KR101583671B1 - Method for preparing of novel ligand compoun and transition metal compound - Google Patents

Abstract

The present invention relates to a novel ligand compound and a process for producing a transition metal compound. The ligand compound having a novel structure and the transition metal compound containing the same according to the production method of the present invention can be used as a polymerization reaction catalyst in the production of an olefinic polymer.

Description

[0001] The present invention relates to a method for preparing a ligand compound and a transition metal compound,

The present invention relates to a method for producing a ligand compound and a transition metal compound.

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.

European Patent EP 1462464 discloses a polymerization example using a hafnium metallocene compound having a chloride, benzyl, trimethylsilylmethyl group. Also, it has been reported that the production energy of the activated species varies depending on the alkyl ligand bound to the center metal (J. Am. Chem. Soc. 2000, 122, 10358). Korean Patent No. 820542 discloses a catalyst for the polymerization of olefins having a quinoline ligand, and this patent relates to a catalyst having a living group containing silicon and germanium atoms other than the methyl group.

Dow has disclosed in the early 1990s [Me ₂ Si (Me ₄ C ₅ ) N t Bu] TiCl ₂ (Constrained-Geometry Catalyst, CGC) in U.S. Patent No. 5,064,802. In the copolymerization reaction of ethylene and alpha-olefin, CGC (1) high molecular weight polymers with high activity at high polymerization temperatures, and (2) 1-hexene (1-hexene) And 1-octene are also excellent in the copolymerization of alpha-olefins with large steric hindrance. 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.

As another approach, a large amount of compounds composed of oxydolides were synthesized instead of the amido ligands of CGC, and some polymerization using the compounds was attempted.

However, among all these attempts, only a few catalysts have actually been applied to commercial plants.

In order to solve the above problems, it is an object of the present invention to provide a novel method for producing a ligand compound.

It is another object of the present invention to provide a process for producing a novel transition metal compound containing the ligand compound.

In order to accomplish the above object, the present invention provides a process for preparing a compound represented by the following formula (5) by reacting a compound represented by the following formula (3) and a compound represented by the following formula (4) And

Reacting a compound represented by the following formula (5) or a lithium salt thereof with a compound represented by the following formula (6).

(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

[Chemical Formula 1]

In the above Formulas 1, 3, 4, 5, and 6,

n is an integer of 1 to 2,

R ₁ to R ₁₀ are the same or different and each independently represents hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, An arylalkyl group having 7 to 20 carbon atoms or a silyl group, and R ₁ to R ₁₀ At least two adjacent to each other may be linked to each other by an alkylidene group containing an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms to form a ring;

R ₁₁ is hydrogen, a halogen group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms;

X ₃ is a halogen group;

Q is carbon or silicon.

The present invention also provides a process for preparing a transition metal compound represented by the following general formula (2), which comprises reacting a ligand compound represented by the following general formula (1) and a compound represented by the following general formula (7)

[Chemical Formula 1]

(7)

M (X ₁ X ₂ ) ₂

(2)

In the above formulas (1), (2) and (7)

n is an integer of 1 to 2,

R ₁ to R ₁₀ are the same or different and each independently represents hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, An arylalkyl group having 7 to 20 carbon atoms or a silyl group, and R ₁ to R ₁₀ At least two adjacent to each other may be linked to each other by an alkylidene group containing an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms to form a ring;

R ₁₁ is hydrogen, a halogen group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms;

Q is carbon or silicon;

M is a Group 4 transition metal;

X ₁ and X ₂ are the same or different and each independently represents a halogen, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, An arylamino group having 1 to 20 carbon atoms, an alkylamino group having 1 to 20 carbon atoms, an arylamino group having 6 to 20 carbon atoms, or an alkylidene group having 1 to 20 carbon atoms.

The transition metal compound obtained according to the production method of the present invention can be usefully used as a catalyst for the polymerization reaction in the production of an olefinic polymer.

The terminology used herein is for the purpose of describing exemplary embodiments only and is not intended to be limiting of the invention. The singular expressions include plural expressions unless the context clearly dictates otherwise. In this specification, the terms "comprising," "comprising," or "having ", and the like are intended to specify the presence of stated features, But do not preclude the presence or addition of one or more other features, integers, steps, components, or combinations thereof.

While the invention is susceptible to various modifications and alternative forms, specific embodiments thereof are shown by way of example in the drawings and will herein be described in detail. It should be understood, however, that the invention is not intended to be limited to the particular forms disclosed, but on the contrary, is intended to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention.

Hereinafter, the present invention will be described in detail.

The method for preparing a ligand compound of the present invention comprises the steps of: reacting a compound represented by the following formula (3) and a compound represented by the following formula (4) to prepare a compound represented by the following formula (5); And a compound represented by the following formula (5) or a lithium salt thereof and a compound represented by the following formula (6).

(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

[Chemical Formula 1]

In the above Formulas 1, 3, 4, 5, and 6,

n is an integer of 1 to 2,

R ₁ to R ₁₀ are the same or different and each independently represents hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, An arylalkyl group having 7 to 20 carbon atoms or a silyl group, and R ₁ to R ₁₀ At least two adjacent to each other may be linked to each other by an alkylidene group containing an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms to form a ring;

R ₁₁ is hydrogen, a halogen group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms;

X ₃ is a halogen group;

Q is carbon or silicon.

Each of the substituents defined in Formulas 1, 3, 4, 5 and 6 will be described in detail as follows.

The alkyl group includes a linear or branched alkyl group.

The alkenyl group includes a linear or branched alkenyl group.

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

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

The halogen group means a fluorine group, a chlorine group, a bromine group or an iodine group.

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.

The arylamino group means an amino group substituted by the aryl group, and includes, but is not limited to, a diphenylamino group and the like.

The silyl group includes trimethylsilyl, triethylsilyl, tripropylsilyl, tributylsilyl, trihexylsilyl, triisopropylsilyl, triisobutylsilyl, triethoxysilyl, triphenylsilyl, tris (trimethylsilyl) , But are not limited to these examples.

The aryl group preferably has 6 to 20 carbon atoms, and specifically includes phenyl, naphthyl, anthracenyl, pyridyl, dimethylanilinyl, anisolyl, and the like, but is not limited thereto.

In the method for preparing a ligand compound of the present invention, the compound represented by Formula 5 is prepared by first reacting the compound represented by Formula 3 with the compound represented by Formula 4.

More specifically, according to one embodiment of the present invention, the indanyl halide derivative represented by the formula (3) and the indoline or tetrahydroquinoline derivative represented by the formula (4) are subjected to a coupling reaction in the presence of a base and a palladium catalyst To form a CN bond, whereby a compound represented by the above formula (5) can be prepared. The palladium catalyst to be used at this time is not particularly limited. For example, Bis (tri (tertiarybutyl) phosphine)) palladium (((tert-Bu) ₃ P) ₂ Pd) Tetrakis (triphenylphosphine) palladium _{(Pd (PPh 3) 4)} , palladium chloride (PdCl _2), palladium acetate (Pd (OAc) ₂₎ or bis (dibenzylideneacetone) palladium (Pd (dba) ₂₎ Etc. may be used.

Next, the ligand compound represented by the above formula (1) can be obtained by reacting the compound represented by the above formula (5) or its lithium salt with the compound represented by the above formula (6).

More specifically, according to one embodiment of the present invention, the compound represented by Chemical Formula 5 is reacted with an organic lithium compound such as n-BuLi to produce a lithium salt of the compound represented by Chemical Formula 5. Next, after the compound represented by the formula (6) is mixed, the mixture is reacted by stirring. Thereafter, the reaction product is filtered to wash the resulting precipitate, and dried under reduced pressure to obtain a ligand compound represented by the above formula (1) wherein the indenyl group derivative is C2-symmetrically crosslinked by Q (carbon or silicon).

Here, the ligand compound represented by Formula 1 may be represented by one of the following structural formulas, but the present invention is not limited thereto.

In the above structural formula, Me represents a methyl group, and Ph represents a phenyl group.

The compound represented by the formula (1) obtained according to the production method of the present invention may be a ligand compound capable of forming a chelate with a metal.

According to the production process of the present invention, the ligand compound can be obtained in one of two forms of racemic and meso compounds, or in the form of a mixture of racemic and meso.

A method of preparing a transition metal compound according to another aspect of the present invention includes reacting a ligand compound represented by the following formula (1) with a compound represented by the following formula (7).

[Chemical Formula 1]

(7)

M (X ₁ X ₂ ) ₂

(2)

In the above formulas (1), (2) and (7)

n is an integer of 1 to 2,

R ₁ to R ₁₀ are the same or different and each independently represents hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, An arylalkyl group having 7 to 20 carbon atoms or a silyl group, and R ₁ to R ₁₀ At least two adjacent to each other may be linked to each other by an alkylidene group containing an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms to form a ring;

R ₁₁ is hydrogen, a halogen group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms;

Q is carbon or silicon;

M is a Group 4 transition metal;

X ₁ and X ₂ are the same or different and each independently represents a halogen group, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, An alkylamino group having 1 to 20 carbon atoms, an arylamino group having 6 to 20 carbon atoms, or an alkylidene group having 1 to 20 carbon atoms.

According to an embodiment of the present invention, the transition metal of Group 4 corresponding to M may be Ti, Zr, Hf or the like, but is not limited thereto.

More specifically, the ligand compound represented by Formula 1 is reacted with an organolithium compound such as n-BuLi to produce a lithium salt, followed by mixing with a metal source represented by Formula 7, and then the mixture is reacted by stirring . Thereafter, the reaction product is filtered to wash the resulting precipitate and dried under reduced pressure to obtain an organometallic compound represented by the general formula (2) in a complex form in which a metal atom is bonded to the ligand compound.

According to an embodiment of the present invention, the transition metal compound represented by Formula 2 may be represented by one of the following structural formulas, but is not limited thereto.

In the above structural formula, Me represents a methyl group, and Ph represents a phenyl group.

According to the production method of the present invention, the transition metal compound represented by the formula (2) can be obtained in two forms of a racemic and a meso compound, or a mixture of a racemic mixture and meso ≪ / RTI > In the case of a mixture of a racemic mixture and meso, a transition metal compound of only racemate can finally be obtained through a recrystallization step.

The ligand compound and the transition metal compound obtained by the production method of the present invention form a structure in which a bisindenyl group is bridged by carbon or silicon and an indoline group or a tetrahydroquinoline group is connected to the indenyl group, ≪ / RTI > As described above, the transition metal compound according to the production method of the present invention includes an electronically enriched indoline group or a tetrahydroquinoline group, so that the electron density of the center metal is increased and high temperature stability and high molecular weight polyolefin polymer, And can be usefully used for synthesizing a polyolefin-based polymer, for example, isotatic polypropylene.

The ligand compounds and transition metal compounds of the novel structure obtained according to the production method of the present invention can be used as polymerization catalysts in the production of olefinic polymers.

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.

< Example >

In the following examples, the term " overnight "or" overnight "means approximately 12 to 16 hours and" normal temperature "refers to a temperature of 20 to 30 ° C. The organic reagents and solvents used 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 were obtained using a 500 MHz nuclear magnetic resonance (NMR) system to demonstrate the structure of the resulting compound.

Ligand  Synthesis of compounds and transition metal compounds

Example  One

1- (2- methyl -One H - inden -4- yl ) -1,2,3,4- tetrahydroquinole Synthesis of

To a 500 ml 2-neck Schlenk flask was added 4-bromo-2-methyl-1 H -indene (15.7 g, 75.63 mmol), 1,2,3,4-tetrahydroquinone (11.08 g, 83.19 mmol), LiOtBu (18.16 g, 226.89 mmol) and Pd (P (tBu) ₃ ) ₂ (0.77 g, 1.5 mmol) were added, and 252 mL of dry toluene was added. The starting material was dissolved and stirred overnight at 110 ° C in an oil bath. After cooling to room temperature, 151 mL of deionized water was added to terminate the reaction.

The organic layer was separated and the water layer was extracted twice with 50 mL of dichloromethane (DCM). Combined organic layers after drying Na ₂ SO _4, filtered and evaporated in vacuo and dried overnight at 60 ℃ juhwangbit compound (15.8g, 4-bromo-2 -methyl-1 H -indene than quantitative yield, 80% from the starting material Yield).

_{^{1 H-NMR (CDCl 3)}} : δ7.30-7.20 (m, 3H in isomers), 7.15-7.10 (d, J = 7.5Hz, 2H in isomers), 7.15-7.10 (d, J = 8.0Hz, 1H in isomers), 7.10-7.05 (d, J = 8.0Hz, 1H in isomers), 7.05-7.00 (d, J = 7.5Hz, 3H in isomers), 7.00-6.95 (d, J = 7.5Hz, 2H in isomers ), 6.90-6.80 (t, J = 7.5Hz, 3H in isomers), 6.65-6.58 (m, 3H in isomers), 6.48 (d, J = 8.0 Hz, 1H in isomers), 6.25-6.22 (d, J = 8.0 Hz, 2H in isomers), 3.62-3.59 (t, J = 5.5 Hz, 6H in 2-quinolinyl of isomers) 3H-1H-indene of isomers), 3.10 (s, 3H in 1H-indene of isomers), 3.00-2.85 (m, 6H in 4-quinolinyl of isomers), 2.22-2.00 quinolinyl and 2-Me of isomers)

Bis (4- (3,4- dihydroquinoline -1 (2 H ) - yl )-2- methyl -One H - inden -One- yl ) - dimethyl silane Synthesis of

Into the 1- (2-methyl-1 H -inden-4-yl) -1,2,3,4-tetrahydroquinole (15.8g, 60.5mmol) in 500mL of Schlenk flask was added dry diethyl ether 300mL dissolve the starting material , N-BuLi (2.5 M in n-Hx) (26.6 mL) was added at -78 ° C, and the mixture was stirred at room temperature overnight. Then, it was filtered using glass frit (G4). The solid remaining in the glass frit was vacuum dried to obtain a lithiated product (14.4 g, 89% yield) of a white solid. In the glove box, the lithiated product (14.2 g, 53.1 mmol) was placed in a 500 mL Schlenk flask and dissolved by adding 152 mL of dry toluene and 7.6 mL of THF. After the temperature was lowered to -30 ° C, Me ₂ SiCl ₂ (3.2 mL, 26.6 mmol) was added and the mixture was stirred at room temperature for 1 day. Then, the mixture was stirred for 5 hours under an oil bath at 140 ° C. After cooling to room temperature, 50 mL of deionized water was added to terminate the reaction.

The organic layer was separated and the water layer was extracted twice with 50 mL of dichloromethane (DCM). The organic layer was collected, dried with K ₂ CO ₃ , filtered, distilled, and vacuum-dried at 60 ° C. overnight to obtain a brownish white solid ligand compound (15.8 g, quantitative yield relative to lithiated product, 89% yield based on starting material) . ¹ H-NMR analysis showed that the ratio of rac: meso was about 1: 1.

_{^{1 H-NMR (CDCl 3)}} : δ 7.40 (d, J = 7.5Hz, 2H, 7,7'-H in indenyl of rac -isomer), 7.25 (d, J = 7.5Hz, 2H, 7,7 ' -H in indenyl of meso -isomer), 7.15 (t, J = 7.5Hz, 2H, 6,6'-H in indenyl of rac -isomer), 7.12 (t, J = 8.0Hz, 2H, 6,6 ' -H in indenyl of meso -isomer), 7.10 (d, J = 7.5Hz, 2H, 5,5'-H in quinolinyl of of rac -isomer), 7.08 (d, J = 7.5Hz, 2H, 5,5 -H in quinolinyl of meso- isomer), 7.02 (dd, J ₁ = 7.0 Hz, J ₂ = 1.0 Hz, 4H, 5,5'-H indenyl of rac- and meso- isomers), 6.85-6.81 (m, 4H, 7,7 ' -H in quinolinyl of rac - and meso -isomers), 6.60 (td, J 1 = 7.5 Hz, J 2 = 1.0Hz, 4H, 6,6'-H in quinolinyl of rac - and meso -isomers), 6.46 (s, 4H, 3 , 3'-H in indenyl of rac- and meso- isomers), 6.26 (d, J = 8.0 Hz, 4H, 8,8'-H in quinolinyl of rac- and meso- isomers), 3.81 Indenyl of rac- isomer), 3.79 (s, 2H, 1,1'-H indenyl of meso- isomer), 3.69-3.57 (m, 8H, 2,2'-H in quinolinyl of rac - and meso -isomers), 2.92 (t, J = 6.0Hz, 8H, 4,4'-H in quinolinyl of rac - and meso -isomers), 2.21 (d, J = 0.5Hz, 6H, 2, 2'-Me in meso- isomer), 2.13 (d, J = 1.0 Hz, 6H, 2,2'-Me in rac -isomer), 2.13-2.08 (m, 8H, 3,3'- rac - and meso -isomers), -0.27 (s, 3H, SiMe of meso -isomer), -0.29 (s, 6H, SiMe 2 of rac -isomer), -0.30 (s, 3H, SiMe'-of meso - isomer)

rac - dimethylsilylene -bis (4- (3,4- dihydroquinoline -1 (2 H ) - yl )-2- methyl -indenyl) zircoium dichloride  synthesis

To a 500 mL Schlenk flask was added 10.4 g (18 mmol, rac: meso = 1 (4-dihydroquinolin-1 ( 2H ) -yl) -2-methyl-1H- inden- : 1) and 285 mL of dry toluene was added to dissolve the starting material. 14.4 mL of n-BuLi (2.5M in n-Hx) was added at -78 ° C and the mixture was stirred at room temperature for 5 hours. The mixture was cooled to -78 ° C and transferred to a Schlenk flask containing 4.2 g (18 mmol in 60 mL toluene) of ZrCl ₄ solution prepared at -78 ° C. using a cannula, and the mixture was stirred at room temperature overnight. After completion of the reaction, the mixture was filtered with a glass frit (G4) containing celite. The solid remaining in the glass frit was washed three times with about 5 mL of dry toluene. The toluene solution was vacuum dried to obtain a red solid. Solids remaining in the glass frit were dissolved in dichloromethane (DCM). The DCM filtrate was vacuum dried to give a red solid. ¹ H-NMR analysis showed that both solids were Zr complexes with rac: meso = 1: 1. The crude product was collected and placed in an oil bath at 45 ° C and dissolved in 50 mL of dry toluene while stirring. This was stored in a -30 ° C freezer for 3 days and recrystallized. The resulting red solid was filtered with glass frit (G4), washed twice with 5 mL of dry n-hexane, and dried in vacuo to give racemic final product, 1.3 g (1.9 mmol, 10.4% yield).

^{1 H-NMR (Tol-d} 3): δ 7.19 (d, J = 8.5Hz, 2H, 7,7'-H in indenyl), 7.02 (d, J = 7.5Hz, 2H, 5,5'-H in quinolinyl), 6.92 (d, J = 7.5Hz, 2H, 5,5'-H in indenyl), 6.85-6.82 (m, 2H, 7,7'-H in quinolinyl), 6.76 (dd, J 1 = _{8.5 Hz, J 2 = 7.5Hz,} 2H, 6,6'-H in indenyl), 6.70-6.68 (m, 2H, 6,6'-H in quinolinyl), 6.67 (s, 2H, 3,3'- (M, 4H, 2,2'-H in quinolinyl), 2.65-2.54 (m, 1H), 6.54 (d, J = 8.5Hz, 2H, 4H, 4,4'-H in quinolinyl), 1.95 (s, 6H, 2,2'-Me), 1.90-1.70 SiMe ₂ )

Example  2

rac - dimethylsilylene - bis (4- (3,4- dihydroquinoline -1 (2 H ) - yl )-2- methyl - indenyl ) hafnium  Synthesis of dichloride

3 g (5.2 g) of the bis (4- (3,4-dihydroquinolin-1 (2 H ) -yl) -2-methyl-1H-inden-1-yl) -dimethyl silane prepared in Example 1 was added to a 250 mL Schlenk flask. (2.5M in n-Hx) was added thereto at -78 ° C, and the mixture was stirred at room temperature for 5 hours. The mixture was cooled to -78 ° C and transferred to a Schlenk flask containing 1.7 g (5.2 mmol in 20 mL toluene) of HfCl ₄ solution at -78 ° C, which had been previously prepared, using a cannula, and the mixture was stirred at room temperature overnight. After completion of the reaction, the mixture was filtered with a glass frit (G4) containing celite. The solid remaining in the glass frit was washed three times with about 3 mL of dry toluene. The toluene solution was vacuum dried to obtain a red solid. Solids remaining in the glass frit were dissolved in dichloromethane (DCM). The DCM filtrate was vacuum dried to give a red solid. ^{As a} result of ¹ H-NMR analysis, both solids were Hf complexes of rac: meso = 1: 1. The crude product was collected and placed in an oil bath at 45 ° C and dissolved in 50 mL of dry toluene while stirring. This was stored in a -30 ° C freezer for 3 days and recrystallized. The resulting red solid was filtered with glass frit (G4), washed twice with 3 mL of dry n-hexane and dried in vacuo to give 1.0 g (1.2 mmol, 23% yield) of racemic final product.

^{1 H-NMR (Tol-d} 3): δ 7.23 (d, J = 9.0Hz, 2H, 7,7'-H in indenyl), 6.98 (d, J = 7.5Hz, 2H, 5,5'-H in quinolinyl), 6.90 (d, J = 7.0Hz, 2H, 5,5'-H in indenyl), 6.82-6.79 (m, 2H, 7,7'-H in quinolinyl), 6.72 (dd, J 1 = _{8.5 Hz, J 2 = 7.5Hz,} 2H, 6,6'-H in indenyl), 6.68-6.65 (m, 2H, 6,6'-H in quinolinyl), 6.57 (s, 2H, 3,3'- (M, 4H, 2,2'-H in quinolinyl), 2.63-2.53 (m, 1H), 6.51 (d, J = 8.5Hz, 2H, 4H, 4,3'-H quinolinyl), 2.03 (s, 6H, 2,2'-Me), 1.87-1.67 SiMe ₂ )

Comparative Example  One

rac -1, 1'- dimethytylsilylene - bis ( indenyl ) hafnium dichloride

The rac-1,1'-dimethytylsilylene-bis (indenyl) hafnium dichloride compound is disclosed in U.S. Pat. 5,905,162, which is incorporated herein by reference.

Preparation of propylene homopolymer

Example  3

A toluene solvent (200 mL) was added to a 300 mL minicable reactor, and then the temperature of the reactor was preheated to 70 占 폚. (5 x 10 ^-4 M, 1 mL) of the above-mentioned Example 1 treated with triisobutylaluminum compound in 5 mL of a 1 x 10 ^-3 M dimethylanilinium tetrakis (pentafluorophenyl) Lt; / RTI &gt; Polymerization was initiated while continuously injecting propylene (5 bar). After the polymerization reaction was carried out for 10 minutes, the remaining gas was taken out and the polymer solution was poured into an excessive ethanol-containing beaker to induce precipitation. The obtained polymer was washed with ethanol and acetone two to three times, respectively, and dried in a vacuum oven at 80 캜 for 12 hours or more, and then the physical properties thereof were measured.

Example  4

An olefin polymer was prepared in the same manner as in Example 3 except that the transition metal compound of Example 2 was used.

Comparative Example  2

An olefin polymer was prepared in the same manner as in Example 3 except that the transition metal compound of Comparative Example 1 was used.

The melting point (Tm) of the polymer was measured using Q100 from TA. The measurements were obtained through a second melting step, which was ramped to 10 ° C per minute to eliminate the thermal history of the polymer.

The properties of Examples 3 and 4 and Comparative Example 2 were measured in the same manner as described above, and the results are shown in Table 1 below.

Catalytic activity
(Unit: kg / mmol hr) Polymer weight
(Unit: g) Melting point
(Unit: ℃) Example 3 101 8.4 132.8 Example 4 204 17.0 144.8 Comparative Example 2 151 12.6 122.5

Referring to Table 1 above, the propylene polymer produced by Examples 3 and 4 exhibited a higher melting point (Tm) than the polymer of Comparative Example 2. That is, it was confirmed that an olefin polymer having a high isotacticity was obtained when the transition metal compound of the present invention was used as a catalyst.

Preparation of Ethylene-Propylene Copolymer

Example  5

A toluene solvent (0.8 L) and propylene (100 g) were added to a 2 L autoclave reactor, and then the temperature of the reactor was preheated to 70 캜. The transition metal compound (5 x 10 ^-4 M, 2 mL) of Example 1 treated with triisobutylaluminum compound was placed in a catalyst storage tank, and a high pressure argon pressure was applied to the reactor. The reactor was charged with 1 x 10 ^-3 M of dimethyl And 10 mL of anilinium tetrakis (pentafluorophenyl) borate co-catalyst were put in a reactor under high-pressure argon pressure in this order. 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 80 캜 for 12 hours or more, and then the physical properties thereof were measured.

Comparative Example  3

An olefin polymer was prepared in the same manner as in Example 5 except that the transition metal compound of Comparative Example 1 was used.

The density of the polymer was measured on a Mettler balance by making a sheet of 3 mm in thickness and 2 mm in radius with a 190 占 폚 press mold and cooling at 10 占 폚 / min. The melt flow rate (MFR) was measured in accordance with ASTM D-1238 (condition E, 230 캜, 2.16 kg load). The melting point (Tm) was measured using Q100 from TA. The measurements were obtained through a second melting step, which was ramped to 10 ° C per minute to eliminate the thermal history of the polymer.

The physical properties of Example 5 and Comparative Example 3 were measured in the same manner as described above, and the results are shown in Table 2 below.

Polymer weight
(Unit: g) density
(Unit: g / cc) Melt Index
(Unit: g / 10 min) Melting point
(Unit: ℃) Catalytic activity
(Unit: kg / mmol hr) Example 5 87.1 0.873 15 86 1045 Comparative Example 3 86.6 0.856 13 - 1040

Claims (7)

Reacting a compound represented by the following formula (3) and a compound represented by the following formula (4) to prepare a compound represented by the following formula (5); And
A process for producing a ligand compound represented by the following formula (1), comprising reacting a compound represented by the following formula (5) or a lithium salt thereof with a compound represented by the following formula (6)
(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

[Chemical Formula 1]

In the above Formulas 1, 3, 4, 5, and 6,
n is an integer of 1 to 2,
R ₁ to R ₁₀ are the same or different and each independently represents hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, An arylalkyl group having 7 to 20 carbon atoms or a silyl group, and R ₁ to R ₁₀ At least two adjacent to each other may be linked to each other by an alkylidene group containing an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms to form a ring;
R ₁₁ is hydrogen, a halogen group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms;
X ₃ is a halogen group;
Q is carbon or silicon.
The compound according to claim 1, wherein R ₁ to R ₁₀ in Formula 1 are each independently hydrogen or an alkyl group having 1 to 20 carbon atoms, and R ₁₁ is an alkyl group having 1 to 20 carbon atoms Or an aryl group having 6 to 20 carbon atoms.
The method for producing a ligand compound according to claim 1, wherein the compound represented by Formula 1 is represented by one of the following formulas:

A process for producing a transition metal compound represented by the following formula (2), comprising the step of reacting a ligand compound represented by the following formula (1) with a compound represented by the following formula (7)
[Chemical Formula 1]

(7)
M (X ₁ X ₂ ) ₂
(2)

In the above formulas (1), (2) and (7)
n is an integer of 1 to 2,
R ₁ to R ₁₀ are the same or different and each independently represents hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, An arylalkyl group having 7 to 20 carbon atoms or a silyl group, and R ₁ to R ₁₀ At least two adjacent to each other may be linked to each other by an alkylidene group containing an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms to form a ring;
R ₁₁ is hydrogen, a halogen group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms;
Q is carbon or silicon;
M is a Group 4 transition metal;
X ₁ and X ₂ are the same or different and each independently represents a halogen, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, An arylamino group having 1 to 20 carbon atoms, an alkylamino group having 1 to 20 carbon atoms, an arylamino group having 6 to 20 carbon atoms, or an alkylidene group having 1 to 20 carbon atoms.
The method for producing a transition metal compound according to claim 4, wherein R ₁ to R ₁₀ are each independently hydrogen or an alkyl group having 1 to 20 carbon atoms, and R ₁₁ is an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms.
5. The method for producing a transition metal compound according to claim 4, wherein M is selected from the group consisting of Ti, Zr and Hf.
The method for producing a transition metal compound according to claim 4, wherein the transition metal compound represented by Formula 2 is represented by one of the following formulas: