KR100676302B1 - Preparation method of ansa-metallocene compounds - Google Patents

Abstract

The present invention provides a process for preparing an ansa-metallocene compound having a substituent only at the alpha position, which is particularly suitable for the copolymerization of ethylene with alpha olefins or cycloolefins.

Since the method for preparing an ansa-metallocene compound according to the present invention can be easily and economically prepared, it is possible to commercially mass produce the ansa-metallocene compound.

Ansa-metallocenes, catalysts, bridges, silicones, olefins

Description

Preparation method of ansa-metallocene compound {Preparation method of ansa-metallocene compounds}

The present invention relates to a method for synthesizing ansa-metallocene catalyst having a substituent only at the alpha position.

The metallocene compound refers to a Group 4 transition metal compound having one or two cyclopentadienyl groups as ligands, which can be used as a catalyst for olefin polymerization by activating with methylaluminoxane or boron compound. 5,580,939; Macromol. Chem. Phys., Vol. 197, 1996, 3707-3945) Since these metallocene catalysts have a uniform activity point, the molecular weight distribution of the polymer is narrow, the copolymerization is easy, and the distribution of the second monomer Is uniform, and in the case of propylene polymerization, there is an advantage in that the steric structure of the polymer can be controlled according to the symmetry of the catalyst. In particular, existing Ziegler-Natta catalysts can only produce isotactic polypropylene, but with metallocene catalysts, isotactic, syndiotactic, atactic and of course hemiisotactic Various polypropylenes, such as hemisotactic, can be produced stereoregularly. For example, the syndiotactic polypropylene synthesized using metallocene has low crystallinity, moderate stiffness and hardness, transparency, and high impact resistance.

Thanks to the development of this catalyst system, LLDPE, VLDPE, EPM, EPDM, which are copolymers of ethylene and alpha olefins, cycloolefin copolymers (COC), which are copolymers of ethylene and cycloolefins or alpha and cycloolefins, ethylene and alpha olefins and styrene Efforts have been made to find suitable catalysts for the production of copolymers. Commonly required catalyst conditions for the preparation of these products are that they must be capable of producing polymers with good activity, good reactivity to the second monomer, and a uniform distribution of the second monomer.

On the other hand, metallocene catalysts are more economically valuable because they have higher activity than conventional Ziegler-Natta catalysts. In particular, when the reactivity to the second monomer is good, even if the second monomer is added in a small amount, There is an advantage that a polymer containing a large amount of monomers can be obtained.

In general, it is known that bridged catalysts are highly reactive with the second monomer. Specifically, FJ Karol's research indicates that in order to produce LLDPE products with a density of 0.930 using 1-hexene as the second monomer, For bridged catalysts it was found that the ratio of ethylene and hexene only needs to be 0.004 to 0.005, but for bridged catalysts the ratio is required to 0.02 (April 18, 1997, Palm Coast, FL, Polymer Reaction Engineering Foundation). Conference).

Therefore, attention is focused on bridged catalysts to produce the above-mentioned copolymers, which also have the advantage that the molecular structure of the propylene polymer can be adjusted according to the symmetry of the molecules. Bridged catalysts studied so far can be classified into three types depending on the type of bridge. (-Linked by - (CH ₂ CH ₂₎ - the two cyclopentadienyl ligands connected to an ethylene bridge the catalyst (a), -SiR ₂ by the silicon-bridged catalyst (b) connected by a, -CR ₂ This is methylene bridged catalyst (c) The general synthesis method thereof is represented by the following reaction scheme.

The two cyclopentadienyl rings in the bridged catalyst may be variously substituted with various substituents starting from the absence of any substituents. However, when the ligand was synthesized by the conventional method, it was impossible to substitute the substituent only at the alpha position. The reason for this is as shown in the above synthesis method, and the existing method of synthesizing the bridged ligand is a cyclopentadienyl anion having a substituent. Is synthesized by nucleophilic substitution of ethylenedibromide, dialkylsiliconedichloride or fulven, in which case the substituents go to the beta position of cyclopentadienyl due to steric hindrance. When reacted with a cyclopentadienyl anion having two substituents at the 1,3-position, only ligands having substituents at the alpha position and the beta position are generated, and no ligands having substituents at the alpha position are generated.

In the metallocene catalyst, the portion where the monomer enters and the polymer grows is opposite the bridge, ie the beta position of cyclopentadienyl. Therefore, in the case of the metallocene compound having a substituent only at the alpha position of cyclopentadienyl, since there is no substituent at the beta position of the cyclopentadienyl, monomers having high steric hindrance can be easily accommodated and copolymerization becomes easy. There is this. Catalysts with the least steric hindrance are catalysts with only bridges and no substituents, but these catalysts generally have low activity and poor copolymerization. This is because not only the steric hindrance effect but also the electronic effect affects the activity and copolymerization of the catalyst. In other words, when a substituent giving an electron such as an alkyl group is substituted with a cyclopentadienyl ring, activity and copolymerization increase.

Korean Patent Publication No. 398740 discloses an ansa-metallocene catalyst having a substituent only at an alpha position and a method of preparing the same, but the synthesis of the starting material 1,4-pentadiene is not economical, and a series of The production process must be carried out under conditions of high temperature and high pressure, and there are many reaction steps, which makes it difficult to produce the catalyst in commercial quantities.

The first technical problem to be achieved by the present invention is to provide a method for preparing an ansa-metallocene compound bridged by silicon atoms.

The second technical problem to be achieved by the present invention is to provide a method for preparing an ansa-metallocene compound bridged with carbon atoms.

The third technical problem to be achieved by the present invention is to provide another method for preparing an ansa-metallocene compound bridged with carbon atoms.

The present invention to achieve the first technical problem,

(a) reacting a compound of formula 1 with lithium chloride or Grignard reactant with a compound of formula 5, followed by acid treatment to prepare a compound of formula 6; And

(b) preparing a compound of Formula 7 from a compound of Formula 6;                     

[Formula 1]

[Formula 5]

R ³ R ⁴ SiX ₂

[Formula 6]

[Formula 7]

In the above formula, R ¹ , R ² , R ³ R ⁴ and R ⁵ are each independently a hydrogen atom; An alkyl group having 1 to 20 carbon atoms; An alkoxy group having 1 to 10 carbon atoms; Aryl groups having 6 to 20 carbon atoms; Aryloxy groups having 6 to 10 carbon atoms; Alkenyl having 2 to 20 carbon atoms; Alkylaryl groups having 7 to 40 carbon atoms; Arylalkyl groups having 7 to 40 carbon atoms; Arylalkenyl having 8 to 40 carbon atoms; Alkynyl having 2 to 10 carbon atoms; Or a metalloid radical of a Group 14 metal substituted with hydrocarbyl, wherein R ₁ and R ₂ are not simultaneously hydrogen, and R ³ and R ⁴ comprise an alkyl of 1 to 20 carbon atoms or an aryl radical of 6 to 20 carbon atoms. Can be linked to each other by an alkylidine radical to form a ring; Q ¹ and Q ² are each independently a halogen atom; Alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 10 carbon atoms, alkylaryl having 7 to 40 carbon atoms, or arylalkyl having 7 to 40 carbon atoms; Aryl having 6 to 20 carbon atoms; Substituted or unsubstituted alkylidene having 1 to 20 carbon atoms; Substituted or unsubstituted amino group; Alkylalkoxy having 2 to 20 carbon atoms; Or an aryl alkoxy group having 7 to 40 carbon atoms; X is a halogen atom; M is a Group 4 transition metal.

The present invention to achieve the second technical problem,

(a) reacting a compound of formula 1 with lithium chloride or Grignard reactant with a compound of formula 8 and then reacting R ⁶ -Y with acid to prepare a compound of formula 9;

(b) preparing a compound of formula 12 by reacting alkyllithium with the compound of formula 9 prepared in (a); And

(c) provides a method for preparing an ansa-metallocene compound of formula 10 comprising the step of preparing a compound of formula 10 from the compound of formula 12 prepared in (b).

[Formula 8]

R ³ C (O) OR ⁴

[Formula 9]

[Formula 10]

[Formula 12]

R ¹ , R ² , R ³ , R ⁴ , M, Q ¹ and Q ² in the formula are the same as defined above; R ⁶ is an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an alkenyl having 2 to 20 carbon atoms, or an alkylaryl having 7 to 40 carbon atoms. A metalloid radical of a Group 14 metal substituted with a group, an arylalkyl group having 7 to 40 carbon atoms, arylalkenyl having 8 to 40 carbon atoms, alkynyl having 2 to 10 carbon atoms, or hydrocarbyl; R ⁷ is a hydrogen atom; An alkyl group having 1 to 20 carbon atoms; An alkoxy group having 1 to 10 carbon atoms; Aryl groups having 6 to 20 carbon atoms; Aryloxy groups having 6 to 10 carbon atoms; Alkenyl having 2 to 20 carbon atoms; Alkylaryl groups having 7 to 40 carbon atoms; Arylalkyl groups having 7 to 40 carbon atoms; Arylalkenyl having 8 to 40 carbon atoms; Alkynyl having 2 to 10 carbon atoms; Or a metalloid radical of a Group 14 metal substituted with hydrocarbyl; Y is a halogen or sulfonyl group.

The present invention to achieve the third technical problem,

(a) reacting the compound of Formula 1 with lithium chloride or Grignard reactant with the compound of Formula 8 and then reacting R ⁶ -Y with acid to prepare a compound of Formula 9;

(b) preparing a compound of formula 11 by reacting a base with the compound of formula 9 produced in step (a);

(c) preparing a compound of Chemical Formula 12 by reacting an alkyllithium or Grignard reactant with the compound of Chemical Formula 11 produced in (b); And

(d) provides a method for preparing the ansa-metallocene compound of Formula 10 comprising the step of preparing the compound of Formula 10 from the compound of Formula 12 produced in (c).

[Formula 11]

In the above formula, R ¹ , R ² , R ³ , R ⁶ are the same as defined above. Y is the same as defined above.

By using the above-described preparation method, an anza-metallocene compound having a substituent only at an alpha position can be more easily and economically produced.

Hereinafter, the present invention will be described in more detail.

The present invention provides an ansa-metallocene compound of Formula 7 and a method of preparing ansa-metallocene compound of Formula 10.                     

[Formula 7]

[Formula 10]

The compound of Chemical Formula 7 may be prepared by the following Scheme 1.

Scheme 1

In Reaction Scheme 1, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , M, X, Q ¹ and Q ² are as described above.

The compound of (1) which is a starting material in Scheme 1 may be prepared by the following Scheme 2. That is, the 2-bromo-3-alkyl-2-cyclopenten-l-one compound was dissolved in THF solvent and then reacted for 1 hour by adding R ¹ Li at -78 ° C to R ₅ -X (X = Halogen) to give the compound of (1). This starting material was dissolved in THF solvent, and then reacted with butyllithium at -78 ° C to prepare lithium salt or treated with Grignard reagent instead of butyllithium to prepare Grignard reactant, and the lithium salt prepared as described above or To the Grignard reactant, 0.5 equivalent of the compound represented by the following Chemical Formula 5 at -30 ° C was reacted for about 5 hours while slowly raising to room temperature, followed by acid treatment to obtain the compound of Chemical Formula 6, and to the ligand by a known method. The ansa-metallocene compound of the formula (7) can be prepared.

The method for preparing the ansa-metallocene compound of Chemical Formula 7 in the compound of Chemical Formula 6 will be described in detail as follows. However, the following contents are not limited thereto.

When the lithium salt or sodium salt of formula 6 is reacted with TiCl ₄ or ZrCl ₄ as a catalyst precursor with simple stirring, lithium chloride or sodium chloride is precipitated to prepare a compound of formula 7. In addition, TiCl ₃ (THF) ₃ or ZrCl ₄ (THF) ₂ may be used as the catalyst precursor, in which case M is a Group 4 transition metal such as Ti, Zr, Hf, and Q ¹ and Q ² correspond to a halogen group. In another method, the compound of Formula 6 is dehydrated by reacting Formula 6 and M (alkyl) ₄ , M (aryl) ₄ , M (amino) ₄ , or M (alkoxy) ₄ as a catalyst precursor with simple stirring. There is also a method for preparing a compound of formula 7 while being digested. In this case, M is a Group 4 transition metal such as Ti, Zr, Hf, and Q ¹ and Q ² are alkyl, aryl, amino, alkoxy groups, and the like.

Scheme 2

In Scheme 2, R ¹ , R ² , R ⁵ , and X are as described above.

On the other hand, the compound of Formula 10 may be prepared by the following Scheme 3.

Scheme 3

In Scheme 3, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , M, X, Y, Q ¹ and Q ² are as described above.

A lithium salt is prepared by reacting a starting compound with butyllithium or a Grignard reagent instead of butyllithium to prepare a Grignard reactant, and 0.5 g of the lithium salt or Grignard reactant prepared as described above. When an equivalent amount of the compound of formula 8 is added and subsequently reacted with R ₆ Y to react with acid, an ether compound of formula 9 is obtained, and an alkali is treated with the ether compound to obtain a fulvene compound of formula 11. When 3 equivalents of an alkyllithium or Grignard reactant is added to the fulvene compound of Formula 11 obtained as described above, a lithium compound of Formula 12 is obtained, and the ansa-metallocene compound of Formula 10 is attached to the metal by various methods known in the art. Can be prepared.

The method for preparing the ansa-metallocene compound of Formula 10 from the compound of Formula 12 will be described in detail as follows, but the following contents are not limited thereto.

When the lithium salt or sodium salt of formula 12 is reacted with TiCl ₄ or ZrCl ₄ as a catalyst precursor with simple stirring, lithium chloride or sodium chloride is precipitated to prepare a compound of formula 10. In addition, TiCl ₃ (THF) ₃ or ZrCl ₄ (THF) ₂ may be used as the catalyst precursor, in which case M is a Group 4 transition metal such as Ti, Zr, Hf, and Q ¹ and Q ² correspond to a halogen group. In another method, the compound of formula 12 is dehydrogenated by reacting with formula 12 and M (alkyl) ₄ , M (aryl) ₄ , M (amino) ₄ , or M (alkoxy) ₄ as a catalyst precursor with simple stirring. There is also a method for preparing a compound of formula (10). In this case, M is a Group 4 transition metal such as Ti, Zr, Hf, and Q ¹ and Q ² are alkyl, aryl, amino, alkoxy groups, and the like.

On the other hand, when a lithium compound of Formula 12 is obtained, R ⁶ OLi is produced as a by-product, which can be easily separated due to a difference in solubility. The alkali is preferable that the NaH, and also R ⁶ Y is preferably CH ₃ I.

In addition, the compound of Formula 10 may also be prepared by the following Scheme 4.                     

Scheme 4

In Scheme 3, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , M, X, Y, Q ¹ and Q ² are as described above.

A lithium salt is prepared by reacting a starting compound with butyllithium or a Grignard reagent instead of butyllithium to prepare a Grignard reactant, and 0.5 g of the lithium salt or Grignard reactant prepared as described above. When an equivalent amount of the compound of Formula 8 is added and subsequently reacted with R ⁶ Y to react with acid, an ether compound of Formula 9 is obtained, and 4 equivalents of an alkyllithium or Grignard reactant is added to the ether compound to form lithium. An ansa-metallocene compound of Formula 10 can be prepared by obtaining a compound and attaching a metal to it in various ways known in the art.

The method for preparing the ansa-metallocene compound of Formula 10 from the compound of Formula 12 will be described in detail as follows, but the following contents are not limited thereto.

When the lithium salt or sodium salt of formula 12 is reacted with TiCl ₄ or ZrCl ₄ as a catalyst precursor with simple stirring, lithium chloride or sodium chloride is precipitated to prepare a compound of formula 10. In addition, TiCl ₃ (THF) ₃ or ZrCl ₄ (THF) ₂ may be used as the catalyst precursor, in which case M is a Group 4 transition metal such as Ti, Zr, Hf, and Q ¹ and Q ² correspond to a halogen group. In another method, the compound of formula 12 is dehydrogenated by reacting with formula 12 and M (alkyl) ₄ , M (aryl) ₄ , M (amino) ₄ , or M (alkoxy) ₄ as a catalyst precursor with simple stirring. There is also a method for preparing a compound of formula (10). In this case, M is a Group 4 transition metal such as Ti, Zr, Hf, and Q ¹ and Q ² are alkyl, aryl, amino, alkoxy groups, and the like.

R ⁶ Y is preferably CH ₃ I.

Hereinafter, the structure and effects of the present invention will be described in more detail with specific examples and comparative examples, but these examples are only intended to more clearly understand the present invention and are not intended to limit the scope of the present invention.

In the following examples, the reagents and solvents were purchased from Aldrich and Merck and purified by standard methods, and the contact between air and moisture was blocked at all stages of the synthesis to increase the reproducibility of the experiment. On the other hand, the spectrum was obtained by using a 400MHz nuclear magnetic resonance to prove the structure of the compound.

Example 1 Bis- (1,3-dimethyl-cyclopenta-1,3-dienyl) -dimethyl-silane titanium dichloride (Bis- (1,3-dimethyl-cyclopenta-1,3-dienyl)- Preparation of Dimethyl-silane Titanium Dichloride

(1) of bis- (1,3-dimethyl-cyclopenta-1,3-dienyl) -dimethyl-silane (Bis- (1,3-dimethyl-cyclopenta-1,3-dienyl) -dimethyl-silane) Produce

2-bromo-3-methoxy-1,3-dimethyl-cyclopentene (5-bromo-3-methoxy-1,3-dimethyl-cyclopentene) (5 g, 24.38 mmol) dissolved in 30 ml of diethyl ether Using nitrogen, the mixture was made at -30 ° C under nitrogen atmosphere, and then n-butyl lithium (6.67 g) was added and the temperature was increased to react for 15 minutes. At this time, when a white solid was formed, the mixture was lowered to -30 ° C, and 0.5 equivalent of Me ₂ SiCl ₂ (1.57 g) was added thereto, followed by reaction for 5 hours while slowly raising to room temperature. To this, 20 ml of water and 20 ml of ethyl acetate were added and the water layer was washed once again with 20 ml of ethyl acetate, stirred for 3 minutes with 50 ml of 1N HCl, neutralized with 50 ml of saturated sodium bicarbonate, and then the solvent was rotated with a rotary evaporator. Removed and water was removed with magnesium sulfate. Finally, purification was performed by column chromatography using silica (nucleic acid) to obtain bis- (2,5-dimethyl-cyclopenta-1,4-dienyl) -dimethyl-silane at a yield of 66%.

(2) bis- (1,3-dimethyl-cyclopenta-1,3-dienyl) -dimethyl-silane titanium dichloride (Bis- (1,3-dimethyl-cyclopenta-1,3-dienyl) -dimethyl- Preparation of silane titanium dichloride

After dissolving the compound (1.85g, 7.98mmol) prepared in step (1) in 20ml of tetrahydrofuran, the temperature was lowered to -78 ° C in a nitrogen atmosphere using a Schlenkline, and n-butyl lithium (4.42g , 15.95 mmol) and 2 equivalents were added and reacted for 12 hours. At this time, the lithium salt produced in white was filtered and washed with a small amount of hexane to obtain a lithium salt.

¹ H NMR (pyridine-d ₅ ): δ6.49 (s, 4H, Cp-H), 2.79 (s, 12H, C H ₃ ), 1.22 (s, 6H, SiC H ₃ ).

The mass of lithium salt (300 mg, 0.87 mmol) and TiCl ₃ (THF) ₃ (324.2 mg, 0.87 mmol) obtained in the above was placed in a flask, and 2.5 ml of pyridine at −30 ° C. was added and reacted for 2 hours. Pyridine was removed under reduced pressure, PbCl ₂ (242 mg) was added, and the reaction was carried out in 2 ml of solvent tetrahydrofuran for 1 hour, and then the solvent was removed using reduced pressure, and then dissolved in methylene chloride and filtered. Next, the methylene chloride was removed and pentane was used to obtain a solid resultant compound. (Yield: 52%)

¹ H NMR (CDCl ₃ ): δ 7.05 (s, 4H, Cp-H), 2.23 (s, 12H, C H ₃ ), 1.04 (s, 6H, SiC H ₃ )

Example 2 Bis- (1,3-dimethyl-cyclopenta-1,3-dienyl) -dimethyl-silane zirconium dichloride (Bis- (1,3-dimethyl-cyclopenta-1,3-dienyl)- Preparation of Dimethyl-silane Zirconium Dichloride

After dissolving the compound (1.85g, 7.98mmol) prepared in Example 1 (1) in 20ml of tetrahydrofuran, the temperature was lowered to -78 ° C in a nitrogen atmosphere using a Schlenkline, and n-butyl lithium (4.42 g, 15.95 mmol) 2 equivalents were added and reacted for 12 hours. At this time, the lithium salt produced in white was filtered and washed with a small amount of hexane to obtain a lithium salt.

¹ H NMR (pyridine-d ₅ ): δ6.49 (s, 4H, Cp-H), 2.79 (s, 12H, C H ₃ ), 1.22 (s, 6H, SiC H ₃ ).

The mass of the lithium salt (50mg, 0.22mmol) and ZrCl ₄ (49mg, 0.22mmol) obtained in the above was placed in a flask and reacted for 3 hours by adding 2 ml of pyridine at -30 ° C. Pyridine was removed under reduced pressure, dissolved in toluene, filtered to remove toluene, and pentane was used to obtain a solid resultant compound (yield: 47% (28 mg)).

Example 3 Preparation of ethylidene bis- (1,3-dimethyl-cyclopenta-1,3-dienyl) zirconium dichloride (zideconium dichloride)

(1) Preparation of ethylidene bis- (1,3-dimethyl-cyclopenta-1,3-diene)

2-Bromo-3-methoxy-1,3-dimethyl-cyclopentene (4 g, 19.5 mmol) was added to 20 ml of ether in a Schlenk flask under a nitrogen atmosphere, and n-butyllithium (5.41 g, 19.5mmol) was dropped one by one and stirred at room temperature for 30 minutes to form a white lithium salt. Again, the temperature was lowered to -30 ° C, ethyl formate (0.72 g, 9.75 mmol) was added dropwise, and stirred for 1 hour at room temperature.

The ether was removed using reduced pressure and 20 ml of dimethylformamide was incorporated as fresh solvent. Then, sodium hydride (NaH) (0.47 g, 19.5 mmol) was added under a nitrogen atmosphere and stirred for 1 hour, followed by dropwise addition of methyl iodide (CH ₃ I) (8.30 g, 58.5 mmol) to 30 ° C. Stir for one day while heating. The resultant was extracted with 40 ml of water and 40 ml of hexane, washed three times with 20 ml of brine, hexane was removed, dehydrogenated with 4 ml of ethyl acetate and 12 ml of 2N hydrogen chloride, and neutralized with 16 ml of sodium bicarbonate. Finally, water was removed with magnesium sulfate (MgSO ₄ ), and the solvent was removed under reduced pressure to obtain a result. (Yield: 90%).

¹ H-NMR (CDCl ₃ ): δ 5.83 (d, J = 1.6 Hz, 2H, Cp-H ³ ), 5.03 (s, 1H, CH ₃ O CH ), 3.33 (d, 3H, CH ₃ O), 2.83 (t, J = 1.6 Hz, 4H, Cp-H ⁴ ), 2.04 (s, 6H, CH ₃ Cp), 2.83 (q, J = 1.6 Hz, 6H, CH ₃ Cp) ppm. ¹³ C {1H} NMR (CDCl 3): 143.42, 140.30, 136.90, 124.27, 76.08, 56.18, 44.97, 14.97, 14.44 ppm.

(2) Preparation of ethylidene bis- (1,3-dimethyl-cyclopenta-1,3-dienyl) dilithium salt

The compound (1.48g, 6.43mmol) obtained in the above (1) was added to a Schlenk flask, and 1.6M methyllithium (14.1ml, 22.51mmol) was dropped one drop at -78 ° C, followed by two days of reaction at room temperature. Then filtered while washing with 20 ml of ether. The ether was removed and filtered through 20 ml of a mixed solvent of benzene / tetrahydrofuran (1/1) to obtain a yellow salt having 1.8 coordination of tetrahydrofuran. (Yield: 74%)

¹ H-NMR (pyridine-d ₅ ): δ 6.01 (s, 4H, Cp-H ^1,2 ), 4.75 (q, J = 7.6 Hz, 1H, CH ₃ CH ), 2.46 (s, 12H, CH ₃ Cp), 2.02 (d, J = 6.8 Hz, 3H, CH CH ₃ ) ppm.

¹³ C {1H} NMR (pyridine-d ₅ ): 122.94, 111.32, 101.27, 67.96, 33.15, 26.04, 24.83, 16.48 ppm.

(3) Preparation of ethylidene bis- (1,3-dimethyl-cyclopenta-1,3-dienyl) zirconium dichloride (ethylidene bis- (1,3-dimethylcyclopentadienyl) zirconium dichloride)

Compound (0.77g, 0.34mmol) prepared in (2) and ZrCl ₄ (THF) ₂ (0.13g, 0.34mmol) were reacted in 10 ml of pyridine for 12 hours. The pyridine was then removed under reduced pressure to give brown tar, solidified with pentane and recrystallized at -30 ° C with toluene to give a carbon bridged ansa-metallocene compound containing zirconium. (Yield 91%)

¹ H-NMR (benzene-d ₆ ): δ 6.25 (dd, J = 7.6, 3.6 Hz, 4H, Cp-H ^2,3 ), 4.15 (q, J = 7.6Hz, 1H, CH ₃ CH ), 2.08 (s, 6H, CH ₃ Cp ^1or4 ), 1.83 (s, 6H, CH ₃ Cp ^1or4 ), 1.56 (d, J = 7.6 Hz, 3H, CH CH ₃ ) ppm.

Example 4 Preparation of ethylidene bis- (1,3-dimethyl-cyclopenta-1,3-dienyl) zirconium dichloride (zideconium dichloride)

(1) Preparation of ethylidene bis- (1,3-dimethyl-cyclopenta-1,3-diene)

2-Bromo-3-methoxy-1,3-dimethyl-cyclopentene (4 g, 19.5 mmol) was added to 20 ml of ether in a Schlenk flask under a nitrogen atmosphere, and n-butyllithium (5.41 g, 19.5mmol) was dropped one by one and stirred at room temperature for 30 minutes to form a white lithium salt. Again, the temperature was lowered to -30 ° C, ethyl formate (0.72 g, 9.75 mmol) was added dropwise, and stirred for 1 hour at room temperature.

The ether was removed using reduced pressure and 20 ml of dimethylformamide was incorporated as fresh solvent. Methyl iodide (CH ₃ I) (11.07 g, 78.0 mmol) was then added dropwise and stirred for one day while heating to 30 ° C. The resultant was extracted with 40 ml of water and 40 ml of hexane, washed three times with 20 ml of brine, hexane was removed, dehydrogenated with 4 ml of ethyl acetate and 12 ml of 2N hydrogen chloride, and neutralized with 16 ml of sodium bicarbonate. Finally, water was removed with magnesium sulfate (MgSO ₄ ), and the solvent was removed under reduced pressure to obtain a result. (Yield: 90%).

¹ H-NMR (pyridine-d ₅ ): δ 6.01 (s, 4H, Cp-H ^1,2 ), 4.75 (q, J = 7.6 Hz, 1H, CH ₃ CH ), 2.46 (s, 12H, CH ₃ Cp), 2.02 (d, J = 6.8 Hz, 3H, CH CH ₃ ) ppm.

¹³ C {1H} NMR (pyridine-d ₅ ): 122.94, 111.32, 101.27, 67.96, 33.15, 26.04, 24.83, 16.48 ppm.

(2) Preparation of ethylidene bis- (1,3-dimethyl-cyclopenta-1,3-dienyl) zirconium dichloride (ethylidene bis- (1,3-dimethylcyclopentadienyl) zirconium dichloride)

Compound (0.77g, 0.34mmol) prepared in (1) and ZrCl ₄ (THF) ₂ (0.13g, 0.34mmol) were reacted in 10 ml of pyridine for 12 hours. The pyridine was then removed under reduced pressure to give brown tar, solidified with pentane and recrystallized at -30 ° C with toluene to give a carbon bridged ansa-metallocene compound containing zirconium. (Yield 91%)

¹ H-NMR (benzene-d ₆ ): δ 6.25 (dd, J = 7.6, 3.6 Hz, 4H, Cp-H ^2,3 ), 4.15 (q, J = 7.6Hz, 1H, CH ₃ CH ), 2.08 (s, 6H, CH ₃ Cp ^1or4 ), 1.83 (s, 6H, CH ₃ Cp ^1or4 ), 1.56 (d, J = 7.6 Hz, 3H, CH CH ₃ ) ppm.

Although described in detail with respect to preferred embodiments of the present invention as described above, those of ordinary skill in the art, without departing from the spirit and scope of the invention as defined in the appended claims Various modifications may be made to the invention. Therefore, changes in the future embodiments of the present invention will not be able to escape the technology of the present invention.

The method for preparing an ansa-metallocene compound according to the present invention facilitates the preparation of an ansa-metallocene compound to be prepared by reducing the number of steps required to prepare the ansa-metallocene compound and making the process conditions more mild. Since it can be manufactured economically and economically, there is an effect that allows the commercial mass production of the ansa-metallocene compound.

Claims (7)

(a) reacting a compound of formula 1 with lithium chloride or Grignard reactant with a compound of formula 5, followed by acid treatment to prepare a compound of formula 6; And (b) A process for preparing the ansa-metallocene compound of formula (7) comprising the step of preparing a compound of formula (7) from a compound of formula (6). [Formula 1]

[Formula 5] R ³ R ⁴ SiX ₂ [Formula 6]

[Formula 7]

(In the above formula, R ¹ , R ² , R ³ , R ⁴ and R ⁵ are each independently a hydrogen atom; an alkyl group having 1 to 20 carbon atoms; an alkoxy group having 1 to 10 carbon atoms; an aryl group having 6 to 20 carbon atoms; Aryloxy group having 6 to 10 carbon atoms, alkenyl having 2 to 20 carbon atoms, alkylaryl group having 7 to 40 carbon atoms, arylalkyl group having 7 to 40 carbon atoms, aryl alkenyl having 8 to 40 carbon atoms, alkynyl having 2 to 10 carbon atoms; Or a metalloid radical of a Group 14 metal substituted with hydrocarbyl, wherein R ¹ and R ² are not simultaneously hydrogen, and R ³ and R ⁴ comprise an alkyl of 1 to 20 carbon atoms or an aryl radical of 6 to 20 carbon atoms. Q ¹ and Q ² are each independently a halogen atom; alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 10 carbon atoms and alkylaryl having 7 to 40 carbon atoms. Or 7 to 40 carbon atoms Arylalkyl; aryl having 6 to 20 carbon atoms; substituted or unsubstituted alkylidene having 1 to 20 carbon atoms; substituted or unsubstituted amino group; alkylalkoxy having 2 to 20 carbon atoms; or aryl alkoxy group having 7 to 40 carbon atoms; X Is a halogen atom; M is a Group 4 transition metal) (a) reacting a compound of formula 1 with lithium chloride or Grignard reactant with a compound of formula 8 and then reacting R ⁶ -Y with acid to prepare a compound of formula 9; (b) preparing a compound of formula 12 by reacting alkyllithium with the compound of formula 9 prepared in (a); And (c) a method for preparing an ansa-metallocene compound of formula 10 comprising the step of preparing a compound of formula 10 from the compound of formula 12 prepared in (b). [Formula 1]

[Formula 8] R ³ C (O) OR ⁴ [Formula 9]

[Formula 10]

[Formula 12]

(In the above formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , M, X, Q ¹ and Q ² are the same as defined in claim 1, R ⁶ is an alkyl group having 1 to 20 carbon atoms, 1 carbon number An alkoxy group having 10 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an alkenyl having 2 to 20 carbon atoms, an alkylaryl group having 7 to 40 carbon atoms, an arylalkyl group having 7 to 40 carbon atoms, and 8 carbon atoms. A metalloid radical of a Group 14 metal substituted with arylalkenyl having from 40 to 40 carbon atoms, alkynyl having 2 to 10 carbon atoms, or hydrocarbyl; R ⁷ is a hydrogen atom; an alkyl group having 1 to 20 carbon atoms; an alkoxy group having 1 to 10 carbon atoms Aryl groups having 6 to 20 carbon atoms; aryloxy groups having 6 to 10 carbon atoms; alkenyl having 2 to 20 carbon atoms; alkylaryl groups having 7 to 40 carbon atoms; arylalkyl groups having 7 to 40 carbon atoms; aryl alcohols having 8 to 40 carbon atoms; Kenyl; alkynyl having 2 to 10 carbon atoms; or a Group 14 metal substituted with hydrocarbyl A metalloid radical; Y is a halogen or sulfonyl group.) [4] The method for preparing an ansa-metallocene compound of formula (10) according to claim 2, wherein 4 equivalents of alkyllithium is reacted in (b). (a) reacting a compound of formula 1 with lithium chloride or Grignard reactant with a compound of formula 8 and then reacting R ⁶ -Y with acid to prepare a compound of formula 9; (b) preparing a compound of formula 11 by reacting a base with the compound of formula 9 produced in step (a); (c) preparing a compound of formula 12 by reacting an alkyllithium or Grignard reactant with the compound of formula 11 produced in (b); And (d) A method for preparing an ansa-metallocene compound of formula 10 comprising the step of preparing a compound of formula 10 from the compound of formula 12 produced in (c). [Formula 1]

[Formula 8] R ³ C (O) OR ⁴ [Formula 9]

[Formula 10]

[Formula 11]

[Formula 12]

(R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , M, X, Y, Q ¹ and Q ² in the formula are the same as defined in claim 1 and 2. ) The method for preparing an ansa-metallocene compound of claim 10, wherein the base is NaH. The method for preparing an ansa-metallocene compound of formula (10) according to claim 4, wherein 3 equivalents of the alkyllithium or Grignard reactant is reacted in (c). 5. The process for preparing the ansa-metallocene compound of formula (10) according to claim 2 or 4, wherein R ⁶ Y is CH ₃ I.