JP3537234B2 - Catalyst component for producing polyolefin, catalyst for producing polyolefin containing the component, and method for producing polyolefin - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a polyolefin, particularly an isotactic poly (α-olefin), using a novel metallocene compound as a catalyst component.

[0002]

2. Description of the Related Art As an olefin polymerization catalyst, a metallocene catalyst (a catalyst comprising a metallocene compound and a Lewis acid compound such as methylaluminoxane) is known. In particular,
By choosing the ligand structure of the metallocene compound, α
-Isotactic polymerization of olefins has become possible. In this case, the difference in the ligand and the substituent changes the stereoregularity of the polymer, the molecular weight, or the amount of heterogeneous bonds in the polymer chain (in the case of polypropylene, caused by 2, 1 insertion, 1, 3 insertion). Is known to greatly affect the heat resistance, rigidity, and impact resistance of polymers (Macr
omolecules 1988,21,617, Polymer, 1992,33,254, Organom
etallics 1994,13,964, Angew.Chem.Int.Ed.Engl.199
5,34,1143).

At present, the metallocene compounds capable of isotactic polymerization are overwhelmingly C ₂ -symmetric metallocene compounds. For example, a crosslinked bisindene compound or a derivative thereof is known. JP-A-61-130314 as an ethylidene cross-linked bisindene compound or a derivative thereof,
Rac-ethylidenebis (indenyl) zirconium dichloride and rac-ethylidenebis (tetrahydroindenyl) zirconium dichloride disclosed in JP-A-63-295607 and the like produce isotactic polypropylene in the presence of methylaluminoxane. Furthermore, JP-A-2-131488
Discloses a silicon-bridged bisindene compound.

Further, in order to improve the stereoregularity and the molecular weight of the polymer, various crosslinked bisindene compounds having a substituent introduced into an indene ring have been invented (Japanese Patent Application Laid-Open No. HEI 9-208572).
4-268307, JP-A-4-268308, JP-A-4-3000087, JP-A-5
306304, JP-A-6-184179, JP-A-7-2920, JP-A-7-1498
15, JP-A-5-290014).

On the other hand, rac-dimethylsilylenebis (2,3,5-trimethylcyclopentadienyl) zirconium dichloride (Japanese Patent Application Laid-Open Nos. 1-301704 and 3-12406) or rac-dimethylsilylenebis (2,3,5-trimethylcyclopentadienyl) -Dimethylsilylenebis (3-t-butyl-5-methylcyclopentadienyl) zirconium dichloride, etc.
No. 211694) and methylaluminoxane are disclosed for the production of isotactic polypropylene.

On the other hand, when an asymmetric (C ₁ symmetric) metallocene compound having a compound structure essentially different from that of a C ₂ symmetric metallocene compound is used, there are very few examples of producing isotactic polypropylene. In particular, the following reports have been reported on the polymerization of α-olefins using C ₁ symmetric metallocene compounds containing a cyclopentadienyl ring and an indenyl ring. JP-A-5-148284 describes isopropylidene (3
A method for producing isotactic polypropylene using -t-butylcyclopentadienyl) (3-t-butylindenyl) zirconium dichloride is disclosed.

Further, Macromol. Chem. 193, 1643 (1992) discloses the production of isotactic polypropylene having a melting point of 128 ° C. using rac-isopropylidene (3-methylcyclopentadienyl) (indenyl) zirconium dichloride. It has been reported. On the other hand, J. Am. Chem. Soc., 11
2, 2030 (1990) J. Am. Chem. Soc., 113, 8569 (1991) M
acromolecules, 24, 850 (1991) Macromolecules, 25, 1
242 (1992) J. Poly. Sci. Part A: Poly. Chem., 30, 2
601 (1992), Macromolecules, 28, 3771 (1995), Macromolole
cules, 28, 3779 (1995), etc., report a method for producing a thermoplastic elastomer, but do not give a higher melting point isotactic polymer.

[0008]

An object of the present invention is to provide a polyolefin, particularly a high melting point isotactic poly (α).
To produce new metallocene catalysts for the production of olefins).

[0009]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, unlike the conventional C ₂ symmetric type, a bridged type having a cyclopentadienyl ring and an indenyl ring. The present inventors have found that a metallocene compound having a specific substituent in the group of metallocene compounds can be an excellent catalyst component for solving the above-mentioned problems, and reached the present invention.

That is, the present invention provides a compound represented by the general formula (1):

Embedded image [Wherein, M represents a transition metal atom of any of Ti, Zr, and Hf. X ¹ and X ² may be the same or different from each other, and may be a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may contain a halogen atom, an OR group, an SR group, an OCOR group, an SO ₂ group. R group, OSO ₂
R group and NRR ′ group (here, R and R ′ mean a hydrogen atom or a hydrocarbon group having 1 to 7 carbon atoms, and may include a halogen atom). R ¹ and R ² may be the same or different from each other, and may be a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or an OR group or an SR group (where R is a hydrogen atom or a carbon atom having 1 carbon atom). To 7 and may include a halogen atom), and may combine with each other to form a ring. R ³ represents a hydrocarbon group having 1 to 20 carbon atoms, and may include a silicon atom. R ^{4 to} R ⁶ are a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, and may contain a silicon atom.
R ^{7 to} R ¹⁰ may be the same or different from each other, may be a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, may contain a silicon atom, and may be bonded to each other to form a ring. In particular, X ¹ and X ² represent a halogen atom, R ¹ and R ² represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R ^{7 to} R ¹⁰ represent The core of the present invention is to use a compound representing a hydrocarbon group having 1 to 20 carbon atoms which may contain a hydrogen atom or a silicon atom as a catalyst component,
(A) the metallocene compound, (B) a Lewis acid compound,
The object is achieved by producing a polyolefin by using a metallocene catalyst system comprising (C) an organoaluminum compound and, if necessary, (D) a fine particle carrier.

Hereinafter, a method for producing a polyolefin using the olefin polymerization catalyst according to the present invention will be specifically described. The novel metallocene compound as the first catalyst component in the polymerization method of the present invention is represented by the general formula (1). Hereinafter, the general formula (1) will be specifically described.

R ¹ and R ² may be the same or different and are each a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an OR group or an SR group (where R is a hydrogen atom or a carbon atom (Which means a hydrocarbon group having 1 to 7 atoms and may contain a halogen atom), which may be bonded to each other to form a ring. Specifically, it has 1 to 2 carbon atoms.
The hydrocarbon group of 0 is methyl, ethyl, n-propyl,
i-propyl, n-butyl, i-butyl, t-butyl,
alkyl groups such as n-pentyl, cyclopentyl and cyclohexyl, vinyl, alkenyl groups such as propenyl,
Phenyl, tolyl, 2,6-dimethylphenyl, 2,
An aryl group such as 4,6-trimethylphenyl and an arylalkyl group such as benzyl, phenylmethyl, diphenylmethyl, triphenylmethyl and phenylethyl are meant. The OR group means a hydroxy group, an alkoxy group such as methoxy, ethoxy, propoxy, butoxy, or an aryloxy group such as phenoxy, and the SR group means a mercapto group, an alkylthio group such as methylthio, or an arylthio group such as phenylthio. Preferably, R is selected from a methyl group, an ethyl group, and a phenyl group.

R ³ means a hydrocarbon group having 1 to 20 carbon atoms which may contain a silicon atom. In particular,
Alkyl groups such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-pentyl, cyclopentyl, cyclohexyl, octyl, nonyl, adamanril, and alkenyl groups such as vinyl and propenyl , Phenyl, tolyl, 2,6-dimethylphenyl, 2,4,6-trimethylphenyl, naphthyl,
Aryl groups such as anthracenyl, benzyl, phenylmethyl, diphenylmethyl, triphenylmethyl, arylalkyl groups such as phenylethyl, methylsilyl,
Examples thereof include alkylsilyl groups such as dimethylsilyl and trimethylsilyl, and silylalkyl groups such as tris (trimethylsilyl) methyl group.

R ^{4 to} R ⁶ represent a hydrocarbon group having 1 to 5 carbon atoms which may contain a hydrogen atom or a silicon atom. Specifically, methyl, ethyl, n-propyl, i
-Propyl, n-butyl, i-butyl, t-butyl, n
-Alkyl groups such as pentyl and cyclopentyl, and alkylsilyl groups such as trimethylsilyl. Among them, R ⁴ to R ⁶ are preferably selected from a hydrogen atom or a methyl group, an ethyl group, an n-propyl group, or an i-propyl group. R ^{7 to} R ¹⁰ may be the same or different and represent a hydrocarbon group having 1 to 20 carbon atoms which may contain a hydrogen atom or a silicon atom. Specifically, it means a hydrogen atom or the same group as R ³ . Further, R ^{7 to} R ¹⁰ may combine with each other to form a ring. In particular, adjacent groups are bonded to each other to form an aromatic 6
It is desirable to form a member ring. Specifically, in the general formula (1), it means that the indene ring is 4,5-benzoindene, 5,6-benzoindene, 6,7-benzoindene or the like. In this case, the case where the indene ring is 4,5-benzoindene is preferable.

X ¹ and X ² may be the same or different from each other, and may be a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may contain a halogen atom, an OR group, an SR group, an OCOR group. , SO ₂ R group, OSO ₂ R
Group, NRR ′ group (here, R and R ′ mean a hydrogen atom or a hydrocarbon group having 1 to 7 carbon atoms, and may include a halogen atom). Specifically, the halogen atom means fluorine, chlorine, bromine, iodine, or the like. 1 to 20 carbon atoms which may contain halogen atoms
And the hydrocarbon group of methyl, ethyl, n-propyl, i
-Propyl, n-butyl, i-butyl, t-butyl, n
Alkyl groups such as pentyl, cyclopentyl and cyclohexyl, alkenyl groups such as vinyl and propenyl, phenyl, tolyl, 2,6-dimethylphenyl, 2,4 and
Aryl groups such as 6-trimethylphenyl, benzyl,
It means an arylalkyl group such as phenylmethyl, diphenylmethyl, triphenylmethyl, and phenylethyl; a halogenated alkyl group such as trifluoromethyl; a halogenated aryl group such as pentafluorophenyl. The OR group is a hydroxy group or an alkoxy group such as methoxy, ethoxy, propoxy, butoxy or an aryloxy group such as phenoxy, the SR group is an alkylthio group such as mercapto group or methylthio, or an arylthio group such as phenylthio, and the OCOR group is a carboxy group. Group or an alkoxycarbonyl group such as methoxycarbonyl, SO ₂ R group is a sulfino group or an alkylsulfino group such as methylsulfino or an arylsulfino group such as phenylsulfino, and OSO ₂ R group is a sulfo group or a methylsulfo group. An alkylsulfo group or phenylsulfo,
An arylsulfo group such as p-toluenesulfo is
The RR 'group means an amino group, an alkylamino group such as methylamino, dimethylamino, diethylamino, dibutylamino, or an arylamino group such as phenylamino. Of these, X ¹ and X ² are desirably selected from a halogen atom or an alkyl group such as a methyl group.

As the metallocene compound of the present invention, Me ₂ Si [3-MeCp] (Ind) ZrCl ₂ Me ₂ Si [3-EtCp] (Ind) ZrCl ₂ Me ₂ Si [3-i-PrCp] (Ind ) ZrCl ₂ Me ₂ Si [3-t-BuCp] (Ind) ZrCl ₂ Me ₂ Si [2,4-Me ₂ Cp] (Ind) ZrCl ₂ Me ₂ Si [2-Me-5-t-BuCp] ( Ind) ZrCl ₂ Me ₂ Si [2-Et-5-t-BuCp] (Ind) ZrCl ₂ Me ₂ Si [2,4,5-Me ₃ Cp] (Ind) ZrCl ₂ Me ₂ Si [2,5- Me ₂ -4-t-BuCp] (Ind) ZrCl ₂

Me ₂ Si [3-MeCp] (2-MeInd) ZrCl ₂ Me ₂ Si [3-EtCp] (2-MeInd) ZrCl ₂ Me ₂ Si [3-i-PrCp] (2-MeInd) ZrCl ₂ Me ₂ Si [3-t-BuCp] (2-MeInd) ZrCl ₂ Me ₂ Si [2,4-Me ₂ Cp] (2-MeInd) ZrCl ₂ Me ₂ Si [2-Me-5-t-BuCp] (2-MeInd) ZrCl ₂ Me ₂ Si [2-Et-5-t-BuCp] (2-MeInd) ZrCl ₂ Me ₂ Si [2,4,5-Me ₃ Cp] (2-MeInd) ZrCl ₂ Me _{2 Si [2,5-Me 2 -4} -t-BuCp] (2-MeInd) ZrCl 2

Me ₂ Si [3-MeCp] (2,4-Me ₂ Ind) ZrCl ₂ Me ₂ Si [3-t-BuCp] (2,4-Me ₂ Ind) ZrCl ₂ Me ₂ Si [2,4 -Me ₂ Cp] (2,4-Me ₂ Ind) ZrCl ₂ Me ₂ Si [2-Me-5-t-BuCp] (2,4-Me ₂ Ind) ZrCl ₂ Me ₂ Si [2-Et-5 -t-BuCp] (2,4-Me ₂ Ind) ZrCl ₂ Me ₂ Si [2,4,5-Me ₃ Cp] (2,4-Me ₂ Ind) ZrCl ₂ Me ₂ Si [2,5-Me ₂ -4-t-BuCp] (2,4-Me ₂ Ind) ZrCl ₂

Me ₂ Si [3-MeCp] (2,4,7-Me ₃ Ind) ZrCl ₂ Me ₂ Si [3-t-BuCp] (2,4,7-Me ₃ Ind) ZrCl ₂ Me ₂ Si [2,4-Me ₂ Cp] (2,4,7-Me ₃ Ind) ZrCl ₂ Me ₂ Si [2-Me-5-t-BuCp] (2,4,7-Me ₃ Ind) ZrCl ₂ Me ₂ Si [2-Et-5-t-BuCp] (2,4,7-Me ₃ Ind) ZrCl ₂ Me ₂ Si [2,4,5-Me ₃ Cp] (2,4,7-Me ₃ Ind ) ZrCl ₂ Me ₂ Si [2,5-Me ₂ -4-t-BuCp] (2,4,7-Me ₃ Ind) ZrCl ₂

Me ₂ Si [3-MeCp] (2-Me-4-PhInd) ZrCl ₂ Me ₂ Si [3-t-BuCp] (2-Me-4-PhInd) ZrCl ₂ Me ₂ Si [2,4 -Me ₂ Cp] (2-Me-4-PhInd) ZrCl ₂ Me ₂ Si [2-Me-5-t-BuCp] (2-Me-4-PhInd) ZrCl ₂ Me ₂ Si [2-Et-5 -t-BuCp] (2-Me-4-PhInd) ZrCl ₂ Me ₂ Si [2,4,5-Me ₃ Cp] (2-Me-4-PhInd) ZrCl ₂ Me ₂ Si [2,5-Me ₂ -4-t-BuCp] (2-Me-4-PhInd) ZrCl ₂

Me ₂ Si [3-MeCp] (2-Me-4-NaphInd) ZrCl ₂ Me ₂ Si [3-t-BuCp] (2-Me-4-NaphInd) ZrCl ₂ Me ₂ Si [2,4 -Me ₂ Cp] (2-Me-4-NaphInd) ZrCl ₂ Me ₂ Si [2-Me-5-t-BuCp] (2-Me-4-NaphInd) ZrCl ₂ Me ₂ Si [2-Et-5 -t-BuCp] (2-Me-4-NaphInd) ZrCl ₂ Me ₂ Si [2,4,5-Me ₃ Cp] (2-Me-4-NaphInd) ZrCl ₂ Me ₂ Si [2,5-Me ₂ -4-t-BuCp] (2-Me-4-NaphInd) ZrCl ₂

Me ₂ Si [3-MeCp] (2-MeBenzind) ZrCl ₂ Me ₂ Si [3-t-BuCp] (2-MeBenzind) ZrCl ₂ Me ₂ Si [2,4-Me2Cp] (2-MeBenzind) ZrCl ₂ Me ₂ Si [2-Me-5-t-BuCp] (2-MeBenzind) ZrCl ₂ Me ₂ Si [2-Et-5-t-BuCp] (2-MeBenzind) ZrCl ₂ Me ₂ Si [2, 4,5-Me ₃ Cp] (2-MeBenzind) ZrCl ₂ Me ₂ Si [2,5-Me ₂ -4-t-BuCp] (2-MeBenzi
nd) ZrCl ₂ and corresponding titanium, hafnium compounds and the like.

However, the above terms correspond to the following. Me = methyl group, Et = ethyl group, iPr = isopropyl group,
tBu = t-butyl group, Ph = phenyl group, Naph = naphthyl group, Cp = cyclopentadienyl group, Ind = indenyl group, Benzind = 4,5-benzoindenyl group, Si [] = silylene group, Zr = Zirconium, Cl = chloride

In the general formula (1), the numbers indicating the positions of the substituents on the cyclopentadienyl ring and the indenyl ring are as follows:
This is shown in equation (3).

Embedded image The metallocene compounds of the present invention can be used alone or in combination of two or more.

A typical synthetic route of the metallocene compound is briefly described below. However, this does not limit the synthesis route. Substituted cyclopentadiene compound as raw material (4)

Embedded image And substituted indene compounds (5)

Embedded image Is commercially available or can be synthesized by a known method. The following is an example.

Next, the substituted cyclopentadiene compound (4) is deprotonated in a solvent using a strong base such as n-butyllithium, sodium hydride, potassium hydride, or metallic sodium or metallic potassium. , Cyclopentadienyl anion (6)

Embedded image In the formula, M ² means an alkali metal atom such as lithium, sodium, and potassium.

The above cyclopentadienyl anion (6) and silicon compound (7)

Embedded image In the formula, X ³ and X ⁴ may be the same or different from each other, and may be a halogen atom, an OR group, an SR group, an OCOR.
Group, OSO ₂ R group and NRR ′ group. Where R,
R ′ represents a hydrogen atom or a hydrocarbon group having 1 to 7 carbon atoms. And the compound (8)

Embedded image Get. The reaction is carried out in a molar ratio of (6) :( 7) of 1: 0.5 to 1:50, especially 1: 1 to 1:20, and the concentration of the substrate is 0.1 mol / l to 10 mol / l. And the reaction temperature is in the range of -78 ° C to 120 ° C.
At this time, as the reaction solvent, aliphatic hydrocarbons such as pentane, hexane, heptane and the like, aromatic hydrocarbons such as benzene and toluene, ethers such as diethyl ether and tetrahydrofuran (THF) are preferable.

Further, the compound (8) and the substituted indene compound (5) are deprotonated with the above-mentioned strong base to obtain an indenyl anion (9).

Embedded image Wherein M ³ represents an alkali metal atom such as lithium, sodium or potassium, in a molar ratio of 1: 0.5 to 1:50, especially 1: 1 to 1:20, Compound (10)

Embedded image Get. In the above reaction, the concentration of the substrate was 0.1 mol /
1 to 10 mol / l, the reaction temperature is −78 ° C.
To 120 ° C, in particular, from -20 ° C to 20 ° C. As a reaction solvent, aliphatic hydrocarbons such as pentane, hexane and heptane, aromatic hydrocarbons such as benzene and toluene, diethyl ether, tetrahydrofuran (T
Ethers such as HF) are preferred.

Compound (10) thus synthesized
Is converted into a metallocene compound by a known method conventionally known from the literature (J. Am. Chem. Soc., 1988, 110, 976, JA
m. Chem. Soc., 1985, 107, 8103, Organometallics 1995, 1
4,5 etc.).

That is, the compound (10) is deprotonated with the above-mentioned strong base to give the dianion (11)

Embedded image In the formula, M ⁴ means an alkali metal atom such as lithium, sodium and potassium.

Then, the compound (12) M ¹ (X ¹ _n X ² _4-n ) (12) wherein X ¹ and X ² may be the same or different from each other, and may be a halogen atom or an OR group. , SR group, OCOR
Group, OSO ₂ R group and NRR ′ group. Where R,
R ′ represents a hydrogen atom or a hydrocarbon group having 1 to 7 carbon atoms. Further, n is an integer of 1 to 3. "
And a compound (10) or a dianion (11) to obtain a metallocene compound (1) (provided that X ¹ ,
X ² is an alkyl group).

In the above reaction, the substrate concentration was 0.01 m
ol / l to 10 mol / l, the reaction temperature is −
It is carried out in the range from 78 ° C to 120 ° C, especially from -78 ° C to 30 ° C. As a reaction solvent, aliphatic hydrocarbons such as pentane, hexane and heptane, aromatic hydrocarbons such as benzene and toluene, halogenated hydrocarbons such as dichloromethane, diethyl ether, tetrahydrofuran (THF)
Preferred are ethers and the like.

In the general formula (1), when X ¹ and X ² are hydrocarbon groups, the general formula (13) R ¹³ -M ⁷ (13) wherein R ¹³ is a hydrocarbon having 1 to 20 carbon atoms. Hydrogen group, M
⁷ means an alkali metal atom such as lithium, sodium and potassium. , The metallocene compound represented by the general formula (1) is synthesized.

The second catalyst component used for polymerization in the present invention is a Lewis acid compound, and is roughly classified into the following two types.

One is an organic aluminoxy compound represented by the general formula (14) or (15).

Embedded image [In the formulas (14) and (15), R ¹⁴ , R ¹⁵ , and R ¹⁶ are a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, preferably a methyl group, an ethyl group, or a propyl group. , A butyl group and an isobutyl group, particularly preferably a methyl group and an isobutyl group. R ¹⁷ may be the same or different and is a hydrocarbon group having 1 to 10 carbon atoms;
Preferably, methyl group, ethyl group, propyl group, butyl group, isobutyl group, particularly preferably methyl group,
It is an isobutyl group. n is an integer of 1 to 100, preferably an organic aluminoxy compound composed of a mixture of 3 to 100. Further, a mixture of (14) and (15) may be used. ]

A known method can be used for producing this kind of compound. For example, a method of adding trialkylaluminum to a suspension of salts having water of crystallization in a hydrocarbon solvent suspension of (copper sulfate hydrate, aluminum sulfate hydrate), or a solid,
Examples of a method of applying liquid or gaseous water can be given. When n is 2 or more and R ¹⁷ is the same, 1
When different types of trialkyl aluminum are used and each R ¹⁷ is different, two or more types of trialkyl aluminum may be used, or one or more types of trialkyl aluminum and one or more types of dialkyl aluminum monohalides may be used. Specifically, trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, tri-n-butylaluminum,
Trialkylaluminums such as triisobutylaluminum, tris-butylaluminum, trit-butylaluminum, tripentylbutylaluminum, trihexylbutylaluminum, tricyclohexylbutylaluminum, dialkylaluminum halides such as dimethylaluminum chloride and diisobutylaluminum chloride, dimethyl It is selected from dialkylaluminum aryloxides such as aluminum methoxide. Among them, it is preferable to be selected from trialkylaluminums, particularly trimethylaluminum and triisobutylaluminum.

Further, the organic aluminoxy compound used in the present invention is obtained by further reacting with a compound having active hydrogen such as water to crosslink the organic aluminoxy compound of the general formulas (14) and (15). Is also good. Alternatively, it may be an addition reaction product with an organic polar compound having at least one atom selected from a phosphorus atom, a nitrogen atom, a sulfur atom and an oxygen atom in a molecule and having no active hydrogen. Further, the organic aluminoxy compound may be a compound to which an additive such as alcohol is added in order to suppress the change with time. As organic polar compounds,
Trimethyl phosphate, triethyl phosphate and the like.
In this case, it is possible to polymerize a polyolefin excellent in powder properties without adhesion of the polymer to the polymerization vessel wall.

Another group of second catalyst components are other Lewis acid compounds which react with the metallocene compound to form an ionic complex. Among them, a boron compound is preferable, and a boron compound having a pentafluorophenyl group, a p-methyltetrafluorophenyl group, a pt-butyltetrafluorophenyl group, and a p-trimethylsilyltetrafluorophenyl group is particularly preferable. Specifically, tri (pentafluorophenyl) boron, tri (n-butyl) ammonium tetra (pentafluorophenyl) borate, tetra (pentafluorophenyl)
Dimethylanilinium borate, pyridinium tetra (pentafluorophenyl) borate, ferrocenium tetra (pentafluorophenyl) borate, triphenylcarbenium tetra (pentafluorophenyl) borate, tri (pentafluorophenyl) (4-methyl- 2,3
5,6-tetrafluorophenyl) triphenylcarbenium borate, tri (pentafluorophenyl) (4-
t-butyl-2,3,5,6-tetrafluorophenyl) triphenylcarbenium borate or tri (pentafluorophenyl) (4-trimethylsilyl-2,
Triphenylcarbenium (3,5,6-tetrafluorophenyl) borate and the like can be mentioned.

The third catalyst component used for polymerization in the present invention is an organoaluminum compound. For example, trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, trin-butylaluminum, triisobutylaluminum, trisec-butylaluminum, trite
trialkylaluminums such as rt-butylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, trisichexylaluminum, etc., dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, diisobutylaluminum chloride, dimethylaluminum methoxide, diethyl It is selected from dialkylaluminum alkoxides such as aluminum ethoxide, dialkylaluminum aryloxides such as diethylaluminum phenoxide, and aluminoxanes. Among them, it is preferable to be selected from trialkylaluminums, particularly trimethylaluminum, triethylaluminum, triisobutylaluminum, and trioctylaluminum. Further, organic aluminoxy compounds represented by the general formulas (14) and (15) may be used instead.

The fourth catalyst component used for the polymerization in the present invention is a fine particle carrier. Each or all of the first to third catalyst components of the present invention can be supported on a fine particle carrier (hereinafter, a carrier). The fine particle carrier used in the present invention has an average particle size of 10 to 300 µm, preferably 20 to 200 µm. In the form of fine particles,
There is no particular limitation as long as it is solid in the polymerization medium, and it is selected from organic substances and inorganic substances. The inorganic substance is preferably selected from inorganic oxides, inorganic chlorides, inorganic carbonates, inorganic sulfates, inorganic hydroxides, and organic polymers. For example, inorganic carriers include oxides such as silica and alumina, chlorides such as magnesium chloride, carbonates such as magnesium carbonate and calcium carbonate, sulfates such as magnesium sulfate and calcium sulfate, magnesium hydroxide, calcium hydroxide, and the like. Hydroxide and the like. Examples of the organic substance include an organic polymer carrier, and examples thereof include fine particles of polyethylene, polypropylene, polystyrene, and the like. Preferably, inorganic oxides, especially silica,
It is desirable to be selected from alumina and its composite oxide. Among these, a porous fine particle carrier is preferable. In this case, adhesion of the polymer to the inner wall of the reaction vessel is small, and the bulk density of the obtained polymer is high, which is particularly preferable. The porous fine particles according to the present invention have a specific surface area of 10 to 100.
0 m ² / g, preferably 100 to 8
It is preferably in the range of 00 m ² / g, particularly preferably in the range of 200 to 600 m ² / g. The pore volume is preferably in the range of 0.3 to 3 cc / g, more preferably in the range of 0.5 to 2.5 cc / g, and particularly preferably in the range of 1.0 to 2 cc / g. 0.0cc /
g. In addition, the amount of adsorbed water and the amount of surface hydroxyl groups vary depending on the treatment conditions. As preferred ranges thereof, the water content is 5% by weight or less, and the surface hydroxyl group content is 1 / nm ² or more based on the surface area. The control of the water content and the amount of surface hydroxyl groups can be performed by treating with a firing temperature, an organic aluminum compound, an organic boron compound, or the like.

Further, a prepolymerized olefin can also be used. The polymerization catalyst of the present invention can contain other components useful for olefin polymerization, in addition to the above components.

In the present invention, the olefin used for polyolefin polymerization includes ethylene, propylene, 1-
Butene, 1-pentene, 1-hexene, 1-heptene,
1-octene, 3-methyl-1-butene, 4-methyl-
Examples thereof include 1-pentene, cyclopentene, cyclohexene, and styrene. The olefin represented by the general formula (2) used for the polymerization in the present invention includes propylene, 1-butene, 1-pentene, 1-hexene,
-Heptene, 1-octene, 3-methyl-1-butene,
4-methyl-1-pentene, cyclopentene, cyclohexene, styrene and the like. Ethylene and formula (2)
As the olefin of the formula (2) used in the copolymerization with the olefin represented by the following formula, propylene, 1-butene,
1-hexene and 1-octene are preferred, and propylene is particularly preferred. In the method of (co) polymerizing one or more olefins represented by the formula (2), homopolymerization of propylene, copolymers of propylene and 1-butene, and propylene and 1-hexene are exemplified. Among them, propylene homopolymer is preferable. Further, a polyvalent ene can be subjected to the polymerization. In this case, the polyvalent ene to be subjected to the polymerization has a carbon number of 5 having at least two non-conjugated vinyl groups and at least two vinyl-type double bonds.
A polyvalent ene having a molecular weight of up to 80 and a molecular weight of 1100 or less is effective. Particularly effective polyvalent enes have from 8 to 20 carbon atoms. Specifically, 1
, 4-pentadiene, 1,5-hexadiene, 1,6
Heptadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, 1,13-tetradecadiene, 3-methyl-1,4-pentadiene, 4-methyl-1,5-hexadiene, 3 -Methyl-1,5-hexadiene, 1,5,9-decatriene and the like. In particular, 1,5-hexadiene, 1,7-octadiene,
1,9-decadiene is preferred. The polyvalent ene subjected to the polymerization is based on the olefin represented by the general formula (2).
A range of 0.05% to 2% is preferred.

The timing of the contact between the first catalyst component and other catalyst components during the polymerization reaction can be arbitrarily selected. For example, the first catalyst component and the second catalyst component are brought into contact with each other in advance (pre-contact), while the reaction container is charged with the third catalyst component and an olefin to be used for polymerization, and added to this to start the polymerization reaction. Method. Or the third in the reaction vessel
The polymerization reaction may be started by charging a catalyst component and an olefin to be used for polymerization, and separately adding the first catalyst component and the second catalyst component. In particular, the second catalyst component has the general formula (14):
In the case of the organic aluminoxy compound of (15), when the first catalyst component and the second catalyst component are supplied to the reaction system after being brought into contact in advance, the polymerization activity is significantly improved.

Further, the first to third catalyst components can be supported on the fourth catalyst component at a necessary time when necessary. The order of the loading method at this time can be arbitrarily selected, but preferably, the fourth catalyst component is mixed and contacted with the second catalyst component and then brought into contact with the first catalyst component or the first catalyst component and the second catalyst component. After the catalyst component is pre-contacted, a method of mixing and contacting the fourth catalyst component is selected.

The above components may be mixed with aromatic hydrocarbons such as benzene, toluene and xylene, aliphatic hydrocarbons such as pentane, hexane, heptane, octane and decane;
It can be prepared in a solvent such as an alicyclic hydrocarbon such as cyclopentane or cyclohexane, in the presence or absence of an olefin. The temperature during mixing is -70 ° C
~ 200 ° C, preferably -20 ° C to 120 ° C,
The mixing time is between 1 minute and 600 minutes. The concentration at the time of mixing is such that the first catalyst component is used at a concentration of 10 ^-6 to 10 ^-3 mol per 1 g of the fourth catalyst component.

The polymerization method used in the present invention may be any method known in the art such as a solution polymerization, a slurry polymerization, a gas phase polymerization or a high-temperature melt polymerization, and may be either continuous or continuous. It can be performed discontinuously and in one or more stages. The polymerization conditions are not particularly limited except for the conditions in the use process, but the polymerization temperature is from 0 ° C. to 300 ° C., particularly 2 ° C.
It is generally used at 0 ° C to 150 ° C, more preferably at 40 ° C to 90 ° C.

The concentration of the catalyst component for polyolefin polymerization of the present invention is not particularly limited, but the concentration of the metallocene compound as the first catalyst component is 10 ^-3 to 10 ^-10 mol / l with respect to the solvent or the volume of the reaction vessel. preferable. In the case of the second catalyst component, the concentration of the organic aluminoxy compound of the general formulas (14) and (15) is 10 to 10000, particularly preferably a molar ratio of (aluminum atom in the organic aluminoxy compound) / (metallocene compound). , And 100 to 5,000. In the case of another Lewis acid compound, the molar ratio of (Lewis acid compound) / (metallocene compound) is 0.1.
To 100, particularly preferably in the range of 0.2 to 10. Third
In the case of the catalyst component, the molar ratio of the metallocene compound of the first catalyst component to the organoaluminum compound (aluminum atom in the organoaluminum compound) / (metallocene compound)
And 10 to 100,000, preferably 100 to 10
000. The organoaluminum compound used in the polymerization may be used in contact with the first catalyst component or the second catalyst component in advance, or may be used without prior contact. The adjustment of the molecular weight during the polymerization can be carried out by known means, for example, by selecting the temperature or introducing hydrogen.

The invention is further described in the following examples, which do not limit the scope of the invention.

[0049]

EXAMPLES In the following examples, the metallocene compounds of the present invention were identified by the following method. ¹ H-NMR: measured at 30 ° C. in deuterated chloroform. Mass spectrometry: A sample was introduced by a direct introduction method, ionized by an electron impact method (70 eV), and measured.

The physical properties of the polymer were measured as follows. ¹³ C-NMR: carried out at 120 ° C. in a mixed solvent of heavy benzene and 1,3,5-trichlorobenzene (1: 3 wt ratio) (measurement mode: proton decoupling method, pulse width: 8.0 μs, pulse repetition) Time: 3.0 s, cumulative number: 20,000 times, internal standard: hexamethyldisiloxane). The stereoregularity of polypropylene, Macrolecules
According to 6,925 (1973) and ibid 8,687 (1975), evaluation was made as an intensity ratio of mm, mr, and rr signals derived from a methyl group. Gel permeation chromatography (GPC):
The reaction was performed in 1,2,4-trichlorobenzene at a column temperature of 135 ° C. and a solvent flow rate of 1 ml / mim. Differential scanning calorimetry (DSC): 23 ° C. after heating to 230 ° C.
The sample was held at 0 ° C. for 5 minutes, the heat of crystallization was measured by a cooling scan at 20 ° C./min, and again held at 25 ° C. for 5 minutes, and the heat of fusion was measured by a heating scan at 20 ° C./min.

The analytical instruments used for measuring the physical properties are as follows. NMR JEOL EX-400 Mass spectrometry JEOL AX-500 GPC Waters 150C (Shodex; GPC AT-806MS column) DSC Perkin Elmer DSC7

(Synthesis of Metallocene Compound) Example 1 (1) Synthesis of (3-t-butyl-1-cyclopentadienyl) dimethylchlorosilane 64.5 g (0.5 mol) of dimethyldichlorosilane was dried with n-hexane (Na- Dissolved in 1000 ml of dry K alloy), 12.2 g (0.1 mol) of t-butylcyclopentadienyl lithium solution (t-butylcyclopentadiene) was dissolved in 200 ml of dry THF, and 62.5 ml of a 1.6 M nBuLi hexane solution was added at -78 ° C. The mixture was added dropwise and stirred at room temperature for 3 hours) under ice-cooling. The mixture was stirred at room temperature for 3 hours. A white salt of lithium chloride precipitated. After allowing to stand and allowing the white salt to settle, the supernatant was collected. The product was purified by distillation under reduced pressure under an argon atmosphere to obtain the desired product (95-100 ° C, 8 mmHg). As a result, 13g
(61 mmol) was obtained. Yield 61%. MS (GC method, EI, 70 eV); m / z (%) 214 (12, M ⁺ ), 199 (28, M ⁺ -M
e), 179 (3, M ⁺ -Cl), 93 (100, M ^{+ -t} Bu)

(2) Synthesis of dimethyl (3-t-butyl-1-cyclopentadienyl) (1-indenyl) silane In a 500 ml flask, 6.50 g (55.9 g) of indene (distilled after refluxing with calcium hydride). mmol) in n-hexane 200m
l) and dissolved in n-butyllithium (1.67M hexane solution)
33.5 ml was added dropwise at 0 ° C. to obtain a white suspension of indenyl lithium. Here, 10.0 g (46.6 mmol) of dimethyl (3-t-butyl-1-cyclopentadienyl) chlorosilane was
Added at 0 ° C. The mixture was further stirred at room temperature for 10 hours to obtain a pale yellow suspension. The reaction solution was added with a saturated aqueous solution of ammonium chloride in an ice bath, the organic layer was washed with water, dried over anhydrous magnesium sulfate, and purified by distillation under reduced pressure (110 ° C., 0.4 mmHg) to obtain 10.3 g of the desired product as an orange-brown oil. (35 mmol) was obtained. yield
75%. ^{From 1} H-NMR, it is a mixture of isomers. ¹ H-NMR (400 MHz, CDCl ₃ ) δ-0.32-0.10 (6H, Si-Me), 1.14-
1.20 (9H, ^t Bu), 2.70-3.61 (2H, allyl), 5.67-7.49 (9H, arom
atic) MS (direct introduction method, EI, 70 eV); m / z 294 ((M) ⁺ ), 236 ((M- ^t Bu)
⁺ )

(3) rac-Me ₂ Si (3-tBuCp) (Ind) ZrCl
₂ Reaction with zirconium tetrachloride according to the synthesis method of (A). All operations were performed under an argon atmosphere. 100 ml of dry THF
Dimethyl (3-t-butyl-1-cyclopentadienyl)
Dissolve 5.40 g (18.4 mmol) of (1-indenyl) silane,
24.2 ml of n-butyllithium (1.67M hexane solution)
Was added at -78 ° C. After reacting for 3 hours at room temperature, THF
Was distilled off under reduced pressure. While cooling to -78 ° C, 80 ml of dry dichloromethane was added to obtain a red solution of the dilithium salt. 4.3 g (18.4 mmol) of zirconium tetrachloride was suspended in 100 ml of dry methylene chloride in a separately prepared 300 ml flask. This was cooled to −78 ° C., and the methylene chloride solution was added with a cannula while cooling. After the addition, the refrigerant was removed, the temperature was gradually raised to room temperature, and the mixture was further stirred at room temperature for 10 hours. During that time, the reaction solution changed from a dark red solution to a yellow suspension. Methylene chloride was distilled off from the reaction solution under reduced pressure. The residue was dissolved in 200 ml of dry toluene, and the by-product salt was separated by centrifugation. The supernatant was concentrated. Since crystals precipitated during the concentration process, they were dissolved by heating and then recrystallized at room temperature. As a result, yellow crystals were obtained. ¹ H-NMR (400 MHz, CDCl ₃ ) δ 0.771, 1.018 (s, 2H, Si-Me), 1.
299 (s, 9H, tBu), 5.820 (t, J = 2.44Hz, 1H, Cp-H), 5.89 (t, J =
2.93Hz, 1H, Cp-H), 6.185 (d, J = 3.42Hz, 1H, Ind-H), 6.559 (d
d, J = 1.95,2.93Hz, 1H, Cp-H), 6.956 (d, J = 3.42Hz, 1H, Ind-
H), 7.091 (t, J = 7.32,1H, Ind-H), 7.388 (t, J = 7.82Hz, 1H, In
dH), 7.554 (d, J = 8.79Hz, 1H, Ind-H), 7.696 (d, J = 8.30Hz, 1
H, Ind-H) (Fig. 1) MS (direct introduction method, EI, 70 eV); m / z 454 ((M) ⁺ ), 401 ((M- ^t Bu)
⁺ )

Example 2 (1) Synthesis of dimethyl (3-tert-butyl-1-cyclopentadienyl) (2-methyl-4-phenyl-1-indenyl) silane 11.5 g (55.9 mmol) of phenyl-1-indene (synthesized according to the method described in Organometallics, 13,954 (1994)) was mixed with 150 ml of toluene and T
HF was dissolved in 7 ml of a mixed solvent, and n-butyllithium (1.67
33.5 ml of M hexane solution was added dropwise at 0 ° C. After stirring at room temperature for 1 hour, the mixture was heated to 90 ° C. for 1 hour to obtain a yellow suspension of 2-methyl-4-phenyl-1-indenyllithium. To this was added 10.0 g (46.6 mmol) of dimethyl (3-t-butyl-1-cyclopentadienyl) chlorosilane at 0 ° C. The yellow solution immediately after dropping became a yellow-white suspension as the temperature was raised to room temperature. The mixture was further stirred at room temperature for 10 hours, and the reaction solution became a milky white suspension. To the reaction solution, a saturated aqueous solution of ammonium chloride was added in an ice bath, the organic layer was washed with water, dried over anhydrous magnesium sulfate, and the solvent was distilled off with an evaporator to obtain a reaction mixture of a reddish brown oil. The reaction mixture was subjected to column purification (800 g of silica gel, developing solvent; n-hexane: methylene chloride = 95: 5 vol%) to collect 4.6 g (11.9 mmol) of the target compound as an orange-brown oil. Yield 26%. ^{From 1} H-NMR, it is a mixture of isomers. ¹ H-NMR (400 MHz, CDCl ₃ ) δ-0.15-0.22 (6H, Si-Me), 1.10-
1.52 (9H, t-Bu), 2.51-3.50 (2H, allyl), 5.65-7.55 (12H, ar
omatic) MS (direct introduction, EI, 70 eV); m / z 384 ((M-1) ⁺ )

(2) rac-Me ₂ Si (3-tBuCp) (2-Me-4-PhInd)
Synthesis of ZrCl ₂ (B) As in Example 1 (3), all operations were performed in an argon atmosphere. The ligand dimethyl (3-t-) was added to 60 ml of dry THF.
Dissolve 3.2 g (8.31 mmol) of butyl-1-cyclopentadienyl) (2-methyl-4-phenyl-1-indenyl) silane and add n-butyllithium (1.67 M hexane solution) 1
0.9 ml was added at -78 ° C. After reacting for 3 hours at room temperature,
THF was distilled off under reduced pressure. Further, 50 ml of dry dichloromethane was added while cooling to -78 ° C to obtain a red solution of the dilithium salt. 1.94 g (8.3 mmol) of zirconium tetrachloride in a separately prepared 200 ml flask and 50 ml of dry methylene chloride
Was suspended. This was cooled to −78 ° C., and the methylene chloride solution was added with a cannula while cooling. After addition,
When the cooling medium was removed and the temperature was gradually raised to room temperature, the solution changed from a homogeneous yellow solution to a yellow suspension solution, and the reaction proceeded. 10 at room temperature
After stirring for an hour, the reaction was aged. Methylene chloride was distilled off from the reaction solution under reduced pressure. The residue was extracted into n-hexane, and the extract was concentrated to deposit a yellow powder. This yellow powder was redissolved in toluene, and a yellow solid was obtained by recrystallization. ¹ H-NMR (400 MHz, CDCl ₃ ) δ 0.925, 1.057 (s, 2H, Si-Me), 1.
323 (s, 9H, tBu), 2.230 (s, 3H, Ind-Me), 5.811 (t, J = 1.95Hz,
1H, Cp-H), 5.914 (t, J = 2.39Hz, 1H, Cp-H), 6.577 (dd, J = 1.9
5,2.93Hz, 1H, Cp-H), 6.917 (s, 1H, Ind-H), 7.077-7.116 (m,
1H, Ind-H), 7.333-7.377 (m, 2H, Ind-H, Ph-H (p)), 7.427-7.
465 (m, 2H, Ph-H (m)), 7.514 (d, J = 8.79Hz, 1H, Ind-H), 7.651
-7.672 (m, 2H, Ph-H (o)) (Fig.2) MS (direct introduction method, EI, 70eV); m / z 543 ((M-2) ⁺ ), 401 ((M-2-
^t Bu) ⁺ )

(Polymerization of Propylene) Example 3 300 ml of purified toluene and methylaluminoxane (total aluminum equivalent: 2.
4.9 ml of a 70 mol / l toluene solution) was added. On the other hand, rac-Me ₂ Si (3-tBuCp) (Ind) ZrCl ₂ (A) 26.0 mg (1
3.2 μmol) and methylaluminoxane (MAO) 4.9
ml in 10 ml toluene and mixed at room temperature for 10 minutes.
Stirred. This solution was added to the reactor and cooled to 3 ° C. Then, 2 mol of propylene was charged and polymerization was performed for 1 hour. After the reaction, the catalyst component was decomposed in 3 liters of hydrochloric methanol, filtered, and the obtained polypropylene was dried.
As a result, 9.64 g of white powdery isotactic polypropylene was obtained. 0.73K activity per metallocene
g-PP / mmol-Zr · h.

Example 4 The procedure of Example 3 was repeated except that the polymerization temperature was changed to 30 ° C.

Example 5 A 1.5-liter SUS autoclave, which had been sufficiently purged with nitrogen, was charged into a triisobutylaluminum (TIB).
A) A toluene solution (0.5 M, 19.2 ml) was charged, followed by 8 mol of liquid propylene, and kept at 0 ° C. On the other hand, ra
c-Me ₂ Si (3-tBuCp) (Ind) ZrCl ₂ (A) 2.9 mg (6.4 μm
ol) in a toluene solution of TIBA (0.5 M, 6.4 ml) and reacted at 30 ° C. for 5 minutes (catalyst A). Also, triphenylcarbenium tetra (pentafluorophenyl) borate [Ph ₃ C] [B
(C ₆ F ₅ ) ₄ ] (TPFPB) toluene solution (2.0 m
M, 4.8 ml) was prepared (catalyst B). Immediately after mixing the catalysts A and B, they were added to the reactor and polymerization was carried out at 0 ° C. for 1 hour. As a result, 6.73 g of isotactic polypropylene in the form of a white powder was obtained. The activity per metallocene is 1.05 kg-PP / mmol-Zr · h.

Example 6 The procedure of Example 3 was repeated except that the polymerization temperature was changed to 30 ° C.

Example 7 In Example 3, the metallocene compound was replaced with rac-Me ₂ Si (3-tB
uCp) (2-Me-4-PhInd) ZrCl ₂ (B).

Example 8 The procedure of Example 7 was repeated except that the polymerization temperature was changed to 30 ° C.

Example 9 In Example 5, the metallocene compound was replaced with rac-Me ₂ Si (3-tB
uCp) (2-Me-4-PhInd) ZrCl ₂ (B).

Example 10 The procedure of Example 9 was repeated, except that the polymerization temperature was changed to 30 ° C. Tables 1 and 2 summarize the above polymerization results.

[0065]

[Table 1]

[0066]

[Table 2]

[0067]

By using the novel metallocene compound of the present invention as an olefin polymerization catalyst component, a polyolefin having a high melting point, in particular, an isotactic polyolefin can be produced.

[Brief description of the drawings]

[1] a metallocene compound in Example 1 (A) ¹
1 H-NMR spectrum.

FIG. 2 shows ¹ of metallocene compound (B) in Example 2.
1 H-NMR spectrum.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-7-82309 (JP, A) JP-A-7-118316 (JP, A) JP-A 4-331214 (JP, A) JP-A 8- 231621 (JP, A) (58) Field surveyed (Int. Cl. ⁷ , DB name) C08F 4/64-4/658 CAPLUS (STN)

Claims (5)

(57) [Claims] 1. A compound of the general formula (1) [Wherein, M represents a transition metal atom of any of Ti, Zr, and Hf. X ¹ and X ² may be the same or different and each represents a halogen atom. R ¹ and R ² may be the same or different and each represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. R ³ represents a hydrocarbon group having 1 to 20 carbon atoms, and may include a silicon atom. R ^{4 to} R ⁶ are a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, and may contain a silicon atom. R ^{7 to} R ¹⁰ may be the same or different from each other;
A hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms,
It may contain a silicon atom. ] The catalyst component for polyolefin manufacture which consists of a metallocene compound represented by these. 2. A catalyst for producing a polyolefin comprising (A) the catalyst component according to claim 1, (B) a Lewis acid compound, and (C) an organoaluminum compound. 3. The catalyst component according to claim 1, wherein: (B) a Lewis acid compound, (C) an organoaluminum compound, and (D) A catalyst for producing polyolefin comprising a fine particle carrier. 4. A method for producing a polyolefin, comprising using the catalyst according to claim 2 or 3. 5. The catalyst according to claim 2 or 3, wherein R ¹¹ -CH = CH-R ¹² (2) wherein R ¹¹ and R ¹² are the same as each other. They may be different and represent a hydrogen atom or a hydrocarbon group having 1 to 14 carbon atoms, and may form a ring with each other. However, ethylene is excluded. A method for producing an isotactic poly (α-olefin) which polymerizes an α-olefin represented by the formula: