JPH059213A - Catalyst and process for producing syndiotactic poly-alpha-olefin - Google Patents

Abstract

PURPOSE:To obtain a catalyst which can give a poly-alpha-olefin in high catalytic activity even when the amount of the aluminoxane used is small by mixing a specified transition metal compound with an aluminoxane and an organoaluminum compound. CONSTITUTION:A catalyst comprising a transition metal compound of the formula (wherein A<1> is a cyclopentadinyl group which may be mono- to tetra- substituted; A<2> is a mono- to tetra-substituted fluorenyl group; A<3> and A<4> are each a 1-10 C alkyl group or the like: Q is a C-, Si-, Ge or Sn-containing hydrocarbon group through which A<1> and A<2> are connected; A<3> and A<4> may be combined with each other to form a ring structure containing A<3>, A<4> and Q; R<1> and R<2> are each halogen, H 1-10 C alkyl, 6-20 C aryl, alkylaryl, or arylalkyl; and M is Ti, Zr or Hf), an aluminoxane in an amount which can give a molar ratio to the transition metal compound (in terms of an A<1>/M ratio) of 0.01-1000, and an organoaluminum compound.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a process for producing syndiotactic poly-α-olefins. Specifically, it relates to a method for producing a syndiotactic poly-α-olefin with high activity by using a small amount of aluminoxane. More specifically, it relates to a method for producing a syndiotactic poly-α-olefin with a high activity using a specific transition metal compound and using a small amount of aluminoxane.

[0002]

A transition metal compound having a cyclopentadienyl group, an indenyl group, a fluorenyl group, or a derivative thereof as a ligand, a so-called metallocene compound, is used together with a cocatalyst such as an aluminoxane to polymerize an α-olefin. It is known that a poly-α-olefin can be produced by

Japanese Patent Application Laid-Open No. 58-19309 discloses (cyclopentadienyl) ₂ MeRHal (wherein R is cyclopentadienyl, C ₁ -C ₆ alkyl and halogen, and Me is a transition metal. Yes, Ha
1 is a halogen) and a method of polymerizing or copolymerizing ethylene and / or α-olefin in the presence of a catalyst composed of a transition metal compound represented by the formula (1) and aluminoxane. JP-A-60-35008 describes that poly-α-olefin having a wide molecular weight distribution can be produced by using a catalyst composed of at least two kinds of metallocene compounds and aluminoxane. Japanese Patent Laid-Open No. 61-130314 describes a method for producing a polyolefin using a catalyst composed of a sterically fixed zircon chelate compound and aluminoxane. Further, the publication discloses a method for producing a polyolefin having a high degree of isotacticity by using ethylene-bis- (4,5,6,7-tetrahydro-1-indenyl) zirconium dichloride as a transition metal compound. Have been described. JP-A-64-661
Japanese Unexamined Patent Publication No. 24 discloses a catalyst for producing a stereoregular olefin polymer containing a transition metal compound having a silicon-crosslinked cyclopentadienyl compound as a ligand and an aluminoxane as an active ingredient. JP-A No. 2-41303 discloses that the following formula R ″ (Cp R _n ) (CpR ′ _m ) MeQ _k (where each Cp is cyclopentadienyl or a substituted cyclopentadienyl ring; _n may be the same or different, from 1 to 20 a hydrocarbyl residue having a carbon atom; may optionally each R _'m mother same or different, is a hydrocarbyl residue having 1 to 20 carbon atoms; R "is the structural bridge between the Cp rings that gives the catalyst steric rigidity; Me is 4b, 5 of the Periodic Table of the Elements.
a metal of group b or 6b; each Q is a hydrocarbyl residue having 1 to 20 carbon atoms or a halogen; 0 ≦
k ≦ 3: 0 ≦ n ≦ 4: and 1 ≦ m ≦ 4; and R ′
_m is (CpR _'m) is (CpR _n) and sterically different and is selected as the metallocene catalyst used to produce the syndiotactic polyolefin is denoted by. It is described that a poly-α-olefin having good syndiotacticity can be produced by using a catalyst containing 1 component as a component. Further, the same publication describes that the syndiotactic poly-α-olefin having a wide molecular weight distribution can be produced by using two or more kinds of the above metallocene compounds.
Japanese Unexamined Patent Publication No. 2-274703 discloses the following formula (Formula 3).

[0004]

[Chemical 3] [In the formula, M ¹ is titanium, zirconium, vanadium, niobium or tantalum, R ¹ and R ² may be the same or different from each other, a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, 1 carbon atom
An alkoxy group having 10 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an arylalkyl group having 7 to 40 carbon atoms, and a carbon atom. A C 7-40 alkylaryl group or a C 8-40 arylalkenyl group, wherein R ³ and R ⁴ are different and the central atom M
¹ means a mononuclear- or polynuclear hydrocarbon group capable of forming a sandwich structure together with ^1, and R ⁵ is

[0005]

[Chemical 4] = BR⁶, = AlR⁶, -Ge-, -Sn-, -O-,
-S-, = SO, = SO, = NR⁶, = CO, = PR⁶
Or = P (O) R⁶Means R in that case⁶, R ⁷And
And R⁸Can be the same or different from each other,
Child, halogen atom, alkyl group having 1 to 10 carbon atoms,
Fluoroalkyl group having 1 to 10 carbon atoms, number of carbon atoms
6-10 fluoroaryl group, 6-20 carbon atoms
Aryl group, C1-C10 alkoxy group, carbon
Alkenyl group having 2 to 10 atoms, having 7 to 40 carbon atoms
Arylalkyl group, an aryl group having 8 to 40 carbon atoms
Lukenyl group or alkyl aryl having 7 to 40 carbon atoms
Means a radical or R⁶And R⁷Or R⁶Oh
And R⁸Are each made up of the atoms that they bond to
Form a ring, and M²Is silicon, germanium or
It is tin. ] A transition metal component represented by
Polymerizing olefins in the presence of a catalyst consisting of Sun
High molecular weight syndiotactic polyolefin
A method of manufacturing is described.

Further, JP-A-2-274704 describes a method for producing a high molecular weight syndiotactic polyolefin by using the same hafnium compound. However, in the catalyst system using these aluminoxanes, it is necessary to use a large amount of expensive aluminoxane in order to express high catalytic activity.

On the other hand, the active species of the above-mentioned so-called Kaminsky type catalyst is [Cp ' ₂ MR] ⁺ (where Cp' = cyclopentadienyl derivative, M = Ti, Zr, Hf, R
= Alkyl), some catalyst systems that do not use aluminoxanes as co-catalysts have been reported since they were suggested to be transition metal cations. Taube et al.
Organometall. Chem., 347 , C9 (1988) [Cp ₂ T
Ethylene polymerization has been successful using a compound represented by iMe (THF)] ⁺ [BPh ₄ ] ^- (Me = methyl group, Ph = phenyl group). Jordan et al., J. Am. Chem. S.
oc., 109 , 4111 (1987), [Cp ₂ ZrR (L)] ⁺
It is shown that zirconium complexes such as (R = methyl group, benzyl group, L = Lewis base) polymerize ethylene. Japanese Patent Publication No. 1-501950, Japanese Patent Publication No. 1-50
No. 2036 describes a method of polymerizing an olefin using a catalyst composed of a cyclopentadienyl metal compound and an ionic compound capable of stabilizing a cyclopentadienyl metal cation. Zambelli et al. Reported in Macromolecules, 22 , 2186 (1989) that isotactic polypropylene can be produced with a catalyst that combines a zirconium compound having a cyclopentadiene derivative as a ligand and trimethylaluminum and fluorodimethylaluminum. is doing.

Attempts have also been made to use an organoaluminum compound in combination in order to reduce the amount of aluminoxane used. JP-A-2-22307 discloses a method for polymerizing an olefin using a catalyst composed of a specific hafnium compound, an aluminoxane, and an organoaluminum compound. However, in the publication, only a hafnium compound having an indenyl group or a derivative thereof bonded through a lower alkylene group as a ligand is described as the hafnium compound, and syndiotactic poly-α as in the present invention is described. -Transition metal compounds with substituted fluorenyl groups as ligands for producing olefins are not mentioned.

[0009]

As described above, the so-called Kaminsky catalyst system requires a large amount of expensive aluminoxane, so that the amount of aluminoxane used can be reduced,
Several catalyst systems have been proposed that do not use aluminoxanes. In a system using an ionic compound as a cocatalyst without using aluminoxane, there are problems that the polymerization activity is low and that an ionic compound that is difficult to synthesize must be used in order to obtain high activity. Further, the above-mentioned Japanese Patent Laid-Open No. 2-2
As described in 2307, a method for reducing the amount of aluminoxane used in producing isotactic poly-α-olefins has been found. Nothing is known about how to make it.

[0010]

[Means for Solving the Problems] The inventors of the present invention have solved the above problems and, as a result of extensive studies on a method for producing a syndiotactic poly-α-olefin with high activity even when the amount of aluminoxane used is reduced, The inventors have found that the above-mentioned object can be achieved by using a catalyst composed of (A) a specific transition metal compound (B) aluminoxane (C) organoaluminum compound, and have completed the present invention.

That is, the present invention provides (A) general formula (I) (formula 5)

[0012]

[Chemical 5] (Here, A ¹ is a cyclopentadienyl group, a 1 to 4 substituted cyclopentadienyl group, A ² is a 1 to 4 substituted fluorenyl group. A ³ and A ⁴ are alkyl groups having 1 to 10 carbon atoms, An aryl group having 6 to 20 carbon atoms, an alkylaryl group, an arylalkyl group, a halogenated aryl group, or a hydrocarbon group containing a hetero atom such as oxygen, sulfur, nitrogen, or silicon, or a hydrogen atom, and Q is A ¹ , A carbon or silicon connecting ^two, a hydrocarbon group containing germanium, tin. Further, a ^3, a ⁴ is a ³ are bonded to each other, a
^A ring structure may be formed between ⁴ and Q. R ¹ , R ²
Represents a halogen atom, a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group, or an arylalkyl group. M is titanium, zirconium, or hafnium. ), A transition metal compound represented by
The present invention provides a catalyst for producing syndiotactic poly-α-olefin, which comprises an aluminoxane in an amount of 0.01 to 1000 mol / M, and (C) an organoaluminum compound, and the present invention further comprises α in the presence of the above catalyst. A method of polymerizing an olefin to produce a syndiotactic poly-α-olefin.

In the general formula (I) of the transition metal compound used in the present invention, A ¹ is a cyclopentadienyl group, 1
4 to 4 substituted cyclopentadienyl groups are shown. Specific examples of A ¹ include a cyclopentadienyl group, a methylcyclopentadienyl group, a tetramethylcyclopentadienyl group, and the like. A ² represents a 1 to 4 substituted fluorenyl group, and specific examples thereof include a 1-methylfluorenyl group and a 2,7-di-t-butylfluorenyl group. A ³ and A ⁴ are an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group, an arylalkyl group, a halogenated aryl group or oxygen, sulfur,
It is a hydrocarbon group or hydrogen atom containing a hetero atom such as nitrogen or silicon. Specific examples of A ³ and A ⁴ include hydrogen atom, methyl group, ethyl group, propyl group, phenyl group, toluyl group, fluorophenyl group, methoxyphenyl group,
Examples thereof include a benzyl group. Q is A ¹ , A ²
Is a hydrocarbon group containing carbon or silicon, germanium or tin, which is preferably a carbon atom or a silicon atom. Also, A ^3, A ⁴ are bonded to each other A ^3,
A ring structure may be formed between A ⁴ and Q, and in such a case, the group formed by A ³ , A ⁴ and Q is, for example, a cyclopentylidene group, a cyclohexylidene group, or tetrahydropyran-4-. Examples thereof include an ylidene group. R
¹ , R ² represents a halogen atom, a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group or an arylalkyl group, preferably a chlorine atom, a methyl group or a benzyl group. is there. M represents titanium, zirconium or hafnium, preferably zirconium or hafnium.

Specific examples of the transition metal compound represented by the general formula (I) include isopropylidenecyclopentadienyl (2,7-di-t-butyl-9-fluorenyl).
Zirconium dichloride, isopropylidenecyclopentadienyl (2,7-dit-butyl-9-fluorenyl) zirconium dimethyl, isopropylidene (methylcyclopentadienyl) (2,7-dit-butyl-9-
Fluorenyl) zirconium dichloride, isopropylidene (methylcyclopentadienyl) (2,7-di-t-
Butyl-9-fluorenyl) zirconium dimethyl, cyclopentylidene cyclopentadienyl (2,7-dit
-Butyl-9-fluorenyl) zirconium dichloride, cyclopentylidene cyclopentadienyl (2,7
-Di-t-butyl-9-fluorenyl) zirconium dimethyl, cyclopentylidene (methylcyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, cyclopentylidene (methylcyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dimethyl, tetrahydro-4-
Ylidenecyclopentadienyl (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, tetrahydro-4-ylidenecyclopentadienyl (2,7-
Di-t-butyl-9-fluorenyl) zirconium dimethyl, tetrahydro-4-ylidene (methylcyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, tetrahydro-4-ylidene (methylcyclopenta) Dienyl) (2,7-di-t-
Butyl-9-fluorenyl) zirconium dimethyl, dimethylsilylene cyclopentadienyl (2,7-di-t-
Butyl-9-fluorenyl) zirconium dichloride,
Dimethylsilylene cyclopentadienyl (2,7-dit
-Butyl-9-fluorenyl) zirconium dimethyl,
Dimethylsilylene (methylcyclopentadienyl)
Similar hafnium compounds other than (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, dimethylsilylene (methylcyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dimethyl, etc. Can be mentioned.

The transition metal compound represented by the general formula (I) used in the present invention can be synthesized, for example, by the following route. When Q is a carbon ^{atom, A 3 A 4 Q = A} 1 + HA 2 Li + HCl ── → A 3 A 4 QHA 1 HA 2 + LiCl (1) A 3 A 4 QHA 1 HA 2 + 2n-BuLi ─ ^{─ → a 3 a 4 QA 1} a 2 Li 2 + 2BuH (2) a 3 a 4 QA 1 a 2 Li 2 + MX 4 ── → a 3 a 4 QA 1 a 2 MX 2 + 2LiX (3) Q is In the case other than carbon atom, HA ¹ Li + A ³ A ⁴ QX ¹ ₂ ---> A ³ A ⁴ QHA ¹ X ¹ + LiX ¹ (4) A ³ A ⁴ QHA ¹ X ¹ + HA ² Li ---> A ³ A ⁴ QHA ¹ HA ² + LiX ¹ (5) A ³ A ⁴ QHA ¹ HA ² + 2n-BuLi ── → A ³ A ⁴ QA ¹ A ² Li ₂ + 2BuH (6) A ³ A ⁴ QA ¹ A _{^{2 Li 2 + MX 4 ── →}} a 3 a 4 QA 1 a 2 MX 2 + 2LiX (7) ( wherein X, X ¹ is a halogen atom.) further , A ³ A ⁴ QA ¹ A ² MX ₂ is RLi or RMgX (R
Is an alkyl group, an aryl group, an arylalkyl group) or the like, and a compound in which at least one of X is substituted with R can be obtained by reacting with an organometallic compound of Groups 1A and 2A of the periodic table.

A ³ A ⁴ Q = A used in the reaction formula (1)
^The fulvene compound represented by ¹ is, for example, J. Org. Che.
m., 33 , 2368 (1968), J. Org. Chem., 49 , 1849 (1
984) and the like. Ethers such as tetrahydrofuran and diethyl ether are preferably used as the solvent used when carrying out the reaction formulas (1) and (2) or the reaction formulas (4), (5) and (6). Reaction formulas (3) and (7)
As the solvent used when performing, in addition to ethers such as tetrahydrofuran and diethyl ether, halogenated hydrocarbons such as chloroform and dichloromethane,
Aliphatic or aromatic hydrocarbon media such as pentane, hexane, benzene, toluene can also be used.

The aluminoxane used as the component (B) in the present invention is represented by the following general formula (Formula 6).

[0018]

[Chemical 6] (Here, R is a hydrocarbon group having 1 to 10 carbon atoms, and n is an integer of 2 or more.), And aluminoxane in which R is a methyl group or an isobutyl group is preferably used. The aluminoxanes may be mixed with some alkylaluminum compounds.
As the method for producing the aluminoxane, generally, (1) crystallization water such as copper sulfate hydrate, aluminum sulfate hydrate, and magnesium chloride hydrate in a medium such as benzene, toluene, diethyl ether, and tetrahydrofuran is used. A method of reacting a salt containing with a trialkylaluminum (2) A method of directly reacting a trialkylaluminum with water in a medium such as benzene, toluene, diethyl ether, or tetrahydrofuran is used.

The ratio of aluminoxane to the transition metal compound used as the component (A) is 0.01 to 1000 mole times, preferably 0.1 to 500 mole times, as aluminum atom.

In the present invention, the organoaluminum compound used as the component (C) has the general formula AlR ₃ (R is an alkyl group having 1 to 20 carbon atoms, an aryl group, an alkylaryl group or an arylalkyl group. ) Can be represented. Specific examples include trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-octylaluminum, triphenylaluminum and the like. Preferably,
Triethyl aluminum and triisobutyl aluminum.

The ratio of the organoaluminum compound to the transition metal compound (A) used is 0.1 to 0.1%.
The amount is 1000 mol times, preferably 1 to 500 mol times.

Syndiotactic poly-in the present invention
The catalyst for α-olefin production is SiO ₂ ,
It may be used by supporting it on a known carrier that supports a Ziegler type catalyst such as Al ₂ O ₃ and MgCl ₂ .

There are no particular restrictions on the polymerization method and the polymerization conditions used in the method of the present invention, and known methods used in the polymerization of α-olefins may be used, including a solvent polymerization method using an inert hydrocarbon medium, or a substantial method. A bulk polymerization method or a gas phase polymerization method in which an inert hydrocarbon medium does not exist can also be used, and it is general to carry out at a polymerization temperature of −100 to 200 ° C. and a polymerization pressure of normal pressure to 100 kg / cm ^2. . The pressure is preferably −50 to 100 ° C. and atmospheric pressure to 50 kg / cm ² .

Examples of the hydrocarbon medium used in the treatment or polymerization of the catalyst component in the present invention include saturated hydrocarbons such as butane, pentane, hexane, heptane, octane, nonane, decane, cyclopentane and cyclohexane, and benzene. Aromatic hydrocarbons such as toluene, xylene, etc. can also be used. As the α-olefin used in the polymerization, propylene, 1-
Butene, 4-methyl-1-pentene, 1-hexene, 1
Examples thereof include α-olefins having 3 to 25 carbon atoms such as octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene and 1-octadecene. In the present invention, not only homopolymerization of α-olefins, but also ethylene or α-olefins having about 2 to 25 carbon atoms such as propylene and ethylene, propylene and 1-butene, etc., as long as they substantially represent a syndiotactic structure. It can also be used when producing a copolymer.

[0025]

EXAMPLES The present invention will be specifically described below with reference to examples.

Example 1 [Synthesis of Transition Metal Compound] Isopropylidenecyclopentadienyl (2,7-dit)
-Butyl-9-fluorenyl) zirconium dichloride 2,7-dit-butyl-9-fluorene was lithiated with methyllithium and then reacted with 6,6-dimethylfulvene to obtain isopropylidenecyclopentadiene (2 , 7-di-t-butyl-9-fluorene)
By lithiation of 10.0 g with n-butyllithium, isopropylidenecyclopentadiene (2,7-
A dilithium salt of (di-t-butyl-9-fluorene) was prepared.

Next, 6.1 g of zirconium tetrachloride was suspended in 100 ml of dichloromethane in a 500 ml glass flask which had been sufficiently replaced with nitrogen. To this suspension was added the isopropylidenecyclopentadienyl (2,7-dit) prepared above.
300 ml of a solution of -butyl-9-fluorenyl) dilithium in dichloromethane was added at -78 ° C. After slowly warming to room temperature and stirring for 15 hours, the reaction solution was filtered off, the filtrate was concentrated, and cooled at -30 ° C for 24 hours to give an orange isopropylidenecyclopentadienyl (2,7-diene). 3.8 g of t-butyl-9-fluorenyl) zirconium dichloride was obtained. The physical properties of this compound are shown below. Elemental analysis value C ₂₉ H ₃₄ ZrCl ₂ ¹ H-NMR spectrum (CDCl ₃ solution) (ppm) 8.00 (d, 2H), 7.71 (s, 2H), 7.6.
4 (d, 2H) 6.31 (t, 2H), 5.66 (t,
2H), 2.39 (s, 6H), 1.35 (s, 18)
H) [Polymerization] 0.75 l of propylene was charged into a 1.5 l autoclave which had been sufficiently replaced with nitrogen, and then isopropylidenecyclopentadienyl (2,7-di-t-
Butyl-9-fluorenyl) zirconium dichloride 2
5 ml of a toluene solution containing x10 ^-3 mmol, 5.3 mg of methylaluminoxane (polymerization degree: 17.7) manufactured by Tosoh Akzo Ltd. and 72.5 mg of triisobutylaluminum was pressed under nitrogen. The polymerization temperature was 40 ° C. and the polymerization was carried out for 1 hour. Polymerization was stopped by introducing a small amount of methanol into the system, unreacted propylene was purged, and dried to obtain 78.0 g of syndiotactic polypropylene powder. 135 ℃ of powder
Intrinsic viscosity (hereinafter abbreviated as [η]) measured with a tetralin solution of 1.01 dl / g, and molecular weight dispersity (Mw / Mn) measured with GPC (gel permeation chromatography) is 2.3. there were. ^The syndiotactic pentad fraction determined from the peak intensity attributed to a methyl group at about 20.2 ppm by ¹³ C-NMR measurement was 0.910.
Met.

Comparative Example 1 [Polymerization] of Example 1 except that isopropylidenecyclopentadienyl-9-fluorenylzirconium dichloride synthesized by the method described in JP-A-2-41303 was used as the transition metal catalyst component. Propylene polymerization was carried out in the same manner as in. The amount of the syndiotactic polypropylene powder obtained was 2.0 g.

As described above, even when a transition metal catalyst component giving the same syndiotactic poly-α-olefin is used, the syndiotactic poly-α-olefin is highly active with a small amount of aluminoxane as in the present invention. Couldn't get

Example 2 [Polymerization] of Example 1 except that 41.9 mg of triethylaluminum was used as the organoaluminum compound component.
Propylene polymerization was carried out in the same manner as in. As a result, 3 syndiotactic polypropylene powders were obtained.
8.6 g, [η] of powder is 0.97 dl / g, Mw
/ Mn was 2.4, and the syndiotactic pentad fraction was 0.902.

Comparative Example 2 Propylene polymerization was carried out in the same manner as in [Polymerization] of Example 1 without using methylaluminoxane, but syndiotactic polypropylene could not be obtained.

[0032]

Industrial Applicability By using the catalyst of the present invention and carrying out the method of the present invention, a syndiotactic poly-α-olefin can be produced with high activity with a small amount of aluminoxane used, and industrially. Extremely valuable.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Yoshiho Sonobe             Mitsui, 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa             Toatsu Chemical Co., Ltd. (72) Inventor Kazumi Mizutani             Mitsui, 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa             Toatsu Chemical Co., Ltd.

Claims (2)

[Claims] 1. (A) General formula (I) (Chemical formula 1) (Here, A ¹ is a cyclopentadienyl group, a 1 to 4 substituted cyclopentadienyl group, A ² is a 1 to 4 substituted fluorenyl group. A ³ and A ⁴ are alkyl groups having 1 to 10 carbon atoms, An aryl group having 6 to 20 carbon atoms, an alkylaryl group, an arylalkyl group, a halogenated aryl group, or a hydrocarbon group containing a hetero atom such as oxygen, sulfur, nitrogen, or silicon, or a hydrogen atom, and Q is A ¹ , A carbon or silicon connecting ^two, a hydrocarbon group containing germanium, tin. Further, a ^3, a ⁴ is a ³ are bonded to each other, a
^A ring structure may be formed between ⁴ and Q. R ¹ , R ²
Represents a halogen atom, a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group, or an arylalkyl group. M is titanium, zirconium, or hafnium. ), A transition metal compound represented by the formula
Aluminoxane in a ratio of 0.01 to 1000 mol times,
And (C) a catalyst for producing a syndiotactic poly-α-olefin, which comprises an organoaluminum compound. 2. A method for producing a syndiotactic poly-α-olefin by polymerizing an α-olefin, wherein (A) general formula (I) (chemical formula 2) (Here, A ¹ is a cyclopentadienyl group, a 1 to 4 substituted cyclopentadienyl group, A ² is a 1 to 4 substituted fluorenyl group. A ³ and A ⁴ are alkyl groups having 1 to 10 carbon atoms, An aryl group having 6 to 20 carbon atoms, an alkylaryl group, an arylalkyl group, a halogenated aryl group, or a hydrocarbon group containing a hetero atom such as oxygen, sulfur, nitrogen, or silicon, or a hydrogen atom, and Q is A ¹ , A carbon or silicon connecting ^two, a hydrocarbon group containing germanium, tin. Further, a ^3, a ⁴ is a ³ are bonded to each other, a
^A ring structure may be formed between ⁴ and Q. R ¹ , R ²
Represents a halogen atom, a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group, or an arylalkyl group. M is titanium, zirconium, or hafnium. ), A transition metal compound represented by the formula
Aluminoxane in a ratio of 0.01 to 1000 mol times,
And (C) a method of producing a syndiotactic poly-α-olefin, which comprises using a catalyst composed of an organoaluminum compound.