KR101725350B1 - Supported catalyst and method for preparing olefin polymer using the same - Google Patents

Supported catalyst and method for preparing olefin polymer using the same Download PDF

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KR101725350B1
KR101725350B1 KR1020150172416A KR20150172416A KR101725350B1 KR 101725350 B1 KR101725350 B1 KR 101725350B1 KR 1020150172416 A KR1020150172416 A KR 1020150172416A KR 20150172416 A KR20150172416 A KR 20150172416A KR 101725350 B1 KR101725350 B1 KR 101725350B1
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carbon atoms
hydrocarbyl
supported catalyst
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박성호
김대환
이기수
정승환
홍복기
홍대식
조경진
이승민
김동은
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주식회사 엘지화학
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    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00Polymerisation catalysts
    • C08F4/42Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62Refractory metals or compounds thereof
    • C08F4/64Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/6592Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
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    • C08F10/00Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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    • C08F4/00Polymerisation catalysts
    • C08F4/42Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
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    • C08F4/00Polymerisation catalysts
    • C08F4/42Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
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    • C08F4/656Pretreating with metals or metal-containing compounds with silicon or compounds thereof

Abstract

According to the present invention, not only a high activity can be exhibited in the olefin polymerization reaction, but also the properties such as the chemical structure and the molecular weight of the synthesized olefin polymer can be easily controlled and the supported catalyst comprising the transition metal compound And a process for producing an olefin polymer using the supported catalyst may be provided.

Description

TECHNICAL FIELD [0001] The present invention relates to a supported catalyst, and a method for producing the olefin polymer using the same. BACKGROUND ART [0002]

The present invention relates to a supported catalyst comprising a transition metal compound having a novel structure and a process for producing an olefin polymer using the supported catalyst.

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, from the viewpoints of polymerization activity, high molecular weight, introduction amount of comonomer, or stereoregularity, further improvement of metallocene catalyst is required.

An object of the present invention is to provide a supported catalyst comprising a transition metal compound having a novel structure capable of improving the copolymerization property of ethylene and providing a high molecular weight olefin polymer, having high polymerization activity and supported stability.

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

According to one embodiment of the present invention, there is provided a transition metal compound represented by the following general formula (1); And a carrier for supporting the transition metal compound.

[Chemical Formula 1]

Figure 112015118983763-pat00001

In the above formula (1), C 1 is any one of the ligands represented by the following formulas (2) to (5)

(2)

Figure 112015118983763-pat00002

(3)

Figure 112015118983763-pat00003

[Chemical Formula 4]

Figure 112015118983763-pat00004

[Chemical Formula 5]

Figure 112015118983763-pat00005

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 is Ti, Zr or Hf,

X 1 and X 2 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,

T is

Figure 112015118983763-pat00006
or
Figure 112015118983763-pat00007
ego,

T 1 is C, Si, Ge, Sn or Pb,

Y 1 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) group having 1 to 30 carbon atoms, A silyl group, a halogen-substituted hydrocarbyl group having 1 to 30 carbon atoms, and -NR 9 R 10 ,

Y 2 is any one of a hydrocarbyl oxyhydrocarbyl group having 2 to 30 carbon atoms,

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

Specifically, R 1 to R 4 in the general formulas (2) to (5) are the same 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 and R 6 are the same or different from each other Independently, a hydrocarbyl group having 1 to 10 carbon atoms.

Z is -NR < 7 > - and R < 7 > is any one of hydrocarbyl groups having 1 to 10 carbon atoms.

The T

Figure 112015118983763-pat00008
, T 1 is C or Si, Y 1 is any one of a hydrocarbyl group having 1 to 30 carbon atoms and a hydrocarbyloxy group having 1 to 30 carbon atoms, and Y 2 is a hydrocarbyl oxyhydrocarbyl group having 2 to 30 carbon atoms And the like.

X 1 and X 2 may be the same or different from each other and each independently halogen.

For example, the compound of Formula 1 may be a transition metal compound of any one of the compounds represented by Chemical Formulas 6 to 9 below.

[Chemical Formula 6]

Figure 112015118983763-pat00009

(7)

Figure 112015118983763-pat00010

[Chemical Formula 8]

Figure 112016109617678-pat00056

[Chemical Formula 9]

Figure 112015118983763-pat00012

In formulas (6) to (9), 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 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 is any one of a hydrocarbyl group having 1 to 30 carbon atoms and a hydrocarbyloxy group having 1 to 30 carbon atoms,

And Y 2 is any one of a hydrocarbyl oxyhydrocarbyl group having 2 to 30 carbon atoms.

The carrier may be, for example, silica, alumina, magnesia or a mixture thereof.

The supported catalyst may further include at least one cocatalyst selected from the group consisting of compounds represented by the following general formulas (10) to (12).

[Chemical formula 10]

R 12 - [Al (R 11 ) -O] n -R 13

In Formula 10,

R 11 , R 12 and R 13 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,

(11)

D (R 14) 3

In Formula 11,

D is aluminum or boron,

R 14 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 12]

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

In Formula 12,

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 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 preparation method can produce an ultra-high molecular weight olefin polymer having a weight average molecular weight of 950,000 to 5,000,000 g / mol by using a supported catalyst containing the transition metal compound having the specific structure described above.

According to the present invention, not only a high activity can be exhibited in the olefin polymerization reaction, but also the properties such as the chemical structure and the molecular weight of the synthesized olefin polymer can be easily controlled and the supported catalyst comprising the transition metal compound And a process for producing an olefin polymer using the supported catalyst may be provided.

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

According to one embodiment of the present invention, there is provided a transition metal compound represented by the following general formula (1); And a carrier for supporting the transition metal compound.

[Chemical Formula 1]

Figure 112015118983763-pat00013

In the above formula (1), C 1 is any one of the ligands represented by the following formulas (2) to (5)

(2)

Figure 112015118983763-pat00014

(3)

Figure 112015118983763-pat00015

[Chemical Formula 4]

Figure 112015118983763-pat00016

[Chemical Formula 5]

Figure 112015118983763-pat00017

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 is Ti, Zr or Hf,

X 1 and X 2 are the same or different from each other and each independently represents a halogen, a nitro group, an amido group, a phospho group, a phosphido 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

Figure 112015118983763-pat00018
or
Figure 112015118983763-pat00019
ego,

T 1 is C, Si, Ge, Sn or Pb,

Y 1 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) group having 1 to 30 carbon atoms, A silyl group, a halogen-substituted hydrocarbyl group having 1 to 30 carbon atoms, and -NR 9 R 10 ,

Y 2 is any one of a hydrocarbyl oxyhydrocarbyl group having 2 to 30 carbon atoms,

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

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 transition metal compound represented by the formula (1) comprises a cyclic compound containing thiophene as a different ligand and a base compound containing a group 14 or 15 group atom, and the different ligand is -T- And has a structure in which M (X 1 ) (X 2 ) exists between different ligands. The supported catalyst carrying the transition metal compound having such a specific structure is applied to the polymerization reaction of the olefin polymer to exhibit high activity and can provide a high molecular weight olefin polymer.

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

Particularly, as a ligand of C 1 , R 1 to R 4 in formulas (2) to (5) 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 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 transition metal compound represented by the above formula (1), the Z ligand may affect, for example, the polymerization activity of the olefin.

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 the olefin polymerization process.

The ligand of C 1 and the ligand of Z may be crosslinked by -T- to exhibit excellent support stability and polymerization activity. For this effect, the -T-

Figure 112015118983763-pat00020
Wherein T 1 is C or Si, Y 1 is any one of a hydrocarbyl group having 1 to 30 carbon atoms and a hydrocarbyloxy group having 1 to 30 carbon atoms, Y 2 is a hydrocarbon group having 2 to 30 carbon atoms And a hydrocarbyl oxyhydrocarbyl group. More specifically, Y 1 is any one of a methyl group, an ethyl group, an n-propyl group and an n-butyl group, and Y 2 is a methoxymethyl group, a methoxyethyl group, an ethoxymethyl group, An ethyl group, an iso-propoxyhexyl group, a tert-butoxymethyl group, a tert-butoxyethyl group, a tert-butoxyhexyl group and a phenoxyhexyl group.

On the other hand, there exist M (X 1 ) (X 2 ) between the bridged C 1 ligand and Z ligand, and M (X 1 ) (X 2 ) may affect the storage stability of the metal complex.

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 one example, the compound represented by the above formula (1), which has superior activity and can improve the copolymerization of ethylene and can express an ultrahigh polymer, can be exemplified by the compounds represented by the following formulas (6) to (9).

[Chemical Formula 6]

Figure 112015118983763-pat00021

(7)

Figure 112015118983763-pat00022

[Chemical Formula 8]

Figure 112016109617678-pat00057

[Chemical Formula 9]

Figure 112015118983763-pat00024

In formulas (6) to (9), 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 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 is any one of a hydrocarbyl group having 1 to 30 carbon atoms and a hydrocarbyloxy group having 1 to 30 carbon atoms,

And Y 2 is any one of a hydrocarbyl oxyhydrocarbyl group having 2 to 30 carbon atoms.

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

On the other hand, the transition metal compound represented by Formula 1 has the above-described structural characteristics and can be stably supported on the carrier.

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 supported catalyst may further include a cocatalyst to activate the transition metal compound which is a catalyst precursor. 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 general formulas (10) to (12).

[Chemical formula 10]

R 12 - [Al (R 11 ) -O] n -R 13

In Formula 10,

R 11 , R 12 and R 13 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.

(11)

D (R 14) 3

In Formula 11,

D is aluminum or boron,

Each of the three R < 14 > s independently is any one 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 12]

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

In Formula 12,

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

W is a Group 13 element, 4 A is 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 (10) include methyl aluminoxane, ethyl aluminoxane, isobutyl aluminoxane, and tert-butyl aluminoxane. Non-limiting examples of the compound represented by the formula (11) 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. Finally, non-limiting examples of the compound represented by the formula (12) 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 -Dodecyl anilinium tetrakis (pentafluorophenyl) borate or methyldi (dodecyl) ammonium tetrakis (pentafluorophenyl) borate, and the like.

Such a supported catalyst can be produced, for example, by carrying a promoter on a support and supporting the transition metal compound, which is a catalyst precursor, on the catalyst support carrier.

Specifically, in the step of supporting the carrier on the carrier, the co-catalyst may be prepared by adding the co-catalyst to the carrier dried at a high temperature and stirring the carrier at a temperature of about 20 to 120 ° C.

In the step of supporting the catalyst precursor on the catalyst supporting carrier, a transition metal compound is added to the catalyst supporting carrier obtained in the step of supporting the catalyst on the carrier, and the resulting mixture is stirred at a temperature of about 20 to 120 ° C to carry A catalyst can be produced.

In the step of supporting the catalyst precursor on the catalyst supporting carrier, the supported catalyst may be prepared by adding a transition metal compound to the catalyst supporting carrier, stirring the mixture, and further adding a co-catalyst.

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

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

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

As described above, the supported catalyst provides a higher molecular weight olefin polymer than a polyolefin polymerized using a conventional metallocene catalyst due to its specific structure, and can exhibit higher activity in the polymerization of olefin monomers.

Examples of olefin monomers polymerizable with the above-mentioned supported catalyst include ethylene, alpha-olefin, cyclic olefin 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 .

Further, in the above polymerization reaction, the 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 produced by the above-mentioned method can have a remarkably high molecular weight by being produced using the above-mentioned supported catalyst. For example, the olefin polymer may have a weight average molecular weight of 950,000 to 5,000,000 g / mol. In particular, in the production method according to another embodiment, there is provided an olefin polymer having a high molecular weight in the above-mentioned range while exhibiting catalytic activity of 0.5 kg Pol./g cat.h or higher or 1.0 kg Pol./g cat.h .

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.

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.

Figure 112015118983763-pat00025

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.

Figure 112015118983763-pat00026

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).

Figure 112015118983763-pat00027

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).

Figure 112015118983763-pat00028

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).

Figure 112015118983763-pat00029

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.

Figure 112015118983763-pat00030

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

Manufacturing example  2: Preparation of transition metal compound

(1) Preparation of ligand C

A solution prepared by dissolving 9.68 g (100 mmol) of 1-methylthiophene and 8.48 mL (100 mmol) of methacrylic acid in 30 mL of methylene chloride was added to a container containing 100 g of polyphosphoric acid. The mixture thus obtained was stirred at a temperature of about 50 to 60 DEG C for about 2 hours. Then, the mixture was cooled to 0 占 폚 and water was added thereto to quench the reaction. Then, the organic layer was separated from the mixture using diethyl ether, the acid remaining in the organic layer was neutralized with Na 2 CO 3 , and water remaining in the organic layer was removed with K 2 CO 3 . Thereafter, hexane was used to obtain 2,5-dimethyl-4,5-dihydro-6H-cyclopenta [b] thiophen-6-one as yellow oil from the organic layer.

Figure 112015118983763-pat00031

1 H NMR (CDCl 3): 6.72 (s, 1H), 3.22-3.17 (m, 2H), 2.96-2.93 (m, 1H), 2.57 (s, 3H), 1.33-1.31 (d, 3H)

2.27 g (13.65 mmol) of 2,5-dimethyl-4,5-dihydro-6H-cyclopenta [b] thiophen-6-one was dissolved in 30 mL of THF. To this solution was slowly added 12 mL (36 mmol, 3M in diethyl ether) of methylmagnesium bromide solution at about 0 < 0 > C while stirring the solution. Then, the obtained mixture was stirred at about 40 ° C overnight, and then the reaction was quenched by adding water to the mixture. Thereafter, an organic layer was separated from the mixture using an ether solvent, and 2,5,6-trimethyl-4H-cyclopenta [b] thiophene (ligand C) was obtained as a yellow oil from the organic layer.

Figure 112015118983763-pat00032

1 H NMR (CDCl 3): 6.66 (s, 1H), 4.30 (s, 3H), 3.05 (s, 2H), 2.01-1.98 (d, 6H)

(2) Crosslinking of ligands B and C

A ligand C solution was prepared by adding 0.99 g (6.03 mmol) of 2,5,6-trimethyl-4H-cyclopenta [b] thiophene (ligand C) and 30 mL of THF to a 250 mL schlenk flask. After cooling the ligand C solution to -78 ° C, 2.5 mL (6.25 mmol, 2.5 M in hexane) of n-BuLi solution was added to the ligand C solution and stirred overnight at room temperature to obtain a brown solution E.

To a 250 mL schlenk flask was added 1- (6- (tert-butoxy) hexyl) -N- (tert-butyl) -1-chloro-1-methylsilanamine (prepared from ligand B ) And toluene were injected to prepare a solution B as in (3) of Production Example 1. Then, the solution B was cooled to -78 占 폚. The brown solution E prepared before the cooled solution B was slowly injected. And the mixture of solutions B and E was stirred at room temperature overnight. The resulting solid was filtered off to obtain 1- (6- (tert-butoxy) hexyl) -N- (tert-butyl) -1- (> 97.4% yield) of the trimethyl-4H-cyclopenta [b] thiophen-4-yl) silanamine (the bridged product of ligands B and C).

Figure 112015118983763-pat00033

1 H NMR (CDCl 3): 6.63 (s, 1H), 3.31 (m, 2H), 2.51 (s, 3H), 2.10-2.08 (d, 3H), 2.02 (s, 3H), 1.47-1.22 (m , 19 H), 1.18 (s, 9 H), 0.12 (s, 3 H)

(3) Preparation of transition metal compounds

To a 250 mL schlenk flask was added a solution of 1- (6- (tert-butoxy) hexyl) -N- (tert-butyl) -1-methyl- 1- (2,5,6- trimethyl-4H-cyclopenta [b] (Crosslinked product of ligands B and C) were placed in a flask, and 20 mL of toluene and 5 mL of n-hexane were injected into the flask to dissolve the crosslinking product. After cooling the solution to -78 ° C, 5 mL (12.5 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, 4 mL (27 mmol) of trimethylamine was added to the solution, and the solution was stirred at about 40 ° C for about 3 hours to prepare solution F.

Meanwhile, 1.97 g (5.94 mmol) of TiCl 4 (THF) 2 and 20 mL of toluene were added to a separately prepared 250 mL schlenk flask to prepare a solution G in which TiCl 4 (THF) 2 was dispersed in toluene. The solution F prepared before the solution G was slowly poured at -78 ° C, and the mixture of the solutions F and G 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 that did not dissolve in toluene were removed by filtration, and the solvent was removed from the filtered solution to obtain 2.99 g (85% yield) of a transition metal compound in the form of a black oil.

Figure 112015118983763-pat00034

1 H NMR (CDCl 3): 7.00 (s, 1H), 3.31 (m, 3H), 2.50 (s, 3H), 2.35 (s, 3H), 1.86 (s, 3H), 1.47-1.32 (m, 19H ), 1.18 (s, 9H), 0.88 (m, 3H), 0.15 (s, 3H)

Manufacturing example  3: Preparation of transition metal compounds

(1) Preparation of ligand D

A solution prepared by dissolving 9.68 g (100 mmol) of 1-methylthiophene and 10.01 mL (100 mmol) of tiglic acid in 30 mL of methylene chloride was added to a container containing 100 g of polyphosphoric acid. The mixture thus obtained was stirred at a temperature of about 50 to 60 DEG C for about 2 hours. Then, the mixture was cooled to 0 占 폚 and water was added thereto to quench the reaction. Then, the organic layer was separated from the mixture using diethyl ether, the acid remaining in the organic layer was neutralized with Na 2 CO 3 , and water remaining in the organic layer was removed with K 2 CO 3 . Thereafter, hexane was used to obtain 2,4,5-trimethyl-4,5-dihydro-6H-cyclopenta [b] thiophen-6-one as yellow oil from the above organic layer.

Figure 112015118983763-pat00035

1 H NMR (CDCl 3): 6.74 (s, 1H), 3.40-3.34 (m, 0.5H), 3.06-3.00 (m, 0.5H), 2.84-2.80 (m, 0.5H), 2.57 (s, 3H ), 2.45-2.37 (m, 0.5H), 1.32-1.30 (d, 2H), 1.25-1.24 (d, 2H), 1.21-1.16

16.10 g (89.3 mmol) of 2,4,5-trimethyl-4,5-dihydro-6H-cyclopenta [b] thiophen-6-one was dissolved in a mixed solvent of 150 mL of THF and 100 mL of methanol. While stirring the solution, was slowly added NaBH 4 5.07mL (134mmol) to the above solution at about 0 ℃. Then, the resulting mixture was stirred at room temperature overnight, and then the reaction was quenched by adding water to the mixture. Thereafter, the organic layer was separated from the mixture using an ether solvent, and a yellow oil was obtained from the organic layer. The yellow oil was dissolved in 100 mL of THF and 100 mL of water, and 21 mL of a 12% HCl solution was slowly added to the mixture. Then, the mixture was stirred at about 80 캜 for about 3 hours. The mixture was then worked up by the addition of Na 2 CO 3 . The organic layer was separated from the obtained mixture using an ether solvent, and 10.23 g (62.28% yield) of 2,4,5-trimethyl-4H-cyclopenta [b] thiophene (ligand D) .

Figure 112015118983763-pat00036

1 H NMR (CDCl 3): 6.66 (s, 1H), 6.29 (s, 1H), 3.06-3.01 (m, 1H), 2.43 (s, 3H), 2.03 (s, 3H), 1.25-1.21 (d , 3H)

(2) Bridging of ligands B and D

A ligand D solution was prepared by adding 0.821 g (5.0 mmol) of 2,4,5-trimethyl-4H-cyclopenta [b] thiophene (ligand D) and 30 mL of THF to a 250 mL schlenk flask. After cooling the ligand D solution to -78 ° C, 2.5 mL (6.25 mmol, 2.5 M in hexane) of n-BuLi solution was added to the ligand D solution and stirred overnight at room temperature to obtain a brown solution H.

To a 250 mL schlenk flask was added 1- (6- (tert-butoxy) hexyl) -N- (tert-butyl) -1-chloro-1-methylsilanamine (prepared from ligand B ) And toluene were injected to prepare a solution B as in (3) of Production Example 1. Then, the solution B was cooled to -78 占 폚. The brown solution H prepared before the cooled solution B was slowly injected. And the mixture of solutions B and H was stirred at room temperature overnight. The resulting solid was filtered off to obtain 1- (6- (tert-butoxy) hexyl) -N- (tert-butyl) (52.8% yield) of trimethyl-6H-cyclopenta [b] thiophen-6-yl) silanamine (the bridged product of ligands B and D).

Figure 112015118983763-pat00037

1 H NMR (CDCl 3): 6.63 (s, 1H), 3.35-3.27 (m, 2H), 2.50 (s, 3H), 2.05 (s, 3H), 1.40-1.22 (m, 19H), 1.18 (s , 9H), 1.14 (s, 3H), 0.14 (s, 3H)

(3) Preparation of transition metal compounds

To a 250 mL schlenk flask was added a solution of 1- (6- (tert-butoxy) hexyl) -N- (tert-butyl) -1-methyl- 1- (2,4,5- (Bridged product of ligands B and D) was placed in a flask, and 20 mL of toluene and 5 mL of n-hexane were injected into the flask to dissolve the crosslinked product. After cooling the solution to -78 ° C, 2.2 mL (5.5 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, 2 mL (13 mmol) of trimethylamine was added to the solution, and the solution was stirred at about 40 ° C for about 3 hours to prepare solution I.

Meanwhile, 0.876 g (2.64 mmol) of TiCl 4 (THF) 2 and 20 mL of toluene were added to a separately prepared 250 mL schlenk flask to prepare a solution J in which TiCl 4 (THF) 2 was dispersed in toluene. Solution I prepared before solution J was slowly poured at -78 캜, and the mixture of solutions I and J 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 which did not dissolve in toluene were removed by filtration and the solvent was removed from the filtered solution to obtain 1.44 g (91.7% yield) of a transition metal compound in the form of a black oil.

Figure 112015118983763-pat00038

1 H NMR (CDCl 3): 6.67 (s, 1H), 3.35-3.32 (m, 2H), 2.57 (s, 3H), 2.45 (s, 3H), 2.35 (s, 3H), 2.21 (d, 3H ), 1.47-1.25 (m, 19H), 1.18 (s, 9H), 0.73 (s, 3H)

Manufacturing example  4: Preparation of transition metal compounds

(1) Preparation of ligand E

(120 mmol) of t-butylamine and 20 mL of an ether solvent were placed in a 250 mL schlenk flask and 7.7 g (60 mmol) of dichlorodimethylsilane and 40 mL of an ether solvent were added to a 250 mL schlenk flask different from the above flask to prepare a t-butylamine solution and a die And a chlorodimethylsilane solution were respectively prepared. Then, the t-butylamine solution was cooled to -78 ° C, and then a dichlorodimethylsilane solution was slowly poured into the cooled solution, which was then stirred at room temperature for about 2 hours. The resulting white suspension was filtered to obtain N- (tert-butyl) -1-chloro-1,1-dimethylsilanamine (ligand E) which was ivory in color and was in liquid state.

Figure 112015118983763-pat00039

1 H NMR (CDCl 3 ): 1.23 (s, 9H), 0.45 (s, 6H)

(2) Bridging of ligands D and E

A ligand D solution was prepared by adding 1.50 g (9.13 mmol) of 2,4,5-trimethyl-4H-cyclopenta [b] thiophene (ligand D) and 20 mL of THF to a 250 mL schlenk flask. After cooling the ligand D solution to -78 ° C, 3.65 mL (9.13 mmol, 2.5 M in hexane) of n-BuLi solution was added to the ligand D solution and stirred overnight at room temperature to obtain a brown solution H.

On the other hand, N- (tert-butyl) -1-chloro-1,1-dimethylsilanamine (ligand E) prepared in Preparation Example 1 (ligand E) and THF were injected into a 250 mL schlenk flask to prepare a ligand solution K Prepared. Then, the solution K was cooled to -78 占 폚. The brown solution H prepared before the cooled solution K was slowly injected. And the mixture of solutions K and H was stirred at room temperature overnight. The resulting solid was filtered off to obtain N- (tert-butyl) -1,1-dimethyl-1- (2,4,5-trimethyl-6H- cyclopenta [b] (8.89 mmol, 97.4% yield) of the title compound (the crosslinked product of ligands D and E).

Figure 112015118983763-pat00040

1 H NMR (C 6 D 6 ): 6.62 (s, 1H), 3.23 (s, 1H), 2.89 (s, 1H), 2.36 (s, 3H), 2.04 (s, 6H), 1.12 (s, 9H ), 0.13 (s, 3H), -0.02 (s, 3H)

(3) Preparation of transition metal compounds

To a 250 mL schlenk flask was added N- (tert-butyl) -1,1-dimethyl- 1- (2,4,5-trimethyl-6H-cyclopenta [b] thiophen- And crosslinked product of E) were placed in a flask, and 70 mL of toluene and 17 mL of n-hexane were injected into the flask to dissolve the crosslinking product. After cooling the solution to -78 ° C, 7.10 mL (17.8 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, 6.20 mL (44.5 mmol) of trimethylamine was added to the solution, and the solution was stirred at about 40 ° C for about 3 hours to prepare solution N.

Meanwhile, 2.97 g (8.89 mmol) of TiCl 4 (THF) 2 and 40 mL of toluene were added to a separately prepared 250 mL schlenk flask to prepare a solution P in which TiCl 4 (THF) 2 was dispersed in toluene. The solution N prepared before the solution P was slowly injected at -78 캜, and the mixture of the solutions P and N 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 that did not dissolve in toluene were removed by filtration and the solvent was removed from the filtered solution. The resulting product was then dispersed in hexane and filtered again to give 1.50 g (42.0% yield) of a transition metal compound in the form of a dark brown solid.

Figure 112015118983763-pat00041

1 H NMR (C 6 D 6 ): 6.31 (s, 1H), 2.24 (s, 3H), 2.13 (s, 3H), 2.07 (s, 3H), 1.39 (s, 9H), 0.64 (s, 3H ), 0.45 (s, 3H).

Example  One: Manufacturing example  Preparation of supported catalyst using transition metal compound of 1 and preparation of olefin homopolymer using the same

(1) Production of co-catalyst supporting carrier

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

20 g of the dried silica was placed in a glass reactor. Subsequently, a solution of methylaluminoxane (MAO) containing 13 mmol of Al in toluene was placed in the glass reactor. The thus obtained mixture was reacted by stirring at about 40 DEG C for about 1 hour. The reaction product was then washed with a sufficient amount of toluene until the unreacted aluminum compound was completely removed. Then, the reaction product was depressurized at 50 ° C to remove toluene remaining in the reaction product to obtain 32g of a co-catalyst supporting carrier (MAO / SiO 2 ). The obtained MAO / SiO 2 contained 17 wt% of Al.

(2) Preparation of supported catalyst

12 g of the co-catalyst supporting carrier obtained above and 70 mL of toluene were added to a glass reactor and stirred. Then, 1 mmol of the transition metal compound prepared in Production Example 1 was dissolved in toluene and added to the glass reactor. Then, the mixture was reacted by stirring at about 40 캜 for about 1 hour. The reaction product thus obtained was washed with a sufficient amount of toluene and vacuum-dried to obtain a supported catalyst.

(3) 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.

On the other hand, the supported catalyst prepared in (2) 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 above-prepared supported catalyst were added to 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: Manufacturing example  Preparation of Supported Catalyst Using Transition Metal Compound of 2 and Preparation of Olefin Homopolymer Thereof

(1) Production of co-catalyst supporting carrier

A catalyst-supported carrier was prepared in the same manner as in (1) of Example 1.

(2) Preparation of supported catalyst

A supported catalyst was prepared in the same manner as in (2) of Example 1, except that the transition metal compound of Production Example 2 was used in (2) of Example 1.

(3) Production of olefin polymer

An ethylene homopolymer was obtained in the same manner as in (3) of Example 1, except that the supported catalyst (2) in Example 2 was used in (3) of Example 1.

Example  3: Manufacturing example  Preparation of Supported Catalyst Using Transition Metal Compound of 3 and Production of Olefin Homopolymer Thereof

(1) Production of co-catalyst supporting carrier

A catalyst-supported carrier was prepared in the same manner as in (1) of Example 1.

(2) Preparation of supported catalyst

A supported catalyst was prepared in the same manner as in (2) of Example 1, except that the transition metal compound of Production Example 3 was used in (2) of Example 1.

(3) Production of olefin polymer

An ethylene homopolymer was obtained in the same manner as in (3) of Example 1, except that the supported catalyst (2) of Example 3 was used in (3) of Example 1.

Example  4: Manufacturing example  Preparation of supported catalyst using transition metal compound of 1 and preparation of olefin homopolymer using the same

(1) Production of co-catalyst supporting carrier

100 mL of toluene was placed in a glass reactor at room temperature, 10 g of the above silica (XPO2410 from Grace Davison) was added, and the temperature of the reactor was increased to about 40 DEG C while stirring. After the silica was sufficiently dispersed, 60.6 mL of methylaluminoxane (MAO) solution (10 wt% in toluene) was added to the reactor, the temperature of the reactor was raised to about 80 DEG C, and the mixture was stirred at about 200 rpm for about 16 hours. Then, lowering the temperature of the reactor to about 40 ℃, without reaction and washed with a sufficient amount of toluene until no remaining aluminum compound to give a crude catalyst supporting carrier (MAO / SiO 2).

(2) Preparation of supported catalyst

To the reactor containing the co-catalyst supporting carrier (MAO / SiO 2 ), 100 mL of toluene was added, and 1 mmol of the transition metal compound prepared in Preparation Example 1 was added to the reactor, followed by stirring for about 2 hours.

Then, the temperature of the reactor was raised to about 50 DEG C, and 2 mmol of methylaluminoxane (MAO) was further added to the reactor, followed by stirring for about 2 hours. When the reaction was completed, stirring was stopped and the toluene layer was separated and removed. Subsequently, the remaining reaction product was depressurized at about 40 ° C to remove the remaining toluene from the reaction product to obtain a supported catalyst.

(3) 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.

On the other hand, the supported catalyst prepared in (4) of Example 4 was quantitatively measured in a dry box and packed 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 triisobutylaluminum and the above-prepared 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 9 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  5: Manufacturing example  Preparation of Supported Catalyst Using Transition Metal Compound of 3 and Production of Olefin Homopolymer Thereof

(1) Production of co-catalyst supporting carrier

A catalyst-supported carrier was prepared in the same manner as in (4) of Example 4.

(2) Preparation of supported catalyst

A supported catalyst was prepared in the same manner as in (4) of Example 4, except that the transition metal compound of Production Example 3 was used in (2) of Example 4.

(3) Production of olefin polymer

An ethylene homopolymer was obtained in the same manner as in (3) of Example 4 except that the supported catalyst (2) of Example 5 was used in (3) of Example 4.

Example  6: Manufacturing example  Preparation of Supported Catalysts Using Transition Metal Compounds and Preparation of Olefin Copolymers Using the Same

(1) Production of co-catalyst supporting carrier

A catalyst-supported carrier was prepared in the same manner as in (1) of Example 1.

(2) Preparation of supported catalyst

A supported catalyst was prepared in the same manner as in (2) of Example 1.

(3) Production of olefin polymer

In the same manner as in (3) of Example 1, a 600 mL metal alloy reactor and a supported catalyst contained in a glass bottle were prepared. Then, 400 mL of hexane containing 1.0 mmol of triethylaluminum, 33 mL of the above-prepared supported catalyst and 1-hexene were added to the 600 mL metal alloy reactor without air contact. Subsequently, the temperature of the reactor was raised to about 70 DEG C, and ethylene and 1-hexene were polymerized by injecting ethylene gas in the same manner as in (3) of Example 1.

Thereafter, when a desired level of ethylene-1-hexene copolymer was obtained, 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-1-hexene copolymer.

Example  7: Manufacturing example  Preparation of Supported Catalyst Using Transition Metal Compound of 2 and Preparation of Olefin Copolymer Using It

(1) Production of co-catalyst supporting carrier

A catalyst-supported carrier was prepared in the same manner as in (2) of Example 2.

(2) Preparation of supported catalyst

A supported catalyst was prepared in the same manner as in (2) of Example 2.

(3) Production of olefin polymer

An ethylene-1-hexene copolymer was obtained in the same manner as in (3) of Example 6 except that the supported catalyst (2) in Example 7 was used in (3) of Example 6.

Example  8: Manufacturing example  Preparation of Supported Catalyst Using Transition Metal Compound of 3 and Preparation of Olefin Copolymer Using It

(1) Production of co-catalyst supporting carrier

A catalyst-supported carrier was prepared in the same manner as in (3) of Example 3.

(2) Preparation of supported catalyst

A supported catalyst was prepared in the same manner as in (3) of Example 3.

(3) Production of olefin polymer

An ethylene-1-hexene copolymer was obtained in the same manner as in (3) of Example 6 except that the supported catalyst (2) of Example 8 was used in (3) of Example 6.

Example  9: Manufacturing example  Preparation of Supported Catalysts Using Transition Metal Compounds and Preparation of Olefin Copolymers Using the Same

(1) Production of co-catalyst supporting carrier

A catalyst-supported carrier was prepared in the same manner as in (4) of Example 4.

(2) Preparation of supported catalyst

A supported catalyst was prepared in the same manner as in (4) of Example 4.

(3) Production of olefin polymer

In the same manner as in (3) of Example 4, a 600 mL metal alloy reactor and a supported catalyst contained in a glass bottle were prepared. Then, 400 mL of hexane containing 1.0 mmol of triisobutylaluminum, the above-prepared supported catalyst and 8 g of 1-butene were added to the 600 mL metal alloy reactor without air contact.

Then, ethylene gas was injected in the same manner as in (3) of Example 4, and ethylene and 1-butene were polymerized to obtain an ethylene-1-butene copolymer.

Example  10: Manufacturing example  Preparation of Supported Catalyst Using Transition Metal Compound of 3 and Preparation of Olefin Copolymer Using It

(1) Production of co-catalyst supporting carrier

A catalyst-supported carrier was prepared in the same manner as in (5) of Example 5.

(2) Preparation of supported catalyst

A supported catalyst was prepared in the same manner as in (5) of Example 5.

(3) Production of olefin polymer

An ethylene-1-butene copolymer was obtained in the same manner as in (3) of Example 9 except that the supported catalyst (2) of Example 10 was used in (3) of Example 9.

Comparative Example  1: Preparation of supported catalyst using existing transition metal compounds and preparation of olefin homopolymer using the same

(1) Production of co-catalyst supporting carrier

A catalyst-supported carrier was prepared in the same manner as in (1) of Example 1.

(2) Preparation of supported catalyst

A supported catalyst was prepared in the same manner as in (2) of Example 1, except that the transition metal compound of the following formula (13) was used in the step (2) of Example 1.

[Chemical Formula 13]

Figure 112015118983763-pat00042

(3) Production of olefin polymer

An ethylene homopolymer was obtained in the same manner as in (3) of Example 1 except that the supported catalyst (2) of Comparative Example 1 was used in (3) of Example 1.

Comparative Example  2: Preparation of supported catalyst using existing transition metal compound and preparation of olefin homopolymer using the same

(1) Production of co-catalyst supporting carrier

A catalyst-supported carrier was prepared in the same manner as in (1) of Example 1.

(2) Preparation of supported catalyst

A supported catalyst was prepared in the same manner as in (2) of Example 1, except that the transition metal compound of the following formula (14) was used in the step (2) of Example 1.

[Chemical Formula 14]

Figure 112015118983763-pat00043

(3) Production of olefin polymer

An ethylene homopolymer was obtained in the same manner as in (3) of Example 1 except that the supported catalyst (2) of Comparative Example 2 was used in (3) of Example 1.

Comparative Example  3: Preparation of supported catalyst using existing transition metal compound and preparation of olefin homopolymer using the same

(1) Production of co-catalyst supporting carrier

A catalyst-supported carrier was prepared in the same manner as in (1) of Example 1.

(2) Preparation of supported catalyst

A supported catalyst was prepared in the same manner as in (2) of Example 1, except that the transition metal compound of Production Example 4 was used in (2) of Example 1.

(3) Production of olefin polymer

An ethylene homopolymer was obtained in the same manner as in (3) of Example 1 except that the supported catalyst (2) of Comparative Example 3 (3) in Example 1 was used.

Comparative Example  4: Preparation of supported catalyst using existing transition metal compound and preparation of olefin copolymer using the same

(1) Production of co-catalyst supporting carrier

A catalyst-supported carrier was prepared in the same manner as in (1) of Comparative Example 1.

(2) Preparation of supported catalyst

A supported catalyst was prepared in the same manner as in (2) of Comparative Example 1.

(3) Production of olefin polymer

An ethylene-1-hexene copolymer was obtained in the same manner as in (3) of Example 6 except that the supported catalyst (2) of Comparative Example 4 was used in (3) of Example 6.

Comparative Example  5: Preparation of Supported Catalyst Using Existing Transition Metal Compound and Preparation of Olefin Copolymer Using It

(1) Production of co-catalyst supporting carrier

A catalyst-supported carrier was prepared in the same manner as in (1) of Comparative Example 2.

(2) Preparation of supported catalyst

A supported catalyst was prepared in the same manner as in (2) of Comparative Example 2.

(3) Production of olefin polymer

An ethylene-1-hexene copolymer was obtained in the same manner as in (3) of Example 6 except that the supported catalyst (2) of Comparative Example 5 (3) in Example 6 was used.

Comparative Example  6: Preparation of Supported Catalyst Using Existing Transition Metal Compound and Preparation of Olefin Copolymer Using It

(1) Production of co-catalyst supporting carrier

A catalyst-supported carrier was prepared in the same manner as in (1) of Comparative Example 3.

(2) Preparation of supported catalyst

A supported catalyst was prepared in the same manner as in (2) of Comparative Example 3.

(3) Production of olefin polymer

An ethylene-1-hexene copolymer was obtained in the same manner as in (3) of Example 6 except that the supported catalyst (2) of Comparative Example 6 was used in (3) of Example 6.

Test Example

The masses of the polymers prepared in Examples 1 to 10 and Comparative Examples 1 to 6 were measured and the yield was calculated. The unit mass of the catalyst used in the reaction and the mass of the polymer calculated per hour were measured, The activity of the used catalyst was calculated and 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.

Polymerization method Active [kg Pol./g cat. h] Weight average molecular weight Molecular weight distribution Example 1 Homopolymerization 4.6 2,000,000 2.1 Example 2 Homopolymerization 2.8 1,640,000 2.1 Example 3 Homopolymerization 4.2 1,250,000 2.1 Example 4 Homopolymerization 3.4 1,600,000 2.0 Example 5 Homopolymerization 3.1 1,210,000 2.1 Example 6 Copolymerization 1.6 1,700,000 2.1 Example 7 Copolymerization 1.0 1,200,000 2.3 Example 8 Copolymerization 1.2 1,230,000 2.1 Example 9 Copolymerization 1.3 1,250,000 2.1 Example 10 Copolymerization 1.1 970,000 2.2 Comparative Example 1 Homopolymerization ≪ 0.1 1,180,000 2.4 Comparative Example 2 Homopolymerization 1.5 1,200,000 2.4 Comparative Example 3 Homopolymerization ≪ 0.1 1,250,000 2.2 Comparative Example 4 Copolymerization ≪ 0.1 920,000 2.4 Comparative Example 5 Copolymerization 1.0 910,000 2.5 Comparative Example 6 Copolymerization ≪ 0.1 970,000 2.2

Referring to Table 1, it is confirmed that the catalyst using the transition metal compound according to one embodiment of the present invention is used in the homopolymerization reaction as in Examples 1 to 5 to provide a high molecular weight olefin polymer exhibiting high activity. On the contrary, when the olefin polymer of high molecular weight was prepared by using the conventional metallocene catalyst as in Comparative Examples 1 to 3, it was confirmed that the catalytic activity was significantly lowered.

In addition, it is confirmed that the catalyst using the transition metal compound according to one embodiment of the present invention provides the high molecular weight olefin polymer with high catalytic activity even in the copolymerization reaction as in Examples 6 to 10. However, when the conventional metallocene catalysts as in Comparative Examples 4 to 6 were used, the high molecular weight olefin copolymer of the embodiment level was not obtained (in the case of Comparative Example 5), or the olefin copolymer was not forcibly As a result of continuing the reaction, the catalytic activity was remarkably lowered (in the case of Comparative Examples 4 and 6).

Claims (11)

A transition metal compound represented by the following formula (1); And
A supported catalyst comprising a carrier carrying the transition metal compound;
[Chemical Formula 1]
Figure 112016109617678-pat00044

In the above formula (1), C 1 is any one of the ligands represented by the following formulas (2) to (5)
(2)
Figure 112016109617678-pat00045

(3)
Figure 112016109617678-pat00046

[Chemical Formula 4]
Figure 112016109617678-pat00047

[Chemical Formula 5]
Figure 112016109617678-pat00048

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 is Ti, Zr or Hf,
X 1 and X 2 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,
T is
Figure 112016109617678-pat00049
ego,
T 1 is C or Si,
Y 1 is any one of a hydrocarbyl group having 1 to 30 carbon atoms and a hydrocarbyloxy group having 1 to 30 carbon atoms,
And Y 2 is any one of a hydrocarbyl oxyhydrocarbyl group having 2 to 30 carbon atoms.
The compound according to claim 1, wherein R 1 to R 4 in the general formulas (2) to (5) 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, And each independently a hydrocarbyl group having 1 to 10 carbon atoms. The supported catalyst according to claim 1, wherein Z is -NR 7 -, and R 7 is any one of hydrocarbyl groups having 1 to 10 carbon atoms. delete The supported catalyst according to claim 1, wherein X 1 and X 2 are the same or different from each other and each independently any one of halogen. 2. The catalyst according to claim 1, wherein the compound of formula (1) is any one of compounds represented by the following formulas (6) to (9)
[Chemical Formula 6]
Figure 112016109617678-pat00052

(7)
Figure 112016109617678-pat00053

[Chemical Formula 8]
Figure 112016109617678-pat00058

[Chemical Formula 9]
Figure 112016109617678-pat00055

In formulas (6) to (9), 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 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 is any one of a hydrocarbyl group having 1 to 30 carbon atoms and a hydrocarbyloxy group having 1 to 30 carbon atoms,
And Y 2 is any one of a hydrocarbyl oxyhydrocarbyl group having 2 to 30 carbon atoms.
The supported catalyst according to claim 1, wherein the carrier is silica, alumina, magnesia or a mixture thereof. The supported catalyst according to claim 1, further comprising at least one cocatalyst selected from the group consisting of compounds represented by the following formulas (10) to (12):
[Chemical formula 10]
R 12 - [Al (R 11 ) -O] n -R 13
In Formula 10,
R 11 , R 12 and R 13 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,
(11)
D (R 14) 3
In Formula 11,
D is aluminum or boron,
R 14 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 12]
[LH] + [W (A ) 4] - or [L] + [W (A ) 4] -
In Formula 12,
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 supported catalyst of claim 1. The method of claim 9, wherein the olefin monomer is selected from the group consisting of ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, Dodecene, 1-tetradecene, 1-hexadecene, 1-aidosene, norbornene, norbornadiene, ethylidenenorbornene, phenyl norbornene, vinyl norbornene, dicyclopentadiene, 1,4- 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. The process for producing an olefin polymer according to claim 9, which produces an olefin polymer having a weight average molecular weight of 950,000 to 5,000,000 g / mol.
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