KR20190013022A - Ligand compound, transition metal compound, and catalystic composition comprising the same - Google Patents

Abstract

The present invention relates to a novel ligand compound, a transition metal compound, and a catalyst composition containing the same. The novel ligand compound and the transition metal compound, of the present invention, can be usefully used for a polymerization catalyst in manufacturing an olefin-based polymer having low density. In addition, an olefin polymer polymerized by using the catalyst composition containing the transition metal compound is capable of manufacturing a high molecular weight product having a low melting index (MI).

Description

TECHNICAL FIELD [0001] The present invention relates to a ligand compound, a transition metal compound, and a catalyst composition containing the same. BACKGROUND ART [0002] LIGAND COMPOUND, TRANSITION METAL COMPOUND, AND CATALYST COMPOSITION COMPRISING THE SAME [0003]

TECHNICAL FIELD The present invention relates to ligand compounds, transition metal compounds, and catalyst compositions containing the same.

Dow has announced the release of [Me ₂ Si (Me ₄ C ₅ ) N t Bu] TiCl ₂ (hereinafter abbreviated as CGC) (U.S. Patent No. 5,064,802) And alpha-olefins can be summarized in two major ways as compared with the known metallocene catalysts as follows: (1) High activity at high polymerization temperature and high molecular weight (2) the copolymerization of alpha-olefins with large steric hindrance such as 1-hexene and 1-octene is also excellent. In addition, various characteristics of CGC were gradually known during the polymerization reaction, and efforts to synthesize the derivative and use it as a polymerization catalyst have actively been made in academia and industry.

One approach has been attempted to synthesize and polymerize metal compounds in which various other bridges and nitrogen substituents have been introduced instead of silicon bridges. Representative metal compounds known until recently are as follows (Chem. Rev. 2003, 103, 283).

(1)

(2)

(One)

(2)

(3)

(4)

(3)

(4)

(1), ethylene or propylene (2), methylidene (3), and methylene (4) bridges were introduced in place of the silicon bridge of the CGC structure, Or in the case of copolymerization with an alpha-olefin, no improvement in terms of activity or copolymerization performance versus CGC was obtained.

In addition, as another approach, a large amount of compounds composed of oxydolides were synthesized instead of the amido ligands of CGC, and some polymerization using the compounds was attempted. The examples are summarized as follows.

(5)

(6)

(7)

(5)

(6)

(7)

(8)

(8)

Compound (5) is reported by T. J. Marks et al. In which Cp (cyclopentadiene) derivatives and oxydolides are crosslinked by ortho-phenylene groups (Organometallics 1997, 16, 5958). Compounds having the same cross-linking and polymerization using them have also been reported by Mu et al. (Organometallics 2004, 23, 540). Also, Rothwell et al. (Chem. Commun. 2003, 1034) have reported that an indenyl ligand and an oxydol ligand are bridged by the same ortho-phenylene group. Compound (6) is reported by Whitby et al. (Organometallics 1999, 18, 348) in which a cyclopentenylidene ligand and an oxydoligand are bridged by three carbon atoms (Syndiotactic ) Was reported to exhibit activity in polystyrene polymerization. Similar compounds have also been reported by Hessen et al. (Organometallics 1998, 17, 1652). Compound (7) is reported by Rau et al. And is characterized in that it exhibits activity in ethylene polymerization and ethylene / 1-hexene copolymerization at high temperature and high pressure (210 ° C., 150 MPa) (J. Organomet. ). Then, the catalyst synthesis (8) having similar structure and the high temperature and high pressure polymerization using the same were patented by Sumitomo Co. (US Patent No. 6,548,686). However, among the above attempts, only a few catalysts have actually been applied to commercial plants. Therefore, a catalyst showing improved polymerization performance is required, and a method of simply producing such catalysts is required.

US Patent No. 5,064,802 US Patent No. 6,548,686

 Chem. Rev. 2003, 103, 283  Organometallics 1997, 16, 5958  Organometallics 2004, 23, 540  Chem. Commun. 2003, 1034  Organometallics 1999, 18, 348  Organometallics 1998, 17, 1652  J. Organomet. Chem. 2000, 608, 71

A first object of the present invention is to provide a novel transition metal compound.

A second object of the present invention is to provide a novel ligand compound.

A third object of the present invention is to provide a catalyst composition comprising the transition metal compound.

In order to solve the first technical problem, the present invention provides a transition metal compound represented by the following Chemical Formula 1:

[Chemical Formula 1]

In Formula 1,

R ₁ is hydrogen; halogen; Alkyl having 1 to 20 carbon atoms; Cycloalkyl having 3 to 20 carbon atoms; Alkenyl having 2 to 20 carbon atoms; Alkoxy having 1 to 20 carbon atoms; Aryl having 6 to 20 carbon atoms; Arylalkoxy having 7 to 20 carbon atoms; Alkylaryl having 7 to 20 carbon atoms; Or arylalkyl having 7 to 20 carbon atoms,

R ₂ is an alkenyl having 2 to 20 carbon atoms,

R ₃ is hydrogen; halogen; Alkyl having 1 to 20 carbon atoms; Cycloalkyl having 3 to 20 carbon atoms; Alkenyl having 2 to 20 carbon atoms; Alkoxy having 1 to 20 carbon atoms; Or aryl having 6 to 20 carbon atoms,

R ₄ to R ₉ are each independently hydrogen; Silyl; Alkyl having 1 to 20 carbon atoms; Cycloalkyl having 3 to 20 carbon atoms; Alkenyl having 2 to 20 carbon atoms; Aryl having 6 to 20 carbon atoms; Alkylaryl having 7 to 20 carbon atoms; Arylalkyl having 7 to 20 carbon atoms; Or a metalloid radical of a Group 14 metal substituted with a hydrocarbyl of 1 to 20 carbon atoms; Two or more adjacent R < ₃ > to R < ₈ > adjacent to each other may be connected to each other to form a ring,

Q is Si, C, N, P or S,

M is a transition metal of Group 4,

X ₁ and X ₂ are each independently hydrogen; halogen; Alkyl having 1 to 20 carbon atoms; Cycloalkyl having 3 to 20 carbon atoms; Alkenyl having 2 to 20 carbon atoms; Aryl having 6 to 20 carbon atoms; Alkylaryl having 7 to 20 carbon atoms; Arylalkyl having 7 to 20 carbon atoms; Alkylamino having 1 to 20 carbon atoms; Arylamino having 6 to 20 carbon atoms; Or alkylidene having 1 to 20 carbon atoms.

In order to solve the second technical problem, the present invention provides a ligand compound represented by the following formula 2:

(2)

In Formula 2,

R ₁ and R ₁₀ are each independently hydrogen; halogen; Alkyl having 1 to 20 carbon atoms; Cycloalkyl having 3 to 20 carbon atoms; Alkenyl having 2 to 20 carbon atoms; Alkoxy having 1 to 20 carbon atoms; Aryl having 6 to 20 carbon atoms; Arylalkoxy having 7 to 20 carbon atoms; Alkylaryl having 7 to 20 carbon atoms; Or arylalkyl having 7 to 20 carbon atoms,

R ₂ is Alkenyl having 2 to 20 carbon atoms,

R ₃ is hydrogen; halogen; Alkyl having 1 to 20 carbon atoms; Cycloalkyl having 3 to 20 carbon atoms; Alkenyl having 2 to 20 carbon atoms; Alkoxy having 1 to 20 carbon atoms; Or aryl having 6 to 20 carbon atoms,

R ₄ to R ₉ are each independently hydrogen; Silyl; Alkyl having 1 to 20 carbon atoms; Cycloalkyl having 3 to 20 carbon atoms; Alkenyl having 2 to 20 carbon atoms; Aryl having 6 to 20 carbon atoms; Alkylaryl having 7 to 20 carbon atoms; Arylalkyl having 7 to 20 carbon atoms; Or a metalloid radical of a Group 14 metal substituted with a hydrocarbyl of 1 to 20 carbon atoms; Two or more adjacent R < ₆ > to R < ₉ > adjacent to each other may be linked together to form a ring,

Q is Si, C, N, P or S.

In order to solve the third technical problem, the present invention provides a catalyst composition comprising the transition metal compound of the above formula (1).

The novel ligand compounds and transition metal compounds of the present invention can be usefully used as catalysts for the polymerization reaction in the production of olefinic polymers having a high molecular weight in a low density region and can be obtained as high molecular weight polymers having a low melt index .

Hereinafter, the present invention will be described in detail in order to facilitate understanding of the present invention.

The terms and words used in the present specification and claims should not be construed as limited to ordinary or dictionary terms and the inventor may appropriately define the concept of the term in order to best describe its invention It should be construed as meaning and concept consistent with the technical idea of the present invention.

The transition metal compound of the present invention is represented by the following formula (1).

[Chemical Formula 1]

In Formula 1,

R ₁ is hydrogen; halogen; Alkyl having 1 to 20 carbon atoms; Cycloalkyl having 3 to 20 carbon atoms; Alkenyl having 2 to 20 carbon atoms; Alkoxy having 1 to 20 carbon atoms; Aryl having 6 to 20 carbon atoms; Arylalkoxy having 7 to 20 carbon atoms; Alkylaryl having 7 to 20 carbon atoms; Or arylalkyl having 7 to 20 carbon atoms,

R ₂ is Alkenyl having 2 to 20 carbon atoms,

R ₃ is hydrogen; halogen; Alkyl having 1 to 20 carbon atoms; Cycloalkyl having 3 to 20 carbon atoms; Alkenyl having 2 to 20 carbon atoms; Alkoxy having 1 to 20 carbon atoms; Or aryl having 6 to 20 carbon atoms,

R ₄ to R ₉ are each independently hydrogen; Silyl; Alkyl having 1 to 20 carbon atoms; Cycloalkyl having 3 to 20 carbon atoms; Alkenyl having 2 to 20 carbon atoms; Aryl having 6 to 20 carbon atoms; Alkylaryl having 7 to 20 carbon atoms; Arylalkyl having 7 to 20 carbon atoms; Or a metalloid radical of a Group 14 metal substituted with a hydrocarbyl of 1 to 20 carbon atoms; Two or more adjacent R < ₃ > to R < ₈ > adjacent to each other may be connected to each other to form a ring,

Q is Si, C, N, P or S,

M is a transition metal of Group 4,

X ₁ and X ₂ are each independently hydrogen; halogen; Alkyl having 1 to 20 carbon atoms; Cycloalkyl having 3 to 20 carbon atoms; Alkenyl having 2 to 20 carbon atoms; Aryl having 6 to 20 carbon atoms; Alkylaryl having 7 to 20 carbon atoms; Arylalkyl having 7 to 20 carbon atoms; Alkylamino having 1 to 20 carbon atoms; Arylamino having 6 to 20 carbon atoms; Or alkylidene having 1 to 20 carbon atoms.

The transition metal compound represented by the formula (1) according to the present invention is a compound in which cyclopentadiene in which benzothiophene is fused by a ring-shaped bond and amido group (NR ₃ ) are bonded to each other by Q (Si, C, N, P or S) Stably cross-linked, and a structure in which a Group 4 transition metal is coordinately bonded is formed.

When the catalyst composition is applied to olefin polymerization, it is possible to produce a polyolefin having such characteristics as high activity, high molecular weight and high copolymerization even at a high polymerization temperature. Particularly, due to the structural characteristics of the catalyst, it is possible to introduce not only linear low density polyethylene having a density of 0.860 g / cc to 0.930 g / cc but also a large amount of alpha-olefin, so that a polymer having a density of less than 0.860 g / ) Can also be prepared.

The term " halogen ", as used herein, unless otherwise indicated, means fluorine, chlorine, bromine or iodine.

The term " alkyl " as used herein, unless otherwise indicated, refers to straight, branched, or branched hydrocarbon residues.

The term " cycloalkyl ", as used herein, unless otherwise indicated, refers to cyclic alkyl including cyclopropyl and the like.

As used herein, the term " aryl " refers to an aromatic group including phenyl, naphthyl anthryl, phenanthryl, crysinyl, pyrenyl and the like unless otherwise specified.

The term " alkenyl ", as used herein, unless otherwise indicated, means a straight chain or branched chain alkenyl group.

In the present specification, the silyl may be a silyl substituted with an alkyl having 1 to 20 carbon atoms, and may be, for example, trimethylsilyl or triethylsilyl.

In the transition metal compound of Formula 1 according to an example of the present invention,

R < ₁ > is hydrogen; halogen; Alkyl having 1 to 20 carbon atoms; Cycloalkyl having 3 to 20 carbon atoms; Alkoxy having 1 to 20 carbon atoms; Aryl having 6 to 20 carbon atoms; Arylalkoxy having 7 to 20 carbon atoms; Alkylaryl having 7 to 20 carbon atoms; Or arylalkyl having 7 to 20 carbon atoms,

Wherein R < _{2 &} Alkenyl having 2 to 12 carbon atoms,

R < ₃ > is hydrogen; halogen; Alkyl having 1 to 12 carbon atoms; Cycloalkyl having 3 to 12 carbon atoms; Alkenyl having 2 to 12 carbon atoms; Alkoxy having 1 to 12 carbon atoms; Or phenyl,

Each of R ₄ to R ₉ is independently hydrogen; Alkyl having 1 to 20 carbon atoms; Cycloalkyl having 3 to 20 carbon atoms; Aryl having 6 to 20 carbon atoms; Alkylaryl having 7 to 20 carbon atoms; Or arylalkyl having 7 to 20 carbon atoms,

Two or more adjacent ones of R ₄ to R ₉ may be connected to each other to form an aliphatic ring having 5 to 20 carbon atoms or an aromatic ring having 6 to 20 carbon atoms; The aliphatic ring or aromatic ring may be substituted with halogen, alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 12 carbon atoms, or aryl having 6 to 12 carbon atoms,

Wherein Q is Si,

M is Ti,

X ₁ and X ₂ are each independently hydrogen; halogen; Alkyl having 1 to 12 carbon atoms; Cycloalkyl having 3 to 12 carbon atoms; Alkenyl having 2 to 12 carbon atoms; Aryl having from 6 to 12 carbon atoms; Alkylaryl of 7 to 13 carbon atoms; Arylalkyl having 7 to 13 carbon atoms; Alkylamino having 1 to 13 carbon atoms; Or an arylamino group having 6 to 12 carbon atoms.

In the transition metal compound of Formula 1 according to another embodiment of the present invention,

R < ₁ > is hydrogen; halogen; Alkyl having 1 to 12 carbon atoms; Cycloalkyl having 3 to 12 carbon atoms; Alkoxy having 1 to 12 carbon atoms; Aryl having from 6 to 12 carbon atoms; Arylalkoxy having 7 to 13 carbon atoms; Alkylaryl of 7 to 13 carbon atoms; Or an arylalkyl group having 7 to 13 carbon atoms,

Wherein R < _{2 &} Alkenyl having 2 to 12 carbon atoms,

R < ₃ > is hydrogen; halogen; Alkyl having 1 to 12 carbon atoms; Cycloalkyl having 3 to 12 carbon atoms; Alkenyl having 2 to 12 carbon atoms; Alkoxy having 1 to 12 carbon atoms; Or phenyl,

Each of R ₄ to R ₉ is independently hydrogen; Alkyl having 1 to 12 carbon atoms; Cycloalkyl having 3 to 12 carbon atoms; Aryl having from 6 to 12 carbon atoms; Alkylaryl of 7 to 13 carbon atoms; Or an arylalkyl group having 7 to 13 carbon atoms,

Two or more adjacent ones of R ₄ to R ₉ may be connected to each other to form an aliphatic ring having 5 to 12 carbon atoms or an aromatic ring having 6 to 12 carbon atoms;

The aliphatic or aromatic ring may be substituted with halogen, alkyl having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or aryl having 6 to 12 carbons,

Wherein Q is Si,

M is Ti,

X ₁ and X ₂ are each independently hydrogen; halogen; Alkyl having 1 to 12 carbon atoms; Or alkenyl having 2 to 12 carbon atoms.

In the transition metal compound of Formula 1 according to still another embodiment of the present invention,

Wherein R &_lt; 1 > is alkyl having 1 to 12 carbon atoms or aryl having 6 to 12 carbon atoms,

R ₂ is alkenyl having 2 to 12 carbon atoms,

R < ₃ > is hydrogen; Alkyl having 1 to 12 carbon atoms; Or an alkenyl having 2 to 12 carbon atoms,

R ₄ and R ₅ are each independently hydrogen; Or alkyl having 1 to 12 carbon atoms,

Each of R ₆ to R ₉ is independently hydrogen or methyl,

Wherein Q is Si,

M is Ti,

X ₁ and X ₂ are each independently hydrogen or alkyl having 1 to 12 carbon atoms.

In the transition metal compound of Formula 1 according to still another embodiment of the present invention,

Wherein R &_lt; 1 > is alkyl having 1 to 6 carbon atoms or phenyl,

R ₂ is an alkenyl having 2 to 6 carbon atoms,

R ₃ is alkyl having 1 to 6 carbon atoms; Or an alkenyl having 2 to 6 carbon atoms,

R ₃ and R ₄ are each independently alkyl having 1 to 6 carbon atoms,

The R ₅ to R ₈ may be hydrogen.

The compound represented by the formula (1) may be any one of compounds represented by the following formulas (1-1) to (1-10).

[Formula 1-1]

[Formula 1-2]

According to another aspect of the present invention, there is provided a ligand compound represented by Formula 2:

(2)

In Formula 2,

R ₁ and R ₁₀ are each independently hydrogen; halogen; Alkyl having 1 to 20 carbon atoms; Cycloalkyl having 3 to 20 carbon atoms; Alkenyl having 2 to 20 carbon atoms; Alkoxy having 1 to 20 carbon atoms; Aryl having 6 to 20 carbon atoms; Arylalkoxy having 7 to 20 carbon atoms; Alkylaryl having 7 to 20 carbon atoms; Or arylalkyl having 7 to 20 carbon atoms,

R ₂ is Alkenyl having 2 to 20 carbon atoms,

R ₃ is hydrogen; halogen; Alkyl having 1 to 20 carbon atoms; Cycloalkyl having 3 to 20 carbon atoms; Alkenyl having 2 to 20 carbon atoms; Alkoxy having 1 to 20 carbon atoms; Or aryl having 6 to 20 carbon atoms,

R ₄ to R ₉ are each independently hydrogen; Silyl; Alkyl having 1 to 20 carbon atoms; Cycloalkyl having 3 to 20 carbon atoms; Alkenyl having 2 to 20 carbon atoms; Aryl having 6 to 20 carbon atoms; Alkylaryl having 7 to 20 carbon atoms; Arylalkyl having 7 to 20 carbon atoms; Or a metalloid radical of a Group 14 metal substituted with a hydrocarbyl of 1 to 20 carbon atoms; Two or more adjacent R < ₆ > to R < ₉ > adjacent to each other may be linked together to form a ring,

Q is Si, C, N, P or S.

The ligand compound of formula (2) described in the present specification is a ligand compound in which cyclopentadiene in which benzothiophene is fused by a bond in the form of a ring and amido group (NR ₃ ) are stable by Q (Si, C, N, P or S) As shown in FIG.

In the ligand compound, the definitions of R ₁ to R ₉ in the compound represented by the general formula (2) may be the same as those in the compound represented by the general formula (1), which is a transition metal compound.

In the ligand compound of Formula 2 according to another embodiment of the present invention,

R ₁ and R ₁₀ are each independently hydrogen; halogen; Alkyl having 1 to 12 carbon atoms; Cycloalkyl having 3 to 12 carbon atoms; Alkoxy having 1 to 12 carbon atoms; Aryl having from 6 to 12 carbon atoms; Arylalkoxy having 7 to 13 carbon atoms; Alkylaryl of 7 to 13 carbon atoms; Or an arylalkyl group having 7 to 13 carbon atoms,

Wherein R < _{2 &} Alkenyl having 2 to 12 carbon atoms,

Each R < ₃ > is independently hydrogen; halogen; Alkyl having 1 to 12 carbon atoms; Cycloalkyl having 3 to 12 carbon atoms; Alkenyl having 2 to 12 carbon atoms; Alkoxy having 1 to 12 carbon atoms; Or phenyl,

Each of R ₄ to R ₉ is independently hydrogen; Alkyl having 1 to 12 carbon atoms; Cycloalkyl having 3 to 12 carbon atoms; Aryl having from 6 to 12 carbon atoms; Alkylaryl of 7 to 13 carbon atoms; Or an arylalkyl group having 7 to 13 carbon atoms,

Two or more adjacent ones of R ₃ to R ₈ may be connected to each other to form an aliphatic ring having 5 to 12 carbon atoms or an aromatic ring having 6 to 12 carbon atoms;

The aliphatic ring or aromatic ring may be substituted with halogen, alkyl having 1 to 12 carbon atoms, alkenyl having 2 to 12 carbon atoms, or aryl having 6 to 12 carbon atoms,

The Q may be Si.

In the above formula (2)

Wherein R &_lt; 1 > is alkyl having 1 to 12 carbon atoms or aryl having 6 to 12 carbon atoms,

R ₂ is alkenyl having 2 to 12 carbon atoms,

R < ₃ > is hydrogen; Alkyl having 1 to 12 carbon atoms; Or an alkenyl having 2 to 12 carbon atoms,

R ₄ and R ₅ are each independently hydrogen; Or alkyl having 1 to 12 carbon atoms,

Each of R ₆ to R ₉ is independently hydrogen or methyl,

Wherein R < ₁₀ > is hydrogen,

Wherein Q is Si,

The M may be Ti.

In the above formula (2)

Wherein R &_lt; 1 > is alkyl having 1 to 6 carbon atoms or phenyl,

R ₂ is an alkenyl having 2 to 6 carbon atoms,

R ₃ is alkyl having 1 to 6 carbon atoms; Or an alkenyl having 2 to 6 carbon atoms,

R ₄ and R ₅ are each independently alkyl having 1 to 6 carbon atoms,

The R ₆ to R ₁₀ may be hydrogen.

The compound of formula (2) may be any of compounds represented by the following formulas (2-1) to (2-10).

[Formula 2-1]

[Formula 2-2]

The transition metal compound represented by Formula 1 and the ligand compound represented by Formula 2 can be specifically used to prepare catalysts for polymerization of olefin monomers, but the present invention is not limited thereto and can be applied to all fields in which the above transition metal compound can be used .

The ligand compound represented by the formula (2) of the present invention can be prepared as shown in the following reaction formula (1).

[Reaction Scheme 1]

In the above Reaction Scheme 1, R ₁ to R ₁₀ , and Q are the same as defined in Formula 2 above.

Specifically, the ligand compound of Formula 2 may be prepared by a method comprising the following steps a) to d):

a) reacting a compound represented by the following formula (3) with a compound represented by the following formula (4) to prepare a compound represented by the following formula (5); And

b) reacting a compound represented by the following formula (5) with a compound represented by the following formula (6) to prepare a compound represented by the following formula (2):

(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

(2)

The compound represented by Formula 4 may be prepared as shown in Reaction Scheme 2 below.

[Reaction Scheme 2]

In the above Reaction Scheme 2, R ₄ to R ₉ are the same as defined in Formula 1 or Formula 2.

The transition metal compound represented by the formula (1) of the present invention can be prepared by using the ligand compound represented by the formula (2) as shown in the following reaction formula (3).

[Reaction Scheme 3]

Wherein R ₁ to R ₁₀ , Q, M, X _1, and X ₂ are the same as defined in Formula 1 or Formula 2.

According to an embodiment of the present invention, the transition metal compound represented by Formula 1 may be a compound in which a Group 4 transition metal is coordinated to the compound represented by Formula 2 as a ligand.

Specifically, as shown in Reaction Scheme 3, the compound represented by Chemical Formula 2 is reacted with the compound represented by Chemical Formula 7 and the organolithium compound, which is a metal precursor, to convert the compound represented by Chemical Formula 2 as a ligand into a quaternary transition metal The coordination-bonded transition metal compound of the formula (1) can be obtained.

(2)

(7)

[Chemical Formula 1]

Wherein R ₁ to R ₁₀ , Q, M, X ₁ and X ₂ are the same as defined in the above formula (1).

The organolithium compound may be selected from the group consisting of n-butyl lithium, sec-butyl lithium, methyl lithium, ethyl lithium, isopropyl lithium, cyclohexyl lithium, allyl lithium, vinyl lithium, phenyl lithium, Or more.

The compound represented by Formula 2 and the compound represented by Formula 7 may be mixed in a molar ratio of 1: 0.8 to 1: 1.5, specifically 1: 1.0 to 1: 1.1.

The organic lithium compound may be used in an amount of 180 to 250 parts by weight based on 100 parts by weight of the compound represented by the general formula (2).

According to the preparation method according to an embodiment of the present invention, the reaction may be performed at a temperature ranging from -80 ° C to 140 ° C for 1 to 48 hours.

According to an embodiment of the present invention, the compound represented by Formula 3 and the compound represented by Formula 6 may be used in a molar ratio of 1: 0.8 to 1: 5.0, specifically 1: 0.9 to 1: 4.5, 1: 1 to 1: 4.0.

According to an embodiment of the present invention, the compound represented by Formula 4 and the compound represented by Formula 5 may be used in a molar ratio of 1: 0.8 to 1: 5.0, specifically 1: 0.9 to 1: 4.0, Specifically, it may be a molar ratio of 1: 1 to 1: 3.0.

In addition, the reaction may be carried out at a temperature ranging from -80 DEG C to 140 DEG C for 1 to 48 hours.

The present invention also provides a catalyst composition comprising the compound of formula (1).

The catalyst composition may further comprise a cocatalyst. As the cocatalyst, those known in the art can be used.

For example, the catalyst composition may further include at least one of the following formulas (8) to (10) as a cocatalyst.

[Chemical Formula 8]

- [Al (R ₁₁ ) -O] _a -

Wherein each R < ₁₁ > is independently a halogen radical; A hydrocarbyl radical having from 1 to 20 carbon atoms; Or a hydrocarbyl radical having 1 to 20 carbon atoms substituted with halogen; a is an integer of 2 or more;

[Chemical Formula 9]

D (R ₁₁ ) ₃

Wherein D is aluminum or boron; R < ₁₁ > are each independently as defined above;

[Chemical formula 10]

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

Wherein L is a neutral or cationic Lewis acid; H is a hydrogen atom; Z is a Group 13 element; A is independently an aryl having 6 to 20 carbon atoms or an alkyl having 1 to 20 carbon atoms in which at least one hydrogen atom may be substituted with a substituent; The substituent is halogen, hydrocarbyl of 1 to 20 carbon atoms, alkoxy of 1 to 20 carbon atoms, or aryloxy of 6 to 20 carbon atoms.

As a method of preparing the catalyst composition, first, a step of contacting a transition metal compound represented by the formula (1) with a compound represented by the formula (8) or (9) to obtain a mixture; And a step of adding the compound represented by the formula (10) to the mixture.

Secondly, a method for preparing a catalyst composition by contacting the transition metal compound represented by the formula (1) with the compound represented by the formula (10) is provided.

In the first method of the catalyst composition manufacturing method, the molar ratio of the compound represented by the formula (8) or (9) to the transition metal compound represented by the formula (1) may be 1: 2 to 1: 5,000, : 10 to 1: 1,000, and more specifically from 1:20 to 1: 500.

The molar ratio of the compound represented by Formula 10 to the transition metal compound represented by Formula 1 may be 1: 1 to 1:25, and may be 1: 1 to 1:10. More specifically, the molar ratio of the compound represented by Formula 10 may be 1: To 1: 5.

When the molar ratio of the compound represented by the formula (8) or the compound represented by the formula (9) to the compound represented by the formula (1) is less than 1: 2, the alkylation of the metal compound may not proceed completely, The alkylation of the metal compound is carried out but there is a problem that the activation of the alkylated metal compound can not be completely achieved due to the side reaction between the remaining excess alkylating agent and the activating agent of the above formula (10). When the ratio of the compound represented by the general formula (10) to the transition metal compound of the general formula (2) is less than 1: 1, the amount of the activator is relatively small and the activity of the catalyst composition If there is a problem of falling, and if the ratio is more than 1:25, activation of the metal compound is completely performed. However, there is a problem that the unit cost of the catalyst composition is insufficient due to the excess activator remaining or the purity of the produced polymer is low.

The molar ratio of the compound represented by the general formula (10) to the transition metal compound represented by the general formula (1) may be 1: 1 to 1: 500, specifically 1: 1 to 1: 50, more specifically from 1: 2 to 1:25. When the molar ratio is less than 1: 1, the amount of the activating agent is relatively small and the activation of the metal compound is not completely performed. Thus, there is a problem that the activity of the resulting catalyst composition is low. However, there is a problem that the unit cost of the catalyst composition is insufficient due to the remaining excess activator and the purity of the produced polymer is low.

As the reaction solvent, hydrocarbon solvents such as pentane, hexane, heptane and the like and aromatic solvents such as benzene, toluene and the like may be used in the preparation of the composition, but not always limited thereto, and all solvents usable in the related art are used .

The transition metal compound of Formula 1 and the cocatalyst may be used in the form of being supported on a carrier. As the carrier, silica or alumina can be used.

The compound represented by the formula (8) is not particularly limited as long as it is alkylaluminoxane. Specific examples thereof include methyl aluminoxane, ethyl aluminoxane, isobutyl aluminoxane and butyl aluminoxane, and more specifically, methyl aluminoxane.

The compound represented by the above formula (9) is not particularly limited, and specific examples thereof include trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, dimethylchloroaluminum, triisopropylaluminum, 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, dimethyl aluminum Trimethylboron, triethylboron, triisobutylboron, tripropylboron, tributylboron and the like. More specifically, it is selected from trimethylaluminum, triethylaluminum and triisobutylaluminum.

Examples of the compound represented by Formula 10 include triethylammonium tetraphenylboron, tributylammonium tetraphenylboron, trimethylammonium tetraphenylboron, tripropylammonium tetraphenylboron, trimethylammonium tetra (p-tolyl) boron, trimethylammonium tetra (p-dimethylphenyl) boron, tributylammonium tetra (ptrifluoromethylphenyl) boron, trimethylammonium tetra (p-trifluoromethylphenyl) boron, tributylammonium tetrapentafluorophenylboron, N, N -Diethylanilinium tetraphenylboron, N, N-diethylanilinium tetraphenylboron, N, N-diethylanilinium tetrapentafluorophenylboron, diethylammonium tetrapentafluorophenylboron, triphenyl Phosphonium tetraphenylboron, trimethylphosphonium tetraphenylboron, triethylammonium tetraphenyl aluminum, tributylammonium tetraphenyl aluminum, trimethylammonium te (O, p-dimethylphenyl) aluminum, tributylammonium tetra (p-tolyl) aluminum, tripropylammonium tetra (p-trifluoromethylphenyl) aluminum, trimethylammonium tetra (ptrifluoromethylphenyl) aluminum, tributylammonium tetrapentafluorophenylaluminum, N, N-diethylaniliniumtetraphenylaluminum, N, N, N-diethylanilinium tetrapentafluorophenyl aluminum, diethylammonium tetrapentatetraphenyl aluminum, triphenylphosphonium tetraphenyl aluminum, trimethylphosphonium tetraphenyl aluminum, triethyl ammonium Tetraphenyl aluminum, tributyl ammonium tetraphenyl aluminum, trimethyl ammonium tetraphenyl boron, tripropyl ammonium tetra (O, p-dimethylphenyl) boron, trimethylammonium tetra (p-tolyl) boron, tripropylammonium tetra (p- tolyl) boron, triethylammonium tetra Boron, tributylammonium tetra (ptrifluoromethylphenyl) boron, trimethylammonium tetra (p-trifluoromethylphenyl) boron, tributylammonium tetrapentafluorophenylboron, N, N-diethylanilinium tetraphenylboron , N, N-diethylanilinium tetraphenylboron, N, N-diethylanilinium tetrapentafluorophenylboron, diethylammonium tetrapentafluorophenylboron, triphenylphosphonium tetraphenylboron, triphenylcarbonium (Ptrifluoromethylphenyl) boron, triphenylcarbonium tetrapentafluorophenylboron, and the like.

A transition metal compound represented by Formula 1; And at least one compound selected from the compounds represented by the general formulas (8) to (10) may be contacted with one or more olefin monomers to prepare a polyolefin homopolymer or copolymer.

The specific preparation process using the catalyst composition is a solution process, and it is also applicable to a slurry or a gas phase process when such a composition is used together with an inorganic carrier such as silica.

In the production process, the activated catalyst composition may be an aliphatic hydrocarbon solvent having 5 to 12 carbon atoms suitable for the olefin polymerization process, such as pentane, hexane, heptane, nonane, decane and isomers thereof and aromatic hydrocarbon solvents such as toluene and benzene, Methane, chlorobenzene, or the like, or injected by dilution. The solvent used here is preferably used by removing a small amount of water or air acting as a catalyst poison by treating with a small amount of alkylaluminum, and it is also possible to use a further cocatalyst.

Examples of the olefin-based monomer polymerizable with the metal compound and the cocatalyst include ethylene, alpha-olefin, cyclic olefin, etc., diene olefin-based monomers or triene olefin-based 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.

Particularly, in the production process of the present invention, the catalyst composition has a high molecular weight in the copolymerization reaction of a monomer having a large steric hindrance such as ethylene and 1-octene even at a high reaction temperature of 90 ° C or more, It is possible to manufacture a composite body.

According to one embodiment of the present invention, the polymer produced by the production process of the present invention has a density of less than 0.9 g / cc.

According to one embodiment of the present invention, the polymer produced by the production method of the present invention has a density of 0.895 g / cc or less.

According to an embodiment of the present invention, when a polymer is formed using the transition metal catalyst of Formula 1, the peak of Tm (melting temperature) may have a single peak or two peaks.

The Tm can be obtained using a Differential Scanning Calorimeter (DSC) 6000 manufactured by PerkinElmer. The temperature of the polymer is increased to 100 ° C, held at that temperature for 1 minute, then lowered to -100 ° C , And the temperature can be increased again to measure the melting point of the top of the DSC curve (melt temperature)

According to one embodiment of the present invention, the polymer produced by the production method of the present invention has a Tm of 94 or less.

According to one embodiment of the present invention, the polymer produced by the production method of the present invention may have a Tm of 1 or 2 peaks.

According to one embodiment of the present invention, the polymer produced by the production method of the present invention may have a melt index (MI) of less than 1.

According to one embodiment of the present invention, the polymer produced by the production method of the present invention may have a melt index (MI) of 0.8 or less.

According to one embodiment of the present invention, the polymer produced by the production method of the present invention may have a melt index (MI) of 0.61 or less.

According to an embodiment of the present invention, when the melt index is as low as less than 1, production of a polymer having a high molecular weight may be possible, and thus the polymer can be usefully used as a multilayer film or automobile compound for coatings requiring a high molecular weight polymer .

Hereinafter, the present invention will be described more specifically based on the following examples. These examples are provided to aid understanding of the present invention and the scope of the present invention is not limited thereto.

Synthesis of ligands and transition metal compounds

Organic reagents and solvents were purchased from Aldrich unless otherwise noted and purified by standard methods. At every stage of the synthesis, the contact between air and moisture was blocked to improve the reproducibility of the experiment. Compounds in which tetramethylcyclobutadiene is substituted in the ketone compounds of formula (I) are described in Organometallics According to the 2002, 21, 2842-2855], abbreviated Comparative Example 1 in the _{CGC (Me 2 Si (Me 4} C 5) NtBu] TiMel 2 (Constrained-Geometry Catalyst, hereinafter to CGC) is United States Patent No. 6,015,916 No. .

≪ Preparation of ligand compound >

Example 1

[Formula 2-1]

Chloro -1- (1, 2-dimethyl-3H- Benzo [b] cyclopenta [d] thiophene Yl) -1,1- (allyl) ( methyl ) Preparation of silane

5.21 g (26.01 mmol) of 1,2-dimethyl-3H-benzo [b] cyclopenta [d] thiophene and 100 mL of THF were placed in a 100 mL Schlenk flask, and 10.9 mL (27.31 mmol, 2.5 M in Hexane) was added dropwise at -30 째 C, followed by stirring at room temperature overnight. The stirred Li-complex THF solution was cannulated at -78 ° C in a Schlenk flask containing 7.6 mL (52.02 mmol) of allyl dichloro (methyl) silane and 100 mL of THF, and stirred overnight at room temperature. After stirring and vacuum drying, the mixture was extracted with 100 mL of hexane, dried in vacuo, and washed with hexane to obtain 8.1 g of a brown liquid (98%, dr = 1: 1).

N-allyl-1- (1, 2-dimethyl-3H- Benzo [b] cyclopenta [d] thiophene Yl) -1,1- (allyl) ( methyl ) Preparation of Silane Amines

(2.60 g, 8.560 mmol) was added to the solution, and then 45 mL of hexane was added thereto. 593 mg (9.41 mmol) of prop-2en-1-amino lithium was added thereto at 0 ° C, and the reaction was allowed to proceed at room temperature for 1 day. After the reaction, it was extracted with 50 mL of hexane. After drying the solvent, 2.64 g of brown liquid (91%, dr = 1: 1) was obtained.

_{^{1 H-NMR (CDCl 3,}} 500 MHz): 7.83 (d, 2H), 7.68 (d, 2H), 7.21 (dd, 2H), 7.10 (dd, 2H), 5.81-5.68 (m, 2H), 5.57 (ddd, 1 H), 5.47 (ddd, 1 H), 5.04-4.95 (m, 2H), 4.88-4.83 (m, 2H), 4.77-4.65 3H), 2.01 (s, 3H), 1.46-1.28 (m, 4H), -0.06 (s, 3H), -0.07 , 3H).

Example 2

[Formula 2-2]

N- tert Butyl-1- (1, 2-dimethyl-3H- Benzo [b] cyclopenta [d] thiophene 3-yl) -1,1- (allyl) (methyl) silanamine

Benzo [b] cyclopenta [d] thiophen-3-yl) -1,1- ((2-dimethyl-3H- Allyl) (methyl) silane (2.6 g, 8.152 mmol) was weighed and then 20 mL of hexane was added thereto. 3.4 mL (32.60 mmol) of N-tert-butylamine was added thereto at 0 ° C., and the reaction was allowed to proceed at room temperature for 1 day. After the reaction, it was extracted with 50 mL of hexane. After drying the solvent, 2.64 g (91%, dr = 1: 1) of yellow solid was obtained.

_{^{1 H-NMR (CDCl 3,}} 500 MHz): 7.96 (d, 2H), 7.71-7.68 (m, 2H), 7.26-7.21 (m, 2H), 7.10-7.06 (m, 2H), 5.69 (ddd, 2H), 2.32 (s, 3H), 2.21 (s, 3H), 2.31 (s, 3H) , 2.04 (s, 3H), 1.97 (s, 3H), 1.50-1.45 (m, 2H), 1.24-1.22 , ≪ / RTI > 3H), 0.19 (s, 3H)

≪ Preparation of transition metal compound &

Example 1-1

[Formula 1-1]

To a 100 mL Schlenk flask was added the N-allyl-1- (1,2-dimethyl-3H-benzo [b] cyclopenta [d] thiophen- Methyl) silane amine (1.00 g, 2.95 mmol) and MTBE (15 mL) were added and stirred. 2.4 mL (6.04 mmol, 2.5 M in THF) of n-BuLi was added at -40 ° C, and the reaction was allowed to proceed at room temperature overnight. Then 2.5 mL (7.36 mmol, 3.0 M in diethyl ether) of MeMgBr was slowly added dropwise at -40 ° C, and 3.0 mL (2.95 mmol, 1.0 M in toluene) of TiCl 4 was added in this order and allowed to react overnight at room temperature. The reaction mixture was then filtered through Celite using hexane. After drying the solvent, 1.00 g (82%, d.r. = 2: 1) of a brown solid was obtained.

_{^{1 H-NMR (CDCl 3,}} 500 MHz): δ 7.79-7.77 (d, 2H), 7.38-7.36 (m, 2H), 7.18-7.16 (m, 2H), 7.04-6.99 (m, 2H), 6.05 (s, 3H), 2.33 (s, 3H), 2.03 (s, 3H), 2.54 (d, ), 1.91 (s, 3H), 1.89-1.85 (m, 4H), 0.96-0.84 (m, 4H), 0.65 s, 3H), 0.02 (s, 3H), 0.01 (s, 3H).

Example 2-1

[Formula 1-2]

To a 100 mL Schlenk flask was added N-tert-butyl-1- (1,2-dimethyl-3H-benzo [b] cyclopenta [d] thiophen- ) (Methyl) silane amine (2.50 g, 7.32 mmol) and MTBE (20 mL). 9.4 mL (15.0 mmol, 2.5 M in THF) of n-BuLi was added at -40 ° C, and the reaction was allowed to proceed at room temperature overnight. Then 6.1 mL of MeMgBr (18.3 mmol, 3.0 M in diethyl ether) was slowly added dropwise at -40 ° C, and 7.3 mL (7.32 mmol, 1.0 M in toluene) of TiCl _{4 was} added in this order and allowed to react overnight at room temperature. The reaction mixture was then filtered through Celite using hexane. After drying the solvent, 2.71 g (86%, dr = 1: 1) of a brown solid was obtained.

_{^{1 H-NMR (CDCl 3,}} 500 MHz): δ 7.75-7.72 (m, 2H), 7.39-7.35 (m, 2H), 7.15-7.12 (m, 2H), 7.00-6.96 (m, 2H), 6.15 (ddd, 1H), 5.92 (ddd, 1H), 5.25-5.21 (m, 2H), 5.07-5.01 (m, 2H), 2.32-2.30 (m, 2H), 1.85 (s, 3H), 1.81 (s, 3H), 1.53 (s, 3H) s, 3H), 0.63 (s, 3H), 0.47 (s, 3H), -0.01 (s, 3H).

Comparative Example 1

[Formula 11-1]

<Synthesis of tert-butyl (dimethyl (2,3,4,5-tetramethylcyclopenta-2,4-dien-1-yl) silyl) amino) dimethyltitanium>

CGC (Me ₂ Si (Me ₄ C ₅ ) NtBu] TiMe ₂ (Constrained-Geometry Catalyst) of Comparative Example 1 was synthesized according to US Patent No. 6,015,916.

The comparative ligand compound (2.36 g, 9.39 mmol / 1.0 eq) and 50 mL (0.2 M) of MTBE were added to a 100 ml Schlenk flask and stirred. N-BuLi (7.6 ml, 19.25 mmol / 2.05 eq, 2.5 M in THF) was added at -40 ^° C and the reaction was allowed to proceed overnight at room temperature. Then, MeMgBr (6.4 ml, 19.25 mmol / 2.05 eq, 3.0 M in diethyl ether) was slowly added dropwise at -40 ^° C and then TiCl ₄ (9.4 ml, 9.39 mmol / 1.0 eq, 1.0 M in toluene) And allowed to react overnight at room temperature. The reaction mixture was then filtered through Celite using hexane. After drying the solvent, a yellow solid was obtained in a yield of 2.52 g (82%).

_{^{1 H-NMR (in CDCl 3}} , 500 MHz):

2H), 2.17 (s, 6H), 1.92 (s, 6H), 1.57 (s, 9H), 0.48 (s, 6H), 0.17 (s, 6H).

Comparative Example 2

[Chemical Formula 12]

Synthesis of N-tert-butyl-1- (1,2-dimethyl-3H-benzo [b] cyclopenta [d] thiophen-

To a 100 mL Schlenk flask was added 4.65 g (15.88 mmol) of chloro-1- (1, 2-dimethyl-3H-benzo [b] cyclopenta [d] thiophen- And 80 mL of THF was added thereto. TBuNH ₂ (4eq, 6.68 mL) was added at room temperature and reacted at room temperature for 3 days. After the reaction, the THF was removed, and the solution was filtered with hexane. After drying the solvent, a yellow liquid was obtained in a yield of 4.50 g (86%).

¹ H-NMR (in CDCl ₃ , 500 MHz): 7.99 (d, IH), 7.83 (d, IH), 7.35 (dd, IH), 7.24 s, 3H), 2.17 (s, 3H), 1.27 (s, 9H), 0.19 (s, 3H), -0.17 (s, 3H).

[Formula 12-1]

To a 50 mL Schlenk flask was added N-tert-butyl-1- (1,2-dimethyl-3H-benzo [b] cyclopenta [d] thiophen- Amine (1.06 g, 3.22 mmol / 1.0 eq) and 16.0 mL (0.2 M) of MTBE were added and stirred. N-BuLi (2.64 mL, 6.60 mmol / 2.05 eq, 2.5 M in THF) was added at -40 ° C, and the mixture was reacted at room temperature overnight. Afterwards, MeMgBr (2.68 mL, 8.05 mmol / 2.5 eq, 3.0 M in diethyl ether) was slowly added dropwise at -40 ° C and TiCl _{4 (} 2.68 mL, 3.22 mmol / 1.0 eq, 1.0 M in toluene) And reacted overnight at room temperature. The reaction mixture was then filtered through Celite using hexane. After drying the solvent, a brown solid was obtained in a yield of 1.07 g (82%).

_{^{1 H-NMR (CDCl 3,}} 500 MHz): δ 7.99 (d, 1H), 7.68 (d, 1H), 7.40 (dd, 1H), 7.30 (dd, 1H), 3.22 (s, 1H), 2.67 ( s, 3H), 2.05 (s, 3H), 1.54 (s, 9H), 0.58 (s, 3H), 0.57 (s, 3H), 0.40 (s,

Production Example of Polymer

Experimental Examples 1 and 2, and Comparative Experimental Examples 1 to 3

A hexane solvent (1.0 L) and 1-octene (amounts shown in Table 1) were added to a 2 L autoclave reactor and the temperature of the reactor was preheated to 150 캜. At the same time, the pressure of the reactor was pre-filled with ethylene (35 bar). The third column of the following Table 1, treated with dimethylanilinium tetrakis (pentafluorophenyl) borate (AB) cocatalyst (9 μmol) and triisobutylaluminum (Tibal) compound (0.25 mmol) Was added and introduced into the reactor. Subsequently, the copolymerization reaction was carried out for 8 minutes. Next, the remaining ethylene gas was removed and the polymer solution was added to excess ethanol to induce precipitation. The precipitated polymer was washed with ethanol 2 to 3 times, dried in a vacuum oven at 90 캜 for 12 hours or longer, and then measured for physical properties.

Various polymers were prepared according to the polymerization temperature of Table 1, and the main catalyst and the catalyst, and the results are shown in Table 1.

Property evaluation

&Lt; Melt index of polymer &

The melt index (MI) of the polymer was measured by ASTM D-1238 (condition E, 190 DEG C, 2.16 Kg load).

&Lt; Melting temperature of polymer &

The melting temperature (Tm) of the polymer can be obtained by using a Differential Scanning Calorimeter (DSC) 6000 manufactured by PerkinElmer. The melting temperature of the polymer is about 0.5 mg to 10 mg of the sample, The gas flow rate was 20 mL / min. In order to make the thermal history of the polyolefin resin the same, the sample was heated from 0 ° C to 150 ° C at a rate of 20 ° C / min. The sample was cooled to a temperature of 100 ° C at a rate of 10 ° C / min, and then the temperature of the sample was elevated from -100 ° C to 150 ° C at a rate of 10 ° C / min while the heating curve of the heat flow The peak, that is, the endothermic peak temperature at the time of heating can be measured as the melting temperature.

&Lt; Polymer density &

The density of the polymer was measured on a Mettler scale after the sample was made into a sheet having a thickness of 3 mm and a radius of 2 cm with a 190 占 폚 press mold and annealing at room temperature for 24 hours.

<Measurement of easiness of low density and high molecular weight products according to temperature>

Cat. 1-octene charge
(mL) Cat. (Compound)
(input) Polymerization temperature (캜) Cocat density
(g / cc) Melt Index
(MI)
(g / 10 min) Tm (占 폚) Comparative test example
One 200 Formula 11-1
(2 μmol) 150 AB 0.904 8.42 102.5 Comparative Experimental Example
2 200 12-1
(3 μmol) 150 AB 0.895 0.85 94.4 Comparative Experimental Example 3 250 12-1
(2 μmol) 150 AB 0.872 9.8 50.1 Experimental Example
One 200 (1-1)
(3 μmol) 150 AB 0.891 0.61 58.8 Experimental Example
2 200 1-2
(3 μmol) 150 AB 0.895 0.23 93.5

AB: Dimethylanilinium tetrakis (pentafluorophenyl) borate promoter catalyst

Referring to Table 1, in the case of Experimental Examples 1 and 2 in which the transition metal compounds of Examples 1 and 2 were used as catalysts, compared with Comparative Examples 1 to 3 in which the transition metal compounds of Comparative Examples 1 and 2 were used as catalysts, An olefin-based polymer having a high molecular weight in the region can be obtained.

Claims (17)

A transition metal compound represented by the following general formula (1)
[Chemical Formula 1]

In Formula 1,
R ₁ is hydrogen; halogen; Alkyl having 1 to 20 carbon atoms; Cycloalkyl having 3 to 20 carbon atoms; Alkenyl having 2 to 20 carbon atoms; Alkoxy having 1 to 20 carbon atoms; Aryl having 6 to 20 carbon atoms; Arylalkoxy having 7 to 20 carbon atoms; Alkylaryl having 7 to 20 carbon atoms; Or arylalkyl having 7 to 20 carbon atoms,
R ₂ is Alkenyl having 2 to 20 carbon atoms,
R ₃ is hydrogen; halogen; Alkyl having 1 to 20 carbon atoms; Cycloalkyl having 3 to 20 carbon atoms; Alkenyl having 2 to 20 carbon atoms; Alkoxy having 1 to 20 carbon atoms; Or aryl having 6 to 20 carbon atoms,
R ₄ to R ₉ are each independently hydrogen; Silyl; Alkyl having 1 to 20 carbon atoms; Cycloalkyl having 3 to 20 carbon atoms; Alkenyl having 2 to 20 carbon atoms; Aryl having 6 to 20 carbon atoms; Alkylaryl having 7 to 20 carbon atoms; Arylalkyl having 7 to 20 carbon atoms; Or a metalloid radical of a Group 14 metal substituted with a hydrocarbyl of 1 to 20 carbon atoms; Two or more adjacent R &lt; ₃ &gt; to R &lt; ₈ &gt; adjacent to each other may be connected to each other to form a ring,
Q is Si, C, N, P or S,
M is a transition metal of Group 4,
X ₁ and X ₂ are each independently hydrogen; halogen; Alkyl having 1 to 20 carbon atoms; Cycloalkyl having 3 to 20 carbon atoms; Alkenyl having 2 to 20 carbon atoms; Aryl having 6 to 20 carbon atoms; Alkylaryl having 7 to 20 carbon atoms; Arylalkyl having 7 to 20 carbon atoms; Alkylamino having 1 to 20 carbon atoms; Arylamino having 6 to 20 carbon atoms; Or alkylidene having 1 to 20 carbon atoms.
The method according to claim 1,
R &lt; ₁ &gt; is hydrogen; halogen; Alkyl having 1 to 20 carbon atoms; Cycloalkyl having 3 to 20 carbon atoms; Alkoxy having 1 to 20 carbon atoms; Aryl having 6 to 20 carbon atoms; Arylalkoxy having 7 to 20 carbon atoms; Alkylaryl having 7 to 20 carbon atoms; Or arylalkyl having 7 to 20 carbon atoms,
R ₂ is alkenyl having 2 to 12 carbon atoms,
R &lt; ₃ &gt; is hydrogen; halogen; Alkyl having 1 to 12 carbon atoms; Cycloalkyl having 3 to 12 carbon atoms; Alkenyl having 2 to 12 carbon atoms; Alkoxy having 1 to 12 carbon atoms; Or phenyl,
Each of R ₄ to R ₉ is independently hydrogen; Alkyl having 1 to 20 carbon atoms; Cycloalkyl having 3 to 20 carbon atoms; Aryl having 6 to 20 carbon atoms; Alkylaryl having 7 to 20 carbon atoms; Or arylalkyl having 7 to 20 carbon atoms,
Two or more adjacent ones of R ₄ to R ₉ may be connected to each other to form an aliphatic ring having 5 to 20 carbon atoms or an aromatic ring having 6 to 20 carbon atoms; The aliphatic ring or aromatic ring may be substituted with halogen, alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 12 carbon atoms, or aryl having 6 to 12 carbon atoms,
Wherein Q is Si,
M is Ti,
X ₁ and X ₂ are each independently hydrogen; halogen; Alkyl having 1 to 12 carbon atoms; Cycloalkyl having 3 to 12 carbon atoms; Alkenyl having 2 to 12 carbon atoms; Aryl having from 6 to 12 carbon atoms; Alkylaryl of 7 to 13 carbon atoms; Arylalkyl having 7 to 13 carbon atoms; Alkylamino having 1 to 13 carbon atoms; Or an arylamino group having 6 to 12 carbon atoms.
The method according to claim 1,
R &lt; ₁ &gt; is hydrogen; halogen; Alkyl having 1 to 12 carbon atoms; Cycloalkyl having 3 to 12 carbon atoms; Alkoxy having 1 to 12 carbon atoms; Aryl having from 6 to 12 carbon atoms; Arylalkoxy having 7 to 13 carbon atoms; Alkylaryl of 7 to 13 carbon atoms; Or an arylalkyl group having 7 to 13 carbon atoms,
R ₂ is alkenyl having 2 to 12 carbon atoms,
R &lt; ₃ &gt; is hydrogen; halogen; Alkyl having 1 to 12 carbon atoms; Cycloalkyl having 3 to 12 carbon atoms; Alkenyl having 2 to 12 carbon atoms; Alkoxy having 1 to 12 carbon atoms; Or phenyl,
Each of R ₄ to R ₉ is independently hydrogen; Alkyl having 1 to 12 carbon atoms; Cycloalkyl having 3 to 12 carbon atoms; Aryl having from 6 to 12 carbon atoms; Alkylaryl of 7 to 13 carbon atoms; Or an arylalkyl group having 7 to 13 carbon atoms,
Two or more adjacent ones of R ₄ to R ₉ may be connected to each other to form an aliphatic ring having 5 to 12 carbon atoms or an aromatic ring having 6 to 12 carbon atoms;
The aliphatic or aromatic ring may be substituted with halogen, alkyl having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or aryl having 6 to 12 carbons,
Wherein Q is Si,
M is Ti,
X ₁ and X ₂ are each independently hydrogen; halogen; Alkyl having 1 to 12 carbon atoms; Or an alkenyl group having 2 to 12 carbon atoms.
The method according to claim 1,
Wherein R &_lt; 1 &gt; is alkyl having 1 to 12 carbon atoms or aryl having 6 to 12 carbon atoms,
R ₂ is alkenyl having 2 to 12 carbon atoms,
R &lt; ₃ &gt; is hydrogen; Alkyl having 1 to 12 carbon atoms; Or an alkenyl having 2 to 12 carbon atoms,
R ₄ and R ₅ are each independently hydrogen; Or alkyl having 1 to 12 carbon atoms,
Each of R ₆ to R ₉ is independently hydrogen or methyl,
Wherein R &lt; ₁₀ &gt; is hydrogen,
Wherein Q is Si,
M is Ti,
Wherein X ₁ and X ₂ are each independently hydrogen or alkyl having 1 to 12 carbon atoms.
The method according to claim 1,
Wherein the compound represented by Formula 1 is a compound represented by any one of the following formulas:
[Formula 1-1]

[Formula 1-2]

A ligand compound represented by the following formula (2):
(2)

In Formula 2,
R ₁ and R ₁₀ are each independently hydrogen; halogen; Alkyl having 1 to 20 carbon atoms; Cycloalkyl having 3 to 20 carbon atoms; Alkenyl having 2 to 20 carbon atoms; Alkoxy having 1 to 20 carbon atoms; Aryl having 6 to 20 carbon atoms; Arylalkoxy having 7 to 20 carbon atoms; Alkylaryl having 7 to 20 carbon atoms; Or arylalkyl having 7 to 20 carbon atoms,
R ₂ is Alkenyl having 2 to 20 carbon atoms,
R ₃ is hydrogen; halogen; Alkyl having 1 to 20 carbon atoms; Cycloalkyl having 3 to 20 carbon atoms; Alkenyl having 2 to 20 carbon atoms; Alkoxy having 1 to 20 carbon atoms; Or aryl having 6 to 20 carbon atoms,
R ₄ to R ₉ are each independently hydrogen; Silyl; Alkyl having 1 to 20 carbon atoms; Cycloalkyl having 3 to 20 carbon atoms; Alkenyl having 2 to 20 carbon atoms; Aryl having 6 to 20 carbon atoms; Alkylaryl having 7 to 20 carbon atoms; Arylalkyl having 7 to 20 carbon atoms; Or a metalloid radical of a Group 14 metal substituted with a hydrocarbyl of 1 to 20 carbon atoms; Two or more adjacent R &lt; ₆ &gt; to R &lt; ₉ &gt; adjacent to each other may be linked together to form a ring,
Q is Si, C, N, P or S.
The method according to claim 6,
R ₁ and R ₁₀ are each independently hydrogen; halogen; Alkyl having 1 to 12 carbon atoms; Cycloalkyl having 3 to 12 carbon atoms; Alkoxy having 1 to 12 carbon atoms; Aryl having from 6 to 12 carbon atoms; Arylalkoxy having 7 to 13 carbon atoms; Alkylaryl of 7 to 13 carbon atoms; Or an arylalkyl group having 7 to 13 carbon atoms,
R ₂ and R ₃ are each independently hydrogen; halogen; Alkyl having 1 to 12 carbon atoms; Cycloalkyl having 3 to 12 carbon atoms; Alkenyl having 2 to 12 carbon atoms; Alkoxy having 1 to 12 carbon atoms; Or phenyl,
Each of R ₄ to R ₉ is independently hydrogen; Alkyl having 1 to 12 carbon atoms; Cycloalkyl having 3 to 12 carbon atoms; Aryl having from 6 to 12 carbon atoms; Alkylaryl of 7 to 13 carbon atoms; Or an arylalkyl group having 7 to 13 carbon atoms,
Two or more adjacent ones of R ₃ to R ₈ may be connected to each other to form an aliphatic ring having 5 to 12 carbon atoms or an aromatic ring having 6 to 12 carbon atoms;
The aliphatic ring or aromatic ring may be substituted with halogen, alkyl having 1 to 12 carbon atoms, alkenyl having 2 to 12 carbon atoms, or aryl having 6 to 12 carbon atoms,
And Q is Si.
The method according to claim 6,
The compound represented by Formula 2 is represented by any one of the following formulas:
[Formula 2-1]

[Formula 2-2]

a) reacting a compound represented by the following formula (3) with a compound represented by the following formula (4) to prepare a compound represented by the following formula (5); And
b) reacting a compound represented by the following formula (5) with a compound represented by the following formula (6) to prepare a compound represented by the following formula (2);
Lt; RTI ID = 0.0 &gt; of: &lt; / RTI &gt;
(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

(2)

Wherein R ₁ to R ₁₀ and Q are the same as defined in the above formula (2).
A method for producing a transition metal compound according to claim 1 by reacting a compound represented by the following formula (2) with a compound represented by the following formula (7) and an organolithium compound:
(2)

(7)
M (X ₁ X ₂ ) ₂
[Chemical Formula 1]

Wherein R ₁ to R ₁₀ , Q, M, X ₁ , and X ₂ are as defined in Formula 1 above.
A catalyst composition comprising the transition metal compound according to claim 1, wherein the catalyst composition is a polyethylene polymerization catalyst.
12. The method of claim 11,
&Lt; / RTI &gt; further comprising at least one cocatalyst.
13. The method of claim 12,
Wherein the cocatalyst comprises at least one compound selected from the following formulas (8) to (10).
[Chemical Formula 8]
- [Al (R ₁₁ ) -O] _a -
Wherein each R &lt; ₁₁ &gt; is independently a halogen radical; A hydrocarbyl radical having from 1 to 20 carbon atoms; Or a hydrocarbyl radical having 1 to 20 carbon atoms substituted with halogen; a is an integer of 2 or more;
[Chemical Formula 12]
D (R ₁₁ ) ₃
Wherein D is aluminum or boron; R &lt; ₁₁ &gt; are each independently as defined above;
[Chemical Formula 13]
^{[LH] + [Z (A} ) 4] - or ^{[L] + [Z (A} ) 4] -
Wherein L is a neutral or cationic Lewis acid; H is a hydrogen atom; Z is a Group 13 element; A is independently an aryl having 6 to 20 carbon atoms or an alkyl having 1 to 20 carbon atoms in which at least one hydrogen atom may be substituted with a substituent; The substituent is halogen, hydrocarbyl of 1 to 20 carbon atoms, alkoxy of 1 to 20 carbon atoms, or aryloxy of 6 to 20 carbon atoms.
13. The method of claim 12,
Wherein the catalyst composition further comprises a reaction solvent.
A process for preparing a polymer using the catalyst composition according to claim 11.
16. The method of claim 15, wherein the polymer is a homopolymer or copolymer of a polyolefin.
16. The method of claim 15,
Wherein the polymer has a melt index (MI) of less than 1 and a density of less than 0.9 g / cc.