JP2696635B2 - Method for producing olefin polymer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing an olefin polymer. More specifically, a method for producing a syndiotactic olefin polymer using a catalyst comprising a bridged transition metal compound having a ligand in which an unsubstituted cyclopentadienyl ring and a substituted cyclopentadienyl ring are bridged and an aluminoxane About.

[0002]

2. Description of the Related Art If a ligand of a metallocene compound is selected in a homogeneous catalyst for olefin polymerization (metallocene compound / aluminoxane), any of atactic polypropylene, isotactic polypropylene and syndiotactic polypropylene can be produced by propylene polymerization. It is known that it can be manufactured. (Makromol.
Chem. Rapid Commun. 4,417-4
21 (1983), Angew. Chem. Int. E
d. Engl. 24, 507-508 (1985),
J. Am. Chem. Soc. 1988, 110, 62
55-6256)

As a compound for producing highly syndiotactic polypropylene using such a homogeneous catalyst system, a metallocene compound having a ligand in which a fluorenyl group and an unsubstituted cyclopentadienyl group are cross-linked with carbon is used. It is known. (JP-A-2-41303, JP-A-2-27
4703, JP-A-2-274704, etc.)

[0004]

SUMMARY OF THE INVENTION The above-mentioned cross-linkable catalyst comprises:
Compounds in which a substituent is added to a cyclopentadienyl ring to control syndiotacticity are known.
However, in this method, the types of compounds are limited, and it is difficult to perform sufficient adjustment.

The inventors of the present invention have conducted studies to solve the above-mentioned problems, and as a result, have found that an unsubstituted cyclopentadienyl ring and a substituted cyclopentadienyl ring are used, and that the bridging portion is variously modified. Have succeeded in synthesizing a large number of compounds, and have further found that a catalyst comprising these compounds and an aluminoxane can produce a syndiotactic olefin polymer, and have reached the present invention. As is apparent from the above description, an object of the present invention is to provide a crosslinked transition metal compound having a substituent only on one of the cyclopentadienyl rings, in which various crosslinking groups are modified with various substituents. An object of the present invention is to provide a method for producing an olefin polymer having a high degree of syndiotacticity using a catalyst obtained by combining a compound and an aluminoxane.

[0006]

That is, the present invention provides:
(A) General formula (1)

[0007]

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A transition metal compound represented by the formula (where M is
Zirconium and Y represent carbon or silicon. C ₅ H ₄
Represents an unsubstituted cyclopentadienyl group, R ² _n C ₅ H
_4-n represents a substituted cyclopentadienyl group, and n is an integer of 2 or 4. However, when n = 2, the position is 3
And 4th place. Each R ¹ may be the same or different, and represents a hydrogen or hydrocarbon group. Each R ²
May be the same or different and represent a hydrocarbon group, and two R ² may form a ring structure. X
May be the same or different, and represent a hydrogen, halogen, or hydrocarbon group. ) And (B) general formula (2)

[0009]

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Or the general formula (3)

[0011]

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(Where m is an integer of 4 to 30, and R ³ represents a hydrocarbon group). An olefin is polymerized in the presence of a catalyst containing an aluminoxane as an active ingredient. The present invention relates to a method for producing an atactic olefin polymer.

The configuration and effect of the present invention will be described in detail below. The transition metal compound (1) of the catalyst component (A) used in the present invention is a bridged transition metal compound having a ligand in which an unsubstituted cyclopentadienyl ring and a substituted cyclopentadienyl ring are bridged. is there. M is zirconium
is there. Y is carbon or silicon. Each R ¹ may be the same or different, and represents a hydrogen or hydrocarbon group. Examples of the hydrocarbon group include a methyl group, an ethyl group, a phenyl group and the like. The number of substituents on the substituted cyclopentadienyl ring may be either 2 or 4. In the case of a disubstituted compound, the substituents are located at the 3 and 4 positions. Each R ² may be the same or different from each other, a hydrocarbon group, and two R ² may form a ring structure. Examples of the hydrocarbon group include a methyl group, an ethyl group, a propyl group, a butyl group, and a phenyl group, and examples of the ring structure include an indenyl group and a tetrahydroindenyl group. it can. X may be the same or different and represents hydrogen, a halogen such as fluorine, chlorine, or bromine, or a hydrocarbon group such as a methyl group or an ethyl group.

Non-limiting examples of the above transition metal compounds include isopropylidene (cyclopentadienyl) (3,
4-dimethylcyclopentadienyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl)
(3,4-dimethylcyclopentadienyl) zirconium dichloride, methylidene (cyclopentadienyl)
(2,3-dimethylindenyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (2,
3-dimethylindenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (2,3-dimethylindenyl) zirconium dichloride, diphenylsilylene (cyclopentadienyl) (2,3-dimethylindenyl) zirconium dichloride, methylidene (Cyclopentadienyl) (tetraphenylcyclopentadienyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (tetraphenylcyclopentadienyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (tetraphenylcyclopentadiyl) Enyl) zirconium dichloride, methylidene (cyclopentadienyl) (2,5-dimethyl-3,4
-Diphenylcyclopentadienyl) zirconium dichloride, isopropylidene (cyclopentadienyl)
(2,5-dimethyl-3,4-diphenylcyclopentadienyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (2,5-dimethyl-3,4
-Diphenylcyclopentadienyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl)
(1,3-dimethyl-4,5,6,7-tetrahydro-
Examples include zirconium compounds such as 2-indenyl) zirconium dichloride and dimethylsilylene (cyclopentadienyl) (tetramethylcyclopentadienyl) zirconium dichloride.

Aluminoxane (B), another catalyst component used in the process of the present invention, has the general formula (2)

[0016]

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Or the general formula (3)

[0018]

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An organoaluminum compound represented by the formula: R ³ is a hydrocarbon group such as a methyl group and an ethyl group. m
Is an integer of 4 to 30, preferably 6 or more, and particularly preferably 10 or more. Processes for producing this type of compound are known. For example, trialkyl compounds are added to a hydrocarbon medium suspension of a compound containing adsorbed water or a salt containing water of crystallization (eg, copper sulfate hydrate, aluminum sulfate hydrate). A method of reacting by adding aluminum can be exemplified.

In the method of the present invention, the olefin used for the polymerization reaction is an α-olefin such as propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, and the like. It can also be subjected to polymerization. Further, copolymerization of the above α-olefin and ethylene is also possible. Further, conjugated and non-conjugated dienes,
Or it is also effective for copolymerization with a cyclic olefin.

The polymerization method used in the present invention may be either liquid phase polymerization or gas phase polymerization. The polymerization solvent for liquid phase polymerization is a hydrocarbon compound capable of dissolving both components (A) and (B), and aromatic hydrocarbons such as benzene, toluene and xylene are used, and toluene is preferred. Further, in a solvent in which both components (A) and (B) cannot be dissolved, polymerization can be performed by performing prepolymerization in an aromatic hydrocarbon. Examples of such a solvent include aliphatic hydrocarbons such as pentane, hexane, heptane, and octanedecane; alicyclic hydrocarbons such as cyclopentane and cyclohexane; and petroleum fractions such as gasoline, kerosene, and gas oil. Of these, aliphatic hydrocarbons are preferred. Furthermore, liquefied olefins such as liquefied propylene and liquefied butene-1 can be used as solvents.

As the catalyst component, a mixture of both components (A) and (B) in advance may be supplied to the reaction system, or both components (A) and (B) may be separately supplied to the reaction system. You may. In any case, the concentration and the molar ratio of both components in the polymerization system are not particularly limited, but are preferably in the range of 10 ⁻³ to 10 ⁻¹⁰ mol / l.
The molar ratio of 1 / transition metal atom is 100 or more and 1,000,
000 or less, particularly 1,000 to 100,000 is preferably used. The olefin pressure of the reaction system is not particularly limited, but is preferably from normal pressure to 50 kg / cm ² G
The polymerization temperature is not limited, but is usually -80.
To 230 ° C, preferably -50 to 100 ° C. The molecular weight at the time of polymerization can be adjusted by known means, for example, selection of temperature or introduction of hydrogen.
In the present invention, the syndiotactic olefin polymer is defined as having a probability of r dyad belonging to mr and rr in the mm, mr and rr signals given by the ¹³ C-NMR spectrum of the polymer of 0.5 or more, preferably 0.1 or more.
55 or more. As shown in the examples (polymerization examples) described later, the r value of the polypropylene produced by the method of the present invention was 55 to 81, whereas the r value of the polypropylene obtained in the comparative example was 6.5. Stopped at ~ 26. In the method of the present invention, a poly-α-olefin having an intended r value can be obtained mainly by selecting the type of the transition metal compound represented by the general formula (1).

[0023]

Next, the present invention will be described specifically with reference to examples.

Example 1 [Isopropylidene (cyclopentadienyl) (3,4
-Synthesis of dimethylcyclopentadienyl) zirconium dichloride] All the reactions were performed under an inert gas atmosphere. The reaction solvent used was dried in advance. 200ml
In a glass reactor, 2-cyclopentadienyl-2
After dissolving 2.04 g (10 mmol) of-(3,4-dimethyl-1-cyclopentadienyl) propane in 150 ml of tetrahydrofuran, 13 ml of a 1.58 mol / l hexane solution of normal butyl lithium was added at -78 ° C for 30 minutes. Was dropped. After returning to room temperature in 4 hours, the mixture was stirred at room temperature for 3 hours, and a yellow transparent solution (Li ₂ [Me ₂ C (C
_{5 H 4) (3,4-Me} 2 C 5 H 2)] was obtained. 500
1. Zirconium tetrachloride in a 1 ml glass reaction vessel.
33 g (10 mmol) were cooled to -78 ° C and 200 ml of tetrahydrofuran were added. Next, the yellow transparent solution was added dropwise at -78 ° C for 1 hour. After returning to room temperature in 4 hours and stirring for 18 hours, the solvent was distilled off from the orange-yellow solution.
Add 200 ml of methylene chloride saturated with hydrogen chloride,
The white solid (LiCl) was filtered. The filtrate was concentrated, extracted with 400 ml of hot heptane, filtered, and the solid obtained by distilling off heptane under reduced pressure was washed with pentane and dried to obtain 0.51 g of a yellow solid. Although the present compound can be used as it is, plate-like yellow crystals recrystallized and purified with toluene or the like may be used.

Example 2 [Polymerization] 500 ml of purified toluene and methylaminoxan (molecular weight: 1,100) manufactured by Tosoh Akzo Co., Ltd. were placed in a 1.5 L internal volume SUS autoclave sufficiently purged with nitrogen.
05 mmol and 0.002 mmol of isopropylidene (cyclopentadienyl) (3,4-dimethylcyclopentadienyl) zirconium dichloride were added sequentially,
The temperature was raised to 30 ° C. Subsequently, propylene was continuously introduced into the mixture so that the total pressure was maintained at 3 kg / cm ² G,
Polymerization was carried out for hours. After the reaction, the catalyst component was decomposed with methanol, and the obtained polypropylene was dried. As a result, 6.9 g of polypropylene was obtained. Catalyst activity is 19k
g / gZr · hr. ¹³ C-N of this polymer
According to MR measurement, mm = 16, mr = 43, and rr = 40.

Example 3 [Isopropylidene (cyclopentadienyl) (2,3
-Synthesis of dimethylindenyl) zirconium dichloride] All the reactions were performed under an inert gas atmosphere. The reaction solvent used was dried in advance. 200ml
In a glass reactor, 0.80 g of potassium hydride (2
0 mmol), add 50 ml of tetrahydrofuran, and then add 2-cyclopentadienyl-2- under ice-cooling.
(2,3-dimethyl-1-indenyl) propane 2.5
g (10 mmol) of tetrahydrofuran (50 ml)
The solution was added dropwise over one hour. After stirring at room temperature for 2.5 hours, a dark reddish brown solution (K ₂ [Me ₂ C (C ₅ H ₄ ) (2,3-
Me ₂ C ₉ H ₄ )]) was obtained. In a 500 ml glass reactor, 2.33 g (10 mmol) of zirconium tetrachloride was cooled to -78 ° C and tetrahydrofuran 150
Then, the mixture was returned to room temperature to obtain a colorless and transparent solution. To this, the reddish brown solution was added dropwise in a water bath (18 ° C.).
After stirring at room temperature for 18 hours, the solvent was distilled off from the white turbid yellow solution, toluene was added to the ocher residue, a white solid (KCl) was filtered, and the obtained yellow filtrate was concentrated under reduced pressure. Cooled to 30 ° C. The precipitated crystals were washed with pentane and dried to obtain 0.64 g of orange crystals.

Example 4 [Polymerization] In a 1.5 L internal volume autoclave made of SUS sufficiently purged with nitrogen, 500 ml of purified toluene and methylaminoxan (molecular weight 1,100) manufactured by Tosoh Akzo Co., Ltd.
05 mmol and isopropylidene (cyclopentadienyl) (2,3-dimethylindenyl) zirconium dichloride 0.002 mmol were sequentially added, and the temperature was raised to 30 ° C. Then, propylene was added to this at a total pressure of 3 kg / c.
It was continuously introduced so as to maintain m 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, 2.2 g of polypropylene was obtained. The catalyst activity is 6.0 kg / gZ
r · hr. As a result of ¹³ C-NMR measurement of this polymer, mm = 7, mr = 25, and rr = 68.

Example 5 [Synthesis of methylidene (cyclopentadienyl) (tetraphenylcyclopentadienyl) zirconium dichloride] All the reactions were carried out under an inert gas atmosphere. The reaction solvent used was dried in advance. 200ml
In a glass reactor, 0.60 g of potassium hydride (1
5 mmol), add 50 ml of tetrahydrofuran, and add cyclopentadienyl (2, 3, 4, 5-
Tetraphenylcyclopentadienyl) methane (7.2
Mmol) in tetrahydrofuran (50 ml) was added dropwise. After stirring at room temperature for 2 hours, an ocher suspension (K ₂ [H
_{2 C (C 5 H 4)} (2,3,4,5-Ph 4 C 5)])
I got In a 500 ml glass reaction vessel, 1.68 g (7.2 mmol) of zirconium tetrachloride was cooled to -78 ° C, 150 ml of tetrahydrofuran was added, and the mixture was returned to room temperature to obtain a colorless and transparent solution. To this, the previous suspension,
The solution was added dropwise under a water bath (18 ° C.). After stirring at room temperature for 18 hours,
The solvent was distilled off from the tan solution containing white turbidity, toluene was added to the residue, and a white solid (KCl) was filtered. The obtained yellow filtrate was concentrated under reduced pressure, and the solid precipitated by adding hexane was washed with hexane and dried to obtain 2.56 g of a yellow solid.
I got Although the present compound can be used as it is, yellow crystals purified by recrystallization from methylene chloride-pentane may be used.

Example 6 [Polymerization] Purified toluene (500 ml) and methylaminoxane (molecular weight: 1,100) manufactured by Tosoh Akzo Co., Ltd. in a 1.5 L internal volume SUS autoclave sufficiently purged with nitrogen.
1 mmol and methylidene (cyclopentadienyl)
0.004 mmol of (tetraphenylcyclopentadienyl) zirconium dichloride was sequentially added, and the temperature was raised to 30 ° C. Then, propylene was added to this at a total pressure of 3 kg /
cm ² G was continuously introduced to carry out polymerization for 2 hours. After the reaction, the catalyst component is decomposed with methanol,
The obtained polypropylene was dried. As a result, 3.6 g of polypropylene was obtained. The catalyst activity is 4.9kg / g
Zr · hr. As a result of ¹³ C-NMR measurement of this polymer, mm = 13, mr = 52, and rr = 35.

Example 7 [Dimethylsilylene (cyclopentadienyl) (2,5
-Synthesis of dimethyl-3,4-diphenylcyclopentadienyl) zirconium dichloride] All the reactions were performed under an inert gas atmosphere. The reaction solvent used was dried in advance. 200ml
1.52 g of potassium hydride (3.
8 mmol), 50 ml of tetrahydrofuran was added, and then (cyclopentadienyl) (2,5-
Dimethyl-3,4-diphenylcyclopentadienyl)
A solution of 6.63 g (10 mmol) of dimethylsilane in 50 ml of tetrahydrofuran was added dropwise over 1 hour. After stirring at room temperature for 5 hours, a dark red solution (K ₂ [Me ₂ Si (C
_{5 H 4) (2,5-Me} 2 -3,4-Ph 2 C 5)])
I got In a 500 ml glass reaction vessel, 3.50 g (15 mmol) of zirconium tetrachloride was cooled to -78 ° C, 200 ml of tetrahydrofuran was added, and the mixture was returned to room temperature to obtain a colorless and transparent solution. To this, the red solution
It was added dropwise at -50 ° C. After stirring at room temperature for 12 hours, the solvent was distilled off from the brown suspension, toluene (500 ml) was added to the obtained pale brown solid residue, and the white solid was filtered. Toluene was distilled off from the resulting brown filtrate. This gave a green-yellow solid.
This was dissolved in toluene, concentrated under reduced pressure, added with hexane and cooled to −30 ° C. to obtain 5.06 g of a yellow solid. Although the present compound can be used as it is, colorless crystals recrystallized and purified from toluene may be used.

Example 8 [Polymerization] In a 1.5 L internal volume autoclave made of SUS sufficiently purged with nitrogen, 500 ml of purified toluene and methylaminoxan (molecular weight: 1,100) manufactured by Tosoh Akzo Co., Ltd.
05 mmol and dimethylsilylene (cyclopentadienyl) (2,5-dimethyl-3,4-diphenylcyclopentadienyl) zirconium dichloride 0.002 mmol were sequentially added, and the temperature was raised to 30 ° C. Next, propylene was continuously introduced into the mixture so that the total pressure was maintained at 3 kg / cm ² G, and polymerization was performed for 2 hours. After the reaction, the catalyst component was decomposed with methanol, and the obtained polypropylene was dried. As a result, 3.8 g of polypropylene was obtained. The catalyst activity was 10 kg / gZr · hr. From the ¹³ C-NMR measurement of this polymer, mm = 10, mr =
44, rr = 46.

Example 9 [Dimethylsilylene (cyclopentadienyl) (1,3
-Synthesis of dimethyl-4,5,6,7-tetrahydro-2-indenyl) zirconium dichloride] All the reactions were performed under an inert gas atmosphere. The reaction solvent used was dried in advance. 200ml
In a glass reactor, (cyclopentadienyl)
(1,3-dimethyl-4,5,6,7-tetrahydro-
3.37 g of (2-indenyl) dimethylsilane (12.5
Was dissolved in 50 ml of tetrahydrofuran, and 19 ml of a hexane solution of normal butyl lithium (1.58 mol / l) was added dropwise over 30 minutes under ice-cooling. After stirring at room temperature for 4 hours, a dark red solution (Li ₂ [Me ₂ Si
_{(C 5 H 4) (1,3} -Me 2 C 9 H 8)]) was obtained.
In a 500 ml glass reaction vessel, 2.90 g (12.4 mmol) of zirconium tetrachloride was cooled to -78 ° C, 200 ml of tetrahydrofuran was added, and the mixture was returned to room temperature to obtain a colorless and transparent solution. To this, add the red solution above to -6
It was added dropwise at 0 ° C. After returning to room temperature in 3 hours and stirring for 12 hours, the solvent was distilled off from the orange-yellow solution, and 200 ml of hexane was removed.
And filtered. The pale yellow filtrate was concentrated, pentane was added, and the mixture was cooled to −30 ° C. to obtain 0.27 g of a cream-colored solid. Although the present compound can be used as it is, plate-like colorless crystals purified by recrystallization from hexane may be used.

Example 10 [Polymerization] Purified toluene (500 ml) and methylaminoxan (molecular weight: 1,100) manufactured by Tosoh Akzo Co., Ltd. in a 1.5 L internal volume SUS autoclave sufficiently purged with nitrogen.
05 mmol and dimethylsilylene (cyclopentadienyl) (1,3-dimethyl-4,5,6,7-tetrahydro-2-indenyl) zirconium dichloride 0.0
02 mmol was added sequentially, and the temperature was raised to 30 ° C. Next, propylene was continuously introduced into the mixture so that the total pressure was maintained at 3 kg / cm ² G, and polymerization was performed for 2 hours. After the reaction, the catalyst component was decomposed with methanol, and the obtained polypropylene was dried. As a result, 4.2 g of polypropylene was obtained.
was gotten. The catalyst activity was 12 kg / g Zr-hr. From the ¹³ C-NMR measurement of this polymer, mm = 1
3, mr = 50, rr = 37.

Example 11 [Dimethylsilylene (cyclopentadienyl) (3,4
-Synthesis of dimethylcyclopentadienyl) zirconium dichloride] All the reactions were performed under an inert gas atmosphere. The reaction solvent used was dried in advance. 200ml
In a glass reactor, (cyclopentadienyl)
3.33 g (15.4 mmol) of (3,4-dimethylcyclopentadienyl) dimethylsilane was added to 50 m of pentane.
After dissolving in normal butyl lithium (1.57 m
(l / l) of a hexane solution was added dropwise over 1 hour under ice cooling. After stirring at room temperature for 4 hours, the solvent was evaporated and a white solid (Li ₂ [Me ₂ Si (C ₅ H ₄ ) (3,4-Me
₂ C ₅ H ₂ )]). To this was added 50 ml of tetrahydrofuran to obtain a yellow solution. In a 500 ml glass reaction vessel, 3.50 g of zirconium tetrachloride (15
Mmol) to -78 ° C and tetrahydrofuran 2
After adding 00 ml, the mixture was returned to room temperature to obtain a colorless and transparent solution.
Next, the above yellow solution was added dropwise at -78 ° C. 4 to room temperature
After returning to time and stirring at room temperature for 12 hours, the solvent was distilled off from the pale yellow solution, 200 ml of methylene chloride was added, and the generated white solid (LiCl) was filtered. The obtained yellow filtrate was concentrated, and pentane was added to obtain 3.43 g of a white solid. This was recrystallized from heptane to obtain 1.02 g of colorless crystals.

Example 12 [Polymerization] Purified toluene (500 ml) and methylaminoxan (molecular weight 1,100) manufactured by Tosoh Akzo Co., Ltd. in a 1.5 L internal volume SUS autoclave sufficiently purged with nitrogen.
05 mmol and 0.002 mmol of dimethylsilylene (cyclopentadienyl) (3,4-dimethylcyclopentadienyl) zirconium dichloride were added in sequence,
The temperature was raised to 30 ° C. Subsequently, propylene was continuously introduced into the mixture so that the total pressure was maintained at 3 kg / cm ² G,
Polymerization was carried out for hours. After the reaction, the catalyst component was decomposed with methanol, and the obtained polypropylene was dried. As a result, 13 g of polypropylene was obtained. The catalyst activity is 36kg
/ GZr · hr. ¹³ C-NM of this polymer
From the R measurement, mm = 21, mr = 48, and rr = 31.

Example 13 [Synthesis of dimethylsilylene (cyclopentadienyl) (tetramethylcyclopentadienyl) zirconium dichloride] All the reactions were performed in an inert gas atmosphere. The reaction solvent used was dried in advance. 200ml
2. (Cyclopentadienyl) (tetramethylcyclopentadienyl) dimethylsilane in a glass reactor.
67 g (15 mmol) of tetrahydrofuran in 50 ml
Dissolved in normal butyl lithium (1.50mo
1 / l) of hexane solution was added dropwise over 1 hour under ice cooling. After stirring at room temperature for 4 hours, a pale yellow suspension (Li ₂
[Me ₂ Si (C ₅ H ₄ ) (Me ₄ C ₅ )]) was obtained.
In a 500 ml glass reaction vessel, 3.50 g (15 mmol) of zirconium tetrachloride was cooled to -78 ° C, 200 ml of tetrahydrofuran was added, and the mixture was returned to room temperature to obtain a colorless and transparent solution. Next, the above pale yellow suspension was cooled to -50 ° C.
Was dropped. After returning to room temperature in 3 hours and stirring at room temperature for 12 hours, the solvent was distilled off from the pale yellow solution, and methylene chloride was added.
0 ml was added and the white solid (LiCl) was filtered. The obtained yellow filtrate was concentrated, and pentane was added to obtain a white solid. This was recrystallized from heptane to give 0.32 g of colorless crystals.
I got

Example 14 [Polymerization] In a 1.5 L internal volume autoclave made of SUS sufficiently purged with nitrogen, 500 ml of purified toluene and methylaminoxan (molecular weight: 1,100) manufactured by Tosoh Akzo Co., Ltd.
05 mmol and 0.002 mmol of dimethylsilylene (cyclopentadienyl) (tetramethylcyclopentadienyl) zirconium dichloride were added successively to give 30
The temperature was raised to ° C. Next, propylene was added to this with a total pressure of 3 k.
g / cm ² G was continuously introduced to carry out polymerization for 2 hours. After the reaction, the catalyst component was decomposed with methanol, and the obtained polypropylene was dried. As a result, 7.5 g of polypropylene was obtained. The catalyst activity is 21kg /
gZr · hr. ¹³ C-NMR of this polymer
From the measurements, mm = 13, mr = 49, and rr = 38.

Comparative Example 1 [Polymerization] In a 1.5 L internal volume SUS autoclave sufficiently purged with nitrogen, 500 ml of purified toluene, methylaluminoxane manufactured by Tosoh Akzo Co., Ltd. (molecular weight 1,100)
1.05 mmol and 0.002 mmol of dimethylsilylene (cyclopentadienyl) (3-methylcyclopentadienyl) zirconium dichloride were sequentially added, and 3
The temperature was raised to 0 ° C. Then, propylene was added to this with a total pressure of 3
It was continuously introduced so as to maintain kg / cm ² G, and polymerization was performed for 2 hours. After the reaction, the catalyst component was decomposed with methanol, and the obtained polypropylene was dried. As a result, 27 g of polypropylene was obtained. The catalyst activity is 74 kg /
gZr · hr. ¹³ C-NMR of this polymer
From the measurement, mm = 62, mr = 25, and rr = 13.

Comparative Example 2 [Polymerization] Purified toluene (500 ml) in a 1.5 L SUS autoclave sufficiently purged with nitrogen, and methylaluminoxane (Molecular weight 1,100) manufactured by Tosoh Akzo Co., Ltd.
1.05 mmol and dimethylsilylene (cyclopentadienyl) (2,4-dimethylcyclopentadienyl)
0.002 mmol of zirconium dichloride was sequentially added, and the temperature was raised to 30 ° C. Next, propylene was continuously introduced into the mixture so that the total pressure was maintained at 3 kg / cm ² G, and polymerization was performed for 2 hours. After the reaction, the catalyst component was decomposed with methanol, and the obtained polypropylene was dried. As a result, 21 g of polypropylene was obtained. Catalyst activity is 5
It was 8 kg / gZr · hr. ¹³ C of this polymer
From the NMR measurement, mm = 61, mr = 26, rr = 13
Met.

Comparative Example 3 [Polymerization] Purified toluene (500 ml) and methylaluminoxane (total molecular weight 1,100) manufactured by Tosoh Akzo Co., Ltd. in a 1.5 L SUS autoclave sufficiently purged with nitrogen.
1.05 mmol and 0.002 mmol of dimethylsilylene (cyclopentadienyl) (2,3,5-trimethylcyclopentadienyl) zirconium dichloride were sequentially added, and the temperature was raised to 30 ° C. Next, propylene was continuously introduced into the mixture so that the total pressure was maintained at 3 kg / cm ² G, and polymerization was performed 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 polypropylene was obtained. The catalyst activity was 79 kg / gZr · hr. Of this polymer
^{From 13} C-NMR measurement, mm = 68, mr = 22, rr
= 11.

Comparative Example 4 [Polymerization] In a 1.5 L SUS autoclave sufficiently purged with nitrogen, purified toluene 500 ml, methylaluminoxane manufactured by Tosoh Akzo Co., Ltd. (molecular weight 1,100)
1.05 mmol and 0.002 mmol of dimethylsilylene (3-methylcyclopentadienyl) (3,4-dimethylcyclopentadienyl) zirconium dichloride were sequentially added, and the temperature was raised to 30 ° C. Next, propylene was continuously introduced into the mixture so that the total pressure was maintained at 3 kg / cm ² G, and polymerization was performed for 2 hours. After the reaction, the catalyst component was decomposed with methanol, and the obtained polypropylene was dried. As a result, 7.5 g of polypropylene was obtained. The catalyst activity was 21 kg / gZr · hr. From the ¹³ C-NMR measurement of this polymer, mm = 90, mr = 7, r
r = 3.

[0042]

The catalyst of the present invention using a bridged transition metal compound having a ligand in which an unsubstituted cyclopentadienyl ring and a substituted cyclopentadienyl ring are crosslinked as a zirconium metal compound to be combined with aluminoxane. A syndiotactic olefin polymer can be efficiently produced.

[Brief description of the drawings]

FIG. 1 is a flow sheet showing a method for producing an olefin polymer using a catalyst of the present invention.

Continuation of the front page (56) References JP-A-3-212408 (JP, A) WO 92/1723 (WO, A)

Claims (1)

(57) [Claims] (A) General formula (1) A transition metal compound represented by the formula (where M is zirconium)
And Y represents carbon or silicon. The C ₅ H ₄ is unsubstituted cyclopentadienyl ^{_{group, R 2 n C 5 H 4}} -n each represent a substituted cyclopentadienyl group, n is an integer of 2 or 4. However, when n = 2, the position is in the third and fourth positions. Each R ¹ may be the same or different, and represents a hydrogen or hydrocarbon group. Each R ² may be the same or different from each other, a hydrocarbon group, and two R ² may form a ring structure. Xs may be the same or different and represent a hydrogen, halogen or hydrocarbon group. ) And (B) general formula (2) Or the general formula (3) (Where m is an integer of 4 to 30 and R ³ represents a hydrocarbon group). A syndiotactic olefin characterized in that an olefin is polymerized in the presence of a catalyst containing an aluminoxane as an active ingredient. A method for producing a polymer.