JP2587251B2 - Catalyst for stereoregular olefin polymer production - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a catalyst for producing a stereoregular olefin polymer. More specifically, the present invention relates to a novel transition metal compound having a bis-substituted cyclopentadienyl bridge type bidentate ligand having a bridged structure, and the catalyst comprising aluminoxane.

[Conventional technology and its problems]

As a homogeneous catalyst for olefin polymerization, a so-called Kaminsky catalyst is well known. It is known that this catalyst system has a very high polymerization activity and, for example, in propylene polymerization, both atactic polypropylene and isotactic polypropylene can be produced. (Makromol. Chem., Rapid Commun. 4, 417
−421 (1983), Angew.Chem.Int.Ed.Engl.24,507−508 1
985)) In this catalyst system, many transition metal compounds for producing atactic polymers are known (JP-A-58-19).
309, JP-A-60-130604, JP-A-61-211307), the transition metal compound for producing an isotactic polymer is very limited (J. Am. Chem. Soc., 1984, 106, p6355-6
364, JP-A-61-264010). In addition, there is a problem that the synthesis route of these compounds is long and the yield is poor.

Transition metal compounds having a bis-unsubstituted cyclopentadienyl ligand cross-linked with silicon, phosphine or carbon are known (JP-A-60-35006, JP-A-60-35007,
JP-A-60-35008 and JP-A-61-296008). Examples of the synthesis of transition metal compounds having a bridging ligand using a substituted cyclopentadienyl ring are described in Not even Further, there has been no concrete example of obtaining a stereoregular olefin polymer by polymerizing an olefin using such a compound.

The present inventors have conducted studies to solve the above problems, and as a result, succeeded in efficiently synthesizing the above-mentioned novel transition metal compounds, and furthermore, the catalyst comprising these compounds and aluminoxane has a stereoregularity. The present inventors have found that a water-soluble olefin polymer can be efficiently produced, and have arrived at the present invention based on this finding.

[Means for solving the problem]

That is, the present invention provides (1) (A) a transition metal compound represented by the general formula [I]. (Wherein, M is titanium, transition metals zirconium or hafnium, Y is silicon, showing a germanium or ^{_{tin. (R 1 n -C 5 H}} 4-n) and ^{_{(R 1 q -C 5 H 4}} -q) is Represents an unsubstituted or substituted cyclopentadienyl group, wherein n and q are 0
It is an integer of ~ 4, but does not take the value of 0 at the same time. Each R ¹ may be the same or different from each other, hydrogen, a silyl group or an alkyl group having 1 to 20 carbon atoms, an alkenyl group,
An aryl group, an alkylaryl group, or an arylalkyl group, wherein the position and type of R ¹ on the cyclopentadienyl ring are arranged such that no symmetry plane including M exists, and n- and q are not simultaneously 0. Assumes that R ¹ is not present on the carbon adjacent to the carbon bonded to Y. Each R ² may be the same or different and represents a hydrogen or hydrocarbon group. X may be the same or different and represents a hydrogen, a halogen or a hydrocarbon group. ) And (B) general formula [II] or general formula [III] (However, m is a number of 4 to 30, and R ³ represents a hydrocarbon group.)
A catalyst for producing a stereoregular olefin polymer comprising an aluminoxane represented by the following formula:

(2) As the transition metal compound represented by the general formula [I],
n and q relate to the catalyst for producing a stereoregular olefin polymer according to the above item 1, wherein a transition metal compound having an integer of 0 to 2 is used.

The transition metal compound (A) as a catalyst component used in the method of the present invention is a novel transition metal compound having a bis-substituted cyclopentadienyl bridge type bidentate ligand having a bridged structure. M is a transition metal of titanium, zirconium or hafnium, preferably zirconium. Y is silicon, germanium or tin. The number of substituents on the two cyclopentadienyl rings is
Any of unsubstituted to tetrasubstituted may be used, but at least one of the cyclopentadienyl rings has a substituent. Each R ¹ may be the same or different from each other, and may be a hydrogen, a silyl group or a hydrocarbon group (alkyl having 1 to 20 carbon atoms, alkenyl, aryl, alkylaryl,
And the type and position of R ¹ on the cyclopentadienyl ring are such that there is no symmetry plane including M. Examples of the silyl group include a trimethylsilyl group, a triethylsilyl group, and a triphenylsilyl group. Examples of the hydrocarbon group include a methyl group, an ethyl group, 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. X is hydrogen, halogen such as fluorine, chlorine, bromine and iodine, or the above-mentioned hydrocarbon group.

A typical synthetic route of the compound [I] of the present invention is n = q =
Taking 1 as an example, it can be abbreviated as follows, but is not limited thereto.

Non-limiting examples of the transition metal compound include dimethylsilylbis (methylcyclopentadienyl) zirconium dichloride, diphenylsilylbis (methylcyclopentadienyl) zirconium dichloride, dimethylsilylbis (methylcyclopentadienyl) zirconium dichloride Bromide, dimethylsilylbis (methylcyclopentadienyl) zirconium dimethyl, dimethylsilylbis (methylcyclopentadienyl) zirconium diphenyl, dimethylsilylbis (isopropylcyclopentadienyl) zirconium dichloride, dimethylsilylbis (t-butylcyclopenta Dienyl) zirconium dichloride, dimethylsilyl bis (phenylcyclopentadienyl) zirconium dichloride, dimethylsilyl (cyclopentadienyl) Methylcyclopentadienyl)
Zirconium dichloride, diphenylsilyl (cyclopentadienyl) (methylcyclopentadienyl) zirconium dichloride, dimethylsilyl (cyclopentadienyl) (methylcyclopentadienyl) zirconium dimethyl, dimethylsilyl (cyclopentadienyl) (isopropylcyclo (Pentadienyl) zirconium dichloride, dimethylsilyl (cyclopentadienyl) (t-
Butylcyclopentadienyl) zirconium dichloride, dimethylsilyl (cyclopentadienyl) (phenylcyclopentadienyl) zirconium dichloride, dimethylsilyl (methylcyclopentadienyl) (phenylcyclopentadienyl) zirconium dichloride, dimethylsilyl (methyl) Cyclopentadienyl) (t-butylcyclopentadienyl) zirconium dichloride,
Dimethylgermylbis (methylcyclopentadienyl)
Zirconium dichloride, diphenylgermyl bis (methylcyclopentadienyl) zirconium dichloride,
Dimethylgermylbis (t-butylcyclopentadienyl) zirconium dichloride, dimethylgermylbis (phenylcyclopentadienyl) zirconium dichloride, dimethylgermyl (cyclopentadienyl) (methylcyclopentadienyl) zirconium dichloride,
Dimethylgermyl (cyclopentadienyl) (phenylcyclopentadienyl) zirconium dichloride, dimethylstannylbis (methylcyclopentadienyl) zirconium dichloride, dimethylstannylbis (t-butylcyclopentadienyl) zirconium dichloride, dimethylstannylbis (Phenylcyclopentadienyl)
Zirconium dichloride, dimethylstannyl (cyclopentadienyl) (methylcyclopentadienyl) zirconium dichloride, dimethylstannyl (methylcyclopentadienyl) (phenylcyclopentadienyl) zirconium dichloride, dimethylsilylbis (dimethylcyclopentadiene) Zirconium compounds such as enyl) zirconium dichloride, dimethylsilyl (cyclopentadienyl) (dimethylcyclopentadienyl) zirconium dichloride, dimethylsilylbis (methylcyclopentadienyl) titanium dichloride, dimethylsilylbis (t-butylcyclopentadiene) Enyl) titanium dichloride, dimethylsilyl bis (phenylcyclopentadienyl) titanium dichloride, dimethylsilyl (cyclopentadienyl) Methylcyclopentadienyl) titanium dichloride, dimethylsilyl (cyclopentadienyl) (t-butylcyclopentadienyl) titanium dichloride, dimethylsilyl (cyclopentadienyl)
(Phenylcyclopentadienyl) titanium dichloride, dimethylgermylbis (methylcyclopentadienyl) titanium dichloride, dimethylgermyl (cyclopentadienyl) (methylcyclopentadienyl) titanium dichloride, dimethylstannylbis (methylcyclopenta Dienyl) titanium dichloride, dimethylstannyl (cyclopentadienyl) (methylcyclopentadienyl) titanium dichloride, dimethylsilylbis (dimethylcyclopentadienyl) titanium dichloride, dimethylsilyl (cyclopentadienyl) (dimethylcyclopenta Titanium compounds such as dienyl) titanium dichloride, dimethylsilylbis (methylcyclopentadienyl) hafnium dichloride, dimethylsilyl (cyclopentadienyl) ) (Methylcyclopentadienyl)
Hafnium compounds such as hafnium dichloride can be mentioned.

Aluminoxane (B) as another catalyst component used in the method of the present invention has the general formula [II] or
General formula (III), Is an organoaluminum compound represented by R ³ is a hydrocarbon group such as a methyl group, an ethyl group, a propyl group, and a butyl group, and is preferably a methyl group or an ethyl group. m is 4
An integer of from 30 to 30, preferably 6 or more, and particularly preferably 10 or more. Processes for producing compounds of this type are known. For example, trialkyl is 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 propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene,
-Dodecene, 1-tetradecene, 1-hexadecene, 1
Α-olefins such as -octadecene and 1-eicosene, and a mixture of two or more of these can be used for polymerization. Further, copolymerization of the above-mentioned α-olefins with ethylene is also possible. Further, butadiene, 1,4-hexadiene, 1,4-pentadiene, 1,7-octadiene,
Conjugated and unconjugated dienes such as 1,8-nonadiene, 1,9-decadiene, or styrene, or cyclopropane, cyclobutene, cyclohexene, norbornene,
It is effective for copolymerization with any cyclic olefin such as dicyclopentadiene.

The polymerization method used in the present invention can 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), such as benzene, toluene, o-xylene,
Aromatic hydrocarbons such as m-xylene, p-xylene, ethylbenzene, butylbenzene, mesitylene and naphthalene are used, and toluene and xylene are preferable. Furthermore, in a solvent in which both components (A) and (B) cannot be dissolved, polymerization can be performed by performing prepolymerization in an aromatic hydrocarbon. Such solvents include butane,
Isobutane, pentane, hexane, octane, decane,
Examples thereof include aliphatic hydrocarbons such as dodecane, hexadecane, and octadecane; alicyclic hydrocarbons such as cyclopentane, methylcyclopentane, cyclohexane, and cyclooctane; 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 obtained by previously mixing both components of the transition metal compound (A) and the aluminoxane (B) may be supplied to the reaction system, or both the components (A) and (B) may be separately added to the reaction system. May be supplied. In any case, the concentration of both components in the polymerization system, the molar ratio is not particularly limited, but preferably 10 ^-3 ~ 10 ^-10 mol / transition metal concentration.
The molar ratio of Al / transition metal atoms is preferably 100 or more, particularly 1000 or more. The olefin pressure of the reaction system is not particularly limited, but is preferably normal pressure to 50
in the range of kg / cm ² G, but is not limited to the polymerization temperature is usually -50~230 ℃, preferably in the range from -30 to 100 ° C..
Control of the molecular weight during polymerization can be performed by known means, for example, temperature,
It can be performed by selecting the pressure or introducing hydrogen.

〔The invention's effect〕

By using the catalyst of the present invention using a transition metal compound having a bis-substituted cyclopentadienyl bridge type bidentate ligand having a bridged structure as a novel transition metal compound to be combined with an aluminoxane, a stereoregular polymer can be efficiently used. Can be manufactured well.

〔Example〕

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

Example 1 [Dimethylsilylbis (methylcyclopentadienyl)
Zirconium dichloride] All the reactions were performed under an inert gas atmosphere. The reaction solvent used was previously dried. 300ml
In a glass reaction vessel, a solution of 4.1 g (32 mmol) of dichlorodimethylsilane / 50 ml of diethyl ether was slowly added dropwise at -78 ° C to 38 ml of a 1.6 MTHF solution of sodium methylcyclopentadienyl. After stirring at room temperature for 1 hour, the solvent was distilled off from the white suspension. Hexane (200 ml) was added and the mixture was filtered.
The mixture was washed with ml and filtered to obtain a pale yellow transparent filtrate. The solvent was distilled off under reduced pressure, concentrated to 100 ml, and butyllithium was removed.
40 ml of a 1.6 M hexane solution was slowly added dropwise under cooling. After stirring at room temperature for 1 hour, the solvent was distilled off from the white suspension, and after drying, a white solid (Li ₂ [Me ₂ Si (Me-C ₅ H ₃ ) ₂ ]) was obtained.

Zirconium tetrachloride in a 500 ml glass reaction vessel
5.8 g (25 mmol) was cooled to -78 ° C and 200 ml of THF was added. Next, the white solid (25 mmol) was dissolved in 70 ml of THF, and slowly added dropwise at -78 ° C. After stirring at room temperature for 1 hour, the suspended yellow-brown liquid was heated to reflux for 2 hours.
After cooling, the solvent was distilled off from the pale yellow solution containing a white precipitate, 300 ml of methylene chloride and then 100 ml of dilute hydrochloric acid were added under ice-cooling. After liquid separation, the methylene chloride layer was dried over sodium sulfate. The methylene chloride was distilled off, pentane was added, and the generated solid was filtered to obtain 1.77 g of a pale green solid. Thermal heptane 4
Recrystallization was performed with 00 ml to obtain 1.11 g of pale yellow crystals.

Example 2 [Polymerization] Purified toluene (500 ml), Toyo Stouffer Chemical Co., Ltd. methylaluminoxane (molecular weight: 770) 4.0 mmol and dimethylsilylbis (methylcyclopentadiene) were placed in a 1.5 L internal volume SUS autoclave sufficiently purged with nitrogen. Enyl) zirconium dichloride (0.005 mmol) was sequentially added, and the temperature was raised to 30 ° C. Then, 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, 130 g of isotactic polypropylene was obtained. The catalyst activity was 142 kg / gZr · hr.

Example 3 [Polymerization] In a 1.5 L internal volume SUS autoclave sufficiently purged with nitrogen, 100 ml of purified toluene, 4.0 mmol of methylaluminoxane (molecular weight 770) manufactured by Toyo Stouffer Chemical Co., Ltd., and dimethylsilylbis (methylcyclopentadiene) Enyl) zirconium dichloride (0.005 mmol) 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 1 kg / cm ² G, and polymerization was performed for 10 minutes. After the supply of propylene was stopped and propylene was purged, 1000 ml of purified hexane was added. 30
C., and propylene was continuously introduced into the mixture 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, 125 g of isotactic polypropylene was obtained. The catalyst activity was 137 kg / gZr · hr.

Example 4 [Dimethylsilyl (cyclopentadienyl) (methylcyclopentadienyl) zirconium dichloride] All the reactions were performed under an inert gas atmosphere. The reaction solvent used was previously dried. 300ml
In a glass reactor, 3.9 g of dichlorodimethylsilane
(30 mmol) / diethyl ether 30 ml solution, methylcyclopentadienyl sodium 1.6MTHF solution 19 ml
Was slowly added dropwise at room temperature. After stirring at room temperature for 2 hours, 16 ml of a 1.9MTHF solution of sodium cyclopentadienyl was added dropwise to the pale yellow suspension containing a white solid at room temperature.
After stirring at room temperature for 1 hour, the solvent was distilled off and hexane 200 ml
Was added, followed by filtration to obtain a pale yellow transparent filtrate. to this,
40 ml of a 1.6 M hexane solution of butyllithium was slowly added dropwise while cooling. After stirring at room temperature for 2 hours, the solvent was distilled off,
200 ml of THF was added. The yellow THF solution was cooled to -78 ° C and 4.0 g (17 mmol) of zirconium tetrachloride was added in several portions. After stirring at room temperature for 1 hour, the mixture was heated under reflux for 1 hour. After cooling, the solvent was distilled off from the pale yellow solution containing a white precipitate, 300 ml of methylene chloride and then 100 ml of dilute hydrochloric acid were added under ice-cooling. After liquid separation, the methylene chloride layer was dried over sodium sulfate. The methylene chloride was distilled off, pentane was added, and the generated solid was filtered to obtain 2.44 g of a pale green solid. The crystals were recrystallized from 400 ml of hot heptane to obtain 1.18 g of pale yellow crystals.

Example 5 [Polymer] dimethylsilylbis (methylcyclopentadienyl)
Dimethylsilyl (cyclopentadienyl) (methylcyclopentadienyl) instead of zirconium dichloride
The procedure was performed in the same manner as in Example 2 except that zirconium dichloride was used. The result is isotactic polypropylene 70
g was obtained. The catalyst activity was 77 kg / gZr · hr.

Example 6 [Dimethylsilyl (cyclopentadienyl) (t-butylcyclopentadienyl) zirconium dichloride] Instead of sodium methylcyclopentadienyl, t
The above compound was synthesized in the same manner as in Example 4 except that -butylcyclopentadienyllithium was used. As a result, 0.64 g of pale yellow crystals was obtained.

Example 7 [Polymer] dimethylsilylbis (methylcyclopentadienyl)
Example 2 was repeated except that dimethylsilyl (cyclopentadienyl) (t-butylcyclopentadienyl) zirconium dichloride was used instead of zirconium dichloride. As a result, 75 g of isotactic polypropylene was obtained. The catalyst activity was 82 kg / gZr · hr.

Comparative Example 1 [Polymer] dimethylsilylbis (methylcyclopentadienyl)
Example 2 was repeated except that dimethylsilylbis (cyclopentadienyl) zirconium dichloride was used instead of zirconium dichloride. As a result, 29 g of atactic polypropylene was obtained. Catalyst activity is 32kg / gZ
r · hr.

Comparative Example 2 [Polymer] dimethylsilylbis (methylcyclopentadienyl)
Example 2 was repeated except that zirconium dichloride was replaced by bis (methyl t-butylcyclopentadienyl) zirconium dichloride. As a result, 2.6 g of atactic polypropylene was obtained. 2.9k catalytic activity
g / gZr · hr.

Comparative Example 3 [Polymerization] In a 1.5 L SUS autoclave sufficiently purged with nitrogen, 500 ml of purified toluene, 6.3 mmol of methylaluminoxane (molecular weight: 909) manufactured by Toyo Stouffer Chemical Co., Ltd., and bis (methylcyclopentadienyl) were used. 0.02 mmol of zirconium dichloride was sequentially added, and the temperature was raised to 50 ° C. Then, propylene was continuously introduced into the mixture so that the total pressure was maintained at 8 kg / cm ² G, and polymerization was performed for 4 hours. After the reaction, the catalyst component was decomposed with methanol, and the obtained polypropylene was dried. As a result, 220 g of atactic polypropylene was obtained. The catalyst activity was 30 kg / gZr · hr.

Example 8 [Dimethylsilyl (t-butylcyclopentadienyl)
(Methylcyclopentadienyl) zirconium dichloride] All the reactions were performed under an inert gas atmosphere. The reaction solvent used was dried in advance. 20
In a 0 ml glass reaction vessel, 3.9 g (15 mmol) of dimethyl (t-butylcyclopentadienyl) (methylcyclopentadienyl) silane was dissolved in 50 ml of pentane.
20 ml of a 1.6 M hexane solution of butyllithium was slowly added dropwise while cooling. After stirring at room temperature for 2 hours, the solvent was distilled off to obtain a white solid (Li ₂ [Me ₂ Si (t-BuC ₅ H ₃ ) (MeC ₅ H ₃ )]). To this was added 50 ml of THF to obtain a yellow transparent solution.

3.5 g of zirconium tetrachloride in a 50 ml glass reaction vessel
(15 mmol) was cooled to -78 ° C and tetrahydrofuran
200 ml were added. Next, the yellow THF solution 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 cooling, the solvent was distilled off from the pale yellow solution containing a white precipitate, and under ice-cooling, methylene chloride (200 ml) was added, followed by dilute hydrochloric acid (100).
After adding ml, the layers were separated and the methylene chloride layer was dried over anhydrous sodium sulfate. The methylene chloride was distilled off, pentane was added, and the mixture was filtered. From the pale yellow filtrate, 0.37 g of pale yellowish white crystals were obtained.

Example 9 [Polymerization] Dimethylsilylbis (methylcyclopentadienyl)
Dimethylsilyl (t) instead of zirconium dichloride
-Butylcyclopentadienyl) (methylcyclopentadienyl) zirconium dichloride was used in the same manner as in Example 2. As a result, 59 g of isotactic polypropylene was obtained. The catalyst activity was 65 kg / gZr · hr.

Example 10 [Dimethylsilylbis (t-butylcyclopentadienyl) zirconium dichloride] Instead of dimethyl (t-butylcyclopentadienyl) (methylcyclopentadienyl) silane, dimethylbis (t-butylcyclopentadienyl) silane was used. The above compound was synthesized in the same manner as in Example 8 except that (enyl) silane was used. As a result, 0.28 g of yellow-white crystals was obtained.

Example 11 [Polymerization] Dimethylsilylbis (methylcyclopentadienyl)
Example 2 was carried out in the same manner as in Example 2, except that dimethylsilylbis (t-butylcyclopentadienyl) zirconium dichloride was used instead of zirconium dichloride. As a result, 3.1 g of isotactic polypropylene was obtained. The catalyst activity was 3.4 kg / gZr · hr.

Example 12 [Dimethylgermylbis (methylcyclopentadienyl) zirconium dichloride] Instead of dimethyl (t-butylcyclopentadienyl) (methylcyclopentadienyl) silane, dimethylbis (methylcyclopentadienyl) germane The above compound was synthesized in the same manner as in Example 8 except that
As a result, 0.60 g of yellow-white crystals were obtained.

Example 13 [Polymerization] Dimethylsilylbis (methylcyclopentadienyl)
Example 2 was carried out in the same manner as in Example 2, except that dimethylgermylbis (methylcyclopentadienyl) zirconium dichloride was used instead of zirconium dichloride. As a result, 25 g of isotactic polypropylene was obtained. The catalyst activity was 27 kg / gZr · hr.

Example 14 [Cyclotetramethylenesilyl (methylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride] Instead of dimethyl (t-butylcyclopentadienyl) (methylcyclopentadienyl) silane, cyclotetramethylene ( The above compound was synthesized in the same manner as in Example 8 except that methylcyclopentadienyl) (cyclopentadienyl) silane was used. As a result, yellow-white crystals 0.
39 g were obtained.

Example 15 [Polymerization] Dimethylsilylbis (methylcyclopentadienyl)
Example 2 was repeated except that zirconium dichloride was replaced by cyclotetramethylenesilyl (methylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride. As a result, 3.6 g of isotactic polypropylene was obtained. Catalytic activity is 3.9kg / gZrhr
Met.

Example 16 [Dimethylsilylbis (methylcyclopentanedienyl) hafnium dichloride] The above compound was synthesized in the same manner as in Example 1 except that hafnium tetrachloride was used instead of zirconium tetrachloride. As a result, 3.37 g of yellow-white crystals were obtained.

Example 17 [Polymerization] Dimethylsilylbis (methylcyclopentadienyl)
Example 2 was carried out in the same manner as in Example 2 except that dimethylsilylbis (methylcyclopentadienyl) hafnium dichloride was used instead of zirconium dichloride. As a result, 16 g of isotactic polypropylene was obtained. The catalyst activity was 8.9 kg / gHf · hr.

Example 18 [Dimethylsilyl (methylcyclopentadienyl) (cyclopentadienyl) hafnium dichloride] The above compound was synthesized in the same manner as in Example 4 except that hafnium tetrachloride was used instead of zirconium tetrachloride. . As a result, 1.06 g of yellow-white crystals were obtained.

Example 19 [Polymerization] Dimethylsilylbis (methylcyclopentadienyl)
Dimethylsilyl (methylcyclopentadienyl) (cyclopentadienyl) instead of zirconium dichloride
The procedure was performed in the same manner as in Example 2 except that hafnium dichloride was used. The result is 0.6 g of isotactic polypropylene
was gotten. The catalyst activity was 0.34 kg / gHf · hr.

Example 20 [Dimethylsilylbis (t-butylcyclopentadienyl) hafnium dichloride] The above compound was synthesized in the same manner as in Example 10 except that hafnium tetrachloride was used instead of zirconium tetrachloride. As a result, 1.50 g of yellow-white crystals were obtained.

Example 21 [Polymerization] Dimethylsilylbis (methylcyclopentadienyl)
Example 2 was repeated except that dimethylsilylbis (t-butylcyclopentadienyl) hafnium dichloride was used instead of zirconium dichloride. As a result, 0.3 g of isotactic polypropylene was obtained. The catalyst activity was 0.17 kg / gHf · hr.

[Brief description of the drawings]

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

Continuation of the front page (72) Inventor Hiroshi Yamazaki 2-41-10 Matsugaoka, Tokorozawa-shi, Saitama (56) References JP-A-64-74202 (JP, A) JP-A-63-251405 (JP, A)

Claims (2)

(57) [Claims] 1. A transition metal compound represented by the general formula [I]: (Wherein, M is titanium, transition metals zirconium or hafnium, Y is silicon, showing a germanium or ^{_{tin. (R 1 n -C 5 H}} 4-n) and ^{_{(R 1 q -C 5 H 4}} -q) is Represents an unsubstituted or substituted cyclopentadienyl group, wherein n and q are 0
It is an integer of ~ 4, but does not take the value of 0 at the same time. Each R ¹ may be the same or different from each other, hydrogen, a silyl group or an alkyl group having 1 to 20 carbon atoms, an alkenyl group,
An aryl group, an alkylaryl group, or an arylalkyl group, wherein the position and type of R ¹ on the cyclopentadienyl ring are arranged such that no symmetry plane including M exists, and n- and q are not simultaneously 0. Assumes that R ¹ is not present on the carbon adjacent to the carbon bonded to Y. Each R ² may be the same or different and represents a hydrogen or hydrocarbon group. X may be the same or different and represents a hydrogen, a halogen or a hydrocarbon group. ) And (B) general formula [II] or general formula [III] (However, m is a number of 4 to 30, and R ³ represents a hydrocarbon group.)
A catalyst for producing a stereoregular olefin polymer comprising an aluminoxane represented by the following formula: 2. The stereoregular olefin polymer according to claim 1, wherein a transition metal compound wherein n and q are integers of 0 to 2 is used as the transition metal compound represented by the general formula [I]. Catalyst for coalescence production.