KR20080097019A - New fourth group transition metal compounds having hetero atom - Google Patents

Abstract

A 4 group transition metal oxide including a hetero atom is provided to coordinate a cyclopenta die enyl ligand and to manufacture a catalyst composition of which reactivity is high. A transition metal oxide is indicated by a chemical formula 1. In the chemical formula 1: X1 and X2 are halogen radical, alkyl radical, aryl radical, alkylaryl radical, arylalkyl radical of carbon number 1-20, alkylidene radical of a carbon number 1-20; M is a periodic table 4 group transition metal; Cp1 and Cp2 are cyclopentadienyl, indenyl group, fluorenyl group; CY1 is an aliphatic or an aromatic ring.; Y1 is a hetero atom of a periodic table 15 group or 16 group; R2 is alkyl radical of a carbon number 1 - 20, aryl radical, alkylaryl radical or arylalkyl radical; and R1, and R1' and R1" are hydrogen, halogen radical, alkyl radical, aryl radical, alkoxy radical, aryloxyradical of a carbon number 1 - 20.

Description

New Group 4 transition metal compound containing hetero atoms {NEW FOURTH GROUP TRANSITION METAL COMPOUNDS HAVING HETERO ATOM}

The present invention relates to a novel transition metal compound coordinated with a cyclopentadienyl ligand comprising a hetero atom and a method for preparing the same.

Many examples have been reported of metallocene compounds including nitrogen, phosphorus, oxygen, sulfur, and the like, which are heteroatoms of group 15 or 16 of the periodic table.

In general, the metallocene compound containing such a hetero atom can be roughly divided into two groups.

The first group is a metallocene compound having a ligand structure in which a heterocyclopentadienyl group or a ring containing a hetero atom is fused with a cyclopentadienyl group or a derivative thereof.

WO 95/04087 describes heterocyclopentadienyl metallocene compounds comprising a Group 15 hetero atom of the periodic table. In addition, examples of azaferrocene compounds having a cyclopentadienyl group containing a nitrogen atom have been reported (A. P. Sadomenko et al. Cood. Chem. Rev., 1993, 126, 237).

Many examples are also known of metallocene compounds having a ligand structure in the form of a cyclopentadienyl or derivative thereof in which a heterocycle is fused. Compounds of this structure include both biscyclopentadienyl forms, which are traditional metallocene compounds, and ansa-type metallocene compounds that link cyclopentadienyl groups (WO 98/22486, WO 01 /). 48039, US 6,451,938, WO 03/04551, Gregory C. Fu et al. J. Org.Chem., 1996, 61, 7230.

The second group is a metallocene compound of a structure in which a functional group such as dialkylamine is connected with a cyclopentadienyl group as an additional chain (P. Jutzi et al. J. Organomet. Chem., 1995, 486, 287., P. Jutzi et al. Organometallics, 1996, 4153., P. Jutzi et al. J. Organomet. Chem., 1997, 538, 163., P. Jutzi et al. Eur. J. Inorg.Chem., 1998, 663).

WO 2004/005305 describes the synthesis of titanium (lV) metallocene compounds in which alkylamine functional groups in the form of rings, such as piperidine, are introduced.

The present invention seeks to provide a novel transition metal compound coordinated with a cyclopentadienyl ligand comprising a hetero atom.

In addition, the present invention is to provide a method for producing the transition metal compound.

The present invention provides a novel transition metal compound represented by the following formula (1) to achieve the above object.

In Chemical Formula 1,

X 1 and X 2 are the same as or different from each other, and each independently a halogen radical, an alkyl radical having 1 to 20 carbon atoms, an aryl radical, an alkylaryl radical, an arylalkyl radical, an alkyl amino radical, an aryl amino radical, or an alkyl having 1 to 20 carbon atoms. A leaden radical;

M is a periodic table Group 4 transition metal;

Cp1 and Cp2 are the same as or different from each other, and each independently a cyclopentadienyl group; Indenyl group; Fluorenyl group; Or a cyclopentadienyl derivative substituted with one or more substituents of hydrocarbyl, alkyl, aryl, silyl, halogen, and halohydrocarbyl, coordinated to central metal M in the form of eta-5 (η-5), two The above substituents may be linked to each other to form an aliphatic or aromatic ring;

CY1 is an aliphatic or aromatic ring;

Y 1 is a hetero atom of group 15 or 16 of the periodic table;

R 2 is an alkyl radical having 1 to 20 carbon atoms, an aryl radical, an alkylaryl radical or an arylalkyl radical, and R 2 is absent when Y 1 is a hetero atom of Group 16 of the periodic table;

R1, R1 'and R1 "are the same as or different from each other, and are each independently hydrogen, a halogen radical, an alkyl radical having 1 to 20 carbon atoms, an aryl radical, an alkoxy radical, an aryloxy radical, or an amino radical, and R1, R1' and At least two of R 1 ″ may be linked to each other to form an aliphatic or aromatic ring.

The present invention also provides a novel transition metal compound represented by the following formula (2).

In Chemical Formula 2,

X 1 and X 2 are the same as or different from each other, and each independently a halogen radical, an alkyl radical having 1 to 20 carbon atoms, an aryl radical, an alkylaryl radical, an arylalkyl radical, an alkyl amino radical, an aryl amino radical, or an alkyl having 1 to 20 carbon atoms. A leaden radical;

M is a periodic table Group 4 transition metal;

Cp1 and Cp2 are the same as or different from each other, and each independently a cyclopentadienyl group; Indenyl group; Fluorenyl group; Or a cyclopentadienyl derivative substituted with one or more substituents of hydrocarbyl, alkyl, aryl, silyl, halogen, and halohydrocarbyl, coordinated to central metal M in the form of eta-5 (η-5), two The above substituents may be linked to each other to form an aliphatic or aromatic ring;

CY1 and CY2 are the same as or different from each other, and each independently an aliphatic or aromatic ring;

Y1 and Y2 are the same as or different from each other, and each independently a hetero atom of group 15 or 16 of the periodic table;

R2 and R4 are the same as or different from each other, and each independently an alkyl radical, aryl radical, alkylaryl radical or arylalkyl radical having 1 to 20 carbon atoms, and R2 or R4 is present when Y1 or Y2 is a hetero atom of group 16 of the periodic table. Not;

R1, R1 ', R1 ", R3, R3' and R3" are the same as or different from each other, and each independently hydrogen, a halogen radical, an alkyl radical having 1 to 20 carbon atoms, an aryl radical, an alkoxy radical, an aryloxy radical, or amino It is a radical and at least two of R1, R1 ', and R1 ", or at least two of R3, R3', and R3" may be linked to each other to form an aliphatic or aromatic ring.

In addition, the present invention provides an organic compound represented by the following formula (3).

In Chemical Formula 3,

R1, R1 ', R1 ", R2, CY1, and Y1 are the same as the definition in Formula 1 above;

R5, R6, R7, and R8 are the same as or different from each other, and each independently a hydrogen atom; Alkyl radicals having 1 to 20 carbon atoms; Alkenyl radicals having 2 to 20 carbon atoms; Silyl radicals; Alkylaryl radicals; Or an arylalkyl radical; The R5 to R8 may be connected to each other by an alkylidine radical including an alkyl or aryl radical having 1 to 20 carbon atoms to form a ring.

Hereinafter, each substituent of the above formula will be described in detail.

In Chemical Formulas 1, 2, and 3, a halogen radical means a fluorine group, a chlorine group, a bromine group, or an iodine group.

In Formula 1, Formula 2, and Formula 3, the alkyl radical having 1 to 20 carbon atoms includes a linear or branched alkyl radical.

In Formula 1, Formula 2, and Formula 3, the aryl radical is preferably 1 to 20 carbon atoms, specifically, phenyl, naphthyl, anthracenyl, pyridyl, dimethylanilinyl, anisolyl, and the like. It is not limited.

In Formula 1, Formula 2, and Formula 3, an alkylaryl radical means an aryl radical substituted by the alkyl radical.

In Formula 1, Formula 2, and Formula 3, an arylalkyl radical means an alkyl radical substituted by the aryl radical.

In Formula 1 and Formula 2, an alkyl amino radical means an amino radical substituted by the alkyl radical, and there are dimethylamino group, diethylamino group, and the like, but is not limited thereto.

In Formula 1 and Formula 2, the aryl amino radical means an amino radical substituted by the aryl radical, and specifically, there are diphenylamino groups and the like, but is not limited thereto.

In Formula 1, Formula 2, and Formula 3, the silyl radical is trimethylsilyl, triethylsilyl, tripropylsilyl, tributylsilyl, trihexylsilyl, triisopropylsilyl, triisobutylsilyl, triethoxysilyl, tri Phenylsilyl, tris (trimethylsilyl) silyl, and the like, but are not limited thereto.

In Chemical Formulas 1, 2, and 3, Group 15 elements include N, P, and the like, but are not limited thereto.

In Chemical Formula 1, Chemical Formula 2, and Chemical Formula 3, Group 16 elements include O and S, but are not limited thereto.

In Formula 1 and Formula 2, Group 4 transition metals include Ti, Zr, Hf, and the like.

The transition metal compound of Formula 1 or Formula 2 of the present invention is a transition metal compound characterized in that a cyclopentadienyl ligand comprising a hetero atom is coordinated.

The transition metal compound represented by Chemical Formula 1 or Chemical Formula 2 according to the present invention, and a method of preparing the organic compound represented by Chemical Formula 3 are described in detail in the following examples.

In addition, the present invention provides a catalyst composition comprising the transition metal compound of Formula 1 or Formula 2.

The catalyst composition may include at least one cocatalyst compound of the compounds represented by the following Chemical Formulas 4 to 6 in addition to the compound of Chemical Formula 1.

In Chemical Formula 4,

R9 may be the same or different from each other, and each independently represent a halogen group, a hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group having 1 to 20 carbon atoms substituted with halogen, and n is an integer of 2 or more.

In Chemical Formula 5,

R9 is as defined in Formula 4,

D is aluminum or boron.

In Chemical Formula 6,

L is a neutral or cationic Lewis acid,

H is a hydrogen atom,

Z is a group 13 element,

A may be the same or different from each other, and each independently one or more hydrogen atoms are substituted with a halogen group, a hydrocarbon group having 1 to 20 carbon atoms, alkoxy or phenoxy, or an aryl having 6 to 20 carbon atoms or an alkyl having 1 to 20 carbon atoms. to be.

Examples of the compound represented by the formula (4) include methyl aluminoxane, ethyl aluminoxane, isobutyl aluminoxane, butyl aluminoxane and the like, and more preferred compound is methyl aluminoxane.

Examples of the compound represented by Formula 5 include trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, tripropyl aluminum, tributyl aluminum, dimethylchloro aluminum, triisopropyl aluminum, tri-s-butyl aluminum, 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 ethoxide, Trimethylboron, 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 6 include triethylammonium tetraphenylboron, tributylammonium tetraphenylboron, trimethylammonium tetraphenylboron, tripropylammonium tetraphenylboron, trimethylammonium tetra (p-tolyl) Boron, trimethylammonium tetra (o, p-dimethylphenyl) boron, tributylammonium tetra (p-tripololomethylphenyl) boron, trimethylammonium tetra (p-trifluoromethylphenyl) boron, tributylammonium tetra Pentafluorophenylboron, N, N-diethylamidiumdium tetraphenylboron, N, N-diethylanilidedium tetraphenylboron, N, N-diethylanilinium tetrapentafluorophenylboron, diethyl Ammonium tetrapentafluorophenyl boron, triphenyl phosphonium tetraphenyl boron, trimethyl phosphonium tetraphenyl boron, triethyl ammonium tetraphenyl aluminum, tributyl ammonium tetraphenyl aluminum, Limethyl ammonium tetraphenyl aluminum, tripropyl ammonium tetraphenyl aluminum, trimethyl ammonium tetra (p-tolyl) aluminum, tripropyl ammonium tetra (p-tolyl) aluminum, triethylammonium tetra (o, p-dimethyl Phenyl) aluminum, tributylammonium tetra (p-trifluoromethylphenyl) aluminum, trimethylammonium tetra (p-trifluoromethylphenyl) aluminum, tributylammonium tetrapentafluorophenylaluminum, N, N-diethyl Anilineum tetraphenylaluminum, N, N-diethylanilinium tetraphenylaluminum, N, N-diethylanilinium tetrapentafluorophenylaluminum, diethylammonium tetrapentatentraphenylaluminum, triphenylforce Phosphorus tetraphenyl aluminum, trimethyl phosphonium tetraphenyl aluminum, triethyl ammonium tetraphenyl aluminum, tributyl ammonium tetraphenyl aluminum, trimethyl ammonium Umtetraphenylboron, tripropylammonium tetraphenylboron, trimethylammonium tetra (p-tolyl) boron, tripropylammonium tetra (p-tolyl) boron, triethylammonium tetra (o, p-dimethylphenyl) boron , Trimethyl ammonium tetra (o, p-dimethylphenyl) boron, tributyl ammonium tetra (p-trifluoromethylphenyl) boron, trimethyl ammonium tetra (p-trifluoromethylphenyl) boron, tributyl ammonium tetrapenta Florophenylboron, N, N-diethylanilinium tetraphenylboron, N, N-diethylanilinium tetraphenylboron, N, N-diethylanilinium tetrapentafluorophenylboron, diethylammonium Um tetrapentafluorophenyl boron, a triphenyl phosphonium tetraphenyl boron, a triphenyl carbonium tetra (p-tripulomethyl phenyl) boron, a triphenyl carbonium tetra pentafluoro phenyl boron, etc. are mentioned.

The catalyst composition comprises the steps of: 1) contacting the Group 4 transition metal compound of Formula 1 with the compound represented by Formula 4 or Formula 5 to obtain a mixture; And 2) it may be prepared by a method comprising the step of adding a compound represented by the formula (6) to the mixture. In addition, the catalyst composition may be prepared by a method of bringing the Group 4 transition metal compound of Formula 1 into contact with the compound represented by Formula 4.

Hydrocarbon solvents such as pentane, hexane, heptane, or the like, or aromatic solvents such as benzene, toluene, or the like may be used as a reaction solvent in preparing the catalyst composition including the Group 4 transition metal compounds of Formula 1 and Formula 2. In addition, the transition metal compound and the cocatalyst may be used in a form supported on silica or alumina.

The present invention will be described in more detail with reference to the following examples. However, the following examples are only for illustrating the present invention and do not limit the scope of the present invention by only these.

< Example >

< Ligand  And synthesis of transition metal compounds>

Organic reagents and solvents were purchased from Aldrich and Merck and purified using standard methods. At all stages of the synthesis, the contact between air and moisture was blocked to increase the reproducibility of the experiment. Spectra were obtained using a 400 MHz nuclear magnetic resonator (NMR) to demonstrate the structure of the compound.

Scheme 1

< Example  1>

< Example  1-1> lithium Carbamate ( Lithium carbamate ) (2)

1,2,3,4-tetrahydroquinoline (13.08 g, 98.24 mmol) and diethyl ether (150 mL) were placed in a flask. The flask was immersed in a -78 ^° C. low temperature bath made of dry ice and acetone, stirred for 30 minutes, and then normal butyllithium (39.3 mL, 2.5 M hexane solution, 98.24 mmol) was introduced into a syringe under a nitrogen atmosphere. A light yellow slurry formed. After stirring for 2 hours, it was raised to room temperature while removing the butane gas formed. The flask was again immersed in a -78 ^o C low temperature bath to lower the temperature and CO ₂ gas was added. As the carbon dioxide gas was added, the slurry disappeared and became a transparent solution. After the flask and connected to a bubbler to remove the carbon dioxide gas to raise the temperature to ambient temperature the vacuum walk extra CO ₂ The gas and solvent were removed. The flask was transferred to a dry box, pentane was added thereto, stirred and filtered to obtain a white solid compound. The compound is a compound in which diethyl ether is coordinated. At this time, the yield was 100%.

¹ H NMR (C ₆ D ₆ , C ₅ D ₅ N): δ 8.35 (d, J = 8.4 Hz, 1H, CH), δ 6.93-6.81 (m, 2H, CH), δ 6.64 (t, J = 7.4 Hz, 1 H, CH), δ 3.87 (br, s, 2H, quin-CH ₂ ), δ 3.25 (q, J = 7.2 Hz, 4H, ether), δ 2.34 (br s, 2H, quin-CH ₂ ), δ 1.50 (br s, 2H, quin-CH ₂ ), δ 1.90 (t, J = 7.2 Hz, 6H, ether) ppm.

< Example  1-2> 8- (2,3,4,5- Tetramethyl -1,3- Cyclopentadienyl ) -1,2,3,4- Tetrahydroquinoline (8- (2,3,4,5- Tetramethyl -1,3- cyclopentadienyl ) -1,2,3,4- tetrahydroquinoline )

A lithium carbamate (2) compound (8.47 g, 42.60 mmol) was placed in the flask. Tetrahydrofuran (4.6 g, 63.9 mmol) and 45 mL of diethyl ether were added sequentially. The flask was immersed in a -20 ^o C low temperature bath made of acetone and a small amount of dry ice, stirred for 30 minutes, and then tert- BuLi (25.1 mL, 1.7 M, 42.60 mmol) was added thereto. At this time, it turned red. Stir for 6 hours while maintaining -20 ^o C. CeCl ₃ · 2LiCl solution (129 mL, 0.33 M, 42.60 mmol) dissolved in tetrahydrofuran and tetramethylcyclopentinone (5.89 g, 42.60 mmol) were mixed in a syringe and then introduced into a flask under a nitrogen atmosphere. After slowly raising the temperature to room temperature, the thermostat was removed after 1 hour to raise the temperature to room temperature. After addition of water (15 mL), ethyl acetate was added and filtered to obtain a filtrate. The filtrate was transferred to a separatory funnel, and hydrochloric acid (2N, 80 mL) was added thereto, followed by shaking for 12 minutes. After neutralizing with saturated aqueous sodium hydrogen carbonate solution (160 mL), the organic layer was extracted. Anhydrous magnesium sulfate was added to this organic layer to remove water and filtered, and the filtrate was taken out and the solvent was removed. Column chromatography gave a yellow oil. Hexane: toluene (v / v, 10: 1), hexane: ethyl acetate (v / v, 10: 1), yield was 40%.

¹ H NMR (C ₆ D ₆ ): δ 1.00 (br d, 3H, Cp-CH ₃ ), 1.63-1.73 (m, 2H, quin-CH ₂ ), 1.80 (s, 3H, Cp-CH ₃ ), 1.81 (s, 3H, Cp-CH ₃ ), 1.85 (s, 3H, Cp-CH ₃ ), 2.64 (t, J = 6.0 Hz, 2H, quin-CH ₂ ), 2.84-2.90 (br, 2H, quin -CH ₂ ), 3.06 (br s, 1H, Cp-H), 3.76 (br s, 1H, NH), 6.77 (t, J = 7.2 Hz, 1H, quin-CH), 6.92 (d, J = 2.4 Hz, 1H, quin-CH), 6.94 (d, J = 2.4 Hz, 1H, quin-CH) ppm.

< Example  1-3> lithium 1- (1- methyl -2,3,4- Trihydroquinoline -8-yl) -2,3,4,5-tetramethylcyclopentadienide ( Lithium  1- (1- methyl -2,3,4- trihydroquinolin -8- yl ) -2,3,4,5- tetramethylcyclopentadienide )

8- (2,3,4,5-tetramethyl-1,3-cyclopentadienyl) -1,2,3,4-tetrahydroquinoline (2 g, 7.89 mmol) in methanol (42 mL) Into a formaldehyde 37% aqueous solution (0.88 mL, 11.8 mmol) was added and stirred at room temperature for 30 minutes. Dicaborane (decaborane, 0.29 g, 2.37 mmol) was added to the mixture, followed by further stirring at room temperature for 1 hour. The resulting compound was filtered through a silica pad using hexane and ethyl acetate (v: v = 10: 1) solvent. The compound obtained by removing the solvent of the filtered solution was transferred to a flask, pentane (50 mL) was added, and the temperature was lowered to -78 ^° C. Normal butyllithium (3.2 mL, 2.5 M hexane solution, 7.89 mmol) at −78 ^° C. was introduced by syringe under nitrogen atmosphere. After slowly warming to room temperature, the mixture was further stirred at room temperature for 3 hours. The reaction was filtered under nitrogen atmosphere, washed twice with pentane (10 mL) and dried under vacuum. A yellow salt of a lithium salt was obtained (0.837 g, 39%).

¹ H NMR (pyr-d5): δ 7.31 (br s, 1H, CH), δ 7.10-6.90 (m, 1H, CH), δ 6.96 (s, 1H, CH), δ 3.09 (m, 2H, quinoline -CH ₂ ), δ 2.77 (t, J = 6 Hz, 2H, quinoline-CH ₂ ), δ 2.51-2.11 (m, 15H, Cp-CH ₃ , N-CH ₃ ), δ 1.76 (m, 2H, quinoline -CH ₂ ) ppm.

< Example  1-4> Bis [1- (1- methyl -2,3,4- Trihydroquinoline -8-day) -2,3,4,5- Tetramethylcyclopentadienyl ] Titanium (IV) Dimethyl Compound

In a dry box, TiCl ₄ DME (429 mg, 1.53 mmol) and diethyl ether (25 mL) were added to a flask, and MeLi (1.9 mL, 1.6 M diethyl ether solution, 3.07 mmol) was slowly added thereto while stirring at -30 ° C. After stirring for 15 minutes, the lithium salt compound (838 mg, 3.06 mmol) obtained in Example 1-3 was placed in a flask. Stir for 3 hours while raising the temperature to room temperature. After the reaction was completed, vacuum was applied to remove the solvent, dissolved in pentane, filtered, and the filtrate was extracted. Vacuum to remove pentane and titanium compounds ( titanium complex).

¹ H NMR (C ₆ D ₆ ): δ 6.83 (d, J = 7.2 Hz, 2H, CH), δ 6.78 (d, J = 7.6 Hz, 2H, CH), δ 6.73 (t, J = 7.4 Hz, 2H, CH), δ 2.80 (m, 4H, quin-CH ₂ ), δ 2.52 (t, J = 6.4 Hz, 4H, quin-CH ₂ ), δ 2.26 (s, 6H, N-CH ₃ ), δ 1.96 (s, 12H, Cp-CH ₃ ), δ 1.85 (s, 12H, Cp-CH ₃ ), δ 1.50 (m, 4H, quin-CH ₂ ), δ 1.26 (s, 6H, Ti-CH ₃ ) ppm.

< Example  2>

< Example  2-1> 6- methyl -8- (2,3,4,5- Tetramethyl -1,3- Cyclopentadienyl ) -1,2,3,4-te Trahid Loquinoline

Lithium carbamate compound and 6-methyl-8- (2,3,4,5-tetramethyl-1 in the same manner as in Example 1 using 6-methyl-1,2,3,4-tetrahydroquinoline , 3-cyclopentadienyl) -1,2,3,4-tetrahydroquinoline was prepared. The yield was 34%.

¹ H NMR (CDCl ₃ ): δ 6.70 (s, 1H, CH), δ 6.54 (s, 1H, CH), δ 3.71 (br s, 1H, NH), δ 3.25-3.05 (m, 3H, Cp− CH, quinoline-CH ₂ ), δ 2.76 (t, J = 6.4 Hz, 2H, quinoline-CH ₂ ), δ 2.19 (s, 3H, CH ₃ ), δ 1.93-1.86 (m, 2H, quinoline-CH ₂ ), δ 1.88 (s, 3H, Cp-CH ₃ ), δ 1.84 (s, 3H, Cp-CH ₃ ), δ 1.74 (s, 3H, Cp-CH ₃ ), δ 0.94 (br d, J = 6.8 Hz, 3H, Cp-CH ₃ ) ppm.

< Example  2-2> lithium 1- (6, N-dimethyl-1,2,3,4- Tetrahydroquinoline -8-day) -2,3,4,5-te Tramethylcyclopentadi Enaid

6-methyl-8- (2,3,4,5-tetramethyl-1,3-cyclopentadienyl) -1,2,3,4-tetrahydroquinoline in the same manner as in Example 1 above Prepared.

¹ H NMR (pyr-d5): δ 7.05 (br s, 1H, CH), δ 6.73 (s, 1H, CH), δ 6.96 (s, 1H, CH), δ 3.08 (m, 2H, quinoline-CH ₂ ), δ 2.76 (t, J = 6.4 Hz, 2H, quinoline-CH ₂ ), δ 2.57-2.25 (m, 18H, Cp-CH ₃ , Ph-CH ₃ , N-CH ₃ ), δ 1.76 (m , 2H, quinoline-CH ₂ ) ppm.

< Example  2-3> bis [1- (6, N-dimethyl-1,2,3,4- Tetrahydroquinoline -8-day) -2,3,4,5-te Tramethylcyclophene Tadienyl] Titanium ( lV Dimethyl compound

Lithium salt compound prepared above (lithium 1- (N-methyll-1,2,3,4-tetrahydroquinolin-8-yl) -2,3,4,5-tetramethylcyclopentadienyl) It was prepared in the same manner as in Example 1 above.

¹ H NMR (C ₆ D ₆ ): δ 6.65 (m, 4H, CH), δ 2.83 (m, 4H, quin-CH ₂ ), δ 2.54 (t, J = 7.2Hz, 4H, quin-CH ₂ ) , δ 2.28 (s, 6H, N-CH ₃ ), δ 2.14 (s, 6H, Ph-CH ₃ ), δ 1.99 (s, 12H, Cp-CH ₃ ), δ 1.87 (s, 12H, Cp-CH ₃ ), δ 1.52 (m, 4H, quin-CH ₂ ), δ 1.28 (s, 6H, Ti-CH ₃ ) ppm.

The present invention is a novel transition metal compound coordinated with a cyclopentadienyl ligand comprising a hetero atom, and the transition metal compound according to the present invention can be provided for the preparation of a highly reactive catalyst composition.

Claims (5)

A transition metal compound represented by Formula 1 below: [Formula 1]

In Chemical Formula 1, X 1 and X 2 are the same as or different from each other, and are each independently a halogen radical, an alkyl radical having 1 to 20 carbon atoms, an aryl radical, an alkylaryl radical, an arylalkyl radical, an aryl amido radical, or an alkylidene radical having 1 to 20 carbon atoms. ; M is a periodic table Group 4 transition metal; Cp1 and Cp2 are the same as or different from each other, and each independently a cyclopentadienyl group; Indenyl group; Fluorenyl group; Or a cyclopentadienyl derivative substituted with one or more substituents of hydrocarbyl, alkyl, aryl, silyl, halogen, and halohydrocarbyl, coordinated to central metal M in the form of eta-5 (h-5), two The above substituents may be linked to each other to form an aliphatic or aromatic ring; CY1 is an aliphatic or aromatic ring; Y 1 is a hetero atom of group 15 or 16 of the periodic table; R 2 is an alkyl radical having 1 to 20 carbon atoms, an aryl radical, an alkylaryl radical or an arylalkyl radical, and R 2 is absent when Y 1 is a hetero atom of Group 16 of the periodic table; R1, R1 'and R1 "are the same as or different from each other, and are each independently hydrogen, a halogen radical, an alkyl radical having 1 to 20 carbon atoms, an aryl radical, an alkoxy radical, an aryloxy radical, or an amido radical, and R1, R1' And at least two of R 1 ″ may be linked to each other to form an aliphatic or aromatic ring. A transition metal compound represented by the following formula (2): [Formula 2]

In Chemical Formula 2, X 1 and X 2 are the same as or different from each other, and are each independently a halogen radical, an alkyl radical having 1 to 20 carbon atoms, an aryl radical, an alkylaryl radical, an arylalkyl radical, an aryl amido radical, or an alkylidene radical having 1 to 20 carbon atoms. ; M is a periodic table Group 4 transition metal; Cp1 and Cp2 are the same as or different from each other, and each independently a cyclopentadienyl group; Indenyl group; Fluorenyl group; Or a cyclopentadienyl derivative substituted with one or more substituents of hydrocarbyl, alkyl, aryl, silyl, halogen, and halohydrocarbyl, coordinated to central metal M in the form of eta-5 (h-5), two The above substituents may be linked to each other to form an aliphatic or aromatic ring; CY1 and CY2 are the same as or different from each other, and each independently an aliphatic or aromatic ring; Y1 and Y2 are the same as or different from each other, and each independently a hetero atom of group 15 or 16 of the periodic table; R2 and R4 are the same as or different from each other, and each independently an alkyl radical, aryl radical, alkylaryl radical or arylalkyl radical having 1 to 20 carbon atoms, and R2 or R4 is present when Y1 or Y2 is a hetero atom of group 16 of the periodic table. Not; R1, R1 ', R1 ", R3, R3', and R3" are the same or different from each other, and each independently hydrogen, a halogen radical, an alkyl radical having 1 to 20 carbon atoms, an aryl radical, an alkoxy radical, an aryloxy radical, or an amine Is also a radical and at least two of R1, R1 'and R1 ", or at least two of R3, R3' and R3" may be linked to each other to form an aliphatic or aromatic ring. An organic compound represented by the following formula (3): [Formula 3]

In Chemical Formula 3, R1, R1 ', R1 ", R2, CY1, and Y1 are the same as the definition in Formula 1 above; R5, R6, R7, and R8 are the same as or different from each other, and each independently a hydrogen atom; Alkyl radicals having 1 to 20 carbon atoms; Alkenyl radicals having 2 to 20 carbon atoms; Silyl radicals; Alkylaryl radicals; Or an arylalkyl radical; The R5 to R8 may be connected to each other by an alkylidine radical including an alkyl or aryl radical having 1 to 20 carbon atoms to form a ring. A catalyst composition comprising the transition metal compound of claim 1 or 2. The catalyst composition according to claim 4, further comprising at least one of the compounds represented by the following Chemical Formulas 4 to 6. [Formula 4]

In Formula 4, R9 may be the same or different from each other, and each independently a halogen group, a hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group having 1 to 20 carbon atoms substituted with halogen, n is an integer of 2 or more, [Formula 5]

In Chemical Formula 5, R9 is as defined in Formula 4, D is aluminum or boron, [Formula 6]

In Chemical Formula 6, L is a neutral or cationic Lewis acid, H is a hydrogen atom, Z is a group 13 element, A may be the same as or different from each other, and each independently one or more hydrogen atoms substituted or unsubstituted with a halogen group, a hydrocarbon group having 1 to 20 carbon atoms, alkoxy or phenoxy, aryl having 6 to 20 carbon atoms or alkyl having 1 to 20 carbon atoms to be.