KR100963762B1 - Novel binuclear transition metal compound and the method of preparation the same - Google Patents

Abstract

The present invention provides a ligand compound having a novel structure, a dinuclear transition metal compound prepared using the same, and a method of preparing the same.

Dinuclear transition metal compound, cyclopentadienyl

Description

Novel binuclear transition metal compound and method for producing same {NOVEL BINUCLEAR TRANSITION METAL COMPOUND AND THE METHOD OF PREPARATION THE SAME}

The present invention relates to metallocene catalysts useful as polymerization catalysts.

U.S. Patent 5,453,410, filed December 1, 1992, describes a catalyst of the structure:

The catalyst compound is a structure in which a cyclopentadienyl group (hereinafter referred to as Cp) and a nitrogen group are simultaneously bonded to a metal such as titanium by a silyl bridge.

The general method for preparing the compounds of the above structure is as follows. First, an Me ₂ ClSi-Cp * H compound is prepared by reacting an excess Me ₂ SiCl ₂ compound with a Cp * Li compound, and then a ligand Me ₂ is added by adding RNHLi or an excess RNH ₂ compound to the Me ₂ ClSi-Cp * H compound. Si (Cp * H) (RNH) is prepared. After n-BuLi was added to the obtained ligand, it was reacted with TiCl ₄ or TiCl ₃ (THF) ₃ , which is a transition metal compound, as an oxidizing agent to prepare tetramethylcyclopentadienyldimethylsilylbutylamido titanium dichloride as a metal compound of the above structure. can do.

It is reported that the highest activity of the catalyst in the copolymerization of ethylene / 1-octene using the catalyst compound thus obtained yields 222 g of polymer when 10 μmol of Ti is applied, resulting in a level of 22.2 kg / mmol Ti.

U.S. Patent No. 6,153,776, filed August 28, 1998, describes a catalyst compound of the following structure (representative example).

The catalytic compound is a heteronuclear structure in which a cyclopentadienyl group is linked by a hydrocarbyl bridge.

The method for preparing the transition metal compound having the above structure is as follows. As a first step, a small amount of [1,3-bis (diphenylphosphino) -propane] dinickel (II) was added to the bromoindene compound as a catalyst, followed by pentamethylenebis (magnesium bromide) at -78 ^° C. Slowly add 1 equivalent. Thereafter, the mixture is reacted at room temperature for 2 hours and then purified to obtain a solid compound. As a second step, n-BuLi 1 equivalent is added to the solid compound obtained in the first step, and then reacted with 1 equivalent of t-butylaminodimethylsilyl chloride (ClSi (Me) ₂ NH-t-Bu) to pentamethylenebis ( 1- (t-butylamino) dimethylsilyl inden-2-yl) compound is prepared. As a third step, a titanium metal compound may be prepared by adding 2 equivalents of n-BuLi to the compound obtained in the second step, reacting with TiCl ₃ (THF) _3, and then adding palladium dichloride (PdCl ₂ ).

It is reported that the highest activity of the catalyst during the ethylene polymerization using the catalyst compound is 18.4 g of polymer, which is 47 kg / g Ti level.

The existing methods for preparing the catalyst compound are not easy to introduce a bridge to the nitrogen atom is limited to the synthesis of various catalyst compounds, there is a problem that the method for producing the catalyst compound is complicated.

It is an object of the present invention to provide a ligand compound having a novel structure, a transition metal compound prepared using the same, and a method of preparing the same.

In order to solve the above technical problem, the present invention provides a ligand compound having a novel structure having a bridge, a dinuclear transition metal compound that can be prepared using the same, and a method for preparing the same.

Hereinafter, the present invention will be described in detail.

The present invention provides a ligand compound represented by the following formula (1).

In Chemical Formula 1,

E is a covalent bridging group connecting Cp ¹ and Cp ² and includes an epoxy group; Etipigi; Carbonyl group; Silane group; Disilane group; Substituted or unsubstituted C1-C60 hydrocarbylene group; Or a heterohydrocarbylene group having 1 to 60 carbon atoms containing a Group 4B, Group 5B, or Group 6B element;

Cp ¹ and Cp ² each independently represent a cyclopentadienyl group; Indenyl group; Fluorenyl group; Or a cyclopentadienyl derivative substituted with an alkyl, aryl, silyl, halogen, or halohydrocarbyl group;

A is the same as or different from each other, and each independently is a nitrogen or phosphorus atom,

CY and CY 'is a heterocyclic ring having 3 to 20 carbon atoms including A.

In addition, the present invention provides a transition metal compound represented by the following Chemical Formula 2, which may be prepared using the ligand compound represented by Chemical Formula 1.

In Chemical Formula 2, E, Cp ¹ , Cp ² , A, CY, and CY 'are the same as defined in Formula 1,

M is the same as or different from each other, and each independently a Group 4 transition metal,

Q ₁ and Q ₂ are the same as or different from each other, and each independently halogen; Alkyl amido having 1 to 20 carbon atoms; Arylamido having 6 to 20 carbon atoms; Alkyl having 1 to 20 carbon atoms; Alkenyl having 2 to 20 carbon atoms; Aryl having 6 to 20 carbon atoms; Alkyl aryl having 7 to 20 carbon atoms; Arylalkyl having 7 to 20 carbon atoms; Or an alkylidene radical having 1 to 20 carbon atoms,

Cp ¹ and Cp ² coordinate to the central metal M in the form of eta-5 (η-5).

In addition, the present invention

1) preparing a lithium carbamate compound represented by Chemical Formula 3 by adding 1 equivalent of alkyl lithium or aryl lithium, and an excess of CO ₂ gas to a phenylamine or phenylphosphine compound, and

2) adding a compound represented by the following formula (4) to the lithium carbamate compound obtained in step 1) connected by alkyllithium or aryl lithium, and bridge E

It provides a method for producing a ligand compound represented by the formula (1) comprising a.

In Formulas 3 and 4, CY, A, Cp ¹ , Cp ² , and E are the same as defined in Formula 1 above.

The alkyl lithium in step 1) is preferably n-BuLi, and the alkyl lithium in step 2) is preferably t-BuLi, but is not limited thereto.

In addition, the present invention is a ligand compound represented by the formula (1) obtained by the above production method

3) adding 2 equivalents of alkyllithium or aryl lithium to prepare a dilithium compound, and then reacting the MCl ₂ Q ₁ Q ₂ compound

It further provides a method for producing a transition metal compound represented by the formula (2). Here, M, Q ₁ , and Q ₂ are the same as defined in the formula (2).

The alkyl lithium of step 3) is preferably n-BuLi, but is not limited thereto.

In the present invention, an example of a method for producing the transition metal compound represented by Formula 2 is shown schematically in the following figure. First, the cyclopentadienyl group can be linked by a bridge, and then various quinoline substituents may be introduced. The transition metal compound obtained by using the compound thus obtained as a ligand is a structure in which a cyclopentadienyl group linked by a bridge and a quinoline group containing nitrogen are bonded to Ti metal at the same time.

LDA: lithium diisopropylamide

The dinuclear transition metal compound according to the present invention can be used as a metallocene catalyst useful as a polymerization catalyst.

Hereinafter, the present invention will be described in more detail with reference to Examples. However, the following examples are for illustrating the present invention, and the scope of the present invention is not limited thereto.

< Example >

< Ligand  And synthesis of transition metal compounds>

Organic reagents and solvents were purchased from Aldrich and purified by standard methods unless otherwise noted. At all stages of the synthesis, the contact between air and moisture was blocked to increase the reproducibility of the experiment.

< Example  1> N- (1,2,3,4- Tetrahydroquinolinine ) Carboxylic acid Lithium salt  (1) (N- (1,2,3,4-tetrahydroquinolinine) carboxylic acid lithium salt (One))

1,2,3,4-tetrahydroquinoline (13.08 g, 98.24 mmol) and diethyl ether (150 mL) were placed in a Schlenk flask. The flask was immersed in a -78 ^o C low temperature bath made of dry ice and acetone, stirred for 30 minutes, and then n-BuLi (39.3 mL, 2.5 M, 98.24 mmol) was introduced into a syringe under a nitrogen atmosphere. The temperature was slowly raised to room temperature and stirred for 2 hours. After the temperature was lowered to -78 ° C, CO ₂ was bubbled for 10 minutes. After slowly raising the temperature to room temperature, the solvent was dried in vacuo to obtain the desired compound.

¹ H NMR (C ₆ D ₆ ): δ 1.49 (m, 2H, Cy-CH ₂ ), 2.21 (m, 2H, Cy-CH ₂ ), 3.65 (m, 2H, Cy-CH ₂ ), 6.36-6.83 (m, 3H, PhH), 8.12 (d, 1H, PhH) ppm

< Example  2> 1,2-di- [5- (2- Cyclopentenoyl )] Ethane (2) (1,2- Di -[5- (2- cyclopentenoyl )] ethane (2))

2-cyclopenten-1-one (2-cyclopenten-1-one, 2 g, 23.36 mmol) and diethyl ether (100 mL) were placed in a Schlenk flask. The flask was immersed in a -78 ^° C. low temperature bath made of dry ice and acetone, stirred for 30 minutes, and slowly added dropwise to lithium diisopropylamide (Lithium diisopropylamide, 2.0 M heptane solution / THF, 11.68 mL). -78 ^o After stirring for 1 h at C, 1,2-dibromoethane (8.76 g, 46.72 mmol) is added dropwise. The temperature is slowly raised to room temperature and stirred for 5 hours. 50 mL of distilled water was added thereto, followed by extraction with 100 mL × 2 of ethyl acetate to remove water with MgSO ₄ . The solvent was removed after filtration and the desired compound was obtained by column chromatography.

¹ H NMR (C ₆ D ₆ ): δ 1.23 (m, 4H, CH ₂ -CH ₂ ), 1.69 (d, 2H, CH-CH ₂ ), 2.02 (m, 4H, CH-CH ₂ ), 2.34 (m, 2H, CH-CH), 2.85 (d, 2H, CH-CH) ppm

< Example  3> 1,2-di- [2- {8- (1,2,3,4- Tetrahydroquinolyl ) Cyclopentadienyl }] Ethane (1,2- Di -[2- {8- (1,2,3,4- tetrahydroquinolyl ) cyclopentadienyl }] ethane )

N- (1,2,3,4-tetrahydroquinolinine) carboxylic acid lithium salt (1) (N- (1,2,3,4-tetrahydroquinolinine) carboxylic acid lithium salt (1), 2.0 g, 10 mL of diethyl ether was added to a Schlenk flask containing 10.92 mmol) and the temperature was lowered to -78 ° C while stirring. tert-butyllithium (tert-butyllithium, 8.35 mL, 1.7 M pentane solution) was slowly added dropwise, and the temperature was raised to -30 ° C and stirred for 2 hours. CeCl ₃ (2.69 g, 10.92 mmol) with THF (30 mL), 1,2-di- [5- (2-cyclopentenoyl)] ethane (2) (1,2-Di- {5- (2-cyclopentenoyl )} ethane (2), 2.07 g, 10.92 mmol) was stirred in a separate Schlenk flask for 1 hour and then added dropwise at -30 ° C. After slowly raising the temperature to room temperature, hydrochloric acid (30 mL, 2N aqueous solution) was added. After shaking for 2 minutes in a separatory funnel, saturated aqueous sodium bicarbonate solution was added and the organic layer was separated, treated with MgSO ₄ and filtered. The solvent was removed to afford the desired compound.

¹ H NMR (CDCl ₃ ): δ 0.98 (m, 4H, CH ₂ -Cy) 1.28 (m, 4H, CH ₂ -CH ₂ ), 2.02 (m, 4H, C-CH ₂ ), 2.35 (m, 2H , CH-CH), 2.81 (d, 2H, CH-CH), 2.93 (m, 4H, CH ₂ -Cy), 3.45 (m, 4H, CH ₂ -Cy), 3.97 (br, 2H, NH), 6.45-7.10 (6H, PhH) ppm

< Example  4> [1,2-ethylene (1,2,3,4- Tetrahydroquinoline -8-yl) cyclopentadienyl-e Ta 5, kappa -N] titanium dimethyl ([1,2- Ethylene (1,2,3,4- Tetrahydroquinolin -8- yl ) cyclopentadienyl-eta5, kapa-N] titanium dimethyl )

1,2-di- [2- {8- (1,2,3,4-tetrahydroquinolyl) cyclopentadienyl}] ethane (1,2-di- [2- {8- (1,2 15 mL of diethyl ether was added to a Schlenk flask containing 3,4-tetrahydroquinolyl) cyclopentadienyl}] ethane, 2.0 g, and 4.76 mmol), and the temperature was lowered to -78 ° C while stirring. After n-butyllithium (n-Buthyllithium, 5.95 mL, 1.6 M hexane solution) was slowly added dropwise, the temperature was slowly raised to room temperature and stirred for 6 hours. 15 mL of diethyl ether was added to a separate Schlenk flask containing tetrachloro (1,2-dimethoxyethane) titanium (2.66g, 9.52mmol) and stirred at a temperature of -30 ° C. After lowering to methyllithium (methylllitium, 11.9 mL, 1.6M ether solution) was slowly added dropwise and stirred for 1 hour. The solution was slowly injected at -30 ° C, the temperature was raised to room temperature, stirred for 3 hours, and the solvent was removed. 50 mL of hexane was added and filtered, and then the solvent was removed to obtain the desired compound.

¹ H NMR (CDCl ₃ ): δ 0.72 (s, 12H, CH ₃ -Ti), 1.28 (m, 4H, CH ₂ -CH ₂ ) 2.43 (m, 4H, CH ₂ -Cy), 2.91 (d, 2H , CH-CH), 3.04 (m, 4H, CH ₂ -Cy), 4.24 (m, 4H, CH ₂ -Cy), 6.21-7.23 (12H, ArH) ppm

The present invention can provide a ligand compound having a novel structure, a dinuclear transition metal compound prepared using the same, and a method of preparing the same. In addition, the dinuclear transition metal compound according to the present invention can be used as a metallocene catalyst useful as a polymerization catalyst.

Claims (5)

Ligand compound represented by the following formula (1): [Formula 1]

In Chemical Formula 1, E is a covalent bridging group connecting Cp ¹ and Cp ² and includes an epoxy group; Etipigi; Carbonyl group; Silane group; Disilane group; Substituted or unsubstituted C1-C60 hydrocarbylene group; Or a heterohydrocarbylene group having 1 to 60 carbon atoms containing a Group 4B, Group 5B, or Group 6B element; Cp ¹ and Cp ² each independently represent a cyclopentadienyl group; Indenyl group; Fluorenyl group; Or a cyclopentadienyl derivative substituted with an alkyl, aryl, silyl, halogen, or halohydrocarbyl group; A is the same as or different from each other, and each independently is a nitrogen or phosphorus atom, CY and CY 'is a heterocyclic ring having 3 to 20 carbon atoms including A. A transition metal compound represented by the following formula (2): [Formula 2]

In Chemical Formula 2, E, Cp ¹ , Cp ² , A, CY, and CY 'are the same as defined in Formula 1 of claim 1, M is the same as or different from each other, and each independently a Group 4 transition metal, Q ₁ and Q ₂ are the same as or different from each other, and each independently halogen; Alkyl amido having 1 to 20 carbon atoms; Arylamido having 6 to 20 carbon atoms; 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 an alkylidene radical having 1 to 20 carbon atoms, Cp ¹ and Cp ² coordinate to the central metal M in the form of eta-5 (η-5). 1) preparing a lithium carbamate compound represented by the following Chemical Formula 3 by adding 1 equivalent of alkyl lithium or aryl lithium, and CO ₂ gas to a phenylamine or phenylphosphine compound, and 2) adding a compound represented by the following formula (4) to the lithium carbamate compound obtained in step 1) connected by alkyllithium or aryl lithium, and bridge E Method for preparing a ligand compound represented by Formula 1 of claim 1 comprising: (3)

[Formula 4]

In Formulas 3 and 4, CY, A, Cp ¹ , Cp ² , and E are the same as defined in Formula 1 of claim 1. 1) preparing a lithium carbamate compound represented by Chemical Formula 3 of claim 3 by adding 1 equivalent of alkyl lithium or aryl lithium, and CO ₂ gas to a phenylamine or phenylphosphine compound, 2) preparing a ligand chemical represented by the formula (1) of claim 1 by adding a compound represented by the formula (4) of claim 3 connected by alkyllithium or aryl lithium, and bridge E to the lithium carbamate compound obtained in step 1) Steps, and 3) preparing a dilithium compound by adding 2 equivalents of alkyllithium or aryl lithium to the ligand compound represented by Formula 1 of claim 1 obtained in step 2), and then reacting the MCl ₂ Q ₁ Q ₂ compound Method for preparing a transition metal compound represented by Formula 2 of claim 2 comprising: Here, M, Q ₁ , and Q ₂ are the same as defined in the formula (2) of claim 2. Catalyst composition comprising a transition metal compound represented by Formula 2 of claim 2.