JP2000026489A - Production of cross-linked metallocene compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To efficiently obtain a cross-linked metallocene compound useful as a polymerization catalyst, etc., by reacting a reaction product between a cross-linked cyclopentadiene compound containing a halogen-containing substituent and a base with a transition metal compound in a specific mixed solvent under prescribed conditions. SOLUTION: A reaction product between a cross-linked cyclopentadiene compound containing a halogen-containing substituent of the formula [R1, R2, R4 and R5 are each H, a halogen, a 1-10C (halogenated) hydrocarbon or the like; R3 and R6 are each 3-20C bifunctional hydrocarbon group to form a condensed ring on five-membered rings to which R3 and R6 are bonded; R7 and R8 are each a substituent to be replaced with H on the condensed ring R3 or R6 and is a halogen, a 1-20C (halogenated) hydrocarbon or the like; with the proviso that at least one of R1 to R8 is a halogen or a 1-20C halogenated hydrocarbon; (m) and (n) are each 0-20; Q is silylene or germirene which may contain a 1-20C hydrocarbon group or the like] and a base capable of deprotonating the compound is reacted with a transition metal compound in a mixed solvent of an aromatic hydrocarbon and an ether in the concentration of the compound of the formula of <=0.1 mol/L to give the objective compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing a bridged metallocene compound, and more particularly to a method for producing a bridged metallocene compound having excellent production efficiency.

[0002]

2. Description of the Related Art Metallocene catalysts, which are known as homogeneous catalysts for the polymerization of α-olefins, are characterized by high polymerization activity and the ability to obtain polymers having a narrow molecular weight distribution. In particular, it is known that isotactic polypropylene can be obtained by using a stereorigid transition metal complex having a ligand having a structure in which two cyclopentadienyl groups are crosslinked (Journal of American Chemical Socie).
ty 106 p6355). Furthermore, it is known that a polypropylene having high isotacticity can be obtained by a transition metal complex in which two cyclopentadienyl groups are cross-linked by a silicon atom (JP-A-63-295607; -275609, JP-A-2-131488
No.). In particular, when the cyclopentadienyl derivative is an azulene derivative, a higher melting point and higher molecular weight α-
Japanese Patent Application Laid-Open No. 6-2399 discloses that an olefin polymer can be obtained.
No. 14 discloses this.

In general, when producing a bridged metallocene compound, a method is generally employed in which a base such as alkyllithium is allowed to act on a bridged cyclopentadienyl compound to form a lithium compound and then reacted with a metal compound such as zirconium tetrachloride. is there. At that time, various organic solvents can be used as a reaction medium. For example, a method using tetrahydrofuran alone as a solvent is known (Angew. Chem. Int. E.
d.Engl., 24 (1985) 507, J.Organomet.Chem., 342 (1988) 2
1). JP-A-5-239083 discloses a production method using a weakly basic ether such as diethyl ether alone. JP-A-6-122892,
Organometallics, 13, 954 (1994) also discloses a production method using aliphatic and aromatic hydrocarbons alone.

[0004] A production method using a mixed solvent is also known. For example, JP-A-5-239083 discloses a method of adding an aliphatic hydrocarbon to diethyl ether or the like. Japanese Patent Application Laid-Open No. 6-126292 discloses a production method in which ethers are added to aliphatic and aromatic hydrocarbon solvents. JP-A-10-45786 discloses that a cyclopentadienyl compound is dissolved or suspended in a non-polar solvent such as an aliphatic or aromatic hydrocarbon, and then a solvent such as ethers is added thereto. A lithiation process is disclosed. However, none of the above disclosed technologies has a clear description of the reaction concentration, and particularly in the case of a bridged metallocene compound having a halogen-containing substituent, a problem arises in industrial production.

[0005]

SUMMARY OF THE INVENTION The present invention relates to a method for industrially producing a bridged metallocene compound having a halogen-containing substituent at high yield and efficiency.

[0006]

Means for Solving the Problems The present inventors have studied to achieve the above object, and as a result, using a mixed solvent of an aromatic hydrocarbon and an ether as a reaction medium, and performing a reaction in a certain reaction concentration range. The present inventors have found a method for efficiently producing a bridged metallocene compound having a halogen-containing substituent in high yield, and completed the present invention. That is,
The present invention provides a method for producing a bridged metallocene compound by reacting a transition metal compound with a reaction product of a bridged cyclopentadiene compound having a halogen-containing substituent and a base capable of deprotonating the compound. A method for producing a crosslinked metallocene compound, wherein the reaction with the metal compound is carried out in a mixed solvent of an aromatic hydrocarbon and an ether under the condition that the concentration of the crosslinked cyclopentadiene compound is 0.1 mol / liter or less. Is provided.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION A bridged cyclopentadiene compound having a halogen-containing substituent which can be used in the present invention is represented by the following general formula (I).

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In the general formula (I), R ¹ , R ² , R ⁴ , R ⁵
Each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a silicon-containing hydrocarbon group having 1 to 18 carbon atoms, or a halogenated hydrocarbon group having 1 to 18 carbon atoms. Specific examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Specific examples of the hydrocarbon group having 1 to 10 carbon atoms include alkyl groups such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl and t-butyl, and vinyl. And alkenyl groups such as propenyl, arylalkyl groups such as benzyl and phenylethyl, and aryl groups such as phenyl, tolyl and 1-naphthyl.

Specific examples of the silicon-containing hydrocarbon group having 1 to 18 carbon atoms include trialkylsilyl groups such as trimethylsilyl, triethylsilyl and t-butyldimethylsilyl; triarylsilyl groups such as triphenylsilyl; (Alkyl) (aryl) silyl groups such as phenylsilyl; and alkylsilylalkyl groups such as bis (trimethylsilyl) methyl. 1-18 carbon atoms
In the halogenated hydrocarbon group of the above, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. When the halogen atom is, for example, a fluorine atom, the halogenated hydrocarbon group is a compound in which a fluorine atom is substituted at an arbitrary position of the hydrocarbon group. Specific examples include a fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl, tribromomethyl, iodomethyl group and the like.

In the general formula (I), R ⁷ and R ⁸ are substituents for replacing a hydrogen atom on the condensed ring R ³ or R ⁶ , and each independently represents a hydrocarbon having 1 to 20 carbon atoms. Group, halogenated hydrocarbon group having 1 to 20 carbon atoms, 1 carbon atom
-20 oxygen-containing hydrocarbon groups, amino groups, 1-2 carbon atoms
It represents a nitrogen-containing hydrocarbon group of 0 or a sulfur-containing hydrocarbon group having 1 to 20 carbon atoms. Specific examples of the above halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

Specific examples of the hydrocarbon group having 1 to 10 carbon atoms include alkyl such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl and t-butyl. Groups, alkenyl groups such as vinyl and propenyl, arylalkyl groups such as benzyl and phenylethyl, and aryl groups such as phenyl, tolyl and 1-naphthyl. In the above-mentioned halogenated hydrocarbon group having 1 to 20 carbon atoms, as the halogen atom, a fluorine atom,
Examples include a chlorine atom, a bromine atom and an iodine atom. When the halogen atom is, for example, a fluorine atom, the halogenated hydrocarbon group is a compound in which a fluorine atom is substituted at an arbitrary position of the hydrocarbon group. Specific examples include a fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl, tribromomethyl, iodomethyl group and the like.

Specific examples of the oxygen-containing hydrocarbon group having 1 to 20 carbon atoms include alkoxy groups such as methoxy, ethoxy, propoxy and butoxy, allyloxy groups such as phenoxy, methylphenoxy and naphthoxy, phenylmethoxy and naphthylmethoxy. And an oxygen-containing heterocyclic group such as a furyl group. Specific examples of the nitrogen-containing hydrocarbon group having 1 to 20 carbon atoms include:
Alkylamino groups such as methylamino, dimethylamino, ethylamino, and diethylamino; arylamino groups such as phenylamino and diphenylamino; (alkyl) (aryl) amino groups such as (methyl) (phenyl) amino;
And nitrogen-containing heterocyclic groups such as pyrazolyl and indolyl. Specific examples of the above-mentioned sulfur-containing hydrocarbon group having 1 to 20 carbon atoms include a substituent in which oxygen of the oxygen-containing compound is replaced with sulfur.

However, the above R ¹ , R ² , R ⁴ , R ⁵ , R
^At least one of ⁷ , ⁸ is a halogen atom or a halogenated hydrocarbon group having 1 to 20 carbon atoms. In the general formula (I), R ³ and R ⁶ each independently represent a carbon number of 3 to 3 which forms a condensed ring with respect to the 5-membered ring to which it is bonded.
It represents 10 saturated or unsaturated divalent hydrocarbon groups. Therefore, the condensed ring is a 5- to 12-membered ring.

Specific examples of the above R ³ and R ⁶ include:
Divalent saturated hydrocarbon groups such as trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, etc., propenylene, 2-butenylene, 1,3-butadienylene, 1-pentenylene, 2-pentenylene, 1,3
-Pentadienylene, 1,4-pentadienylene, 1-
Hexenylene, 2-hexenylene, 3-hexenylene,
Divalent unsaturated hydrocarbon groups such as 1,3-hexadienylene, 1,4-hexadienylene, 1,5-hexadienylene, 2,4-hexadienylene, 2,5-hexadienylene, and 1,3,5-hexadienylene are No.

In the general formula (I), m and n each independently represent an integer of 0 to 20. m and n are preferably 1 to 5. When m and / or n is an integer of 2 to 20, a plurality of groups R ⁷ and R ⁸ may be the same or different. When m or n is 2 or more, R ^{7 and} R ⁸ may be connected to each other to form a new ring structure.

Q is a group having 1 carbon atom which connects two 5-membered rings.
A divalent hydrocarbon group having from 20 to 20, a silylene group which may have a hydrocarbon group having from 1 to 20 carbon atoms, an oligosilylene group,
Shows any of the germylene groups. When two hydrocarbon groups or halogenated hydrocarbon groups are present on the silylene group, oligosilylene group or germylene group, they may be bonded to each other to form a ring structure. Specific examples of the above Q include an alkylene group such as methylene and 1,2-ethylene, an arylalkylene group such as (methyl) (phenyl) methylene and diphenylmethylene, and an alkylsilylene group such as methylsilylene, dimethylsilylene and diethylsilylene. (Alkyl) (aryl) silylene groups such as, methylphenylsilylene and methyltolylsilylene;
Arylsilylene groups such as diphenylsilylene, oligosilylene groups such as tetramethyldisilylene, germylene groups,
Examples thereof include an alkylgermylene group and an arylgermylene group in which silicon of a silylene group having a divalent hydrocarbon group having 1 to 20 carbon atoms is substituted with germanium.

In the present invention, after the bridged cyclopentadiene compound represented by the general formula (I) is reacted with a base capable of deprotonating the compound, and subsequently reacted with a transition metal compound, an aromatic compound is used. A crosslinked metallocene compound having a halogen-containing substituent is produced by using a mixed solvent of an aromatic hydrocarbon and an ether and reacting under a condition that the concentration of the crosslinked cyclopentadiene compound is 0.1 mol / L or less.

In the present invention, 1) a crosslinked cyclopentadienyl compound is reacted with a base capable of deprotonating the compound, and the purified cyclopentadienyl compound is purified and isolated by a known method such as solvent evaporation and solvent washing. The salt is dissolved in a mixed solvent of an aromatic hydrocarbon and an ether in a specific concentration range and then reacted with a transition metal compound to produce a bridged metallocene compound. 2) A bridged cyclopentadiene compound is dissolved in a specific concentration range. After being dissolved in a mixed solvent of an aromatic hydrocarbon and ethers, the crosslinked cyclopentadiene compound is reacted with a base capable of deprotonating, followed by reacting with a transition metal compound to produce a crosslinked metallocene compound. A method can be adopted.

In the case of the above 1), the reaction between the crosslinked cyclopentadiene compound and the base is preferably carried out in a solvent. There is no particular limitation on the solvent, aliphatic hydrocarbons,
Alicyclic hydrocarbons, aromatic hydrocarbons, ethers, and the like, and a mixed solvent thereof can be used. The reaction concentration of the crosslinked cyclopentadiene compound at that time is not particularly limited, and the reaction can be performed at a known concentration. In both cases 1) and 2), the reaction concentration of the crosslinked cyclopentadiene compound when reacting with the transition metal compound is 0.1 mol / L or less, and preferably 0.1 mol / L to 0 mol / L. 0.001 mol / L, and more preferably 0.1 mol / L to 0.01 mol / L.

The base used in the present invention is a base capable of deprotonating a bridged cyclopentadiene compound, and is preferably a compound capable of extracting a proton from the cyclopentadienyl ring of the compound.
Industrially advantageous are, for example, alkali metals,
Alkaline earth metals or metal compounds thereof.
Specific examples of the alkali metal include lithium, sodium, potassium and amalgam thereof. Examples of the alkaline earth metal include calcium and magnesium. Examples of the alkali or alkaline earth metal compound include, for example, methyl lithium, ethyl lithium, n-butyl lithium, sec-butyl lithium, tert-butyl lithium, lithium diisopropylamide, and lithium naphthalenide when taking lithium as an example. . Among these, n-butyllithium is preferred.

The above base can be used as a solution. Specific examples include a hexane solution or a toluene solution of n-butyllithium, a diethylether solution of methyllithium, and a cyclohexane solution of sec-butyllithium. In this case, although the solvent from the base solution is added to the above-mentioned mixed solvent of the aromatic hydrocarbon and the ethers, the effect of the present invention is not affected at all under normal conditions. . The amount of the base to be used is generally 0.1 to 5.0, preferably 1.8 to 2.4 mol, per 1 mol of the crosslinked cyclopentadiene compound. The reaction temperature when bringing these bases into contact with the crosslinked cyclopentadiene compound is -100 ° C to 100 ° C, preferably -80 ° C to 30 ° C, and more preferably -10 ° C.
２５25 ° C. Usually, a method of contacting at a low temperature and then gradually raising the temperature to room temperature is used.

The metal compound used in the present invention is a transition metal compound belonging to Groups 4 to 6 of the periodic table, preferably a transition metal compound belonging to Group 4 such as titanium, zirconium and hafnium, and more preferably zirconium or hafnium. Is a compound of These transition metal compounds include a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, The compound may be a compound in which a transition metal is bonded to an oxygen-containing hydrocarbon group, an amino group, a nitrogen-containing hydrocarbon group having 1 to 20 carbon atoms, or the like. Further, a compound to which a compound having an oxygen atom, a sulfur atom, a nitrogen atom, a phosphorus atom, an arsenic atom or the like is added is also included.

Specifically, (1) ZrCl ₄ , HfC
halogen compounds such as l ₄ and ZrBr ₄ , (2) ZrC
_{l 4 · nTHF, ZrCl 4 ·} n (H 2 NCH 2 CH 2
NH ₂₎ halogen compound adducts such as, (3) (C ₅ H
_{5) 2 ZrCl 2, (C} 5 H 5) 2 Zr (CH 3) 2 cyclopentadienyl compounds such as, (4) Zr (aca
c) ₄ , a compound having a chelating ligand such as Zr (acac) ₂ Cl ₂ , (5) Zr (NMe ₂ ) ₂ Cl ₂ ,
Compounds having an amino group such as Hf (NEt ₂ ) ₂ Cl ₂ are exemplified. Preferably, ZrCl ₄ , HfC
l _4, ZrCl ₄ · _nTHF, a HfCl ₄ · nTHF.

Note that acac = acetylacetonate ligand, THF = tetrahydrofuran, Me = methyl group,
Et = ethyl group. The amount of the metal compound to be used is generally 0.5 to 2.0, preferably 0.8 to 1.2 mol, per 1 mol of the crosslinked cyclopentadiene compound.

The aromatic hydrocarbon used in the present invention is an aromatic hydrocarbon having 6 to 10 carbon atoms. Specific examples include benzene, toluene, xylene,
Mesitylene and the like are preferable, and benzene and toluene are preferable. The ethers used in the present invention are ethers having 4 to 10 carbon atoms. Specific examples include diethyl ether, di (n-propyl) ether, di (i-propyl) ether, di (n-butyl) ether, methyl (n-butyl) ether, and methyl (t-
Butyl) ether, 1,4-dioxane, 1,2-dimethoxyethane, tetrahydrofuran, tetrahydropyran and the like. Among them, diethyl ether, di (i-propyl) ether and tetrahydrofuran are preferred. The mixing volume ratio between the aromatic hydrocarbon and the ethers can be set arbitrarily, but is preferably 30/1 to 1
1/1, more preferably 20/1 to 2 /
1, particularly preferably in the range of 10/1 to 2/1.

The amount of the metal compound to be used is generally 0.5 to 2.0, preferably 0.8 to 1.2 mol, per 1 mol of the cyclopentadienyl compound. The reaction temperature when the transition metal compound is brought into contact with the reactant of the bridged cyclopentadienyl compound and the base is -100 ° C to 100 ° C,
Preferably -80 ° C to 30 ° C, more preferably -10
C. to 25C. Normally, a method is used in which a metal compound is allowed to act at a low temperature and then gradually raised to room temperature.

The following compounds are exemplified as the bridged metallocene compound produced according to the present invention. Dichloro [1,1′-dimethylmethylenebis {2-methyl-4
-(4-fluorophenyl) -4H-azulenyl}] zirconium, dichloro [1,1'-dimethylmethylenebis {2-methyl-4- (4-chlorophenyl) -4H-
Azulenyl}] zirconium, dichloro [1,1′-dimethylmethylenebis {2-methyl-4- (4-trifluoromethylphenyl) -4H-azulenyl}] zirconium, dichloro [1,1′-ethylenebis} 2- Methyl-4- (4-fluorophenyl) -4H-azulenyl}] zirconium, dichloro [1,1'-ethylenebis} 2-methyl-4- (4-chlorophenyl) -4H-
Azulenyl}] zirconium, dichloro [1,1′-ethylenebis {2-methyl-4- (4-trifluoromethylphenyl) -4H-azulenyl}] zirconium, dichloro [1,1′-dimethylsilylenebis} 2- Methyl-4- (4-fluorophenyl) -4H-azulenyl}] zirconium, dichloro [1,1'-dimethylsilylenebis} 2-methyl-4- (4-chlorophenyl)
-4H-azulenyl}] zirconium, dichloro [1,
1'-dimethylsilylenebis {2-methyl-4- (3-
Chlorophenyl) -4H-azulenyl}] zirconium, dichloro [1,1′-dimethylsilylenebis} 2-
Methyl-4- (4-trifluoromethylphenyl) -4
H-azulenyl}] zirconium and the like.

Further, dichloro [1,1′-dimethylmethylenebis {2-methyl-4- (4-fluorophenyl) -4H-azulenyl}] hafnium, dichloro [1,1′-dimethylmethylenebis {2-methyl -4-
(4-chlorophenyl) -4H-azulenyl}] hafnium, dichloro [1,1′-dimethylmethylenebis} 2
-Methyl-4- (4-trifluoromethylphenyl)-
4H-azulenyl}] hafnium, dichloro [1,1 ′
-Ethylenebis {2-methyl-4- (4-fluorophenyl) -4H-azulenyl}] hafnium, dichloro [1,1'-ethylenebis {2-methyl-4- (4-chlorophenyl) -4H-azulenyl} ] Hafnium, dichloro [1,1'-ethylenebis {2-methyl-4-
(4-trifluoromethylphenyl) -4H-azulenyl}] hafnium, dichloro [1,1'-dimethylsilylenebis} 2-methyl-4- (4-fluorophenyl)
-4H-azulenyl}] hafnium, dichloro [1,
1'-dimethylsilylenebis {2-methyl-4- (4-
Chlorophenyl) -4H-azulenyl {] hafnium,
Dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (3-chlorophenyl) -4H-azulenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (4- Trifluoromethylphenyl) -4H-azulenyl}] hafnium and the like.

Further, dichloro [1,1′-dimethylmethylenebis {2-methyl-4- (4-fluorophenyl) indenyl}] zirconium, dichloro [1,
1'-dimethylmethylenebis {2-methyl-4- (4-
Chlorophenyl) indenyl}] zirconium, dichloro [1,1′-dimethylmethylenebis} 2-methyl-4
-(4-trifluoromethylphenyl) indenyl}]
Zirconium, dichloro [1,1'-ethylenebis @ 2
-Methyl-4- (4-fluorophenyl) indenyl}] zirconium, dichloro [1,1′-ethylenebis {2-methyl-4- (4-chlorophenyl) indenyl}] zirconium, dichloro [1,1′-ethylene Bis {2-methyl-4- (4-trifluoromethylphenyl) indenyl}] zirconium, dichloro [1,1 ′
-Dimethylsilylenebis {2-methyl-4- (4-fluorophenyl) indenyl}] zirconium, dichloro [1,1'-dimethylsilylenebis {2-methyl-4-
(4-chlorophenyl) indenyl}] zirconium,
Dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (3-chlorophenyl) indenyl}] zirconium, dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (4-trifluoromethyl) Phenyl) indenyl}] zirconium.

[0030]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto unless it exceeds the gist thereof.
It is not limited to the following embodiment.

[Example] Under a nitrogen atmosphere at room temperature, 500
5.66 g (10.0 mmol) of 1,1′-dimethylsilylenebis [2-methyl- (4-chlorophenyl) -1,4-dihydroazulene] was charged into a three-necked 3-ml flask. After adding and dissolving 100 ml of anhydrous diethyl ether, the mixture was cooled to -70 ° C. There, 12.4 ml of n-BuLi n-hexane solution (1.61M) (20.
0 mmol) was added dropwise. Remove the cold bath and leave at room temperature for 2 hours.
After stirring for an hour, the solvent was distilled off under reduced pressure to obtain a dark red solid.

Thereto 6.1 ml of anhydrous diethyl ether,
243.9 ml of anhydrous toluene was added to obtain a homogeneous solution.
After cooling to -70 ° C, 3.20 g of hafnium tetrachloride (1
0.0 mmol) was added. When the cooling bath was removed and the mixture was stirred at room temperature for 16 hours, a yellow slurry solution was obtained. The solvent was distilled off under reduced pressure to obtain a yellow powdery solid. ¹
From H-NMR analysis, dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl)]
-4H-azulenyl}] hafnium 3.42 g (4.2
1 mmol). The yield based on hafnium tetrachloride was 42%, of which 26% was racemic.

Comparative Example At room temperature under a nitrogen atmosphere, 100
5.66 g (10.0 mmol) of 1,1′-dimethylsilylenebis [2-methyl- (4-chlorophenyl) -1,4-dihydroazulene] was charged into a three-necked 3-ml flask. After adding and dissolving 22.2 ml of anhydrous diethyl ether, the mixture was cooled to -70 ° C. There n-BuLi
N-hexane solution (1.61M) in 12.4 ml (2
0.0 mmol) was added dropwise. After removing the cooling bath and stirring at room temperature for 2 hours, the solvent was distilled off under reduced pressure to obtain a dark red solid.

Then, 0.6 ml of anhydrous diethyl ether and 24.4 ml of anhydrous toluene were added thereto to obtain a homogeneous solution. −
After cooling to 70 ° C., 3.20 g of hafnium tetrachloride (10.
0 mmol) was added. Remove the cold bath and remove at room temperature
After stirring for an hour, a yellow slurry solution was obtained. The solvent was distilled off under reduced pressure to obtain a yellow powdery solid. ¹ H-N
From MR analysis, dichloro [1,1'-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4H] was obtained.
-Azulenyl}] hafnium 0.73g (0.9mmo
l) was included. The yield based on hafnium tetrachloride is 9
%, Of which 6% was racemic.

Continuation of the front page (72) Inventor Hiroshi Iwane 8-3-1 Chuo, Ami-cho, Inashiki-gun, Ibaraki Pref. F-term in Tsukuba Research Laboratory, Mitsubishi Chemical Corporation

Claims (5)

[Claims] 1. A method for producing a bridged metallocene compound by reacting a transition metal compound with a reaction product of a bridged cyclopentadiene compound having a halogen-containing substituent and a base capable of deprotonating the compound, Producing a crosslinked metallocene compound, wherein the reaction with the transition metal compound is carried out in a mixed solvent of an aromatic hydrocarbon and an ether under the condition that the concentration of the crosslinked cyclopentadiene compound is 0.1 mol / l or less. Method. 2. A crosslinked cyclopentadiene compound represented by the following general formula (I): (In the general formula (I), R ¹ , R ² , R ⁴ , and R ⁵ each independently represent a hydrogen atom, a halogen atom, a carbon atom of 1 to 10;
A silicon-containing hydrocarbon group having 1 to 18 carbon atoms or a halogenated hydrocarbon group having 1 to 18 carbon atoms.
R ³ and R ⁶ each independently represent a saturated or unsaturated divalent hydrocarbon group having 3 to 10 carbon atoms which forms a condensed ring with the 5-membered ring to which it is bonded. R ⁷ and R
^{And 8} is a substituent that replaces a hydrogen atom on the condensed ring R ³ or R ⁶ , and is each independently a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon having 1 to 20 carbon atoms. Group, an oxygen-containing hydrocarbon group having 1 to 20 carbon atoms, an amino group, a nitrogen-containing hydrocarbon group having 1 to 20 carbon atoms, or a sulfur-containing hydrocarbon group having 1 to 20 carbon atoms. However,
At least one of R ¹ , R ² , R ⁴ , R ⁵ , R ⁷ , and R ⁸ is a halogen atom or a halogenated hydrocarbon group having 1 to 20 carbon atoms. m and n are each independently 0
Represents an integer of up to 20. When m or n is 2 or more, R ^{7 and} R ⁸ may be connected to each other to form a new ring structure. When there are two or more R ⁷ and R ⁸ , each of the plurality of R ⁷ and R ⁸ may be the same or different. Q is a divalent hydrocarbon group having 1 to 20 carbon atoms that bonds two 5-membered rings,
It represents any one of a silylene group, an oligosilylene group, and a germylene group which may have 20 hydrocarbon groups. The method for producing a bridged metallocene compound according to claim 1, which is represented by the formula: 3. A compound of the formula (I) wherein at least one of R ³ and R ⁶ has an unsaturated bond derived from R ³ or R ^6.
The method for producing a bridged metallocene compound according to claim 1 or 2, wherein the fused metallocene compound forms a fused ring composed of a membered ring. 4. The method for producing a bridged metallocene compound according to claim 1, wherein the transition metal compound is a transition metal compound belonging to Groups 4 to 6 of the periodic table. 5. The aromatic hydrocarbon used as a reaction medium is an aromatic hydrocarbon having 6 to 10 carbon atoms, and the ethers are aliphatic ethers having 4 to 10 carbon atoms. A method for producing the bridged metallocene compound according to any one of the above.