KR20150016831A - Method for preparing of novel ligand compound and transiton metal compound - Google Patents

Abstract

The present invention relates to a novel ligand compound and a method for producing a transition metal compound, and the ligand compound and the transition metal compound can be used for producing a polyolefin having a high melting point and excellent mechanical properties and processability.

Description

METHOD FOR PREPARING NOVEL LIGAND COMPOUND AND TRANSITON METAL COMPOUND BACKGROUND OF THE INVENTION 1. Field of the Invention [0001]

More particularly, the present invention relates to a novel ligand compound and a transition metal compound capable of providing a polyolefin having a high melting point and excellent mechanical properties and processability. And a manufacturing method thereof.

Ziegler-Natta catalysts of titanium or vanadium compounds have been widely used for the commercial production of polyolefins. Although the Ziegler-Natta catalysts have high activity, they have a wide molecular weight distribution of the produced polymers because of their high activity, The uniformity of the composition is not uniform and there is a limit in ensuring desired physical properties.

Recently, a metallocene catalyst in which a transition metal such as titanium, zirconium, or hafnium and a ligand containing a cyclopentadiene functional group are bonded has been developed and widely used. 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. These metallocene catalysts are single active site catalysts having one kind of active site. The molecular weight distribution of the produced polymer is narrow and the molecular weight, stereoregularity, crystallinity, especially reactivity of the comonomer can be greatly controlled depending on the structure of the catalyst and the ligand There is an advantage. However, the polyolefin polymerized with a metallocene catalyst has a low melting point and a narrow molecular weight distribution. Therefore, when the polyolefin is applied to some products, it is difficult to apply the polyolefin in a field such as the productivity is remarkably decreased due to the influence of extrusion load. We have done a lot of effort to control the distribution.

Particularly, in order to solve the problems of the metallocene catalyst described above, many transition metal compounds in which a ligand compound containing a hetero atom is coordinated have been introduced. Specific examples of such a heteroatom-containing transition metal compound include azaferrocene compound having a cyclopentadienyl group containing a nitrogen atom, a structure in which a functional group such as a dialkylamine is connected to a cyclopentadienyl group as an additional chain Or a titanium (lV) metallocene compound into which a cyclic alkylamine functional group such as piperidine is introduced, and the like.

However, among all of these attempts, the metallocene catalysts actually applied to commercial plants are only a few, and accordingly, polymerization catalysts capable of providing higher polymerization performance and capable of providing polyolefins having excellent physical properties There is still a need for research on available metallocene compounds.

The present invention is to provide a process for producing a novel ligand compound capable of providing a polyolefin having a high melting point and excellent mechanical properties and processability.

The present invention also provides a method for producing a transition metal compound capable of providing a polyolefin having a high melting point and excellent mechanical properties and processability.

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

The present invention also provides a process for producing a transition metal compound represented by the following general formula (2).

Hereinafter, a method for preparing a ligand compound and a transition metal compound according to a specific embodiment of the present invention will be described in detail.

According to an embodiment of the present invention, there is provided a process for preparing a compound represented by the following formula (5) by reacting a compound represented by the following formula (3) with a compound represented by the following formula (4) Reacting a compound represented by the following formula (4) with a compound represented by the following formula (6) to prepare a compound represented by the following formula (7); And a step of reacting a compound represented by the following formula (5) or a lithium salt thereof with a compound represented by the following formula (7).

(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

(R ₁₀ ) ₂ Q (X ₃ ) ₂

(7)

 [Chemical Formula 1]

In the above formulas (1) and (3) to (7)

R ₁ to R ₉ each independently represent 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 alkylaryl group having 7 to 20 carbon atoms , An arylalkyl 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, and a silyl group, or R ₁ to R ₉ Two or more of which are 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.

The R ₁₀ may be 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.

The Q may be carbon or silicon.

X ₁ , X _{2 ,} X _3, and X ₄ may be hydrogen, a halogen group, or an alkyl group having 1 to 20 carbon atoms.

The present inventors have found that, due to the inherent chemical structure of the ligand compound of Formula 1, it is possible to easily control the electronic / stereoscopic environment around the transition metal that can be bonded thereto, and can exhibit high reactivity in the polyolefin polymerization reaction But it has been confirmed through experimentation that a transition metal catalyst capable of easily controlling characteristics of the polyolefin to be synthesized, such as chemical structure, molecular weight distribution, and mechanical properties can be provided.

Particularly, the ligand compound of formula (1) has two indenyl groups connected to an acridine group, and the two indenyl groups have C1 symmetrical crosslinked structure connected by a silicon or carbon bridge, And a polyolefin having a high molecular weight and a high melting point can be produced. In addition, since the ligand compound of Formula 1 contains a large acridine group, it is possible to easily control the electronic and stereoscopic environment around the transition metal, and the transition metal compound containing the ligand compound is used as a catalyst, A polyolefin having regularity and a high molecular weight can be produced.

Each of the substituents defined in the above formulas (1) and (3) to (7) will be described below.

The alkyl group having 1 to 20 carbon atoms may include a linear or branched alkyl group, and the alkenyl group having 2 to 20 carbon atoms may include a straight chain or branched alkenyl group.

The aryl group is preferably an aromatic ring having 6 to 20 carbon atoms. Specific examples thereof include phenyl, naphthyl, anthracenyl, pyridyl, dimethylanilinyl, and anisole. However, the aryl group is not limited thereto.

The alkylamino group refers to an amino group to which one or more straight or branched alkyl groups having 1 to 20 carbon atoms are introduced, and specifically includes, but is not limited to, dimethylamino group, diethylamino group, and the like.

The arylamino group refers to an amino group having at least one aryl group having 6 to 20 carbon atoms introduced thereto, and specifically includes, but is not limited to, a diphenylamino group and the like.

The halogen group means fluorine (F), chlorine (Cl), bromine (Br) and iodine (I).

The silyl group may include a silyl functional group introduced with an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkylsilyl group having 1 to 20 carbon atoms, Specific examples thereof include trimethylsilyl, triethylsilyl, tripropylsilyl, tributylsilyl, trihexylsilyl, triisopropylsilyl, triisobutylsilyl, triethoxysilyl, triphenylsilyl, tris (trimethylsilyl) However, the present invention is not limited to these examples.

R ₁ to R ₉ in Formula 1 are each independently preferably hydrogen, an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and R ₉ is hydrogen or an aryl group having 6 to 20 carbon atoms.

And R ₁₀ in the formula (1) may be hydrogen or an alkyl group having 1 to 20 carbon atoms.

In the method for preparing the ligand compound of the above embodiment, the compound represented by Formula 5 may be prepared by first reacting the compound represented by Formula 3 with the compound represented by Formula 4.

More specifically, the acridine compound represented by Formula 3 and the indenyl compound represented by Formula 4 may be coupled to form a C-N bond.

At this time, the reaction between the compound represented by Formula 3 and the compound represented by Formula 4 below may be carried out in the presence of palladium catalyst. The palladium catalyst is a compound containing palladium, available, but the catalyst is not particularly limited, and tetrakis (triphenylphosphine) palladium (Pd (PPh _{3) 4),} palladium chloride (PdCl _2), palladium acetate (Pd ( OAc) _2), bis (dibenzylideneacetone) palladium (Pd (dba) _2), Pd (tBu ₃ P _2), and it may be more efficient to use a palladium catalyst such as, economically produce the compound represented by formula (5) It is preferable.

In addition, the step of preparing the compound represented by Formula 5 may further include a base. The base can effectively form a compound of the formula (5) by effectively mediating the reaction between the compound represented by the formula (3) and the compound represented by the formula (4), thereby reducing the reaction time .

Use The types of the base is not necessarily to be significantly limited, and specific examples tBuOLi, tribasic potassium (K ₃ PO _4), potassium carbonate (K ₂ CO _3), cesium carbonate (Cs ₂ CO _3), potassium fluoride (KF ), Sodium fluoride (NaF), cesium fluoride (CsF), tetrabutylammonium fluoride (TBAF), or mixtures thereof.

Next, the indenyl compound represented by the formula (4) or its lithium salt and the compound represented by the formula (6) may be reacted to prepare the compound represented by the formula (7). The lithium salt of the indenyl compound represented by Formula 5 may be prepared by reacting an indenyl compound with an organic lithium compound such as nBuLi.

In addition, the ligand compound represented by Formula 1 can be obtained by reacting the compound represented by Formula 5 or its lithium salt with the compound represented by Formula 7. As described above, the lithium salt of the indenyl compound represented by Formula 5 may be prepared by reacting an indenyl compound with an organic lithium compound such as nBuLi.

More specifically, after the compound represented by the formula (5) or the lithium salt thereof is mixed with the compound represented by the formula (7), 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 C1-symmetrically bridged by Q (carbon or silicon) .

The ligand compound of formula (1) prepared by the preparation method of one embodiment may have a mixed molar ratio of rac: meso of 3: 1 to 1: 3. This is because the compound represented by the formula (5) and the compound represented by the formula (7) may be bonded in a racemic structure or in a meso structure.

Meanwhile, the step of preparing the compound represented by the above general formula (5), (7) or (1) can be carried out by applying common organic synthesis conditions known in the art. For example, the reactants are mixed and reacted in a temperature range of -100 ° C to 300 ° C and a pressure range of 1 to 30 atmospheres, usually for about 24 hours until the reaction is completed, to obtain the compound represented by the above formula 5, 7 or 1 Can be manufactured.

At this time, preferred examples of the ligand compound represented by the formula (1) include compounds represented by the following formulas (11) to (14).

(11)

[Chemical Formula 12]

[Chemical Formula 13]

[Chemical Formula 14]

In the above formulas 11 to 14, Me is a methyl group.

According to another embodiment of the present invention, there is provided a process for preparing a transition metal compound represented by the following Chemical Formula 2, which comprises reacting a compound represented by Chemical Formula 1 or a lithium salt thereof with a compound represented by Chemical Formula 8 A method can be provided.

(2)

[Chemical Formula 8]

MX ₄

In the above formulas 2 and 8,

R ₁ to R ₉ each independently represent 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 alkylaryl group having 7 to 20 carbon atoms , An arylalkyl 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, and a silyl group, or R ₁ to R ₉ Two or more of which are 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.

The R ₁₀ may be 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.

The Q may be carbon or silicon.

The M may be a Group 4 transition metal.

X is 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 arylalkyl group having 7 to 20 carbon atoms, An alkylamino group, an arylamino group having 6 to 20 carbon atoms or an alkylidene group having 1 to 20 carbon atoms.

The present inventors have found that the electronic / stereoscopic environment around the transition metal can be easily controlled owing to the chemical structure of the transition metal compound of the above formula (2) in which a ligand compound of a specific structure is bonded to the transition metal, It is possible to provide a transition metal catalyst which can exhibit high reactivity and can easily control the characteristics such as the chemical structure, the molecular weight distribution, and the mechanical properties of the synthesized polyolefin.

In particular, as described above, the transition metal compound represented by Formula 2 includes two indenyl groups connected to an acridine group, and the two indenyl groups are connected to a silicon or carbon bridge via a C1 symmetric bridge structure ligand The inclusion of a chemical structure in which the indenyl group of the ligand is bonded to a transition metal atom enables the polyolefin to exhibit high reactivity in the polyolefin polymerization reaction and to produce a polyolefin having a high molecular weight and a high melting point. The transition metal compound of the above formula (2) contains a large acridine group, so that the electronic and stereoscopic environment around the transition metal can be easily controlled, and a polyolefin having a high stereoregularity and a high molecular weight can be produced .

The transition metal of the fourth group defined as M may be Ti (titanium), Zr (zirconium), hafnium (Hf) or the like, but is not limited thereto.

Each of R ₁ to R ₉ in Formula 2 is preferably independently hydrogen, an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and R ₉ is preferably hydrogen or an aryl group having 6 to 20 carbon atoms Do.

R ₁₀ in Formula 2 may be hydrogen or an alkyl group having 1 to 20 carbon atoms.

More specifically, the transition metal compound represented by Formula 2 may be prepared by mixing the ligand compound represented by Formula 1 or a lithium salt thereof and the metal compound represented by Formula 8, and reacting the mixture by stirring. Then, the reaction product is filtered to wash out the resulting precipitate, and dried under reduced pressure to obtain a transition metal compound represented by the general formula (2) in the form of a complex in which a transition metal atom is bonded to the ligand compound.

The ligand compound represented by the formula (1) may be used as a lithium salt by reacting with an organic lithium compound such as n-BuLi. When the ligand compound is transformed into a salt form and reacted with a transition metal compound, side reactions are less likely to occur and the reaction can proceed more efficiently.

The ligand compound represented by Formula 1 may be mixed with rac: meso at a ratio of 3: 1 to 1: 3. The ligand compound may be reacted with the compound represented by Formula 8, To obtain a racemic-type transition metal compound represented by the general formula (2). Specifically, the racemic and meso compounds differ in solubility, and only a racemic compound can be isolated by a simple recrystallization process.

Particularly, racemic transition metal compounds prepared by the above method can produce isotactic polymers, and thus polyolefins having excellent stereoregularity can be produced.

Meanwhile, the step of preparing the compound represented by the formula (2) may be carried out by applying conventional organic synthesis conditions known in the art. For example, the compound represented by the general formula (1) and the compound represented by the general formula (8) are mixed and reacted at a temperature of -100 ° C. to 300 ° C. and a pressure of 1 to 30 atm for about 24 hours To prepare a compound represented by the above formula (2).

At this time, preferred examples of the ligand compound represented by the formula (2) include compounds represented by the following formulas (21) to (28).

[Chemical Formula 21]

[Chemical Formula 22]

(23)

≪ EMI ID =

(25)

(26)

(27)

(28)

In the above formulas 21 to 28, Me is a methyl group.

According to the present invention, there can be provided a novel ligand compound and a method for producing a transition metal compound capable of providing a polyolefin having a broad molecular weight distribution and excellent mechanical properties and processability.

The invention will be described in more detail in the following examples. However, the following examples are illustrative of the present invention, and the present invention is not limited by the following examples.

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. In addition, a spectrum was obtained using a 400 MHz nuclear magnetic resonance (NMR) to demonstrate the structure of the compound.

< Example : Ligand  Synthesis of Compound and Transition Metal Compound &gt;

Example 1 : rac - dimethylsilylene -(4- phenyl -2- methyl -One H - inden -One- yl ) (4-dihydroacridinyl-2-methyl-1H-inden-1-yl) zirconium dichloride  synthesis

(1) Ligand ((4- phenyl -2- methyl -One H - inden -One- yl )(4- 다 디아라드리닐 -2-methyl-1H-inden-1-yl) dimethyl silane ) Synthesis of

To the 100 mL Schlenk flask, 10- (2-methyl- 1H-inden-4-yl) -9,10-dihydroacridine (5.0 g, 16.2 mmol) was added and 80 mL of dry diethyl ether was added to dissolve the starting material. Was added n-BuLi (2.5 M in n-Hx) (7.1 mL), and the mixture was stirred overnight at room temperature and filtered using glass frit (G4). Then, the solid remaining in the glass frit was vacuum dried to obtain a lithiated product (4.6 g, 90% yield) of a white solid. The lithiated product (2.58 g, 8.18 mmol) and chloro (2-methyl-4-phenyl-1H-inden-1-yl) dimethyl silane (2.45 g, 8.18 mmol) were placed in a 100 mL Schlenk flask, 33 mL of dry diethyl ether was added and the mixture was stirred at room temperature overnight. After completion of the reaction, 100 mL of deionized water was added to terminate the reaction. The organic layer was separated from the water layer, dried over MgSO ₄ , filtered, and vacuum dried to obtain a light yellow solid ligand compound (4.38 g, quantitative yield relative to lithiated product, 90% yield based on starting material). ¹ H-NMR analysis showed that the racemic: meso ratio was about 2: 1.

_{^{1 H-NMR (CDCl 3)}} : δ7.62 ~ 6.83 (m, 29H in rac- and meso-isomers), 6.36 (s, 1H in meso-isomers), 6.18 ~ 6.16 (m, 2H in rac-isomers) , 4.30-4.26 (m, 3H in rac- and meso-isomer), 3.92-3.86 (m, 3H in rac- and meso-isomer), 2.33-2.07 0.21 to -0.23 (m, 9H in rac- and meso-isomer)

(2) Transition metal compound ( rac - dimethylsilylene -(4- phenyl -2- methyl -One H - indedn -1-yl) (4-dihydroacridinyl-2-methyl-1H-inden-1-yl) zirconium dichloride ) Synthesis of

(4-dihydroquinolin-1 (2H) -yl) -2-methyl-1H-inden-1-yl) (2.5M in n-Hx) was added at -78 ° C, and the mixture was stirred at -78 ° C for 2 hours. 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 the lithiated product of the white solid. The lithiated product (2.0 g, 3.5 mmol) and ZrCl ₄ (0.9 g, 3.8 mmol) were placed in a 100 mL Schlenk flask in a glove box, and then 10 mL of dry hexane and 40 mL of diethyl ether were added in this order, followed by stirring at room temperature overnight Respectively. After completion of the reaction, the solution was filtered with a glass frit (G4) containing celite. 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 Zr complex was racemic: meso = 1: 1. The crude product was collected and recrystallized in a -30 ° C freezer with dry toluene and pentane. The resulting red solid was filtered with glass frit (G4), washed twice with 10 mL of dry n-pentane, and dried in vacuo to give 0.24 g (10% yield) of racemic final product.

_{^{1 H-NMR (CDCl 3)}} : δ7.80 ~ 6.67 (m, 21H), 4.09 (s, 2H), 2.35 (d, 6H), 1.36 (s, 3H), 1.31 (s, 3H)

Example  2 : rac - dimethylsilylene -(4- phenyl -2- methyl -One H - inden -One- yl ) (4-dihydroacridinyl-2-methyl-1H-inden-1-yl) hafnium dichloride Synthesis of

A ligand compound and a transition metal compound were synthesized in the same manner as in Example 1, except that HfCl ₄ was used instead of ZrCl ₄ .

_{^{1 H-NMR (CDCl 3)}} : δ7.80 ~ 6.67 (m, 21H), 4.09 (s, 2H), 2.10 (d, 6H), 1.10 (s, 3H), 1.04 (s, 3H)

< Comparative Example  >

Comparative Example 1 : rac -1,1 ' dimethylsilylene - bis ( indenyl ) hafnium dichloride Synthesis of

U.S. Pat. 5,905,162.

< Experimental Example  >

Experimental Example 1 : Preparation of propylene homopolymer

A toluene solvent (0.2 L) was added to a 250 mL minicable reactor, and the temperature of the reactor was preheated to 70 캜. 0.2 ml of a dimethylanilinium tetrakis (pentafluorophenyl) borate co-catalyst of 5 x 10 ^-6 M was put into a reactor with a syringe, and then the transition of the above Examples 1 to 2 and Comparative Example 1 treated with triisobutyl aluminum compound A metal compound (1 x 10 ^-6 M, 0.1 mL) was charged to the reactor. Polymerization was carried out by injecting 5 bar of propylene for 10 minutes. After the polymerization reaction was carried out for 10 minutes, the remaining gas was removed and the polymer solution was cooled by adding excess ethanol 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.

The physical properties of the propylene homopolymer prepared using the transition metal compounds prepared in the above Examples and Comparative Examples are shown in Table 1 below.

catalyst
(μmol) Catalytic activity
(kg / mmol hr) Polymer weight
(g) Melting point
(° C) Example 1 0.3 140 7.0 153.8 Example 2 1.0 9 1.5 146.7 Comparative Example 1 0.1 151 12.6 122.5

As shown in Table 1, the propylene polymer prepared using the catalysts of Examples 1 and 2 exhibited a higher melting point (T _m ) than that of Comparative Example 1. From these results, it can be confirmed that an olefin polymer having a high isotacticity can be prepared by using the transition metal compound of the above-mentioned examples as a catalyst.

Experimental Example 2 : Preparation of Ethylene-Propylene Copolymer

A toluene solvent (0.8 L), propylene (250 g) and ethylene (70 psi) were added to a 2 L autoclave reactor, the pressure was adjusted to 500 psi with hot argon pressure, and the reactor temperature was preheated to 70 캜. Then, 5x10 ^-6 M dimethylanilinium tetrakis (pentafluorophenyl) borate promoter was added to the reactor in the amount shown in Table 2 below, and the amount of the catalyst of Example 1 and Comparative Example 1 treated with triisobutyl aluminum compound The transition metal compound (1 x 10 ^-6 M, 0.1 mL) was placed in the catalyst storage tank and high pressure argon pressure was applied. The reaction heat was removed through a cooling coil inside the reactor, and the polymerization reaction was continued for 10 minutes while maintaining the polymerization temperature at a constant level. After the remaining gas was removed from the reactor, the resulting polymer solution was discharged to the lower portion of the reactor and cooled with excess ethanol to induce precipitation. The polymer thus obtained was washed with ethanol and acetone two to three times, respectively, and then dried in a vacuum oven at 80 캜 for 12 hours or more and the physical properties thereof were measured.

Properties of the ethylene-propylene copolymer prepared using the transition metal compound prepared in the above Examples and Comparative Examples are shown in Table 2 below.

The melt flow rate (MFR) of the polymer was measured by ASTM D-1238 (condition E, 230 ° C, 2.16 kg load) and the melting point (Tm) was measured using Q100 from TA. The measured values were obtained by heating the polymer to 10 ° C / min to eliminate the thermal history of the polymer and then through a second melting.

Amount of cocatalyst
(mL) Catalytic activity
(kg / mmol hr) Polymer weight
(g) density
(g / cc) Melting point
(° C) Melt Index
(g / 10 min) Example 1 0.2 1,049 43.7 0.873 72.4 17.1 Comparative Example 1 1.0 1,040 86.6 0.856 - 13

As shown in Table 2, it can be confirmed that the ethylene-propylene polymer produced by Example 1 exhibits excellent properties such as a high melting point and a melt index as compared with Comparative Example 1.

Claims (14)

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);
Reacting a compound represented by the following formula (4) with a compound represented by the following formula (6) to prepare a compound represented by the following formula (7); And
A process for preparing 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 (7)
(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]
(R ₁₀ ) ₂ Q (X ₃ ) ₂
(7)

[Chemical Formula 1]

In the above formulas (1) and (3) to (7)
R ₁ to R ₉ each independently represent 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 alkylaryl group having 7 to 20 carbon atoms , An arylalkyl 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, and a silyl group,
Alternatively, R ₁ to R ₉ Two or more of which are 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 ₁₀ 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,
X ₁ , X _{2 ,} X ₃ and X ₄ are hydrogen, a halogen group, or an alkyl group having 1 to 20 carbon atoms.
The method according to claim 1,
Wherein the step of preparing the compound represented by the formula (5) is carried out in the presence of a palladium catalyst.
3. The method of claim 2,
The palladium catalyst may be at least one selected from the group consisting of tetrakis (triphenylphosphine) palladium (Pd (PPh ₃ ) ₄ ), palladium chloride (PdCl ₂ ), palladium acetate (Pd (OAc) ₂ ), bis (dibenzylideneacetone) palladium dba) _2), and Pd (tBu ₃ P ₂₎ method of producing a ligand compound comprising at least one catalyst selected from the group consisting of.
The method according to claim 1,
Wherein the step of preparing the compound represented by the general formula (5) is carried out by further comprising a base.
The method according to claim 1,
Wherein each of R ₁ to R ₉ in Formula 1 is independently hydrogen, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms.
The method according to claim 1,
Wherein R ₁₀ in Formula 1 is hydrogen or an alkyl group having 1 to 20 carbon atoms.
The method according to claim 1,
Wherein the ligand compound represented by Formula 1 has a mixed molar ratio of rac: meso of 3: 1 to 1: 3.
The method according to claim 1,
Wherein the compound represented by Formula 1 is a compound selected from the group consisting of compounds represented by Formulas 11 to 14:
(11)

[Chemical Formula 12]

[Chemical Formula 13]

[Chemical Formula 14]

In the above formulas (11) and (14), Me is a methyl group.
A process for producing a transition metal compound represented by the following formula (2), comprising reacting a compound represented by the formula (1) or a lithium salt thereof with a compound represented by the following formula (8)
(2)

[Chemical Formula 8]
MX ₄
In the above formulas 2 and 8,
R ₁ to R ₉ each independently represent 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 alkylaryl group having 7 to 20 carbon atoms , An arylalkyl 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, and a silyl group,
Alternatively, R ₁ to R ₉ Two or more of which are 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 ₁₀ 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 transition metal of Group 4,
X is 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 arylalkyl group having 7 to 20 carbon atoms, An amino group, an arylamino group having 6 to 20 carbon atoms or an alkylidene group having 1 to 20 carbon atoms.
10. The method of claim 9,
Wherein M is selected from the group consisting of Ti, Zr and Hf.
10. The method of claim 9,
Wherein each of R ₁ to R ₉ in Formula 2 is independently hydrogen, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms.
10. The method of claim 9,
Wherein R ₁₀ in Formula 2 is hydrogen or an alkyl group having 1 to 20 carbon atoms.
10. The method of claim 9,
Wherein the transition metal compound represented by Formula 2 is a racemic type.
10. The method of claim 9,
Wherein the transition metal compound represented by Formula 2 is represented by one of the following Chemical Formulas 21 to 28:
[Chemical Formula 21]

[Chemical Formula 22]

(23)

&Lt; EMI ID =

(25)

(26)

(27)

(28)

In the above formulas 21 to 28, Me is a methyl group.