopentadienyl groups and the cyclopentadienyl group is not bridged shows a low copolymerization to alpha-olefin in olefin polymerization, and a low molecular weight polyolefin . 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 polyolefin, the distribution of the monomers copolymerized in the polyolefin chain and the copolymerization properties of the olefin can be easily controlled The physical properties of the objective polyolefin of the present invention 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 a polyolefin 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 polyolefin to be produced. As an example, to provide a broad molecular weight distribution and a high molecular weight polyolefin, 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 polyolefin, the distribution of the copolymerized monomers in the polymer chain, and the copolymerization characteristics of the olefin can be easily controlled to realize the desired physical properties more easily.

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.

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

In Formula 11,

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).

The polyolefin according to one embodiment of the present invention can be provided by a process for producing a polyolefin comprising the step of polymerizing an olefin monomer in the presence of the hybrid supported catalyst.

That is, as described above, the hybrid supported catalyst is a catalyst in which a first and a second transition metal compound having a specific structure are combined and supported on a carrier. As compared with the polyolefin polymerized using a conventional metallocene catalyst, It is possible to provide a polyolefin having a large and high molecular weight, exhibit higher activity upon polymerization of the olefin monomer, and 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 polyolefin 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-1-pentene and 1-octene desirable.

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 polyolefin obtained according to the production method of this embodiment can exhibit excellent processability due to ultrahigh molecular weight, very broad molecular weight distribution, high long chain side branch content, and high molecular weight, and exhibits improved environmental stress cracking resistance, Can be very preferably used for the purposes of the present invention.

Hereinafter, the present invention will be described in detail with reference to examples. However, these embodiments may be modified in various forms, and the scope of the invention should not be construed as being limited by the embodiments described below.

<Examples>

Preparation of transition metal compounds

Production Example 1

(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.

Then, 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) Bridging of Ligand 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.

_{^{1 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 ), 1.38 (s, 9H), 1.18 (s, 9H), 1.80-0.79

Production Example 2

(1) Preparation of ligand compound

fluorene was dissolved in 5 mL of MTBE and 100 mL of hexane, and 5.5 mL of 2.5 M n-BuLi hexane solution was added dropwise in a dry ice / acetone bath and stirred overnight at room temperature. (3.6 g) was dissolved in hexane (50 mL), and the fluorene-Li slurry was transferred for 30 minutes under a dry ice / acetone bath. The mixture was stirred overnight at room temperature. At the same time, 5,8-dimethyl-5,10-dihydroindeno [1,2-b] indole (12 mmol, 2.8 g) was dissolved in 60 mL of THF and 5.5 mL of 2.5 M n-BuLi hexane solution was dissolved in a dry ice / acetone bath And the mixture was stirred at room temperature overnight. dimethyl-5,10-dihydroindeno [1,2-b] indole-2-carboxylic acid was obtained by NMR spectroscopic analysis of the reaction solution of (6- (tert-butoxy) The Li solution was transferred under a dry ice / acetone bath. The mixture was stirred at room temperature overnight. After the reaction, the residue was extracted with ether / water, and the residual water of the organic layer was removed with MgSO ₄ to obtain a ligand compound (Mw = 597.90, 12 mmol). It was confirmed by 1H-NMR that two isomers were formed.

¹ H NMR (500 MHz, d 6 -benzene): -0.30 to -0.18 (3H, d), 0.40 (2H, m), 0.65-1.45 (8H, m), 1.12 D), 3.17 (2H, m), 3.41-3.43 (3H, d), 4.17-4.21 (1H, d), 4.34-4.38

Preparation of 1-2 metallocene compounds

7.2 g (12 mmol) of the ligand compound synthesized in 1-1 above was dissolved in 50 mL of diethylether, and 11.5 mL of 2.5 M n-BuLi hexane solution was added dropwise in a dry ice / acetone bath and stirred overnight at room temperature. And dried in vacuo to obtain a brown color sticky oil. And dissolved in toluene to obtain a slurry. ZrCl ₄ (THF) ₂ was prepared and 50 mL of toluene was added thereto to prepare a slurry. A 50 mL toluene slurry of ZrCl ₄ (THF) ₂ was transferred in a dry ice / acetone bath. It was changed to violet color by stirring overnight at room temperature. The reaction solution was filtered to remove LiCl. Toluene in the filtrate was removed by vacuum drying, and then hexane was added thereto for sonication for 1 hour. The slurry was filtered to give 6 g of dark violet metallocene compound (Mw 758.02, 7.92 mmol, yield 66 mol%), which was a filtered solid. Two isomers were observed in &lt; 1 &gt; H-NMR.

¹ H NMR (500 MHz, CDCl ₃ ): 1.19 (9H, d), 1.71 (3H, d), 1.50-1.70 (4H, m), 1.79 (2H, m), 3.91 (3H, d), 6.66-7.88 (15H, m)

Preparation of hybrid supported catalyst and production of polyolefin using the same

The properties of the ethylene polymer prepared in Examples and Comparative Examples and the activity of the catalyst are shown in Table 1 below.

Hybrid supported catalyst
(Molar ratio) Hydrogen gas input activation Weight average molecular weight
(* 10 ³ g / mol) / molecular weight distribution Example 1 K1: Preparation Example 1 = 2: 1 0 20 280 / 5.47 Example 2 K1: Preparation Example 1 = 3: 1 0 22 215 / 3.9 Example 3 K1: Preparation Example 1 = 4: 1 0 24 193 / 2.94 Example 4 K1: Preparation Example 1 = 2: 1 0.2% 4.7 137 / 9.36 Example 5 K1: Preparation Example 1 = 3: 1 0.2% 7.8 118 / 8.9 Example 6 K1: Preparation Example 1 = 4: 1 0.2% 9.2 102 / 8.7 Comparative Example 1 K1: Preparation Example 2 = 3: 1 0 20 189 / 3.8 Comparative Example 2 K1: Preparation Example 2 = 4: 1 0 21 173 / 3.55 Comparative Example 3 K1: Preparation Example 2 = 3: 1 0.3% 6.8 125 / 8.2 Comparative Example 4 K1: Preparation Example 2 = 4: 1 0.3% 7.5 110 / 9.33

K1: bis (n-butylcyclopentadienyl) -zirconium dichloride

As shown in Table 1, it is possible to provide a hybrid supported catalyst having a high activity compared to the comparative example by employing a specific combination of catalyst precursors in the case of Examples, and when used, polyolefin having ultrahigh molecular weight and broad molecular weight distribution Can be provided.

Claims (6)

A first transition metal compound represented by the following formula (1);
A second transition metal compound represented by the following formula (2); And
Based monomer in the presence of a hybrid supported catalyst comprising a carrier on which the first and second transition metal compounds are supported, wherein the polyolefin:
[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 polyolefin 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 &lt; _{1 &gt;} and X &lt; ₂ &gt; 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 polyolefin of claim 1, wherein Cp ₁ and Cp ₂ comprise a second transition metal compound that is a cyclopentadienyl group.
The polyolefin 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 polyolefin according to claim 1, further comprising at least one cocatalyst selected from the group consisting of compounds represented by the following general 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.
The method according to claim 1, wherein the olefinic monomer is selected from the group consisting of ethylene, propylene, 1-butene, 1-pentene, 4-methyl- Dodecene, 1-tetradecene, 1-hexadecene, 1-eicosene, norbornene, norbornadiene, ethylidene norbornene, phenyl novodene, vinyl novodene, dicyclopentadiene, 1,4 -Butadiene, 1,5-pentadiene, 1,6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene and 3-chloromethylstyrene.