JPH0713075B2 - Zirconium compounds with bridged bis-substituted cyclopentadienyl ligands - Google Patents

Description

TECHNICAL FIELD The present invention relates to a novel zirconium compound having a bis-substituted cyclopentadienyl ligand having a bridge structure. The compound of the present invention is useful as a catalyst component for stereoregular olefin polymerization.

[Prior Art and Its Problems] As a homogeneous catalyst for olefin polymerization, a so-called Kaminsky catalyst (metallocene compound / aluminoxane) is well known. This catalyst system has a very high polymerization activity, and, for example, in propylene polymerization, atactic polypropylene (Makromol. Chem., Rapid Commun.
4,417-421 (1983), JP-A-58-19,309, JP-A-60-13
0,604, JP 61-211,307), and isotactic polypropylene (Angew.Chem.Int.Ed.Engl.24,507-508).
(1985), J. Am. Chem. Soc. 1984, 106, 6355-6364, JP-A 61-264, 010, J. Am. Chem. Soc. 1987, 109, 6544-6545,
It is known that any of JP-A-63-66,206) can be produced.

Among metallocene compounds, transition metal compounds having a bis-unsubstituted cyclopentadienyl ligand cross-linked with silicon, phosphine, amine or carbon are known (Japanese Patent Laid-Open No. Sho 62-62).
-296,008), and dimethylsilylbis (cyclopentadienyl) zirconium dichloride and the like have been synthesized as zirconium compounds (Z.Naturforsch, 38b, 32).
1-325 (1983), Inorg. Chem. 1985, 24, 2539).

Further, as a synthetic example of a transition metal compound having a ligand bridged with silicon using a substituted cyclopentadienyl ring, dimethylsilylbis (methylcyclopentadienyl) titanium dichloride (Monatsh. Chem. 112, 887-89
7 (1981)), dimethylsilylbis (t-butylcyclopentadienyl) scandium hydride (J. Am. Chem. So
c.1988,110,976−978), or Me ₂ Si (Me ₄ C ₅ ) ₂ MCH
[SiMe ₃ ] ₂ (M = Nd, Sm, Lu) type compound, etc. (J.Am.Chem.S
oc.1985,107,8103-8110) is known.

Regarding zirconium compounds, an example of a compound having a dimethylsilylbis (tetramethylcyclopentadienyl) ligand (Chem. Ber. 119, 1750-1754 (1986)) is known, but other substituted cyclopenta compounds are known. There are no examples of synthesizing compounds using a dienyl ring and having a ligand in which silicon and germanium are crosslinked. Further, there has been no specific example of isotactic polymer obtained by polymerizing an olefin using such a compound.

[Problems to be Solved by the Invention] As a result of repeated studies to solve the above problems, the present inventors have succeeded in efficiently synthesizing the novel zirconium compound described above, and It was also confirmed by polymerization experiments that is useful as a catalyst component for stereoregular olefin polymerization.

As is clear from the above description, an object of the present invention is to provide a novel and useful compound as described above and its use.

[Means for Solving Problems] The zirconium compound of the present invention is represented by the following general formula [I].

(However, Y represents silicon or germanium. ▲ R ¹ _n ▼
-C ₅ H _4-n and _{^{▲ R 1 q ▼ -C 5 H}} 4- q represents an unsubstituted or substituted cyclopentadienyl group, but n and q is an integer of 0 to 2, n and q Do not take values of 0 and 2 at the same time.
R ¹ may be the same or different and is hydrogen, a silyl group or a hydrocarbon group. R ^{2 s} may be the same or different and are hydrogen or a hydrocarbon group. Each x may be the same or different and represents hydrogen, halogen, or a hydrocarbon group. ) The compound [I] of the present invention is a novel zirconium compound having a bis-substituted cyclopentadienyl bridge type bidentate ligand having a bridge structure. Depending on the steric positions of the substituents on the two cyclopentadienyl rings, the compound has a racemic body and a meso body, but can have either structure. It also includes a mixture of both at an arbitrary ratio.

As the zirconium compound of the present invention, in the general formula [I], Y is silicon or germanium. The number of substituents on the cyclopentadienyl ring may be any of unsubstituted to 4-substituted, but at least one cyclopentadienyl ring has a substituent, and further, both cyclopentadienyl rings have a substituent. The case where the phenyl ring has 4 substitutions is excluded. Each R ¹ may be the same or different and is hydrogen, a silyl group or a hydrocarbon group (alkyl having 1 to 20 carbon atoms, alkenyl, aryl, alkylaryl,
Arylalkyl and the like).

Examples of the silyl group include a trimethylsilyl group, a triethylsilyl group, a triphenylsilyl group and the like. Examples of the hydrocarbon group include a methyl group, an ethyl group,
Examples thereof include a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, a phenyl group, a tolyl group, a biphenyl group and a naphthyl group. Each R ² may be the same or different and is hydrogen or the above-mentioned hydrocarbon group. Further, each x may be the same or different, or hydrogen, or a halogen such as fluorine, chlorine, bromine or iodine,
Alternatively, it is the above-mentioned hydrocarbon group.

A typical synthetic route for the compound [I] of the present invention is n = q = 1
For example, it can be abbreviated as (1) or (2) below, but is not limited to this.

(1) When the substituents on the cyclopentadienyl ring are the same 2Na (R ¹ -C ₅ H ₄ ) + ▲ R ² ₂ ▼ YCl ₂ → ▲ R ² ₂ ▼ (R ¹ -C
₅ H ₄ ) ₂ + 2NaCl ▲ R ² ₂ ▼ Y (R ¹ -C ₅ H ₄ ) ₂ ＋ 2n-BuLi → Li ₂ [▲ R ² ₂ ▼ Y (R ¹ -C ₅ H ₃ ) ₂ ] + 2C ₄ H ₁₀ Li ₂ [▲ R ² ₂ ▼ Y (R ¹ -C ₅ H ₃ ) ₂ ] + ZrX ₄ → [▲ R ² ₂ ▼ Y (R ¹ -C ₅ H ₃ ) ₂ ] ZrX ₂ + 2LiX (2) Cyclopentadi When the substituents on the enyl ring are different Na (R ¹ -C ₅ H ₄ ) + ▲ R ² ₂ ▼ YCl ₂ → ▲ R ² ₂ ▼ Y (R ¹ -C
₅ H ₄ ) Cl + NaCl Na (R ¹ ′ -C ₅ H ₄ ) + ▲ R ² ₂ ▼ Y (R ¹ -C ₅ H ₄ ) Cl → ▲ R ² ₂ ▼ Y (R ¹ -C ₅ H ₄ ) ( R ¹ ′ -C ₅ H ₄ ) + NaCl ▲ R ² ₂ ▼ Y (R ¹ −C ₅ H ₄ ) (R ¹ ′ -C ₅ H ₄ ) + 2n−BuLi → Li ₂ [▲ R ² ₂ ▼ Y (R _{^{1 -C 5 H 3) (R}} 1 '-C 5 H 3)] + 2C 4
H ₁₀ Li ₂ [▲ R ² ₂ ▼ Y (R ¹ -C ₅ H ₃ ) (R ¹ ′ -C ₅ H ₃ ] + ZrX ₄ → [▲ R ² ₂ ▼ Y (R ¹ -C ₅ H ₃ ) ( R ¹ ′ -C ₅ H ₃ ] ZrX ₂ + 2LiX Bis-substituted cyclopentadienyl bridge type bidentate ligand having a bridge structure (for example, ▲ in the formulas (1) and (2) above).
R ² ₂ ▼ Y (R ¹ -C ₅ H ₄ ) ₂ or ▲ R ² ₂ ▼ Y (R ¹ -C
A method for producing ₅ H ₄ ) (a compound represented by R ¹ ′ -C ₅ H ₄ )) is known. That is, Monatsh. Chem. 112, 887-897 (198
1), J.Am.Chem.Soc.1988,110,976−978, J.Am.Chem.So
c.1985,107,8103-8110 etc.

Such a bidentate ligand can be lithiated with alkyl lithium and used as a lithium compound in the next reaction. It can also be used as a potassium compound or a sodium compound.

ZrX ₄ and a lithium compound (for example, Li ₂ [▲ R ² ₂ ▼ Y (R ¹ -C ₅ H ₃ ) ₂ ] or Li ₂ [▲ in the above formulas (1) and (2)]
The reaction with R ² ₂ ▼ Y (R ¹ -C ₅ H ₃ ) (a compound represented by R ¹ ′ -C ₅ H ₃ ]) may be carried out using ethers, preferably tetrahydrofuran (THF), as a reaction solvent. it can.
The reaction has a lithium compound / ZrX ₄ molar ratio of 1.0 to 1.
It is preferably carried out in the range of 5, especially 1.0 to 1.1.
The reaction temperature is preferably -80 ° C to 100 ° C, particularly preferably 0 ° C to 70 ° C. The produced compound [I] can be purified by recrystallization.

Non-limiting examples of the zirconium compound include dimethylsilylbis (methylcyclopentadienyl) zirconium dichloride, diphenylsilylbis (methylcyclopentadienyl) zirconium dichloride, cyclotrimethylenesilylbis (methylcyclopentadienyl) zirconium Dichloride, cyclotetramethylenesilylbis (methylcyclopentadienyl) zirconium dichloride, cyclopentamethylenesilylbis (methylcyclopentadienyl) zirconium dichloride, dimethylsilylbis (methylcyclopentadienyl) zirconium dibromide, dimethylsilylbis ( Methylcyclopentadienyl) zirconium methyl chloride, dimethylsilylbis (methylcyclopentadienyl) zirconium dimethyl, dimethyl Rylbis (methylcyclopentadienyl) zirconium diphenyl, dimethylsilylbis (ethylcyclopentadienyl) zirconium dichloride, dimethylsilylbis (isopropylcyclopentadienyl) zirconium dichloride, dimethylsilylbis (t-butylcyclopentadienyl) zirconium Dichloride, dimethylsilylbis (phenylcyclopentadienyl) zirconium dichloride, dimethylsilylbis (trimethylsilylcyclopentadienyl) zirconium dichloride, dimethylsilyl (cyclopentadienyl) (methylcyclopentadienyl) zirconium dichloride, diphenylsilyl (cyclo Pentadienyl)
(Methylcyclopentadienyl) zirconium dichloride, cyclotetramethylene silyl (cyclopentadienyl) (methylcyclopentadienyl) zirconium dichloride, dimethylsilyl (cyclopentadienyl) (methylcyclopentadienyl) zirconium dimethyl, dimethylsilyl (Cyclopentadienyl) (methylcyclopentadienyl) zirconium diphenyl, dimethylsilyl (cyclopentadienyl) (isopropylcyclopentadienyl) zirconium dichloride, dimethylsilyl (cyclopentadienyl) (t-butylcyclopentadienyl) ) Zirconium dichloride, dimethylsilyl (cyclopentadienyl) (phenylcyclopentadienyl) zirconium dichloride, dimethylsilyl (cyclopentadienyl) Trimethylsilylcyclopentadienyl) zirconium dichloride, dimethylsilyl (methylcyclopentadienyl) (phenylcyclopentadienyl) zirconium dichloride, dimethylsilyl (methylcyclopentadienyl) (t-butylcyclopentadienyl) zirconium dichloride, dimethyl Germylbis (methylcyclopentadienyl) zirconium dichloride, dimethylgermylbis (t-butylcyclopentadienyl) zirconium dichloride, dimethylgermylbis (phenylcyclopentadienyl) zirconium dichloride, dimethylgermyl (cyclopentadiene (Enyl) (methylcyclopentadienyl) zirconium dichloride, dimethylgermyl (cyclopentadienyl)
(Phenylcyclopentadienyl) zirconium dichloride, dimethylgermyl (cyclopentadienyl) (t
-Butylcyclopentadienyl) zirconium dichloride, dimethylsilyl (methylcyclopentadienyl)
Examples thereof include (dimethylcyclopentadienyl) zirconium dichloride and dimethylgermyl (methylcyclopentadienyl) (dimethylcyclopentadienyl) zirconium dichloride.

The zirconium compound [I] according to the present invention exhibits excellent olefin polymerization activity in the presence of aluminoxane, and is a useful compound as a polymerization catalyst component. Aluminoxane, which is another component of the catalyst used in the polymerization, has the general formula [II] or the general formula [III] It is an organoaluminum compound represented by. R ³ is a hydrocarbon group such as a methyl group, an ethyl group, a propyl group or a butyl group, preferably a methyl group or an ethyl group. m is 4
It is an integer of -30, preferably 6 or more, and particularly preferably 10 or more. The production method of this kind of compound is known, and for example, trialkyl is added to a hydrocarbon medium suspension of a compound containing adsorbed water, a salt containing water of crystallization (sulfate monohydrate, aluminum sulfate hydrate, etc.). The method of adding aluminum and making it react can be illustrated.

In the method of the present invention, the olefin used in the polymerization reaction is an α-olefin such as propylene, 1-butene, 4-methyl-1-pentene, 1-hexene or 1-octene, and a mixed component of two or more of these. Can also be subjected to polymerization. Further, copolymerization of the above α-olefins with ethylene is also possible. Furthermore, butadiene, 1,4-
Of conjugated and non-conjugated dienes such as hexadiene, 1,4-pentadiene, 1,7-octadiene, or styrene, or of a cyclic olefin such as cyclopropane, cyclobutene, norbornene, dicyclopentadiene and an α-olefin It is also effective for copolymerization.

The polymerization method used in the present invention may be either liquid phase polymerization or gas phase polymerization. The liquid phase polymerization solvent is a hydrocarbon compound capable of dissolving both zirconium compound and aluminoxane components, such as benzene, toluene, o-xylene, m-xylene, p-xylene, ethylbenzene, butylbenzene, mesitylene, and naphthalene. The aromatic hydrocarbons are used, and toluene and xylene are preferable. Furthermore, Japanese Patent Application No. 62-287,016
As shown in No. 6, even in a solvent in which both the zirconium compound and the aluminoxane components cannot be dissolved, polymerization can be carried out by prepolymerization in an aromatic hydrocarbon.

Such solvents include butane, isobutane, pentane, hexane, octane, decane, dodecane, hexadecane, octadecane and other aliphatic hydrocarbons, cyclopentane, methylcyclopentane, cyclohexane, cyclooctane and other alicyclic hydrocarbons. , Gasoline, kerosene,
Examples include petroleum fractions such as light oil. Of these, aliphatic hydrocarbons are preferable. Further, liquefied olefin itself such as liquefied propylene and liquefied butene-1 can be used as a solvent.

The catalyst component may be a mixture of both components of the zirconium compound and aluminoxane, which may be supplied to the reaction system in advance,
Alternatively, both components may be supplied to the reaction system. In any case, the concentration in the polymerization system of both components, the molar ratio is not particularly limited, preferably in the zirconium concentration 10 ^-3 ~ 10 ^-10 mol / range, Al / Zr molar ratio Is preferably used in a range of 100 or more, particularly 1000 or more.

The olefin pressure of the reaction system is not particularly limited, but is preferably in the range of normal pressure to 50 kg / cm ² G, and the polymerization temperature is not limited, but is usually -50 to 230 ° C, preferably -30 to 100 ° C. Is the range. The molecular weight at the time of polymerization can be controlled by known means, for example, selection of temperature or introduction of hydrogen.

EFFECTS OF THE INVENTION According to the present invention, a novel zirconium compound having a bis-substituted cyclopentadienyl ligand having a bridged structure can be obtained. When these zirconium compounds are used for olefin polymerization as a catalyst component for olefin polymerization, a stereoregular polymer can be efficiently produced.

[Examples] Next, the present invention will be specifically described with reference to Examples.

Example 1 [Dimethylsilylbis (methylcyclopentadienyl)]
Zirconium dichloride] All reactions were performed in an inert gas atmosphere. Also,
The reaction solvent used was previously dried. 200 ml
After dissolving 3.5 g (16 mmol) of dimethylbis (methylcyclopentadienyl) silane in 50 ml of tetrahydrofuran in a glass reaction container, 1.6 M of n-butyllithium was added.
23 ml of a hexane solution was slowly added dropwise under ice cooling. After stirring for 2 hours at room temperature, a yellow transparent liquid (Li ₂ [Me ₂ Si (Me-C
₅ H ₃ ) ₂ ]) was obtained.

Zirconium tetrachloride 3.5 in a 500 ml glass reaction vessel
g (15 mmol) was cooled to -78 ° C and 200 ml of tetrahydrofuran was added. Next, the yellow transparent liquid was slowly added dropwise at -78 ° C. After stirring at room temperature for 15 hours, the solvent was distilled off from the yellowish-yellow solution containing a white precipitate, 200 ml of methylene chloride and then 100 ml of dilute hydrochloric acid were added under ice-cooling, and the methylene chloride layer was dried over anhydrous sodium sulfate. . Methylene chloride was distilled off, pentane was added, and the produced solid was filtered to obtain 2.87 g of a pale green solid. Recrystallization was performed with 400 ml of hot heptane to obtain 2.02 g of yellowish white crystals. The physical properties of this compound are shown below. The IR spectrum was measured by the KBr method, and the ¹ H-NMR spectrum was measured by using CDCl ₃ as a solvent.

Elemental analysis value: (C ₁₄ H ₁₈ Cl ₂ SiZr) Calculated value (%): C; 44,66, H; 4.82 Measured value (%): C; 45.02, H; 4.91 IR spectrum: shown in FIG.

NMR spectrum: shown in FIG.

Example 2 [Polymerization] 500 ml of purified toluene, 4.0 mmol of methylaluminoxane (molecular weight 770) manufactured by Toyo Stoufer Chemical Co., Ltd., and dimethylsilylbis (methylcyclopentadienyl) were placed in a 1.5 L internal autoclave made of SUS that had been sufficiently replaced with nitrogen. ) 0.005 mmol of zirconium dichloride was sequentially added and the temperature was raised to 30 ° C. Then, propylene was continuously introduced into this so that the total pressure was maintained at 3 kg / cm ² G, and polymerization was carried out for 2 hours. After the reaction, the catalyst component was decomposed with methanol, and the obtained polypropylene was dried. As a result, 130 g of isotactic polypropylene was obtained, and the catalytic activity was
It was 142 kg / gZr · hr. The molecular weight of the polymer is 940.
It was 0.

Example 3 [Dimethylsilyl (cyclopentadienyl) (methylcyclopentadienyl) zirconium dichloride] All reactions were performed under an inert gas atmosphere. Also,
The reaction solvent used was previously dried. 200 ml
In a glass reaction vessel, 3.4 g (17 mmol) of dimethyl (cyclopentadienyl) (methylcyclopentadienyl) silane was dissolved in 50 ml of pentane, and then 24 ml of 1.6M hexane solution of n-butyllithium was cooled with ice. It was dripped slowly. After stirring at room temperature for 2 hours, the solvent was distilled off to obtain a white solid (Li ₂ [Me ₂ Si (C ₅ H ₄ ) (Me-C ₅ H ₃ )]). To this, 50 ml of tetrahydrofuran was added to obtain a yellow transparent liquid.

In a 500 ml glass reaction vessel, zirconium tetrachloride 4.0
g (17 mmol) was cooled to −78 ° C. and 200 ml of tetrahydrofuran was added. Next, the yellow transparent liquid was slowly added dropwise at -78 ° C. After stirring at room temperature for 1 hour, the mixture was heated under reflux for 1 hour. After allowing to cool, the solvent was distilled off from the pale yellow solution containing a white precipitate, and under ice-cooling, 200 ml of methylene chloride and then yellow hydrochloric acid 1
After adding 00 ml and separating the layers, the methylene chloride layer was dried over anhydrous sodium sulfate. Methylene chloride was distilled off, pentane was added, and the produced solid was filtered to obtain 2.44 g of a pale green solid. Recrystallize with 400 ml of hot heptane to give 1.18 g of pale yellow crystals.
Got The physical properties of this compound are shown below. The IR spectrum was measured by the KBr method, and the ¹ H-NMR spectrum was measured by using CDCl ₃ as a solvent.

Elemental _{analysis: (C 13 H 16 Cl 2} SiZr) Calculated (%): C; 43.08, H; 4.45 Found (%): C; 42.86, H; 4.49 IR spectrum: shown in Figure 3.

NMR spectrum: shown in FIG.

Example 4 [Polymerization] Purified toluene (500 ml), methylaluminoxane (molecular weight: 770) 4.0 mmol, and dimethylsilyl (cyclopentadienyl) (manufactured by Toyo Stoufer Chemical Co., Ltd.) were added to a SUS autoclave having an internal volume of 1.5 L which had been sufficiently replaced with nitrogen. Methylcyclopentadienyl) zirconium dichloride 0.00
5 mmol was added sequentially and the temperature was raised to 30 ° C. Then, propylene was continuously introduced into this so that the total pressure was maintained at 3 kg / cm ² G, and polymerization was carried out for 2 hours. After the reaction, the catalyst component was decomposed with methanol, and the obtained polypropylene was dried. The result is 70 g of isotactic polypropylene.
Was obtained, and the catalytic activity was 77 kg / gZr · hr. The molecular weight of the polymer was 6,600.

Example 5 [Dimethylsilyl (cyclopentadienyl) (t-butylcyclopentadienyl) zirconium dichloride] All reactions were performed under an inert gas atmosphere. Also,
The reaction solvent used was previously dried. 200 ml
In a glass reaction vessel, 5.1 g of dimethyl (cyclopentadienyl) (t-butylcyclopentadienyl) silane
(21 mmol) was dissolved in 50 ml of pentane, and then 29 ml of 1.6 M hexane solution of n-butyllithium was slowly added dropwise under ice cooling. After stirring at room temperature for 2 hours, the solution was distilled off to obtain a white solid (Li ₂ [Me ₂ Si (C ₅ H ₄ ) (t-Bu-C ₅ H ₃ )]). To this, 50 ml of tetrahydrofuran was added to obtain a yellow transparent liquid.

Zirconium tetrachloride 5.0% in a 500 ml glass reaction vessel
g (21 mmol) was cooled to −78 ° C. and 200 ml of tetrahydrofuran was added. Next, the yellow transparent liquid was slowly added dropwise at -78 ° C. After stirring at room temperature for 2 hours, the mixture was heated under reflux for 2 hours. After allowing to cool, the solvent was distilled off from the pale yellow solution containing a white precipitate, and 200 ml of methylene chloride was added under ice cooling, followed by dilute hydrochloric acid 1
After adding 00 ml and separating the layers, the methylene chloride layer was dried over anhydrous sodium sulfate. Methylene chloride was distilled off, pentane was added, and the produced solid was filtered to obtain a pale green solid. Recrystallization with 400 ml of hot heptane gave 0.8 g of pale yellow crystals.
The physical properties of this compound are shown below. The IR spectrum is KB
The r method and ¹ H-NMR spectrum were measured using CDCl ₃ as a solvent.

Elemental analysis value: C ₁₆ H ₂₂ Cl ₂ SiZr) Calculated value (%): C; 47.50, H; 5.48 Measured value (%): C; 47.65, H; 5.61 IR spectrum: shown in FIG.

NMR spectrum: shown in FIG.

Example 6 [Polymerization] Purified toluene (500 ml), methylaluminoxane (molecular weight: 770) 4.0 mmol, dimethylsilyl (cyclopentadienyl) (manufactured by Toyo Stoufer Chemical Co., Ltd.) and dimethylsilyl (cyclopentadienyl) t-
Butylcyclopentadienyl) zirconium dichloride
0.005 mmol was sequentially added, and the temperature was raised to 30 ° C. Then, propylene was continuously introduced into this so that the total pressure was maintained at 3 kg / cm ² G, and polymerization was carried out for 2 hours. After the reaction, the catalyst component was decomposed with methanol, and the obtained polypropylene was dried. As a result, 75 g of isotactic polypropylene was obtained, and the catalytic activity was 82 kg / gZr · hr. The molecular weight of the polymer was 4,300.

Example 7 [Dimethylsilyl (methylcyclopentadienyl) (t
-Butylcyclopentadienyl) zirconium dichloride] All reactions were performed under an inert gas atmosphere. Also,
The reaction solvent used was previously dried. 200 ml
Dimethyl (methylcyclopentadienyl) (t-butylcyclopentadienyl) silane in a glass reaction vessel
After dissolving 3.9 g (15 mmol) in 50 ml of pentane, n-
20 ml of 1.6 M hexane solution of butyl lithium was slowly added dropwise under ice cooling. After stirring at room temperature for 2 hours, the solvent was evaporated, and a white solid (Li ₂ [Me ₂ Si (Me-C ₅ H ₃ ) (t-Bu-C
₅ H ₃ )]) was obtained. To this, 50 ml of tetrahydrofuran was added to obtain a yellow transparent liquid.

Zirconium tetrachloride 3.5 in a 500 ml glass reaction vessel
g (15 mmol) was cooled to -78 ° C and 200 ml of tetrahydrofuran was added. Next, the yellow transparent liquid was slowly added dropwise at -78 ° C. After stirring at room temperature for 18 hours, the mixture was heated under reflux for 4 hours.

After allowing to cool, the solvent was distilled off from the pale yellow solution containing a white precipitate, 200 ml of methylene chloride and then 100 ml of dilute hydrochloric acid were added under ice cooling, and after separating the layers, the methylene chloride layer was dried over anhydrous sodium sulfate. Methylene chloride was distilled off, pentane was added, and the mixture was filtered to obtain 0.37 g of pale yellow crystals from the pale yellow filtrate. The physical properties of this compound are shown below. The IR spectrum is based on the KBr method, ¹
The 1 H-NMR spectrum was measured using CDCl ₃ as a solvent.

Elemental analysis value: (C ₁₇ H ₂₄ Cl ₂ SiZr) Calculated value (%): C; 48.78, H; 5.78 Measured value (%): C; 48.81, H; 5.82 IR spectrum: shown in FIG. 7.

NMR spectrum: shown in FIG.

Example 8 [Polymerization] 500 ml of purified toluene, 4.0 mmol of methylaluminoxane (molecular weight 770) manufactured by Toyo Stoufer Chemical Co., Ltd., and dimethylsilyl (methylcyclopentadienyl) were placed in an autoclave made of SUS having an internal volume of 1.5 L that had been sufficiently replaced with nitrogen.
0.005 mmol of (t-butylcyclopentadienyl) zirconium dichloride was sequentially added, and the temperature was raised to 30 ° C.
Then, propylene was continuously introduced into this so that the total pressure was maintained at 3 kg / cm ² G, and polymerization was carried out for 2 hours. After the reaction
The catalyst component was decomposed with methanol, and the obtained polypropylene was dried. As a result, 59 g of isotactic polypropylene was obtained, and the catalytic activity was 65 kg / gZr · hr. The molecular weight of the polymer was 6,400.

Example 9 [Dimethylsilylbis (t-butylcyclopentadienyl) zirconium dichloride] All reactions were performed under an inert gas atmosphere. Also,
The reaction solvent used was previously dried. 200 ml
In a glass reaction vessel, 4.6 g (15 mmol) of dimethylbis (t-butylcyclopentadienyl) silane was added to pentane.
After dissolving in 50 ml, 21 ml of a 1.6 M hexane solution of n-butyllithium was slowly added dropwise under ice cooling. After stirring at room temperature for 4 hours, the solvent was distilled off, and a white solid (Li ₂ [Me ₂ Si (t-
Bu-C ₅ H ₃ ) ₂ ]) was obtained. Tetrahydrofuran 50
ml was added to obtain a yellow transparent liquid.

Zirconium tetrachloride 3.5 in a 500 ml glass reaction vessel
g (15 mmol) was cooled to −78 ° C. and 250 ml of tetrahydrofuran was added. Next, the yellow transparent liquid was slowly added dropwise at -78 ° C. After leaving it to return to room temperature, it was heated under reflux for 84 hours.

After allowing to cool, the solvent was distilled off from the yellow transparent solution, 300 ml of methylene chloride and then 100 ml of dilute hydrochloric acid were added under ice cooling, and after liquid separation, the methylene chloride layer was dried over anhydrous sodium sulfate. Methylene chloride was distilled off, pentane was added and the mixture was filtered. From the yellow filtrate, 2.35 g of yellowish white crystals were obtained. The physical properties of this compound are shown below. The IR spectrum was measured by the KBr method, and the ¹ H-NMR spectrum was measured by using CDCl ₃ as a solvent.

Elemental _{analysis: (C 20 H 30 Cl 2} SiZr) Calculated (%): C; 52.15, H; 6.56 Found (%): C; 52.01, H; 6.58 IR spectrum: shown in Figure 9.

NMR spectrum: shown in FIG.

Example 10 [Polymerization] 500 ml of purified toluene, 4.0 mmol of methylaluminoxane (molecular weight 770) manufactured by Toyo Stoufer Chemical Co., Ltd., and dimethylsilylbis (t-butylcyclopenta) in an autoclave made of SUS having an internal volume of 1.5 L that had been sufficiently replaced with nitrogen. 0.005 mmol of dienyl) zirconium dichloride was sequentially added, and the temperature was raised to 30 ° C. Then, propylene was continuously introduced into this so that the total pressure was maintained at 3 kg / cm ² G, and polymerization was carried out for 2 hours. After the reaction, the catalyst component was decomposed with methanol, and the obtained polypropylene was dried. . As a result, 3.1 g of isotactic polypropylene was obtained, and the catalytic activity was 3.4 kg / gZr · hr. The molecular weight of the polymer was 9,600.

Example 11 [Dimethylgermylbis (methylcyclopentadienyl) zirconium dichloride] All reactions were performed under an inert gas atmosphere. Also,
The reaction solvent used was previously dried. 200 ml
In a glass reaction vessel, 1.2 g (8 mmol) of dimethylbis (methylcyclopentadienyl) germane was added to pentane.
After dissolving in 50 ml, 11 ml of a 1.6 M hexane solution of n-butyllithium was slowly added dropwise under ice cooling. After stirring at room temperature for 2 hours, the solvent was evaporated, and a white solid (Li ₂ [Me ₂ Ge (Me-
C ₅ H ₃ ) ₂ ]) was obtained. To this, 50 ml of tetrahydrofuran was added to obtain a yellow transparent liquid.

In a 500 ml glass reaction vessel, zirconium tetrachloride 1.8
g (8 mmol) was cooled to −78 ° C. and 150 ml of tetrahydrofuran was added. Next, the yellow transparent liquid was slowly added dropwise at -78 ° C. After stirring at room temperature for 14 hours, the mixture was heated under reflux for 2 hours. After allowing to cool, the solvent was distilled off from the yellow transparent solution, 200 ml of methylene chloride and 100 ml of dilute hydrochloric acid were added under ice cooling, and after separating the layers, the methylene chloride layer was dried over anhydrous sodium sulfate. Methylene chloride was distilled off, pentane was added, the mixture was filtered, and after concentration, 0.31 g of yellow white crystals was obtained from the pale yellow filtrate.
The physical properties of this compound are shown below. The IR spectrum is KB
The r method and ¹ H-NMR spectrum were measured using CDCl ₃ as a solvent.

Elemental _{analysis: (C 14 H 18 Cl 2} GeZr) Calculated (%): C; 39.94, H; 4.31 Found (%): C; 40.38, H; 4.38 IR spectrum: shown in Figure 11.

NMR spectrum: shown in FIG.

Example 12 [Polymerization] Purified toluene (500 ml), methylaluminoxane (molecular weight: 770) 4.0 mmol, and dimethylgermylbis (methylcyclopentadiene) manufactured by Toyo Stoufer Chemical Co. 0.005 mmol of (enyl) zirconium dichloride was sequentially added, and the temperature was raised to 30 ° C. Then, propylene was continuously introduced into this so that the total pressure was maintained at 3 kg / cm ² G, and polymerization was carried out for 2 hours. After the reaction, the catalyst component was decomposed with methanol, and the obtained polypropylene was dried. As a result, 25 g of isotactic polypropylene was obtained, and the catalytic activity was 2
It was 7 kg / gZr · hr. The molecular weight of the polymer is 7600.
Met.

Example 13 [Cyclotetramethylenesilyl (cyclopentadienyl) (methylcyclopentadienyl) zirconium dichloride] All reactions were performed under an inert gas atmosphere. Also,
The reaction solvent used was previously dried. 200 ml
After dissolving 3.4 g (15 mmol) of cyclotetramethylene (cyclopentadienyl) (methylcyclopentadienyl) silane in 50 ml of pentane in a glass reaction vessel, n
22 ml of 1.6 M hexane solution of -butyllithium was slowly added dropwise under ice cooling. After stirring at room temperature for 3 hours, the solvent was evaporated and the white solid (Li ₂ [(CH ₂ ) ₄ Si (C ₅ H ₄ ) (Me-C
₅ H ₃ )]) was obtained. To this, 50 ml of tetrahydrofuran was added to obtain a yellow transparent liquid.

Zirconium tetrachloride 3.5 in a 500 ml glass reaction vessel
g (15 mmol) was cooled to −78 ° C. and 250 ml of tetrahydrofuran was added. Next, the yellow transparent liquid was slowly added dropwise at -78 ° C. After stirring at room temperature for 48 hours, the solvent was distilled off from the yellow solution containing white precipitate, and methylene chloride 20
0 ml was added, the produced white solid was filtered, the obtained yellow filtrate was concentrated, and pentane was added. After cooling at -30 ° C, 0.39 g of yellowish white crystals were obtained. The physical properties of this compound are shown below.
The IR spectrum is KBr method, and the ¹ H-NMR spectrum is CDCl ₃
Was used as the solvent and measured.

Elemental analysis value: (C ₁₅ H ₁₈ Cl ₂ SiZr) Calculated value (%): C; 46.37, H; 4.67 Measured value (%): C; 47.03, H; 4.82 IR spectrum: shown in FIG.

NMR spectrum: shown in FIG.

Example 14 [Polymerization] Purified toluene (500 ml), methylaluminoxane (molecular weight: 770) 4.0 mmol, manufactured by Toyo Stoufer Chemical Co., Ltd., and 4.0 mmol, and cyclotetramethylenesilyl (cyclopentadienyl) were placed in a SUS autoclave having an internal volume of 1.5 L, which was sufficiently replaced with nitrogen. ) (Methylcyclopentadienyl) zirconium dichloride (0.005 mmol) was sequentially added, and the temperature was raised to 30 ° C. Then, propylene was continuously introduced into this so that the total pressure was maintained at 3 kg / cm ² G, and polymerization was carried out for 2 hours. After the reaction, the catalyst component was decomposed with methanol, and the obtained polypropylene was dried. As a result, 3.6 g of isotactic polypropylene was obtained, and the catalytic activity was 3.9 kg / gZr · hr. The molecular weight of the polymer was 4,200.

Example 15 [Dimethylsilyl (methylcyclopentadienyl) (dimethylcyclopentadienyl) zirconium dichloride] All reactions were performed under an inert gas atmosphere. Also,
The reaction solvent used was previously dried. 200 ml
Dimethyl (methylcyclopentadienyl) (dimethylcyclopentadienyl) silane in a glass reactor 3.
After dissolving 5 g (15 millimoles) in 50 ml of pentane, 22 ml of a 1.6 M hexane solution of n-butyllithium was slowly added dropwise under ice cooling. After stirring at room temperature for 5 hours, the solvent was distilled off to obtain a white solid (Li ₂ [Me ₂ Si (Me-C ₅ H ₃ ) (Me ₂ -C ₅ H ₂ )]). To this, 50 ml of tetrahydrofuran was added to obtain a yellowish brown transparent liquid.

Zirconium tetrachloride 3.5 in a 500 ml glass reaction vessel
g (15 mmol) was cooled to −78 ° C. and 250 ml of tetrahydrofuran was added. Next, the above yellowish brown transparent liquid is -78 ° C.
Then slowly dripped. After stirring at room temperature for 18 hours, the mixture was heated under reflux for 6 hours.

The solvent was distilled off from the yellow solution, 300 ml of methylene chloride was added, the produced white solid was filtered, the obtained yellow filtrate was concentrated, and pentane was added. The produced solid was filtered and recrystallized with 200 ml of hot heptane to obtain 1.08 g of yellowish white crystals. The physical properties of this compound are shown below. The IR spectrum is KBr
Method, ¹ H-NMR spectrum was measured using CDCl ₃ as a solvent.

Elemental analysis value: (C ₁₅ H ₂₀ Cl ₂ SiZr) Calculated value (%): C; 46.13, H; 5.16 Measured value (%): C; 46.22, H; 5.16 IR spectrum: shown in FIG.

NMR spectrum: shown in FIG.

Example 16 [Polymerization] Purified toluene (500 ml), methylaluminoxane (molecular weight: 770) 4.0 mmol, and dimethylsilyl (methylcyclopentadienyl), manufactured by Toyo Stoufer Chemical Co., Ltd., were placed in a SUS autoclave having an internal volume of 1.5 L that had been sufficiently replaced with nitrogen.
0.005 mmol of (dimethylcyclopentadienyl) zirconium dichloride was sequentially added, and the temperature was raised to 30 ° C. Then, propylene was continuously introduced into this so that the total pressure was maintained at 3 kg / cm ² G, and polymerization was carried out for 2 hours. After the reaction, the catalyst component was decomposed with methanol, and the obtained polypropylene was dried. As a result, 45 g of isotactic polypropylene was obtained, and the catalytic activity was 49 kg / gZr · hr.
The molecular weight of the polymer was 5,600.

Comparative Example 1 [Polymerization] Purified toluene (500 ml), methylaluminoxane (molecular weight: 770) 4.0 mmol, and dimethylsilylbis (cyclopentadienyl) manufactured by Toyo Stoufer Chemical Co., Ltd. were placed in a SUS autoclave having an internal volume of 1.5 L, which was sufficiently replaced with nitrogen. Zirconium dichloride 0.005 mmol was added sequentially,
The temperature was raised to ° C. Next, propylene was added to this at a total pressure of 3 kg /
It was continuously introduced so as to maintain cm ² G, and polymerization was carried out for 2 hours. After the reaction, the catalyst component was decomposed with methanol, and the obtained polypropylene was dried. As a result, 29 g of atactic polypropylene was obtained, and the catalytic activity was 32 kg / g Zr · h.
It was r. The molecular weight of the polymer was 5,300.

[Brief description of drawings]

Figures 1, 3, 5, 7, 9, 11, 13, 15 show IR of the following compounds
The spectrum is also shown as
Figure 16 shows the NMR spectra of the following compounds.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Takaya Mise 21-11, Suwa Town, Kawagoe City, Saitama Prefecture (72) Inventor Hiroshi Yamazaki 2-41 Matsugaoka, Tokorozawa City, Saitama Prefecture (56) References 60-35006 (JP, A) JP 60-35007 (JP, A) JP 60-35008 (JP, A) Special table 63-501369 (JP, A)

Claims (1)

[Claims] 1. A zirconium compound represented by the following general formula [I]: (However, Y represents silicon or germanium. ▲ R ¹ _n ▼
-C ₅ H _4-n and _{^{▲ R 1 q ▼ -C 5 H}} 4- q represents an unsubstituted or substituted cyclopentadienyl group, but n and q is an integer of 0 to 2, n = q = The case of 0 and n = q = 2 is excluded. Each R ¹ may be the same or different and is hydrogen, a silyl group or a hydrocarbon group. Each R ² may be the same or different and is hydrogen or a hydrocarbon group. Also,
Each X may be the same or different, and hydrogen, halogen,
Or a hydrocarbon group).