KR20170095033A - Novel transition metal compound - Google Patents

Abstract

The present invention relates to a novel transition metal compound represented by chemical formula 1. The novel transition metal compound according to the present invention can be usefully used as a catalyst of a polymerization reaction when olefin-based polymers having high crystallinity, densities, and molecular weights are manufactured. A method for manufacturing the transition metal compound comprises: (1) a step of preparing a compound represented by chemical formula 3 by reacting a compound represented by the following formula 2 and peroxides; and (2) a step of preparing a compound represented by formula 1 by reacting a compound represented by the following chemical formula 3 with a compound represented by the following chemical formula 4, MQ_1Q_2Q_3.

Description

NOVEL TRANSITION METAL COMPOUND [0002]

The present invention relates to novel transition metal compounds.

Metallocene catalysts for olefin polymerization have been developed for a long time. The metallocene compound is generally activated by using aluminoxane, borane, borate or other activator. For example, a metallocene compound having a ligand containing a cyclopentadienyl group and two sigma chloride ligands uses aluminoxane as an activator. When the chloride group of such a metallocene compound is substituted with another ligand (for example, benzyl or trimethylsilylmethyl group (-CH ₂ SiMe ₃ )), there has been reported an example in which the catalytic activity is increased.

Dow has disclosed in the early 1990's [Me ₂ Si (Me ₄ C ₅ ) NtBu] TiCl ₂ (Constrained-Geometry Catalyst, CGC) in U.S. Patent No. 5,064,802 and the like. In the copolymerization reaction of ethylene and alpha-olefin, Compared to the known metallocene catalysts, the superior aspects can be summarized broadly as follows:

(1) High molecular weight polymers are produced with high activity even at high polymerization temperatures,

(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 is to synthesize and incorporate a variety of metal compounds into which various bridges and nitrogen substituents have been introduced instead of silicon bridges. Representative metal compounds that have been known up to now include phosphorus, ethylene or propylene, methylidene and methylene bridges instead of CGC-structured silicon bridges. However, when applied to ethylene polymerization or copolymerization of ethylene and alpha olefins, But did not show excellent results in terms of activity or copolymerization performance.

In another approach, a compound composed of an oxydol ligand instead of the amido ligand of the CGC was synthesized, and some polymerization using this compound was attempted.

In addition, a variety of asymmetric non-crosslinked metallocenes have been developed. For example, metallocenes composed of (cyclopentadienyl) (indenyl) and (cyclopentadienyl) (fluorenyl) metallocene, (substituted indenyl) (cyclopentadienyl) have.

However, from the viewpoint of commercial application, the above-mentioned catalyst compositions of non-crosslinked metallocenes do not sufficiently exhibit the polymerization activity of olefins, and it is difficult to polymerize high molecular weight polyolefins.

U.S. Patent No. 5,064,802

A problem to be solved by the present invention is to provide a novel method for producing a transition metal compound.

In order to solve the above problems,

There is provided a transition metal compound represented by the following formula (1).

 [Chemical Formula 1]

Wherein Q ₁ to Q ₃ are each independently selected from the group consisting of hydrogen, halogen, alkyl of 1 to 20 carbon atoms, alkenyl of 2 to 20 carbon atoms, aryl of 6 to 20 carbon atoms, alkylaryl of 6 to 20 carbon atoms, Arylalkyl having 1 to 20 carbon atoms, alkylamido having 1 to 20 carbon atoms, arylamido having 6 to 20 carbon atoms, or alkylidene having 1 to 20 carbon atoms; M is Ti, Zr or Hf;

R ₁ to R ₆ each independently represent hydrogen, silyl, alkyl having 1 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 hydrocarbyl having from 1 to 20 carbon atoms; Two or more of R ₄ to R ₆ 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 20 carbon atoms, or aryl having 6 to 20 carbon atoms; n is 1 or 2;

The transition metal compound according to the present invention can be usefully used as a catalyst for the polymerization reaction in the production of olefinic polymers having high crystallinity, high density and high molecular weight.

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 according to the present invention is represented by the following general formula (1).

[Chemical Formula 1]

Wherein Q ₁ to Q ₃ are each independently selected from the group consisting of hydrogen, halogen, alkyl of 1 to 20 carbon atoms, alkenyl of 2 to 20 carbon atoms, aryl of 6 to 20 carbon atoms, alkylaryl of 6 to 20 carbon atoms, Arylalkyl having 1 to 20 carbon atoms, alkylamido having 1 to 20 carbon atoms, arylamido having 6 to 20 carbon atoms, or alkylidene having 1 to 20 carbon atoms; M is Ti, Zr or Hf;

R ₁ to R ₆ each independently represent hydrogen, silyl, alkyl having 1 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 hydrocarbyl having from 1 to 20 carbon atoms; Two or more of R ₄ to R ₆ 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 20 carbon atoms, or aryl having 6 to 20 carbon atoms; n is 1 or 2;

In Formula 1, Q ₁ to Q ₃ each independently represent hydrogen, alkyl having 1 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, alkylaryl having 6 to 20 carbon atoms, or arylalkyl having 7 to 20 carbon atoms have.

In Formula 1, R ₁ to R ₆ are each independently hydrogen, alkyl having 1 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 Have; Two or more of R ₄ to R ₆ 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 of 1 to 20 carbon atoms, or aryl of 6 to 20 carbon atoms.

The compound of formula (1) of the present invention may be specifically any one of the following compounds.

[Formula 1a]

[Chemical Formula 1b]

Wherein Bn represents benzyl.

Each of the substituents defined in the present specification will be described in detail as follows.

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

The term " alkyl ", as used herein, unless otherwise indicated, means a linear or branched hydrocarbon residue.

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

Wherein the branched chain is selected from the group consisting of alkyl of 1 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; Or arylalkyl having 7 to 20 carbon atoms.

According to one embodiment of the present invention, the silyl group is selected from the group consisting of trimethylsilyl, triethylsilyl, tripropylsilyl, tributylsilyl, trihexylsilyl, triisopropylsilyl, triisobutylsilyl, triethoxysilyl, Silyl) silyl, and the like, but are not limited to these examples.

According to an embodiment of the present invention, the aryl group preferably has 6 to 20 carbon atoms, and specifically includes phenyl, naphthyl, anthracenyl, pyridyl, dimethylanilinyl, anisolyl, and the like.

The alkylaryl group means an aryl group substituted by the alkyl group.

The arylalkyl group means an alkyl group substituted by the aryl group.

The ring (or heterocyclic group) means a monovalent aliphatic or aromatic hydrocarbon group having 5 to 20 carbon atoms and containing at least one hetero atom, and may be a single ring or a condensed ring of two or more rings. The heterocyclic group may be substituted or unsubstituted with an alkyl group. Examples thereof include indoline, tetrahydroquinoline and the like, but the present invention is not limited thereto.

The alkylamino group means an amino group substituted by the alkyl group, and includes, but is not limited to, dimethylamino group, diethylamino group, and the like.

According to an embodiment of the present invention, the aryl group preferably has 6 to 20 carbon atoms, and specifically includes phenyl, naphthyl, anthracenyl, pyridyl, dimethylanilinyl, anisolyl and the like, no.

The transition metal compound of the present invention can be prepared by the following production method. Specifically, the transition metal compound of the present invention comprises: (1) reacting a compound of the following formula (2) with a peroxide to prepare a compound of the formula (3); And (2) reacting a compound of the following formula (3) with a compound of the following formula (4) to prepare a compound of the formula (1).

[Chemical Formula 1]

(2)

(3)

[Chemical Formula 4]

In the above formulas, Q ₁ to Q ₃ , R ₁ to R ₆ , M and n are as defined in Formula 1, respectively.

(1) reacting a compound of formula (II) with a peroxide to prepare a compound of formula (III)

[Reaction Scheme 1]

In step (1), the compound of formula (2) is reacted with a peroxide to produce a compound of formula (3).

In the above step (1), the compound of Formula 2 and the peroxide may be reacted at a molar ratio of 1: 5 to 1:20, and specifically at a molar ratio of 1: 5 to 1:15.

The reaction of step (1) may be carried out in an organic solvent such as tetrahydrofuran, or by adding the peroxide to the compound of formula (2) in an organic solvent.

The peroxide may be at least one selected from the group consisting of hydrogen peroxide, t-butyl hydroperoxide, benzoyl peroxide, cumyl hydroperoxide, propionyl peroxide, lauryl peroxide, and acetyl peroxide, .

The reaction of step (1) may be carried out by adding the peroxide to the compound of formula (2) in a temperature range of 0 ° C to 30 ° C, then raising the temperature to 0 ° C to 140 ° C and then allowing the reaction to proceed for 1 to 48 hours Specifically, the peroxide is added to the compound of Formula 2 at a temperature ranging from 20 ° C to 30 ° C, the temperature is raised to 20 ° C to 30 ° C, and the reaction is performed for 1 to 48 hours ≪ / RTI >

At this time, the compound of formula (2) may be prepared through the reaction represented by the following reaction formula (2).

[Reaction Scheme 2]

Wherein R ₆ to R ₉ and n are the same as defined in the above formula (2).

The compound of formula (2-1) is placed in an organic solvent such as hexane and n-BuLi is added in the temperature range of -80 ° C to 0 ° C. At this time, the n-BuLi may be reacted at a molar ratio of 1: 1 to 1: 2 with respect to the compound of the formula (2-1), and specifically at a molar ratio of 1: 1.1 to 1: 1.2. After the addition of n-BuLi, the reaction was carried out at room temperature for 1 to 48 hours, followed by filtration. The solvent was then added to the obtained compound, and CO ₂ was bubbled at -160 캜 to -20 캜, -2 can be obtained. T-BuLi is added to the obtained compound of formula (2-2) and the reaction is carried out at a temperature ranging from -80 ° C to 0 ° C to obtain the compound of formula (2-3). The compound of formula (2-3) may be added to the compound of formula (2-3) at a temperature of -150 ° C to -20 ° C, followed by gradually raising the temperature to room temperature to obtain the compound of formula (2). In this case, distilled water (H ₂ O) is added, the organic layer is separated with an organic solvent such as diethylether, and then the water is dried using Na ₂ SO ₄ or the like.

(2) reacting a compound of formula (3) with a compound of formula (4) to produce a compound of formula

[Reaction Scheme 2]

In step (2), the compound of formula (2) is reacted with the compound of formula (4) to produce the compound of formula (1).

In step (2), the compound of formula (3) and the compound of formula (4) may be reacted at a molar ratio of 1: 0.8 to 1: 1.8, specifically 1: 1 to 1: 1.2 .

The reaction of the step (2) can be carried out by adding the compound of the formula (4) to the compound of the formula (3) in a temperature range of -20 ° C to 60 ° C and then allowing the reaction to proceed for 1 to 48 hours. Adding the compound of formula (4) to the compound of formula (3) in a temperature range of 0 ° C to 30 ° C, and allowing the compound of formula (4) to react for 4 to 12 hours.

The compound of formula (1) prepared through steps (1) and (2) may be further subjected to a recrystallization step (3), and thus, a method of producing a transition metal compound according to an example of the present invention may include , (3) recrystallizing the compound of formula (1).

The recrystallization may be carried out using an organic solvent such as an ether, such as a reaction solvent, and purified through recrystallization to obtain a pure compound of the formula (1).

The transition metal compound represented by the formula (1) according to the present invention is activated by reacting with a further promoter to produce a polyolefin having high crystallinity, high density and high molecular weight even at a high polymerization temperature when it is applied to olefin polymerization It is possible.

Particularly, it is possible to produce a polymer having a narrow MWD as compared to the CGC, excellent copolymerization, and a high molecular weight even in a low-density region by using the catalyst composition comprising the transition metal compound.

More specifically, the transition metal compound according to the present invention may be used alone or in the form of a composition further comprising at least one of the promoter compounds represented by the following general formulas (5), (6) and (7) Can be used as a catalyst.

≪ Formula 5 >

- [Al (R ₇ ) -O] _m -

In Formula 5,

R ₇ may be the same or different from each other, and each independently halogen; Hydrocarbons having 1 to 20 carbon atoms; Or a hydrocarbon having 1 to 20 carbon atoms substituted with halogen;

m is an integer of 2 or more;

(6)

J (R ₇ ) ₃

In Formula 6,

R ₇ is as defined in Formula 5 above;

J is aluminum or boron;

≪ Formula 7 >

[EH] ⁺ [ZA ₄ ] ^- or [E] ⁺ [ZA ₄ ] ^-

In Formula 7,

E is a neutral or cationic Lewis base;

H is a hydrogen atom;

Z is a Group 13 element;

A may be the same as or different from each other, and independently at least one hydrogen atom is an aryl group having 6 to 20 carbon atoms or an alkyl group having 1 to 20 carbon atoms substituted or unsubstituted with halogen, hydrocarbon having 1 to 20 carbon atoms, alkoxy or phenoxy .

Examples of the compound represented by the general formula (5) include methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, and butylaluminoxane. A more preferred compound is methylaluminoxane.

Examples of the compound represented by Formula 6 include trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, dimethylchloroaluminum, triisopropylaluminum, tri-s-butylaluminum, tricyclopentylaluminum , Tripentyl aluminum, triisopentyl aluminum, trihexyl aluminum, trioctyl aluminum, ethyl dimethyl aluminum, methyldiethyl aluminum, triphenyl aluminum, tri-p-tolyl aluminum, dimethyl aluminum methoxide, dimethyl aluminum ethoxide, Boron, triethylboron, triisobutylboron, tripropylboron, tributylboron and the like, and more preferred compounds are selected from trimethylaluminum, triethylaluminum and triisobutylaluminum.

Examples of the compound represented by Formula 7 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 tetrapentafluorophenylboron, diethylammonium tetrapentafluorophenylboron, triphenylphosphonium tetraphenylboron, trimethylphosphonium tetraphenylboron, dimethyl Anilinium tetrakis (pentafluorophenyl) borate, triethylammonium tetraphenyl aluminum, tributylammonium tetraphenyl aluminum, Trimethylammonium tetra (p-tolyl) aluminum, tripropylammonium tetra (p-tolyl) aluminum, triethylammonium tetra (o, p-dimethylphenyl) aluminum, tributyl (P-trifluoromethylphenyl) aluminum, trimethylammonium tetra (ptrifluoromethylphenyl) aluminum, tributylammonium tetrapentafluorophenylaluminum, N, N-diethylaniliniumtetraphenylaluminum, N, N - diethyl anilinium tetrapentafluorophenyl aluminum, diethyl ammonium tetrapentatetraprapaluminum aluminum, triphenylphosphonium tetraphenyl aluminum, trimethylphosphonium tetraphenyl aluminum, tripropylammonium tetra (p-tolyl) boron, triethyl Ammonium tetra (o, p-dimethylphenyl) boron, triphenylcarbonium tetra (p-trifluoromethylphenyl) boron or triphenylcarbamoyl Tetra-pentafluoropropane, and the like phenylboronic.

Specifically, aluminoxane can be used, and more specifically, methylaluminoxane (MAO), which is an alkylaluminoxane, can be used.

The catalyst composition comprises, as a first method, 1) contacting a transition metal compound represented by Formula 1 with a compound represented by Formula 5 or 6 to obtain a mixture; And 2) adding the compound represented by Formula 7 to the mixture.

The catalyst composition may be prepared by a method of contacting the transition metal compound represented by Formula 1 and the compound represented by Formula 5 as a second method.

In the first method of the catalyst composition, the molar ratio of the transition metal compound represented by Formula 1 to the compound represented by Formula 5 or Formula 6 is preferably 1 / 5,000 to 1/2, Preferably 1 / 1,000 to 1/10, and most preferably 1/500 to 1/20. When the molar ratio of the transition metal compound represented by the formula (1) / the compound represented by the formula (5) or the formula (6) exceeds 1/2, the amount of the alkylating agent is so small that the alkylation of the metal compound can not proceed completely If the molar ratio is less than 1 / 5,000, alkylation of the metal compound is carried out, but there is a problem that the alkylated metal compound can not be completely activated due to the side reaction between the excess of the alkylating agent and the activating agent . The molar ratio of the transition metal compound represented by Formula 1 to the compound represented by Formula 7 is preferably 1/25 to 1, more preferably 1/10 to 1, and most preferably 1/5 Lt; / RTI > When the molar ratio of the transition metal compound represented by the formula (1) / the compound represented by the formula (7) is more than 1, the activation of the metal compound is not completely achieved due to the relatively small amount of the activator, If the molar ratio is less than 1/25, the activation of the metal compound is completely performed. However, there is a problem that the unit cost of the catalyst composition is not economical due to the excess activator remaining or the purity of the produced polymer is low.

In the second method of the catalyst composition, the molar ratio of the transition metal compound represented by Formula 1 to the compound represented by Formula 5 is preferably 1 / 10,000 to 1/10, more preferably 1 / 5,000 to 1/100, and most preferably 1/3000 to 1/500. When the molar ratio is more than 1/10, the amount of the activator is relatively small and the activation of the metal compound is not achieved completely. Therefore, there is a problem in that the activity of the catalyst composition is decreased. Although the activation is completely performed, there is a problem that the unit cost of the catalyst composition is not economical due to the excess activator remaining or the purity of the produced polymer is low.

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

In addition, the catalyst composition may contain the transition metal compound and the cocatalyst compound in the form of being carried on a carrier.

Specifically, the polymerization reaction for polymerizing olefinic monomers in the presence of the catalyst composition comprising the transition metal compound can be carried out by a solution polymerization process, a continuous polymerization process, a continuous slurry polymerization reactor, a loop slurry reactor, a gas phase reactor or a solution reactor, Slurry process or gas phase process. Further, homopolymerization with one olefin monomer or copolymerization with two or more kinds of monomers can be carried out.

The polymerization of the polyolefin may be carried out by reacting at a temperature of from about 25 ° C to about 500 ° C and from about 1 to about 100 kgf / cm ² .

In particular, the polymerization of the polyolefin may be carried out at a temperature of from about 25 to about 500 캜, preferably from about 25 to 200 캜, more preferably from about 50 to 100 캜. The reaction pressure can also be carried out at from about 1 to about 100 kgf / cm ² , preferably from about 1 to about 50 kgf / cm ² , and more preferably from about 5 to about 40 kgf / cm ² .

Examples of the polymerizable olefin-based monomer using the transition metal compound and the cocatalyst according to an embodiment of the present invention include ethylene, alpha-olefin, cyclic olefin, etc., and diene olefins having two or more double bonds Based monomers or triene olefin-based monomers can also be polymerized.

Specific examples of the olefin-based monomer in the polyolefin produced according to an exemplary embodiment of the present invention include ethylene, propylene, 1-butene, 1-pentene, 4-methyl- Octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-aidocene and the like.

The polyolefin may be a propylene polymer, but is not limited thereto.

The polymer may be either a homopolymer or a copolymer. When the olefin polymer is a copolymer of ethylene and other comonomers, the monomers constituting the copolymer are preferably selected from the group consisting of ethylene and propylene, 1-butene, 1-hexene, and 4-methyl- Is at least one comonomer selected from the group consisting of < RTI ID = 0.0 >

Hereinafter, preferred embodiments of the present invention will be described to facilitate understanding of the present invention. The following examples are intended to illustrate the invention and are not intended to limit the scope of the invention.

Synthesis of ligands and transition metal compounds

Organic reagents and solvents were purchased from Aldrich and Merck 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. Spectra and schematics were obtained using 500 MHz nuclear magnetic resonance (NMR) to verify the structure of the compounds.

< Examples >

Example 1

Synthesis of 8- (dicyclohexylphosphanyl) -2-methyl-1,2,3,4-tetrahydroquinoline

2-methyltetrahydroquinoline (6.12 g, 41.6 mmol) and hexane (0.536 M, 77.5 mL) were placed in a 250 mL Schlenk flask. N-BuLi (1.1 eq, 18.3 mL) was added at -20 &lt; 0 &gt; C and allowed to stand at room temperature overnight. Filtered through glass frit (G4) and vacuum dried to obtain phosphine-amide lithium. Phosphine-amide lithium (1.83 g, 11.9 mmol) was added to diethyl ether (0.423 M, 28.2 mL) and bubbled with CO ₂ at -78 ° C for 1 hour. THF (1.1 eq, 1.07 mL) and t-BuLi (1.1 eq, 8.4 mL) were added at -20 ° C and kept for 2 hours. Chlorodicyclohexylphosphine (0.85 eq, 2.36 g) and diethyl ether (0.359 M, 28.2 mL) were added at the same temperature and maintained at the same temperature for 1 hour. After slowly reacting at room temperature overnight, 50 mL of distilled water was added at 0 ° C, and the mixture was stirred at room temperature for 30 minutes. Work-up with diethyl ether and drying of the water with MgSO ₄ followed by the addition of 1.86 g of a pale yellow solid in 45.3% yield via a hexane and diethyl ether 50: 1 column.

^{1 H-NMR (C6D6):} 7.18 (d, 1H), 6.97 (d, 1H), 6.75 (t, 1H), 5.70 (d, 1H), 3.16 (m, 1H), 2.65 (m, 1H), 6H), 1.28 (m, 6H), 0.98 (d, 3H), 1.55 (m,

Example 2

Synthesis of 8- (diisopropylphosphanyl) -2-methyl-1,2,3,4-tetrahydroquinoline

2-methyl THQ (7.0 mL, 48.5 mmol) and hexane (0.536 M, 90.5 mL) were placed in a 250 mL Schlenk flask. N-BuLi (1.1 eq, 21.3 mL) was added at -20 &lt; 0 &gt; C and allowed to stand at room temperature overnight. Filtered through glass frit (G4) and vacuum dried to obtain phosphine-amide lithium. Phosphine-amide lithium (3.0 g, 19.6 mmol) and diethyl ether (0.423 M, 46.3 mL) were added and bubbled CO ₂ at -78 ° C for 1 hour. THF (1.1 eq, 1.75 mL) and t-BuLi (1.1 eq, 12.7 mL) were added at -20 ° C and kept at this temperature for 2 hours. Chlorodiisopropylphosphine (0.85 eq, 2.54 g) and diethyl ether (0.359 M, 46.3 mL) were added at the same temperature and maintained at the same temperature for 1 hour. After slowly reacting at room temperature overnight, 50 mL of distilled water was added at 0 ° C., and the mixture was stirred at room temperature for 30 minutes. After work-up with diethylether and drying the water with MgSO ₄ , 3.1 g of a yellow solid were obtained in 60% yield via a 50: 1 hexane and diethyl ether column.

^{1 H-NMR (C6D6):} 7.07 (d, 1H), 6.94 (d, 1H), 6.70 (t, 1H), 5.60 (d, 1H), 3.12 (m, 1H), 2.63 (m, 1H), 3H), 1.12 (d, 3H), 1.00 (m, 9H), 1.50 (m,

Example 3

Dicyclohexyl (2- methyl -1,2,3,4- Tetrahydroquinoline -8-yl) Phosphine oxide  synthesis

8- (dicyclohexylphosphanyl) -2-methyl-1,2,3,4-tetrahydroquinoline (0.70 g, 2.04 mmol) and THF (10.0 mL) were placed in a 100 mL Schlenk flask. 30 drops of H ₂ O ₂ (28%) were added at room temperature, and the mixture was allowed to stand at room temperature overnight. The reaction was followed by vacuum drying to obtain the ligand in a quantitative yield.

^{1 H-NMR (C6D6):} 8.08 (s, 1H), 6.90 (d, 1H), 6.64 (t, 1H), 6.47 (t, 1H), 3.26 (m, 1H), 2.55 (m, 2H), 2H), 1.63 (m, 2H), 1.63 (m, 2H), 2.20 (d,

Example 4

Diisopropyl (2- methyl -1,2,3,4- Tetrahydroquinoline -8-yl) Phosphine oxide  synthesis

8- (diisopropylphosphanyl) -2-methyl-1,2,3,4-tetrahydroquinoline (0.95 g, 3.60 mmol) and THF (10.0 mL) were placed in a 100 mL Schlenk flask. 30 drops of H ₂ O ₂ (28%) were added at room temperature, and the mixture was allowed to stand at room temperature overnight. The reaction was followed by vacuum drying to obtain the ligand in a quantitative yield.

^{1 H-NMR (C6D6):} 8.93 (s, 1H), 6.90 (d, 1H), 6.53 (t, 1H), 6.44 (m, 1H), 3.19 (m, 1H), 2.53 (m, 2H), 2H), 1.47 (m, 1H), 1.27 (m, 1H), 1.14 (m, 9H), 0.98

Example 5

8-( Dicyclohexylphosphoryl )-2- methyl -3,4- Dihydroquinoline -1 (2H) -yl) Tribenzyl  Synthesis of zirconium

(0.51 g, 1.42 mmol), Zr (CH ₂ Ph) ₄ (1.0 (2-methyl-1,2,3,4-tetrahydroquinolin-8-yl) phosphine oxide) was added to a 100 mL Schlenk flask. eq, 0.646 g) and toluene (0.154 M, 9.3 mL), and the reaction was allowed to proceed overnight at 25 ° C. After the reaction, the toluene was removed and extracted with pentane (15 mL * 3) to obtain 197 mg of a chocolate-colored solid.

¹ H-NMR (C6D6): difficult to assign peaks due to broad peaks

Example 6

(8-( Diisopropylphosphoryl )-2- methyl -3,4- Dihydroquinoline -1 (2H) -yl) Tribenzyl  Synthesis of zirconium

(2-methyl-1,2,3,4-tetrahydroquinolin-8-yl) phosphine oxide (0.66 g, 2.36 mmol), Zr (CH ₂ Ph) ₄ eq, 1.07 g) and toluene (0.154 M, 15.3 mL), and the reaction was allowed to proceed overnight at 25 ° C. After the reaction, the toluene was removed and extracted with pentane (15 mL * 3) to obtain 226 mg of an ocher-colored solid.

¹ H-NMR (C6D6): difficult to assign peaks due to broad peaks

Example 7

&Lt; Preparation of ethylene-octene copolymer >

A hexane solvent (1.0 L), octene (280 mL) and ethylene (35 bar) were added to a 2 L autoclave reactor, pressure was adjusted to 500 psi under high pressure argon pressure and the reactor temperature was preheated to 120 ° C. 10 eq. Of a 5 x 10 ^-6 M dimethylanilinium tetrakis (pentafluorophenyl) borate co-catalyst was added to the reactor under a high-pressure argon pressure, and the transition metal compound of Example 5 treated with triisobutyl aluminum compound 1 × 10 ^-6 M, 2.0 mL) was placed in a catalyst storage tank, and a high-pressure argon pressure was applied to the reactor. The polymerization reaction was carried out for 10 minutes. The reaction heat was removed through a cooling coil inside the reactor to keep the polymerization temperature at a maximum. After the polymerization reaction was carried out for 10 minutes, the remaining gas was taken out, the polymer solution was discharged to the lower part of the reactor, and excessive ethanol was added to cool the solution to induce precipitation. The obtained polymer was washed with ethanol and acetone two to three times, respectively, and dried in a vacuum oven at 90 캜 for 12 hours or more to prepare an ethylene-octene copolymer.

Example 8

&Lt; Preparation of ethylene-octene copolymer >

The procedure of Example 7 was repeated except that the transition metal compound of Example 6, which was treated with triisobutyl aluminum compound, was used instead of the transition metal compound of Example 5, which was treated with triisobutyl aluminum compound in Example 7, Ethylene-octene copolymer was prepared in the same manner as in Example 1.

Claims (8)

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

Wherein Q ₁ to Q ₃ are each independently selected from the group consisting of hydrogen, halogen, alkyl of 1 to 20 carbon atoms, alkenyl of 2 to 20 carbon atoms, aryl of 6 to 20 carbon atoms, alkylaryl of 6 to 20 carbon atoms, Arylalkyl having 1 to 20 carbon atoms, alkylamido having 1 to 20 carbon atoms, arylamido having 6 to 20 carbon atoms, or alkylidene having 1 to 20 carbon atoms; M is Ti, Zr or Hf;
R ₁ to R ₆ each independently represent hydrogen, silyl, alkyl having 1 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 hydrocarbyl having from 1 to 20 carbon atoms; Two or more of R ₄ to R ₆ 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 20 carbon atoms, or aryl having 6 to 20 carbon atoms; n is 1 or 2;
The method according to claim 1,
Wherein Q ₁ to Q ₃ are each independently selected from the group consisting of hydrogen, alkyl having 1 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, alkylaryl having 6 to 20 carbon atoms, or arylalkyl having 7 to 20 carbon atoms. compound.
The method according to claim 1,
Wherein R ₁ to R ₆ are each independently hydrogen, alkyl having 1 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 of R ₄ to R ₆ 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; Wherein said aliphatic ring or said aromatic ring may be substituted with halogen, alkyl of 1 to 20 carbon atoms, or aryl of 6 to 20 carbon atoms.
The method according to claim 1,
Wherein the compound of Formula 1 is any one of the following compounds:
[Formula 1a]

[Chemical Formula 1b]

A catalyst composition comprising the transition metal compound according to claim 1.
A supported catalyst in which the catalyst composition according to claim 5 is supported on a carrier.
A polymer produced using the catalyst composition according to claim 5.
8. The method of claim 7,
Wherein the polymer is a polyolefin-based polymer.