KR20190086989A - 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 comprising the same. The transition metal compound of the present invention can be usefully used as a catalyst for a polymerization reaction in manufacturing an olefin polymer having a low density. In addition, an olefin polymer polymerized by using the catalyst composition including the transition metal compound can produce a low molecular weight product having a high melt index (MI).

Description

TECHNICAL FIELD [0001] The present invention relates to a transition metal compound and a catalyst composition containing the same. ≪ Desc / Clms Page number 1 >

The present disclosure relates to transition metal compounds of novel structure and to catalyst compositions comprising them.

In general, olefin polymers such as ethylene copolymers have been prepared in the presence of a Ziegler-Natta catalyst system as a useful polymeric material used in materials such as hollow molded articles, extruded articles, films, and sheets. Ziegler-Natta catalysts are heterogeneous catalysts that are used in systems such as liquid reactants-solid catalysts and the like in which the phase of the reactants and the phase of the catalyst are not the same. Such a Ziegler-Natta catalyst is composed of two components. Generally, a halogen compound such as titanium (Ti), vanadium (V), chromium (Cr), molybdenum (Mo), zirconium (Zr) , it consists of a TiCl _4), an alkyl lithium and an alkyl aluminum. However, the Ziegler-Natta catalyst has a disadvantage in that the concentration of the active species is from several% to several tens% with respect to the transition metal atom, and most of the transition metal atoms do not exert their functions, thereby failing to overcome the limitations of the heterogeneous catalyst.

In recent years, metallocene compounds have been attracting attention as a next-generation catalyst capable of overcoming these shortcomings. The metallocene compounds are known to exhibit the desired polymerization activity in olefin polymerization as homogeneous catalysts containing a Group 4 metal. Most metallocene catalysts used in the polymerization consist of a Group 4 metal element such as titanium, zirconium, and hafnium (Hf) and a supporting ligand as their precursors, and are composed of two aromatic o-atoms and two halogen compounds as leaving groups. Of these, the supporting ligands coordinating to the central metal are aromatic cyclopentadienyl groups in general.

When a suitable substituent or a new type of ligand is introduced into the cyclopentadienyl group as the supporting ligand, the spatial or electronic environment around the center metal is changed, thereby changing the properties of the catalyst itself. Further, the organoaluminum When a polymerization reaction is carried out using a zirconocene compound substituted with an amine group capable of interacting with a compound, it is possible to produce polyethylene having a bimodal molecular weight distribution.

Further, when the substituent of the supporting ligand is changed, the molecular weight of the produced polymer can be controlled. Thus, changes in the cyclopentadienyl, the supporting ligand, can affect the polymerisation behavior and the properties of the resulting polymer.

Dow has announced the release of [Me ₂ Si (Me ₄ C ₅ ) N t Bu] TiCl ₂ (hereinafter abbreviated as CGC) (US 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.

Examples of such approaches include modification of the supporting ligand, introduction of various other bridges and nitrogen substituents in place of the silicon bridge, introduction of an oxydol ligand in place of the amido ligand of the CGC, and the like.

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

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 to R ₆ are each independently hydrogen; halogen; Silyl; Alkyl having 1 to 20 carbon atoms; Silyl substituted C 1 -C 20 alkyl; Cycloalkyl having 3 to 20 carbon atoms; Alkenyl having 2 to 20 carbon atoms; Alkoxy having 1 to 20 carbon atoms; Halogen, C 1 -C 12 alkyl, C 3 -C 12 cycloalkyl, C 1 -C 8 alkoxy, C 6 -C 12 aryl, or C 6 -C 20 aryl which is unsubstituted or substituted with aryl having from 6 to 12 carbon atoms; An arylalkyl having 7 to 20 carbon atoms, which is unsubstituted or substituted with halogen, alkyl having 1 to 12 carbon atoms, cycloalkyl having 3 to 12 carbon atoms, alkoxy having 1 to 8 carbon atoms, aryl having 6 to 12 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 two of R ₂ to R ₄ may be connected to each other to form a ring,

R ₇ 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,

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; Silyl; Alkyl having 1 to 20 carbon atoms; Silyl substituted C 1 -C 20 alkyl; 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 (4)

[Chemical Formula 4]

In Formula 4,

R ₁ to R ₆ are each independently hydrogen; halogen; Silyl; Alkyl having 1 to 20 carbon atoms; Silyl substituted C 1 -C 20 alkyl; Cycloalkyl having 3 to 20 carbon atoms; Alkenyl having 2 to 20 carbon atoms; Alkoxy having 1 to 20 carbon atoms; Halogen, C 1 -C 12 alkyl, C 3 -C 12 cycloalkyl, C 1 -C 8 alkoxy, C 6 -C 12 aryl, or C 6 -C 20 aryl which is unsubstituted or substituted with aryl having from 6 to 12 carbon atoms; An arylalkyl having 7 to 20 carbon atoms, which is unsubstituted or substituted with halogen, alkyl having 1 to 12 carbon atoms, cycloalkyl having 3 to 12 carbon atoms, alkoxy having 1 to 8 carbon atoms, aryl having 6 to 12 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 two of R ₂ to R ₄ may be connected to each other to form a ring,

R ₇ 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,

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 transition metal compound of the present invention is excellent in copolymerization and is catalytically polymerizable at a high temperature and can be usefully used as a catalyst for polymerization reaction in the production of olefinic polymers having a high molecular weight in a low density region, A low molecular weight polymer having a high molecular weight (MI) can be obtained.

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 to R ₆ are each independently hydrogen; halogen; Silyl; Alkyl having 1 to 20 carbon atoms; Silyl substituted C 1 -C 20 alkyl; Silyl substituted C 1 -C 20 alkyl; Cycloalkyl having 3 to 20 carbon atoms; Alkenyl having 2 to 20 carbon atoms; Alkoxy having 1 to 20 carbon atoms; Halogen, C 1 -C 12 alkyl, C 3 -C 12 cycloalkyl, C 1 -C 8 alkoxy, C 6 -C 12 aryl, or C 6 -C 20 aryl which is unsubstituted or substituted with aryl having from 6 to 12 carbon atoms; An arylalkyl having 7 to 20 carbon atoms, which is unsubstituted or substituted with halogen, alkyl having 1 to 12 carbon atoms, cycloalkyl having 3 to 12 carbon atoms, alkoxy having 1 to 8 carbon atoms, aryl having 6 to 12 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 two of R ₂ to R ₄ may be connected to each other to form a ring,

R ₇ 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,

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; Silyl; Alkyl having 1 to 20 carbon atoms; Silyl substituted C 1 -C 20 alkyl; 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 of formula (1) according to the present invention is a structure in which indene and amido group (NR ₃ ) are stably crosslinked by Q (Si, C, N, P or S) and a group 4 transition metal is coordinately bonded .

When the catalyst composition is applied to the olefin polymerization, it is possible to produce a polyolefin having such characteristics as high activity, low 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 0.850 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 / cc ) 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, silyl may be silyl substituted or unsubstituted with alkyl having 1 to 20 carbon atoms, and may be, for example, silyl, 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; Alkoxy having 1 to 20 carbon atoms; Cycloalkyl having 3 to 20 carbon atoms; Alkenyl having 2 to 20 carbon atoms; Or an aryl having 6 to 20 carbon atoms, which is substituted or unsubstituted with halogen, alkyl having 1 to 8 carbon atoms, cycloalkyl having 3 to 8 carbon atoms, alkoxy having 1 to 8 carbon atoms, aryl having 6 to 12 carbon atoms;

R ₂ to R ₄ 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; Halogen, C 1-8 alkyl, C 3-8 cycloalkyl, C 1-8 alkoxy, aryl having 6-12 carbon atoms, aryl having 6-20 carbons which is unsubstituted or substituted with aryl having 6-12 carbons; Which may be unsubstituted or substituted with halogen, alkyl having 1 to 8 carbon atoms, cycloalkyl having 3 to 8 carbon atoms, alkoxy having 1 to 8 carbon atoms, aryl having 6 to 12 carbon atoms, or arylalkyl having 7 to 20 carbon atoms; Two or more adjacent two of R ₂ to R ₄ may be connected to each other to form a ring,

R ₅ and R ₆ 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; Halogen, C 1-8 alkyl, C 3-8 cycloalkyl, C 1-8 alkoxy, aryl having 6-12 carbon atoms, aryl having 6-20 carbons which is unsubstituted or substituted with aryl having 6-12 carbons; Or an arylalkyl having 7 to 20 carbon atoms which is unsubstituted or substituted by halogen, alkyl having 1 to 8 carbon atoms, cycloalkyl having 3 to 8 carbon atoms, alkoxy having 1 to 8 carbon atoms, aryl having 6 to 12 carbon atoms,

R < ₇ > is hydrogen; halogen; Alkyl having 1 to 20 carbon atoms; Cycloalkyl having 3 to 20 carbon atoms; Or an alkenyl having 2 to 20 carbon atoms,

Wherein Q may be Si, C, N, P or S,

M may be 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; Or an alkenyl having 2 to 20 carbon atoms.

According to another embodiment of the present invention, the transition metal compound of Formula 1 may be a transition metal compound represented by Formula 2 below.

(2)

In Formula 2,

R < ₁ > is hydrogen; halogen; Alkyl having 1 to 12 carbon atoms; Alkoxy having 1 to 12 carbon atoms; Cycloalkyl having 3 to 12 carbon atoms; Alkenyl having 2 to 12 carbon atoms; Or aryl having from 6 to 12 carbon atoms;

R ₂ to R ₄ are each independently Hydrogen; halogen; Alkyl having 1 to 12 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; Two or more adjacent two of R ₂ to R ₄ may be connected to each other to form a ring,

R < ₅ > is 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; Or arylalkyl having 7 to 13 carbon atoms,

Wherein R ₆ is hydrogen; halogen; Alkyl having 1 to 12 carbon atoms; Or cycloalkyl having 3 to 12 carbon atoms,

R < ₇ > is hydrogen; halogen; Alkyl having 1 to 12 carbon atoms; Or cycloalkyl having 3 to 12 carbon atoms,

X ₁ and X ₂ are each independently hydrogen; halogen; Alkyl having 1 to 12 carbon atoms; Cycloalkyl having 3 to 12 carbon atoms; Or alkenyl having 2 to 12 carbon atoms.

The transition metal compound of Formula 1 according to another embodiment of the present invention may be a transition metal compound represented by Formula 3 below.

(3)

In Formula 3,

Wherein R ₁ may be a C 1 -C 6 alkyl;

R ₂ and R ₃ may be hydrogen, alkyl having 1 to 6 carbon atoms, or alkenyl having 2 to 6 carbon atoms, R ₂ and R ₃ may be connected to each other to form a ring,

R < ₄ > is hydrogen; Or an alkyl having 1 to 8 carbon atoms,

R < ₅ > is hydrogen; Alkyl having 1 to 6 carbon atoms; Or aryl having from 6 to 12 carbon atoms.

Further, in an example of the present invention,

R < ₁ > is methyl; ethyl; Or < / RTI &

R ₂ and R ₃ are independently selected from the group consisting of hydrogen; Or may be connected to each other to form a ring of 5 or 6 carbon atoms,

R ₄ may be alkyl having 4 to 6 carbon atoms,

The R < ₅ > may be phenyl.

The compound represented by the formula (1) may be any one of compounds represented by the following formulas (1-1) to (1-8).

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

[Chemical Formula 1-6]

[Chemical Formula 1-7]

[Chemical Formula 1-8]

According to another aspect of the present invention, there is provided a ligand compound represented by Formula 4:

[Chemical Formula 4]

In Formula 4,

R ₁ to R ₆ are each independently hydrogen; halogen; Silyl; Alkyl having 1 to 20 carbon atoms; Silyl substituted C 1 -C 20 alkyl; Cycloalkyl having 3 to 20 carbon atoms; Alkenyl having 2 to 20 carbon atoms; Alkoxy having 1 to 20 carbon atoms; Halogen, C 1 -C 12 alkyl, C 3 -C 12 cycloalkyl, C 1 -C 8 alkoxy, C 6 -C 12 aryl, or C 6 -C 20 aryl which is unsubstituted or substituted with aryl having from 6 to 12 carbon atoms; An arylalkyl having 7 to 20 carbon atoms, which is unsubstituted or substituted with halogen, alkyl having 1 to 12 carbon atoms, cycloalkyl having 3 to 12 carbon atoms, alkoxy having 1 to 8 carbon atoms, aryl having 6 to 12 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 two of R ₂ to R ₄ may be connected to each other to form a ring,

R ₇ 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,

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

The ligand compound of formula (4) described in this specification has a structure in which indene and amido group (NR ₃ ) are stably crosslinked by Q (Si, C, N, P or S).

In the ligand compound, the definitions of R ₁ to R ₇ and Q in the compound represented by the general formula (4) may be the same as those in the compound represented by the general formula (1), which is a transition metal compound.

According to another embodiment of the present invention, the ligand compound of Formula 4 may be a compound represented by Formula 5 below.

[Chemical Formula 5]

In Formula 5, R ₁ is hydrogen; halogen; Alkyl having 1 to 12 carbon atoms; Alkoxy having 1 to 12 carbon atoms; Cycloalkyl having 3 to 12 carbon atoms; Alkenyl having 2 to 12 carbon atoms; Or aryl having from 6 to 12 carbon atoms;

R ₂ to R ₄ are each independently Hydrogen; halogen; Alkyl having 1 to 12 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; Two or more adjacent R < ₃ > to R < ₈ > adjacent to each other may be connected to each other to form a ring,

R < ₅ > is 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; Or arylalkyl having 7 to 13 carbon atoms,

R < ₇ > is hydrogen; halogen; Alkyl having 1 to 12 carbon atoms; Or cycloalkyl having 3 to 12 carbon atoms.

Further, the ligand compound of Formula 4 according to another embodiment of the present invention may be a transition metal compound represented by Formula 6 below.

[Chemical Formula 6]

In Formula 3,

Wherein R ₁ may be a C 1 -C 6 alkyl;

R ₂ and R ₃ may be hydrogen, alkyl having 1 to 6 carbon atoms, aryl having 6 to 12 carbon atoms, or alkenyl having 2 to 6 carbon atoms, and R ₂ and R ₃ may be connected to each other to form a ring,

R < ₄ > is hydrogen; Or an alkyl having 1 to 8 carbon atoms,

R < ₅ > is hydrogen; Alkyl having 1 to 6 carbon atoms; Or aryl having from 6 to 12 carbon atoms.

Further, in an example of the present invention,

R < ₁ > is methyl; ethyl; Or < / RTI &

R ₂ and R ₃ are independently selected from the group consisting of hydrogen; Or may be connected to each other to form a ring of 5 or 6 carbon atoms,

R ₄ may be alkyl having 4 to 6 carbon atoms,

The R < ₅ > may be phenyl.

The compound of formula (4) may be any of compounds represented by the following formulas (4-1) to (4-8).

[Formula 4-1]

[Formula 4-2]

[Formula 4-3]

[Formula 4-4]

[Formula 4-5]

[Formula 4-6]

[Formula 4-7]

[Formula 4-8]

The transition metal compounds represented by the above formulas (1) to (3) and the ligand compounds represented by formulas (4) to (6) can be specifically used to prepare catalysts for the polymerization of olefin monomers, but the present invention is not limited thereto. It is applicable.

The ligand compound represented by the formula (4) 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 ₆ are as defined in Formula 1 or Formula 4.

The compound of formula (A) is added to the vial and dissolved in a solvent such as THF, and then the organolithium compound is added dropwise at a temperature ranging from -80 ° C to 0 ° C. The organolithium compound may be reacted at a molar ratio of 1: 1 to 1: 1: 1.2 with respect to the compound of formula (A), specifically at a molar ratio of 1: 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.

After the addition of the organolithium compound, the reaction may be carried out at room temperature for 1 hour to 48 hours, particularly for 6 hours to 12 hours.

Next, the compound of formula (B) is added to an organic solvent such as THF in a temperature range of 80 ° C to 0 ° C and the mixture is reacted at room temperature for 1 hour to 24 hours, specifically for 2 hours to 8 hours, Can be obtained.

The compound represented by the formula (B) in the above Reaction Scheme 1 can be prepared according to the following reaction scheme 2. For example, a solution prepared by dissolving R ₇ NH ₂ in R ₅ R ₆ QCl ₂ in a solvent such as methylene chloride is added, To 48 hours, more specifically, for 6 hours to 12 hours.

[Reaction Scheme 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 4 as a ligand.

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 (4) as shown in the following reaction formula (3).

[Reaction Scheme 3]

In the above Reaction Scheme 3, R ₁ to R ₇ , Q, M, X ₁ and X ₂ are as defined in Formula 1 or Formula 4, X may be X ₁ or X ₂ , and Y is halogen.

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 4 as a ligand.

Specifically, as shown in Reaction Scheme 3, the compound represented by Formula 4 is reacted with an organic lithium compound, a Grignard reagent represented by Formula C, and a metal precursor represented by Formula D to obtain a compound represented by Formula 4 As a ligand, a transition metal compound of the formula (1) in which a Group 4 transition metal is coordinated to the transition metal compound can be obtained.

Wherein X is selected from the group consisting of hydrogen, silyl, alkyl of 1 to 20 carbon atoms, silyl substituted alkyl of 1 to 20 carbon atoms, alkenyl of 2 to 20 carbon atoms, aryl of 6 to 20 carbon atoms, alkyl of 6 to 20 carbon atoms Aryl, 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.

When X ₁ and X ₂ are halogen in the compound of Formula 1, the compound represented by Formula 4 is reacted with an organic lithium compound and a compound represented by Formula D, which is a metal precursor, A transition metal compound of the formula (1) wherein a Group 4 transition metal is coordinated to the ligand can be obtained. In this case, X ₁ , X _2, or both of them may be further substituted with X in the halogen by reacting with a Grignard reagent represented by the above formula (C).

The compound represented by Formula 4 and the compound represented by Formula D may be mixed in a molar ratio of 1: 0.9 to 1: 1.1, specifically 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 (4).

According to the preparation method according to an embodiment of the present invention, the reaction can be carried out at a temperature ranging from -80 ° C to 25 ° 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 (7) to (9) as a cocatalyst.

(7)

- [Al (R ₈ ) -O] _a -

Wherein each R < ₈ > 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 8]

D (R ₈ ) ₃

Wherein D is aluminum or boron; Lt; ₈ > are each independently as defined above;

[Chemical Formula 9]

^{[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 (7) or (8) to obtain a mixture; And adding the compound represented by the formula (9) to the mixture.

Secondly, the present invention provides a method for preparing a catalyst composition by contacting the transition metal compound represented by the formula (1) and the compound represented by the formula (9).

In the first method of the catalyst composition manufacturing method, the molar ratio of the compound represented by the formula (7) or (8) 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 the formula (9) to the transition metal compound represented by the formula (1) may be 1: 1 to 1:25, and may be 1: 1 to 1:10, To 1: 5.

When the molar ratio of the compound represented by the formula (7) or (8) 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 activation of the alkylated metal compound is not completely achieved due to the side reaction between the remaining excess alkylating agent and the activating agent of the above formula (9). When the ratio of the compound represented by the general formula (9) to the compound represented by the general formula (9) 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. If there is a problem and the ratio exceeds 1:25, the activation of the metal compound is completely performed, but 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 formula (9) to the transition metal compound represented by the formula (1) may be from 1: 1 to 1: 500, and more preferably from 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 general formula (7) 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 general formula (8) 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 9 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 tetra (P-tolyl) aluminum, triethylammonium tetra (o, p-dimethylphenyl) aluminum, tributylammonium tetra ( p-trifluoromethylphenyl) aluminum, trimethylammonium tetra (p-trifluoromethylphenyl) aluminum, tributylammonium tetrapentafluorophenylaluminum, N, N-diethylaniliniumtetraphenylaluminum, N, Anilinium tetraphenyl aluminum, N, N-diethylanilinium tetrapentafluorophenyl aluminum, diethyl ammonium tetrapentatetraprapaluminum, triphenylphosphonium tetraphenyl aluminum, trimethylphosphonium tetraphenyl aluminum, triethylammonium tetra Phenyl aluminum, tributylammonium tetraphenyl aluminum, trimethylammonium tetraphenylboron, tripropylammonium tetra (O, p-dimethylphenyl) boron, trimethylammonium tetra (p-tolyl) boron, tripropylammonium tetra (p- tolyl) boron, triethylammonium tetra , Tributylammonium tetra (p-trifluoromethylphenyl) boron, trimethylammoniumtetra (p-trifluoromethylphenyl) boron, tributylammonium tetrapentafluorophenylboron, N, N-diethylaniliniumtetraphenylboron, N, N-diethylanilinium tetraphenylboron, N, N-diethylanilinium tetrapentafluorophenylboron, diethylammonium tetrapentafluorophenylboron, triphenylphosphonium tetraphenylboron, triphenylcarbonium Tetra (p-trifluoromethylphenyl) 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 (7) to (9) can 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 and has an extremely low density of less than 0.9 g / cc 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 measured again by melting the top of the DSC curve (melt temperature).

According to one embodiment of the present invention, the polymer produced by the production process of the present invention may exhibit one, two or three peaks at a melting temperature (Tm).

According to one embodiment of the present invention, the polymer produced by the production method of the present invention may have a Tm of 125 DEG C or less.

According to one embodiment of the present invention, the polymer produced by the process of the present invention has a first melting temperature (Tm1) located in the range of 5 DEG C to 45 DEG C and a second melting temperature (Tm2).

According to one embodiment of the present invention, the polymer produced by the production process of the present invention has a first melting temperature (Tm1) and a second melting temperature (Tm2) respectively ranging from 5 ° C to 45 ° C and a second melting temperature Lt; RTI ID = 0.0 > (Tm3) < / RTI >

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 15 or more.

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 15 to 100.

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 50 to 100.

According to one embodiment of the present invention, the polymer produced by the production process of the present invention may exhibit one, two or three peaks of crystallization temperature (Tc).

According to one embodiment of the present invention, the polymer produced by the production method of the present invention may have a Tc of 80 ° C or less.

According to one embodiment of the present invention, the polymer produced by the process of the present invention has a first crystallization temperature (Tc1) located in the range of 5 占 폚 to 40 占 폚 and a second crystallization temperature (Tc2).

According to one embodiment of the present invention, the polymer produced by the production method of the present invention has a first crystallization temperature (Tc1) and a second crystallization temperature (Tc2) respectively ranging from 5 ° C to 40 ° C and a second crystallization temperature And a third crystallization temperature (Tc3) located in the range of < RTI ID = 0.0 >

When the transition metal compound of the present invention is used, it is possible to produce a low molecular weight polymer having a melt index of 15 or more, and the polymer can be usefully used for hot melt adhesives (HMA) requiring a low 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. CGC (Me ₂ Si (Me ₄ C ₅ ) NtBu] TiMel ₂ (hereinafter abbreviated as CGC) of Comparative Example 1 was synthesized according to US Patent No. 6,015,916.

≪ Preparation of ligand compound >

Example  1: N- tert Butyl-1- (4- (4- ( tert -Butyl) phenyl) -2- methyl -1H- Inden -1-yl) -1-methyl-1-phenylsilanamine

[Formula 4-1]

Preparation of N-tert-butyl-1-chloro-1-methyl-1-phenylsilanamine [

7.75 mL (73.1 mmol) of tert-butylamine was dissolved in 120 mL of methylene chloride (MC) and added to a solution of dichloro (methyl) (phenyl) silane 6 mL (36.9 mmol). After stirring at room temperature overnight, methylene chloride was removed and the mixture was filtered with hexane to obtain 7 g (99%) of a clear liquid.

¹ H-NMR (C ₆ D ₆ , 500 MHz): 7.78 (2H, m), 7.17 (3H, m), 1.06 (9H, s), 1.05 (3H, s).

Preparation of N-tert-butyl-1- (4- (4- (tert-butyl) phenyl) -2-methyl-1H-inden-

1.77 g (6.8 mmol) of 4- (4- (tert-butyl) phenyl) -2-methyl-1H-indene and 35 mL of THF were added to a 100 mL Schlenk flask. 4.3 mL (6.8 mmol, 1.6 M in hexane) was added dropwise at -30 ° C, and then the mixture was stirred at room temperature overnight. 1.5 g (6.8 mmol) of N-tert-butyl-1-chloro-1-methyl-1-phenylsilane amine dissolved in THF was slowly added dropwise to the resulting Li- The mixture was stirred at room temperature overnight. After stirring, it was vacuum dried, then extracted with 100 mL of hexane, vacuum dried again, and washed with hexane to obtain 1.6 g (80%, dr = 1: 1.4).

¹ H-NMR (C ₆ D ₆ , 500 MHz): 7.60-7.05 (m, 12H), 6.8 (s, 1H), 3.40 (s, , 0.98 (s, 9H), 0.23 (s, 3H).

Example 2

[Formula 4-2]

N- tert Butyl-1- (4- (4- ( tert -Butyl) phenyl) -2-isopropyl-1H- Inden -1-yl) -1- methyl -1-phenylsilanamine < / RTI >

1.20 g (4.1 mmol) of 4- (4- (tert-butyl) phenyl) -2-isopropyl-1H-indene and 20 mL of THF were placed in a 100 mL Schlenk flask. 2.6 mL M in hexane) was added dropwise at -30 ° C, and the mixture was stirred at room temperature overnight. To the resulting Li-complex solution, 0.93 g (4.1 mmol) of N-tert-butyl-1-chloro-1-methyl-1-phenylsilane amine dissolved in THF was slowly added dropwise at -30 캜 The mixture was stirred at room temperature overnight. After stirring, it was vacuum dried, then extracted with 100 mL of hexane, vacuum dried again, and washed with hexane to obtain 1.3 g (63%, dr = 1: 1.3).

_{^{1 H-NMR (C 6 D}} 6, 500 MHz): 7.95 - 7.20 (m, 12H), 6.86 (m, 1H), 3.70 (m, 1H), 3.29 (s, 1H), 2.86 (m, 6H) , 1.27 (s, 9H), 1.08 (s, 9H), 0.3 (s, 3H).

Example 3

[Formula 4-3]

N- tert -Butyl-1- methyl -1- (2- methyl -4-phenyl-1H- Inden -1-yl) -1- Phenylsilane  Produce

3.69 g (17.9 mmol) of 2-methyl-4-phenyl-1H-indene and 90 mL of THF were added to a 100 mL Schlenk flask and 11.5 mL (18.4 mmol, 1.6 M in hexane) of n-BuLi was added dropwise , And the mixture was stirred at room temperature overnight. The Li-complex THF solution obtained after stirring was substituted with hexane. 4.08 g (17.9 mmol) of N-tert-butyl-l-chloro-l-methyl-l-phenylsilaneamine was dissolved in hexane and slowly added dropwise to the Li-complex solution at -30 ° C. The mixture was stirred at room temperature overnight. After stirring, it was vacuum dried, then extracted with 100 mL of hexane, vacuum dried again, and washed with hexane to obtain 7.1 g (99%, dr = 1: 1.3: 1.7).

_{^{1 H-NMR (C 6 D}} 6, 500 MHz): 7.59 - 7.20 (m, 12H), 6.84 (m, 1H), 3.92 (m, 1H), 2.00 (s, 3H), 0.97 (s, 9H) , 0.21 (s, 3H).

≪ Preparation of transition metal compound &

Example 1a

[Formula 1-1]

To a 100 mL Schlenk flask was added N-tert-butyl-1- (4- (4- (tert-butyl) phenyl) -2-methyl-1H-inden- -Phenylsilanamine (1.23 g, 2.7 mmol) and toluene (10 mL) were added and stirred. 2.2 mL (5.5 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 2.1 mL of MeMgBr (6.2 mmol, 3.0 M in diethyl ether) was slowly added dropwise at -40 ° C, and then 2.7 mL (2.7 mmol, 1.0 M in toluene) of TiCl _{4 was} added in this order and reacted overnight at room temperature. The reaction mixture was then filtered through Celite using hexane. After drying the solvent, 1.00 g (70%, dr = 1: 1.4) of a brown solid was obtained.

¹ H-NMR (C ₆ DC ₆ , 500 MHz): 7.77-7.21 (m, 12H), 6.78 (m, , 1.01 (s, 3H), 0.97 (s, 3H), 0.14 (s, 3H).

Example 2a

[Formula 1-2]

To a 100 mL Schlenk flask was added N-tert-butyl-1- (4- (4- (tert- butyl) phenyl) -2-isopropyl-lH-inden- 1.24 g (2.6 mmol) of 1-phenylsilane amine and 10 mL of toluene were placed and stirred. 2.1 mL (5.3 mmol, 2.5 M in THF) of n-BuLi was added at -40 deg. C, and the mixture was reacted at room temperature overnight. After that, 1.97 mL (6.0 mmol, 3.0 M in diethyl ether) of MeMgBr was slowly added dropwise at -40 ° C, and then 2.6 mL (2.6 mmol, 1.0 M in toluene) of TiCl _{4 was} added in this order and reacted overnight at room temperature. The reaction mixture was then filtered through Celite using hexane. After drying the solvent, 0.85 g (61%, dr = 1: 1.3) of a brown solid was obtained.

_{^{1 H-NMR (C 6 DC}} 6, 500 MHz): 7.78 - 7.18 (m, 12H), 6.78 (m, 1H), 1.55 (s, 9H), 1.24 (s, 9H), 1.07 - 0.20 (s, 16H).

Example 3a

[Formula 1-3]

To a 100 mL Schlenk flask was added 3.33 g (8.4 mmol) of N-tert-butyl-1-methyl-1- (2-methyl- ) And 40 mL of toluene were placed and stirred. 10.5 mL (16.8 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, 6.4 mL (19.3 mmol, 3.0 M in diethyl ether) of MeMgBr was slowly added dropwise at -40 ° C, and then 8.4 mL (8.54 mmol, 1.0 M in toluene) of TiCl _{4 was} added in this order and reacted overnight at room temperature. The reaction mixture was then filtered through Celite using hexane. After drying the solvent, 2.46 g (62%, dr = 1: 1.5) of a brown solid was obtained.

_{^{1 H-NMR (C 6 DC}} 6, 500 MHz): 7.77 - 7.75 (m, 2H), 7.65 - 7.63 (m, 2H), 7.28 - 7.24 (m, 5H), 7.22 - 7.19 (m, 4H), 3H), 1.09 (s, 3H), 0.96 (s, 3H), 0.09 (s, 3H).

Comparative Example 1

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

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.

A 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 mixture was reacted at room temperature overnight. 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): 2.17 (s, 6H), 1.92 (s, 6H), 1.57 (s, 9H), 0.48 (s, 6H), 0.17

Production Example of Polymer

Experimental Examples 1 to 3 and Comparative Experimental Example 1

A hexane solvent (0.95 L) and 1-octene (0.25 mL) were added to a 2 L autoclave reactor, and the temperature of the reactor was preheated to 150 ° C. At the same time, the pressure of the reactor was pre-filled with ethylene (35 bar). (Catalyst) of the following Table 1, which was treated with dimethylanilinium tetrakis (pentafluorophenyl) borate (AB) cocatalyst (3 equivalents) and triisobutylaluminum (Tibal) compound High-pressure argon pressure was applied to 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

≪ 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).

≪ Melting temperature of polymer &

The crystallization temperature (Tc) of the polymer and the melting temperature (Tm) of the polymer can be obtained by using a differential scanning calorimeter (DSC) 6000 manufactured by PerkinElmer. Specifically, , The temperature was increased to 200 ° C, held for 5 minutes, cooled to 30 ° C, and then the temperature was increased and the DSC curve was observed. At this time, the heating rate and the cooling rate were set at 10 ° C / min. In the measured DSC curve, the crystallization temperature was the maximum point of the exothermic peak during cooling and the melting temperature was determined as the maximum point of the endothermic peak at the second temperature rise.

≪ 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. Cat. (Compound)
(input) Polymerization temperature (캜) Cocat density
(g / cc) Melt Index
(MI)
(g / 10 min) Experimental Example
One Formula 1a
(3 μmol) 150 AB 0.862 66 Experimental Example
2 Formula 2a
(3 μmol) 150 AB 0.863 76 Experimental Example
3 Formula 3a
(3 μmol) 150 AB 0.868 79 Comparative Experimental Example
One Formula 11a
(1.5 μmol) 150 AB 0.900 13.8

AB: Dimethylanilinium tetrakis (pentafluorophenyl) borate promoter catalyst

Referring to Table 1, in the case of Experimental Examples 1 to 3 using the transition metal compounds of Examples 1 to 3 as catalysts, compared with Comparative Experimental Example 1 using the transition metal compound of Comparative Example 1 as a catalyst, the melt index Olefin polymer having a high molecular weight and a low molecular weight could be obtained.

Claims (14)

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

In Formula 1,
R ₁ to R ₆ are each independently hydrogen; halogen; Silyl; Alkyl having 1 to 20 carbon atoms; Silyl substituted C 1 -C 20 alkyl; Cycloalkyl having 3 to 20 carbon atoms; Alkenyl having 2 to 20 carbon atoms; Alkoxy having 1 to 20 carbon atoms; Halogen, C 1 -C 12 alkyl, C 3 -C 12 cycloalkyl, C 1 -C 8 alkoxy, C 6 -C 12 aryl, or C 6 -C 20 aryl which is unsubstituted or substituted with aryl having from 6 to 12 carbon atoms; An arylalkyl having 7 to 20 carbon atoms, which is unsubstituted or substituted with halogen, alkyl having 1 to 12 carbon atoms, cycloalkyl having 3 to 12 carbon atoms, alkoxy having 1 to 8 carbon atoms, aryl having 6 to 12 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 two of R ₂ to R ₄ may be connected to each other to form a ring,
R ₇ 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,
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; Silyl; halogen; Alkyl having 1 to 20 carbon atoms; Silyl substituted C 1 -C 20 alkyl; 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 ₁ is hydrogen; halogen; Alkyl having 1 to 20 carbon atoms; Alkoxy having 1 to 20 carbon atoms; Cycloalkyl having 3 to 20 carbon atoms; Alkenyl having 2 to 20 carbon atoms; Or an aryl of 6 to 20 carbon atoms, which is unsubstituted or substituted by halogen, alkyl of 1 to 8 carbon atoms, cycloalkyl of 3 to 8 carbon atoms, alkoxy of 1 to 8 carbon atoms, aryl of 6 to 12 carbon atoms;
R ₂ to R ₄ 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; Halogen, C 1-8 alkyl, C 3-8 cycloalkyl, C 1-8 alkoxy, aryl having 6-12 carbon atoms, aryl having 6-20 carbons which is unsubstituted or substituted with aryl having 6-12 carbons; Halogen, an alkyl of 1 to 8 carbon atoms, a cycloalkyl of 3 to 8 carbon atoms, an alkoxy of 1 to 8 carbon atoms, an arylalkyl of 7 to 20 carbon atoms, which is unsubstituted or substituted with aryl of 6 to 12 carbon atoms; Two or more adjacent two of R ₂ to R ₄ may be connected to each other to form a ring,
R ₅ and R ₆ 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; Halogen, C 1-8 alkyl, C 3-8 cycloalkyl, C 1-8 alkoxy, aryl having 6-12 carbon atoms, aryl having 6-20 carbons which is unsubstituted or substituted with aryl having 6-12 carbons; Or an arylalkyl group having 7 to 20 carbon atoms, which is substituted or unsubstituted with halogen, alkyl having 1 to 8 carbon atoms, cycloalkyl having 3 to 8 carbon atoms, alkoxy having 1 to 8 carbon atoms, aryl having 6 to 12 carbon atoms,
R ₇ is hydrogen; halogen; Alkyl having 1 to 20 carbon atoms; Cycloalkyl having 3 to 20 carbon atoms; Or an alkenyl having 2 to 20 carbon atoms,
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; Or an alkenyl group having 2 to 20 carbon atoms.
The method according to claim 1,
Wherein the transition metal compound is represented by the following formula (2).
(2)

In Formula 2,
R ₁ is hydrogen; halogen; Alkyl having 1 to 12 carbon atoms; Alkoxy having 1 to 12 carbon atoms; Cycloalkyl having 3 to 12 carbon atoms; Alkenyl having 2 to 12 carbon atoms; Or aryl having from 6 to 12 carbon atoms;
R ₂ to R ₄ are each independently Hydrogen; halogen; Alkyl having 1 to 12 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; Two or more adjacent two of R ₂ to R ₄ may be connected to each other to form a ring,
R ₅ is 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; Or an arylalkyl group having 7 to 13 carbon atoms,
Wherein R ₆ is hydrogen; halogen; Alkyl having 1 to 12 carbon atoms; Or cycloalkyl having 3 to 12 carbon atoms,
R &lt; ₇ &gt; is hydrogen; halogen; Alkyl having 1 to 12 carbon atoms; Or cycloalkyl having 3 to 12 carbon atoms,
X ₁ and X ₂ are each independently hydrogen; halogen; Alkyl having 1 to 12 carbon atoms; Cycloalkyl having 3 to 12 carbon atoms; Or an alkenyl group having 2 to 12 carbon atoms.
The method according to claim 1,
Wherein the transition metal compound is represented by the following formula (3).
(3)

In Formula 3,
Wherein R ₁ is an alkyl having 1 to 6 carbon atoms;
Wherein R ₂ and R ₃ are hydrogen, alkyl having 1 to 6 carbon atoms, aryl having 6 to 12 carbon atoms, or alkenyl having 2 to 6 carbon atoms, R ₂ and R ₃ may be connected to each other to form a ring,
R &lt; ₄ &gt; is hydrogen; Or alkyl having 1 to 8 carbon atoms,
R &lt; ₅ &gt; is hydrogen; Alkyl having 1 to 6 carbon atoms; Or an aryl having from 6 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]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

[Chemical Formula 1-6]

[Chemical Formula 1-7]

[Chemical Formula 1-8]

A ligand compound represented by the following formula (4):
[Chemical Formula 4]

In Formula 4,
R ₁ to R ₆ are each independently hydrogen; halogen; Silyl; Alkyl having 1 to 20 carbon atoms; Silyl substituted C 1 -C 20 alkyl; Cycloalkyl having 3 to 20 carbon atoms; Alkenyl having 2 to 20 carbon atoms; Alkoxy having 1 to 20 carbon atoms; Halogen, C 1 -C 12 alkyl, C 3 -C 12 cycloalkyl, C 1 -C 8 alkoxy, C 6 -C 12 aryl, or C 6 -C 20 aryl which is unsubstituted or substituted with aryl having from 6 to 12 carbon atoms; An arylalkyl having 7 to 20 carbon atoms, which is unsubstituted or substituted with halogen, alkyl having 1 to 12 carbon atoms, cycloalkyl having 3 to 12 carbon atoms, alkoxy having 1 to 8 carbon atoms, aryl having 6 to 12 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 two of R ₂ to R ₄ may be connected to each other to form a ring,
R ₇ 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,
Q is Si, C, N, P or S.
The method according to claim 6,
Wherein the ligand compound is represented by the following formula (5).
[Chemical Formula 5]

In Formula 5,
R ₁ is hydrogen; halogen; Alkyl having 1 to 12 carbon atoms; Alkoxy having 1 to 12 carbon atoms; Cycloalkyl having 3 to 12 carbon atoms; Alkenyl having 2 to 12 carbon atoms; Or aryl having from 6 to 12 carbon atoms;
R ₂ to R ₄ are each independently Hydrogen; halogen; Alkyl having 1 to 12 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; 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,
R ₅ is 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; Or an arylalkyl group having 7 to 13 carbon atoms,
R ₇ is hydrogen; halogen; Alkyl having 1 to 12 carbon atoms; Or cycloalkyl having 3 to 12 carbon atoms.
The method according to claim 6,
The ligand compound represented by the formula (4) is represented by any one of the following formulas:
[Formula 4-1]

[Formula 4-2]

[Formula 4-3]

[Formula 4-4]

[Formula 4-5]

[Formula 4-6]

[Formula 4-7]

[Formula 4-8]

A catalyst composition comprising the transition metal compound according to claim 1, wherein the catalyst composition is a polyethylene polymerization catalyst.
10. The method of claim 9,
&Lt; / RTI &gt; further comprising at least one cocatalyst.
11. The method of claim 10,
Wherein the cocatalyst comprises at least one compound selected from the following formulas (7) to (9).
(7)
- [Al (R ₈ ) -O] _a -
Wherein each R &lt; ₈ &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 8]
D (R ₈ ) ₃
Wherein D is aluminum or boron; Lt; ₈ &gt; are each independently as defined above;
[Chemical Formula 9]
^{[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.
11. The method of claim 10,
Wherein the catalyst composition further comprises a reaction solvent.
A process for preparing a homopolymer or copolymer of a polyolefin using the catalyst composition according to claim 9.
14. The method of claim 13,
Wherein the polymer has a melt index (MI) of from 15 to 100 and a density of less than 0.89 g / cc.