JP2883695B2 - New transition metal compounds - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to novel transition metal compounds.

More specifically, the present invention relates to a transition metal compound having two transition metal atoms in one molecule to form a bridged structure.

The compounds of the present invention are useful as catalyst components for the polymerization of ethylene or α-olefins.

[Conventional technology]

Transition metal compounds having a cyclopentadienyl group, an indenyl group, a fluorenyl group or a derivative thereof as a ligand can be used together with a cocatalyst, for example, an aluminoxane, to obtain α
-Highly active poly-α- by polymerizing olefin
It is known that olefins can be produced.

JP-A-58-19309 discloses (cyclopentadienyl) ₂ MeRHal (where R is cyclopentadienyl, C ₁ -C ₆ alkyl and halogen, Me is a transition metal compound, Hal
Is halogen) in the presence of a catalyst comprising a transition compound represented by
-Methods for polymerizing or copolymerizing olefins are described.

JP-A-60-35008 describes that a poly-α-olefin having a wide molecular weight distribution can be produced by using a catalyst comprising at least two kinds of metallocene compounds and an aluminoxane.

JP-A-61-130314 discloses a general formula Wherein R ³ is a cyclic hydrocarbon residue having 1 to 4 carbon atoms or a cyclic hydrocarbon residue having 3 to 6 carbon atoms, and A ¹ and A ² are mononuclear or polynuclear symmetric hydrocarbon residues. A ¹ and A ² may be different or the same as each other, and R ¹ and R ² are a halogen atom or an alkyl group having 1 to 6 carbon atoms, wherein R ¹ And R ² may be different or the same. A method for producing a polyolefin using a catalyst comprising a sterically fixed zircon-chelate compound represented by the formula and an aluminoxane is described. The publication also discloses that ethylene-bis- (4,5,6,7-
It is described that a polyolefin having a high isotacticity can be produced by using (tetrahydro-1-indenyl) -zirconium dichloride.

JP-A-64-66214 discloses a Synchronization Rule IV having at least one fluorenyl group or a derivative thereof as a ligand.
A method for polymerizing or copolymerizing an α-olefin in the presence of a catalyst comprising a group B transition metal compound and an aluminoxane is disclosed.

JP-A-1-301704 discloses a transition metal compound represented by the general formula [I]. (However, M represents a transition metal of titanium, zirconium or hafnium, Y represents silicon, germanium or tin. R ¹ _n- C ₅ H _4-n and R ¹ _q- C ₅ H _4-q are unsubstituted or substituted A cyclopentadienyl group, wherein n and q are integers of 0 to 4, but not simultaneously 0. Each R ¹ may be the same or different and is a hydrogen, silyl group or hydrocarbon And the position and type of R ¹ on the cyclopentadienyl ring shall be such that there is no symmetry plane including M. Each R ² may be the same or different from each other and may be hydrogen or And a hydrocarbon group, and X may be the same or different, and represents hydrogen, a halogen or a hydrocarbon group.) And a catalyst for producing a stereoregular olefin polymer containing aluminoxane as an active ingredient.

The Japanese Patent Publication No. Hei 1-501950 discloses a general formula. Where M is a metal selected from the group consisting of titanium (TI), zirconium (Zr) and hafnium (Hf):
(A-C _P ) is (C _P ) (C _P ) or C _P -A′-C _P , wherein C _P and C _P are the same or different, substituted or unsubstituted cyclopentadienyl groups, optionally 2 independently substituted or unsubstituted groups: A 'is a covalent bond containing an element of group IV-I; L is an olefin, diolefin or alliin ligand: X ₁ and X ₂ are Hydro ride group, hydrocarbyl group, substituted hydrocarbyl group, optionally two substituents alkyl substituents or two hydrides, independently selected from the group consisting of organic metalloid group such as: X _'1 and X' ₂ are metal atoms bind to form a metal-cycle, about 3 to metal, X _'1 and X' ₂ are here
Forming a hydrocarbon group containing 20 carbon atoms: R is a substituent on one of the cyclopentadienyl groups also bound to a metal atom.

In bis (cyclopentadienyl) metal compound and the general formula [L'-H] _{[(CX) a (BX ')} m X "6 ] ^c- (here represented, L'-H is H ^+, Ammonium or hydrocarbyl groups having up to 3 hydrogen atoms and containing 1 to about 20 carbon atoms, or containing 1 to about 20 carbon atoms where one or more hydrogen atoms have been replaced by halogen atoms A substituted ammonium cation substituted by a substituted hydrocarbyl group, a phosphonium group, a hydrocarbyl group in which up to three hydrogen atoms contain from 1 to about 20 carbon atoms, or one in which one or more hydrogen atoms are replaced by halogen atoms Any of such as a substituted phosphonium group substituted with a substituted hydrocarbyl group containing from about 20 carbon atoms, and B and C are boron and carbon, respectively;
X 'and X "are a hydride group, a halide group, 1 to about 20
A hydrocarbyl group comprising 1 to about 20 carbon atoms, a hydrocarbyl group comprising 1 to about 20 carbon atoms wherein one or more hydrogen atoms have been replaced by halogen atoms, a hydrocarbyl group comprising 1 to about 20 carbon atoms An atom, wherein the metal is a group or the like independently selected from the group consisting of organic metalloid groups and the like selected from Group IV-A of the Periodic Table of the Elements; a and b are integers of ≧ 0; c Is an integer ≧ 1; a + b +
c is an even integer from 2 to about 8; m is from 5 to about 22
Is an integer up to. (1) discloses an α-olefin polymerization catalyst comprising a compound represented by the formula:

Japanese Patent Publication No. 1-502036 discloses And a bis (cyclopentadienyl) metal compound represented by the general formula [L'-H] ⁺ [BAr ₁ Ar ₂ X ₃ X ₄ ]-(where L 'is a neutral Lewis base; H is hydrogen Atom; [L '
-H] is a Bronsted acid; B is valent boron; Ar ₁ and Ar ₂ are the same or different aromatic or substituted aromatic hydrocarbon groups containing about 6 to 20 carbon atoms and are mutually linked by a safe bridging group. X ₃ and X ₄ may be linked, wherein the hydride group, the halide group (simultaneously provided that either X ₃ or X ₄ is a halide), a hydrocarbyl containing from 1 to about 20 carbon atoms A substituted hydrocarbyl group comprising 1 to about 20 carbon atoms wherein one or more hydrogen atoms have been replaced by halogen atoms, each hydrocarbyl substituent is
Containing from 1 to about 20 carbon atoms and wherein the metal is
-A olefin polymerization catalyst comprising a compound represented by the formula:-independently selected from the group consisting of hydrocarbyl-substituted metal (organometalloid) groups and the like selected from Group A.

JP-A-2-41303 discloses the following formula: R ″ (CpR _n ) (CpR ′ _m ) MeQ _k (where each Cp is a cyclopentadienyl or substituted cyclopentadienyl ring: each R _n is the same Or may be different and is a hydrocarbyl residue having 1 to 20 carbon atoms: R ″ is the structural bridge between the Cp rings that provides tacticity to the catalyst: Me is 4b of the Periodic Table of the Elements , 5b, or 6b
A hydrocarbyl residue or a halogen having a group A metal atom, wherein 0 ≦ k ≦ 3: 0 ≦ n ≦ 3 and 1 ≦ m ≦ 4;
And R ' _m is selected such that (CpR _n ) is sterically different from (CpR' _m ), wherein the metallocene catalyst is used to produce a syndiotactic polyolefin.

It is described that a poly-α-olefin having good syndiotacticity can be produced by using a catalyst containing as one component.

[Problems to be solved by the invention]

As described above, various transition compounds having a cyclopentadienyl group, an indenyl group, a fluorenyl group, or a derivative thereof useful as a catalyst component for olefin polymerization have been synthesized.

However, one molecule has two transition metal atoms, and a cyclopentadienyl group, an indenyl group, a fluorenyl group,
Alternatively, transition metal compounds having a derivative thereof as a ligand have not been synthesized so far.

[Means for solving the problem]

The present inventors have proposed a useful catalyst component for olefin polymerization.
The present inventors have made intensive studies to synthesize a novel transition metal compound having two transition metal atoms in the molecule and completed the present invention.

That is, the present invention provides a compound represented by the general formula (I): (However, A ¹ , A ² , A ³ , A ⁴ represent a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, a fluorenyl group, a substituted fluorenyl group,
A ⁵ represents a hydrocarbon diylidene group having 4 to 20 carbon atoms. Then, each of A ¹ and A ^2, A ³ and A ⁴ are bonded to the same carbon in the A ^5, results in a crosslinked structure. R ¹ and R ² are a halogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group,
R ¹ and R ² may be the same or different from each other. M ¹ and M ² are selected from titanium, zirconium, and hafnium, and may be the same or different. The novel transition metal compound represented by).

Further, the present invention provides, as an intermediate for synthesizing the above novel transition metal compound, a compound represented by the general formula (II) (However, A ¹ , A ² , A ³ , A ⁴ represent a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, a fluorenyl group, a substituted fluorenyl group,
A ⁵ represents a hydrocarbon diylidene group having 4 to 30 carbon atoms. Then, A ¹ and A ^2, A ³ and A ⁴ are attached to the same carbon in the A ^5, respectively. ) Is provided.

The novel transition metal compound (I) of the present invention contains 2
A novel metallocene compound having two transition metal atoms.

In the general formula (I), A ¹ , A ² , A ³ and A ⁴ represent a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, a fluorenyl group, a substituted fluorenyl group or a derivative thereof. Specifically, for example, a cyclopentadienyl group, a methylcyclopentadienyl group,
Indenyl group, 3-methylindenyl group, 4,5,6,7-tetrahydroindenyl group, fluorenyl group, 1-methylfluorenyl group, 2,7-di-tert-butylfluorenyl group, etc. be able to. A ¹ , A ² , A ³ , and A ⁴ may be the same or different from each other.

A ⁵ represents a hydrocarbon diylidene group having 4 to 30 carbon atoms, specifically, for example, a 2,3-butanediylidene group, 2,4
-Pentanedylidene group, 1,3-cyclopentanediylidene group, 4-cyclopentene-1,3-diylidene group, 2,5
-Hexanediylidene group, 1,4-cyclohexanediylidene group, 6-methyl-2,4-heptanediylidene group, bicyclo [3,3,0] octane-3,7-diylidene group, bicyclo [3,3 , 1] nonane-3,7-diylidene group and 9,10-anthracenediylidene group.

R ¹ and R ² are a halogen atom such as fluorine, chlorine, bromine or iodine, a hydrogen atom, a methyl group, an ethyl group, an isopropyl group, a t-butyl group, an aryl group having 1 to 10 carbon atoms such as a phenyl group, or an alkyl group. And particularly preferably a chlorine atom or a methyl group. R ¹ and R ² may be the same or different from each other.

M ¹ and M ² are selected from titanium, zirconium and hafnium, preferably zirconium and hafnium, which may be the same or different.

The synthetic route of the novel transition metal compound (I) of the present invention can be abbreviated as follows, for example, but is not limited to the following synthetic method.

A ⁵ O ₂ + A ¹ H ₂ + A ³ H ₂ → A ¹ = A ⁵ = A ³ + 2H ₂ O (1) A ¹ = A ⁵ = A ³ + LiA ² H + LiA ⁴ H + 2HCl → HA ¹ (HA ² ) A ⁵ (HA ³ ) A ⁴ H + 2LiCl ・ ・ ・ (2) HA ¹ (HA ² ) A ⁵ (HA ³ ) A ⁴ H + 4C ₄ H ₉ Li → [A ¹ (A ² ) A ⁵ (A ³ ) A ⁴ ] Li ₄ + 4C ₄ H ₁₀ ... (3) [A ¹ (A ² ) A ⁵ (A ³ ) A ⁴ ] Li ₄ + 2MX ₄ → A ⁵ [A ¹ (A ² ) MX ₂ ] [A ³ (A ⁴ ) MX ₂ ] + 4LiCl. (4) (X represents a halogen atom) The method for producing the bisfulvene compound obtained in the reaction (1) is described in J. Org. Chem, 49, 1849 (1984). A method similar to the method can be adopted. That is, it is obtained by reacting a hydrocarbon compound with cyclopentadiene or a derivative thereof in an alcohol in the presence of an amine.

Solvents used for this reaction include alcohols such as methanol, ethanol and isopropanol, as well as diethyl ether, tetrahydrofuran, 1,2
Ethers such as -dimethoxyethane can be used, and examples of amines used as a catalyst during the reaction include triethylamine, pyrrolidine and the like.

The method for producing the compound (II) of the present invention obtained in the reaction (2) is based on the reaction between the bisfluvene compound obtained in the reaction (1) of the present invention and an alkali metal salt of cyclopentadienyl group, indenyl group, fluorenyl or its derivative. It can be obtained by reaction.

The reaction of a fulvene compound with an organic alkali metal compound is known and is described in (Justus Liebig; Ann Chem, 511, 101 (193).
4), J. Organometal. Chem., 303, 213 (1986), J. Am. Chem.
Soc., 112, 2030 (1990), and JP-A-2-41303. ) By reacting according to these methods, the compound of the general formula (II) of the present invention can be produced.

Ethers such as diethyl ether, tetrahydrofuran, and 1,2-dimethoxyethane are used as the solvent used in the reaction (2).

The compound (II) of the present invention obtained by the above reaction formula (2) can be reacted with alkyllithium or metal lithium to form a tetralithium salt, which can be used in the next reaction. Further, it can be similarly used as a tetrapotassium salt or a tetrasodium salt.

As a solvent used when reacting the compound (II) of the present invention, that is, HA ¹ (HA ² ) A ⁵ (HA ³ ) A ⁴ H with an alkali metal or organic alkali metal compound, diethyl ether, tetrahydrofuran, 1,2 Ethers such as dimethoxyethane and saturated hydrocarbon compounds such as heptane, hexane, pentane and the like can be used.

The use ratio of the alkali metal or organic alkali metal compound to HA ¹ (HA ² ) A ⁵ (HA ³ ) A ⁴ H is 3.0 to 10.0, preferably 4.0 to 8.0 mole ratio, and the reaction temperature is −100 ° C. to 150 ° C., preferably Ranges from -80 to 80 ° C.

The solvent used in the reaction of [A ¹ (A ² ) A ⁵ (A ³ ) A ⁴ ] Li ₄ and MX _{4 in the} above reaction formula (3) is a halogenated hydrocarbon compound such as chloroform, methylene chloride, etc. And saturated hydrocarbon compounds such as heptane, hexane and pentane; aromatic hydrocarbon compounds such as benzene, toluene and xylene; and ethers such as diethyl ether, tetrahydrofuran and 1,2-dimethoxyethane.

In this reaction, the molar ratio of [A ¹ (A ² ) A ⁵ (A ³ ) A ⁴ ] Li ₄ / MX ₄ is
0.4-3.0, preferably 0.5-1.0, the reaction temperature is -100 ° C-10
0 ° C, preferably in the range of -90 ° C to 50 ° C.

In addition, A ⁵ [A ¹ (A ² ) MX ₂ ] [A ³ (A ⁴ ) M
X ₂ ] can be easily substituted by an alkyl group by reacting with an alkyl metal compound such as methyllithium or methylmagnesium bromide.

As the solvent used at this time, heptane, hexane, saturated hydrocarbon compounds such as pentane, benzene, toluene, aromatic hydrocarbon compounds such as xylene, diethyl ether, tetrahydrofuran, ethers such as 1,2-dimethoxyethane and the like. Is exemplified. A ⁵ [A ¹ (A ² ) MX
_{^{2] [A 3 (A 4}} ) The proportion of alkyl metal compound to the MX _2] is 1.0 to 10.0, preferably 2.0 to 6.0 times by mole, the reaction temperature is -100 ° C. to 100 ° C., preferably from -90 ° C. to 80 ° C. Range.

The resulting compound of the general formula (I) can be purified by recrystallization or sublimation.

Bisfulvene compounds used for producing the transition metal compound of the present invention include, for example, 2,4-biscyclopentadienylidenepentane, 2,5-biscyclopentadienylidenehexane, 1,4-biscyclopentane Dienylidenecyclohexane, 3,7-biscyclopentadienylidenebicyclo [3,3,0] octane, 3,7-biscyclopentadienylidenebicyclo [3,3,1] nonane, 2,4-bis (3
-Methylcyclopentadienylidene) pentane, 2,5-
Bis (3-methylcyclopentadienylidene) hexane, 1,4-bis (3-methylcyclopentadienylidene) cyclohexane, 3,7-bis (3-methylcyclopentadienylidene) bicyclo [3,3 , 0] octane, 3,7-
Bis (3-methylcyclopentadienylidene) bicyclo [3,3,1] nonane;

Specific examples of the compound of the general formula (II) include 2,2,4,4-tetracyclopentadienylpentane, 2,2,
5,5-tetracyclopentadienylhexane, 1,1,4,4-
Tetracyclopentadienylhexane, 3,3,7,7-tetracyclopentadienylbicyclo [3,3,0] octane,
3,3,7,7-tetracyclopentadienyl bicyclo [3,3,
1) nonane, 2,4-dicyclopentadienyl-2,4-bismethylcyclopentadienylpentane, 2,5-dicyclopentadienyl-2,5-bismethylcyclopentadienylhexane, 1, 4-dicyclopentadienyl-1,4-bismethylcyclopentadienylcyclohexane, 3,7-dicyclopentadienyl-3,7-bismethylcyclopentadienylbicyclo [3,3,0] octane, 3,7-dicyclopentadienyl-3,7-bismethylcyclopentadienylbicyclo [3,3,1] nonane, 2,4-dicyclopentadienyl 2,4-bisindenylpentane, 2, 5-dicyclopentadienyl-2,5-bisindenylhexane, 1,4-dicyclopentadienyl-1,4-bisindenylcyclohexane, 3,7-dicyclopentadienyl-3,7- Bisindenylbicyclo [3,3,0] octane, 3,7-dicyclopenta Dienyl-3,7-bisindenylbicyclo [3,3,1] nonane, 2,4-dicyclopentadienyl-2,4-bisfluorenylpentane, 2,5-dicyclopentadienyl-2 , 5-bisfluorenylhexane, 1,4-dicyclopentadienyl-1,4-bisfluorenylcyclohexane, 3,7-dicyclopentadienyl-3,7-bisfluorenylbicyclo [3 , 3,0] octane, 3,7-dicyclopentadienyl-3,
7-bisfluorenylbicyclo [3,3,1] nonane, 2,4-
Dicyclopentadienyl-2,4-bistetramethylcyclopentanedienylpentane, 2,5-dicyclopentadienyl-2,5-bistetramethylcyclopentadienylhexane, 1,4-dicyclopentadi Enyl-1,4-bistetramethylcyclopentadienylcyclohexane, 3,7
-Dicyclopentadienyl-3,7-bistetramethylcyclopentadienylbicyclo [3,3,0] octane, 3,7
-Dicyclopentadienyl-3,7-bistetramethylcyclopentadienylbicyclo [3,3,1] nonane, 2,4-bismethylcyclopentadienyl-2,4-bisfluorenylpentane, 2 , 5-Bismethylcyclopentadienyl-
2,5-bisfluorenylhexane, 1,4-bismethylcyclopentadienyl-1,4-bisfluorenylcyclohexane, 3,7-methylcyclopentadienyl-3,7-bisfluorenylbicyclo [3,3,0] octane; and 3,7-methylcyclopentadienyl-3,7-bisfluorenylbicyclo [3,3,1] nonane.

Specific examples of the transition metal compound of the general formula (I) of the present invention include, for example, 2,5-hexanediylidenebis (dicyclopentadienylzirconium dichloride), 2,5-hexanediylidenebis (dicyclopentadienyl) Zirhafnium dichloride), 2,5-hexanediylidenebis (dicyclopentadienylzirconium dimethyl), 2,5-hexanediylidenebis (dicyclopentadienylhafnium dimethyl), 2,5-hexanediylidenebis [ (Cyclopentadienyl-3-methylcyclopentadienyl) zirconium dichloride], 2,5-hexanediylidenebis [(cyclopentadienyl-3-methylcyclopentadienyl) hafnium dichloride], 2,5-hexane Diylidenebis [(cyclopentadienyl-3-methylcyclopentadienyl) zirco Dimethyl], 2,5-hexanediylidenebis [(cyclopentadienyl-3-
Methylcyclopentadienyl) hafnium dimethyl],
2,5-hexanediylidenebis [(cyclopentadienyl-1-indenyl) zirconium chloride], 2,5-
Hexanediylidenebis [(cyclopentadienyl-1
-Indenyl) hafnium dichloride], 2,5-hexanediylidenebis [(cyclopentadienyl-1-indenyl) zirconium dimethyl], 2,5-hexanediylidenebis [(cyclopentadienyl-1-indenyl) hafnium Dimethyl], 2,5-hexanediylidenebis [(cyclopentadienyl-9-fluorenyl) zirconium chloride], 2,5-hexanediylidenebis [(cyclopentadienyl-9-fluorenyl) hafnium dichloride], 2 5,5-hexanediylidenebis [(cyclopentadienyl-9-fluorenyl) zirconium dimethyl], 2,5-hexanediylidenebis [(cyclopentadienyl-9-fluorenyl) hafnium dimethyl], 1,4-cyclohexane Diylidenebis (dicyclopentadienyl zirconium dic Lido),
1,4-cyclohexanediylidenebis (dicyclopentadienylhafnium dichloride), 1,4-cyclohexanediylidenebis (dicyclopentadienylzirconium dimethyl), 1,4-cyclohexanediylidenebis (dicyclopentadienyl) Hafnium dimethyl), 1,4
-Cyclohexanediylidenebis [(cyclopentadienyl-3-methylcyclopentadienyl) zirconium dichloride], 1,4-cyclohexanediylidenebis [(cyclopentadienyl-3-methylcyclopentadienyl) hafnium dichloride] 1,4-cyclohexanediylidenebis [(cyclopentadienyl-3-methylcyclopentadienyl) zirconium dimethyl], 1,
4-cyclohexanediylidenebis [(cyclopentadienyl-3-methylcyclopentadienyl) hafnium dimethyl], 1,4-cyclohexanediylidenebis [(cyclopentadienyl-1-indenyl) zirconium dichloride], 1, 4-cyclohexanediylidenebis [(cyclopentadienyl-1-indenyl) hafnium dichloride], 1,4-cyclohexanediylidenebis [(cyclopentadienyl-1-indenyl) zirconium dimethyl], 1,4-cyclohexanediiy Ridenbis [(cyclopentadienyl-1-indenyl) hafnium dimethyl], 1,4-cyclohexanediylidenebis [(cyclopentadienyl-9-fluorenyl) zirconium dichloride], 1,4-cyclohexanediylidenebis [( Cyclopentadienyl-9- Fluorenyl) hafnium dichloride], 1,4-cyclohexanediylidenebis [(cyclopentadienyl-9-fluorenyl)
Zirconium dimethyl], 1,4-cyclohexanediylidenebis [(cyclopentadienyl-9-fluorenyl) hafnium dimethyl], bicyclo [3,3,0] octane-3,7-diylidenebis (dicyclopentadienylzirconium dichloride ), Bicyclo [3,3,0] octane-3,7-diylidenebis (dicyclopentadienylhafnium dichloride), bicyclo [3,3,0] octane-3,7
-Diylidenebis (dicyclopentadienylzirconium dimethyl), bicyclo [3,3,0] octane-3,7-diylidenebis (dicyclopentadienylhafnium dimethyl), bicyclo [3,3,0] octane-3,7 -Diylidenebis [(cyclopentadienyl-3-methylcyclopentadienyl) zirconium dichloride)], bicyclo [3,
3,0] octane-3,7-diylidenebis [(cyclopentadienyl-3-methylcyclopentadienyl) hafnium dichloride)], bicyclo [3,3,0] octane-3,7-
Diylidenebis [(cyclopentadienyl-3-methylcyclopentadienyl) zirconium dimethyl)], bicyclo [3,3,0] octane-3,7-diylidenebis [(cyclopentadienyl-3-methylcyclopentadienyl) ) Hafnium dimethyl)], bicyclo [3,3,0] octane-3,7-diylidenebis [(cyclopentadienyl-1-indenyl) zirconium dichloride)], bicyclo [3,3,0] octane-3,7 -Diylidenebis [(cyclopentadienyl-1-indenyl) hafnium dichloride)], bicyclo [3,3,0] octane-3,7-diylidenebis [(cyclopentadienyl-1-indenyl) zirconium dimethyl)], bicyclo [3,3,0] octane-3,7-diylidenebis [(cyclopentadienyl-1
-Indenyl) hafnium dimethyl)], bicyclo [3,
3,0] Octane-3,7-diylidenebis [(cyclopentadienyl-9-fluorenyl) zirconium dichloride)], bicyclo [3,3,0] octane-3,7-diylidenebis [(cyclopentadienyl-9 -Fluorenyl) hafnium dichloride)), bicyclo [3,3,0] octane-3,7-diylidenebis [(cyclopentadienyl-9
-Fluorenyl) zirconium dimethyl)], bicyclo [3,3,0] octane-3,7-diylidenebis [(cyclopentadienyl-9-fluorenyl) hafnium dimethyl)], bicyclo [3,3,1] nonane-3 , 7-Diylidenebis (dicyclopentadienyl zirconium dichloride), bicyclo [3,3,1] nonane-3,7-diylidenebis (dicyclopentadienylhafnium dichloride), bicyclo [3,3,1] nonane-3 , 7-Diylidenebis (dicyclopentadienylzirconium dimethyl), bicyclo [3,3,1] nonane-3,7-diylidenebis (dicyclopentadienylhafnium dimethyl), bicyclo [3,3,1]
Nonane-3,7-diylidenebis [(cyclopentadienyl-3-methylcyclopentadienyl) zirconium dichloride)], bicyclo [3,3,1] nonane-3,7-diylidenebis [(cyclopentadienyl-3 -Methylcyclopentadienyl) hafnium dichloride)), bicyclo [3,3,1] nonane-3,7-diylidenebis [(cyclopentadienyl-3-methylcyclopentadienyl) zirconium dimethyl)], bicyclo [3 , 3,1) nonane-3,7-
Diylidenebis [(cyclopentadienyl-3-methylcyclopentadienyl) hafnium dimethyl)], bicyclo [3,3,1] nonane-3,7-diylidenebis [(cyclopentadienyl-1-indenyl) zirconium dichloride) ], Bicyclo [3,3,1] nonane-3,7-diylidenebis [(cyclopentadienyl-1-indenyl) hafnium dichloride)], bicyclo [3,3,1] nonane-3,7
-Diylidenebis [(cyclopentadienyl-1-indenyl) zirconium dimethyl)], bicyclo [3,3,
1] nonane-3,7-diylidenebis [(cyclopentadienyl-1-indenyl) hafnium dimethyl)], bicyclo [3,3,1] nonane-3,7-diylidenebis [(cyclopentadienyl-9-fluorenyl) ) Zirconium dichloride)), bicyclo [3,3,1] nonane-3,7-diylidenebis [(cyclopentadienyl-9-fluorenyl)
Hafnium dichloride)], bicyclo [3,3,1] nonane-3,7-diylidenebis [(cyclopentadienyl-9
-Fluorenyl) zirconium dimethyl)], bicyclo [3,3,1] nonane-3,7-diylidenebis [(cyclopentadienyl-9-fluorenyl) hafnium dimethyl)], 1,4-cyclohexanediylidenebis [(tetra Methylcyclopentadienyl-9-fluorenyl) zirconium dichloride], 1,4-cyclohexanediylidenebis [(tetramethylcyclopentadienyl-9-
Fluorenyl) hafnium dichloride], 1,4-cyclohexanediylidenebis [(tetramethylcyclopentadienyl-9-fluorenyl) zirconium dimethyl], 1,4-cyclohexanediylidenebis [(tetramethylcyclopentadienyl-9- Fluorenyl) hafnium dimethyl], 1,4-cyclohexanediylidenebis [(cyclopentadienyl-2,7-di-t-butyl-
9-fluorenyl) zirconium dichloride], 1,4-
Cyclohexanediylidenebis [(cyclopentadienyl-2,7-di-t-butyl-9-fluorenyl) hafnium dichloride], 1,4-cyclohexanediylidenebis [(cyclopentadienyl-2,7-di- t-butyl-
9-fluorenyl) zirconium dimethyl], 1,4-cyclohexanediylidenebis [(cyclopentadienyl-2,7-di-t-butyl-9-fluorenyl) hafnium dimethyl], 1,4-cyclohexanediylidenebis [ (Tetramethylcyclopentadienyl-2,7-di-t
-Butyl-9-fluorenyl) zirconium dichloride], 1,4-cyclohexanediylidenebis [(tetramethylcyclopentadienyl-2,7-di-t-butyl-
9-fluorenyl) hafnium dichloride], 1,4-cyclohexanediylidenebis [(tetramethylcyclopentadienyl-2,7-di-t-butyl-9-fluorenyl) zirconium dimethyl], 1,4-cyclohexanediylidene Bis [(tetramethylcyclopentadienyl-
2,7-di-t-butyl-9-fluorenyl) hafnium dimethyl], 2,4-pentanediylidenebis [(cyclopentadienyltetramethylcyclopentadienyl) zirconium dichloride], 2,4-pentanediylidene Bis [(cyclopentadienyltetramethylcyclopentadienyl) hafnium dichloride], 2,4-pentanediylidenebis [(cyclopentadienyltetramethylcyclopentadienyl) zirconium dimethyl], 2,4-
Pentanedylidenebis [(cyclopentadienyltetramethylcyclopentadienyl) hafnium dimethyl], 2,5-hexanediylidenebis [(cyclopentadienyltetramethylcyclopentadienyl) zirconium dichloride], 2,5- Hexanediylidenebis [(cyclopentadienyltetramethylcyclopentadienyl) hafnium dichloride], 2,5-hexanediylidenebis [(cyclopentadienyltetramethylcyclopentadienyl) zirconium dimethyl], 2,5- Hexanediylidenebis [(cyclopentadienyltetramethylcyclopentadienyl) hafnium dimethyl],
2,5-cyclohexanediylidenebis [(cyclopentadienyltetramethylcyclopentadienyl) zirconium dichloride], 2,5-cyclohexanediylidenebis [(cyclopentadienyltetramethylcyclopentadienyl) hafnium dichloride], 2,5-cyclohexanediylidenebis [(cyclopentadienyltetramethylcyclopentadienyl) zirconium dimethyl],
2,5-cyclohexanediylidenebis [(cyclopentadienyltetramethylcyclopentadienyl) hafnium dimethyl], 3,7-bicyclo [3,3,0] octanediylidenebis [(cyclopentadienyltetramethylcyclo Pentadienyl) zirconium dichloride], 3,7-bischloro [3,3,0] octanediylidenebis [(cyclopentadienyltetramethylcyclopentadienyl) hafnium dichloride], 3,7-bicyclo [3,3 , 0] octanediylidenebis [(cyclopentadienyltetramethylcyclopentadienyl) zirconium dimethyl], 3,7
-Bicyclo [3,3,0] octanediylidenebis [(cyclopentadienyltetramethylcyclopentadienyl)
Hafnium dimethyl], 3,7-bicyclo [3,3,1] nonandylidenebis [(cyclopentadienyltetramethylcyclopentadienyl) zirconium dichloride], 3,
7-bicyclo [3,3,1] nonaneylidenebis [(cyclopentadienyltetramethylcyclopentadienyl) hafnium dichloride], 3,7-bicyclo [3,3,1] nonaneylidenebis [(cyclo Pentadienyltetramethylcyclopentadienyl) zirconium dimethyl], 3,7-
Bicyclo [3,3,1] nonandiylidenebis [(cyclopentadienyltetramethylcyclopentadienyl) hafnium dimethyl], 2,4-pentanediylidenebis [(methylcyclopentadienyl-9-fluorenyl)
Zirconium dichloride], 2,4-pentanediylidenebis [(methylcyclopentadienyl-9-fluorenyl) hafnium dichloride], 2,4-pentanediylidenebis [(methylcyclopentadienyl-9-fluorenyl) zirconium dimethyl ], 2,4-pentanediiylidenebis [(methylcyclopentadienyl-9-fluorenyl) hafnium dimethyl], 2,5-hexanediylidenebis [(methylcyclopentadienyl-9-fluorenyl) zirconium dichloride], 2,5-hexanediylidenebis [(methylcyclopentadienyl-9-fluorenyl) hafnium dichloride], 2,5-hexanediylidenebis [(methylcyclopentadienyl-9-
Fluorenyl) zirconium dimethyl], 2,5-hexanediylidenebis [(methylcyclopentadienyl-9
-Fluorenyl) hafnium dimethyl], 1,4-cyclohexanediylidenebis [(methylcyclopentadienyl-9-fluorenyl) zirconium dichloride],
4-cyclohexanediylidenebis [(methylcyclopentadienyl-9-fluorenyl) [(cyclopentadienyltetramethylcyclopentadienyl) hafnium dichloride], 1,4-cyclohexanediylidenebis [(methylcyclopentadienyl -9-fluorenyl)
Zirconium dimethyl], 1,4-cyclohexanediylidenebis [(methylcyclopentadienyl-9-fluorenyl) hafnium dimethyl], 3,7-bicyclo [3,3,
0] octanediylidenebis [(methylcyclopentadienyl-9-fluorenyl) zirconium dichloride], 3,7-bicyclo [3,3,0] octanediylidenebis [(methylcyclopentadienyl-9-fluorenyl)
Hafnium dichloride], 3,7-bicyclo [3,3,0] octanediylidenebis [(methylcyclopentadienyl-
9-fluorenyl) zirconium dimethyl], 3,7-bicyclo [3,3,0] octanediylidenebis [(methylcyclopentadienyl-9-fluorenyl) hafnium dimethyl], 3,7-bicyclo [3,3, 1] nonanediylidenebis [(methylcyclopentadienyl-9-fluorenyl) zirconium dichloride], 3,7-bicyclo [3,3,
1] nonaneylidenebis [(methylcyclopentadienyl-9-fluorenyl) hafnium dichloride], 3,7
-Bicyclo [3,3,1] nonandylidenebis [(methylcyclopentadienyl-9-fluorenyl) zirconiumdimethyl], 3,7-bicyclo [3,3,1] nonandylidenebis [(methylcyclopentane Dienyl-9-fluorenyl) hafnium dimethyl].

These compounds can be synthesized by the above reaction formula, and specifically, can be synthesized by a method similar to the examples of the present invention.

In the polymerization, as the co-catalyst used together with the transition metal compound of the present invention, in addition to known aluminoxanes, described in JP-A-1-501950 and JP-A-1-502036 described above. Such boron compounds can be used as a co-catalyst, but aluminoxanes are preferred from the viewpoint of activity and availability.

General formulas for aluminoxanes Wherein R is a hydrocarbon group having 1 to 3 carbon atoms and n is an integer of 2 or more. In particular, methyl is aluminoxane in which R is a methyl group and n is 5 or more, preferably 10 or more. Is used. The above aluminoxanes may be mixed with some alkylaluminum compounds.

A method for producing the above aluminoxanes is known, for example, a method of adding a trialkylaluminum to a salt containing water of crystallization (eg, copper sulfate hydrate, magnesium chloride hydrate) in a hydrocarbon bath medium to cause a reaction, or Examples thereof include a method of directly reacting a trialkylaluminum with water in an organic compound solvent.

The novel transition metal compound and / or cocatalyst in the present invention may be used as it is on a known carrier that supports a Ziegler-type catalyst such as SiO ₂ , Al ₂ O ₃ , and MgCl ₂ .

The use ratio of the aluminoxane to the transition metal compound in the present invention is 10 to 10,000 mol times, usually 50 to 5000.
It is molar times.

The polymerization method and polymerization conditions carried out by the method of the present invention are not particularly limited, and a known method carried out in the polymerization of α-olefin is used, and a solvent polymerization method using an inert hydrocarbon catalyst, or a substantially inert carbon method is used. A bulk polymerization method without a hydride medium, a gas phase polymerization method can also be used, and the polymerization temperature is −100 to 200 ° C., and the polymerization pressure is normal pressure to 100 kg / cm ²
It is common to do with. Preferably −50 ° C. to 100 ° C.,
Normal pressure-50 kg / cm ² .

As the hydrocarbon catalyst used in the polymerization, for example, in addition to saturated hydrocarbons such as butane, pentane, hexane, heptane, octane, nonane, decane, cyclopentane and cyclohexane, benzene, toluene, and aromatic hydrocarbons such as xylene Can be used.

As the α-olefin used in the polymerization reaction,
Propylene, 1-butene, 4-methyl-1-pentene,
Examples thereof include α-olefins having 3 to 25 carbon atoms such as 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, and 1-octadecene.

In the present invention, not only homopolymerization of α-olefin, but also, for example, propylene and ethylene, propylene and 1-
It can also be used when producing a copolymer of ethylene or α-olefin having about 2 to 25 carbon atoms such as butene.

〔Example〕

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

Example 1 Synthesis of transition metal compound [1,4-biscyclopentadienylidenecyclohexane] In a 500 ml glass four-necked flask, 15 g of 1,4-cyclohexanedione and 36 g of cyclopentanediene were added to methanol 20
Dissolved in 0 ml. 34 ml of pyrrolidine is added to this solution at 0 ° C for 30 minutes.
After completion of the dropwise addition, the temperature was raised to room temperature, and stirring was continued for 30 minutes. The reaction was stopped by adding 28 ml of acetic acid,
The solid was filtered, washed with methanol, and dried to obtain 39 g of brown 1,4-biscyclopentadienylitenecyclohexane.

[1,1,4,4-Tetracyclopentadienylidenecyclohexane] Cyclopentanediene is dissolved in 150 ml of tetrahydrofuran by dissolving 6.6 g of cyclopentanediene in a 500 ml four-necked flask sufficiently purged with nitrogen, and lithiated with methyllithium to form cyclopentanedienyl. A suspension of lithium in tetrahydrofuran was obtained. A solution obtained by diluting 10.4 g of 1,4-biscyclopentanedenylidenecyclohexane synthesized above with 200 ml of tetrahydrofuran was added to this suspension at −10 ° C. and added dropwise over 30 minutes. After the completion of the dropwise addition, the reaction temperature was raised to room temperature, and the stirring was further continued for 15 hours. The reaction was stopped by charging 200 ml of 3.6% hydrochloric acid, and the ether layer was evaporated to dryness and dried with methanol to obtain 9.2 g of white 1,1,4,4-tetracyclopentadienylidenecyclohexane. Was. The analytical values of this compound are shown below.

Elemental analysis value C ₂₆ H ₂₈ CH Calculated value (%) 91.76 8.24 Observed value (%) 90.85 8.10 [1,4-cyclohexanediylidenebis [(dicyclopentadienyl zirconium dichloride)] Four-necked flask sufficiently purged with nitrogen The above synthesized 1,1,
4,4-tetracyclopentadienylidenecyclohexane
3.6 g was dissolved in 200 ml of tetrahydrofuran and reacted with n-butyllithium to prepare a tetralithium salt of 1,1,4,4-tetracyclopentadienylidenecyclohexane. Next, 5.0 g of zirconium tetrachloride was placed in a 500 ml glass flask which was sufficiently purged with nitrogen, and 100 ml of methylene chloride.
Was suspended. The 1,1,4,
Introducing 300 ml of a tetralithium salt of 4-tetracyclopentadienylidenecyclohexane in methylene chloride,
After stirring at −78 ° C. for 4 hours, the temperature was raised to room temperature, and the reaction was continued at that temperature for another 15 hours. The red-brown solution containing a white precipitate of lithium chloride was filtered off, concentrated, and cooled at -30 ° C for 24 hours to give 1,4-cyclohexanediylidenebis (dicyclopentadienylzirconium dichloride) 1.
2 g were obtained.

 The elemental analysis values of the product are shown below.

Cwt% Hwt% Clwt% Zrwt% Analytical value 48.63 3.91 20.98 26.33 Calculated value 47.27 3.64 21.45 27.64 Polymerization test After replacing 2 l of SUS autoclave with nitrogen, 1 toluene was charged, and the above prepared 1,4-cyclohexanediylidenebis ( 5.0 mg of dicyclopentadienyl zirconium dichloride) and 1.0 g of methylaluminoxane manufactured by Tosoh Akzo (polymerization degree: 17.7) were added. Add ethylene to the system
The polymerization was carried out at 20 ° C. for 1 hour while maintaining the pressure at 5 kg / cm ² G.

After the polymerization, the slurry was taken out and filtered. Drying yielded 82.4 g of polyethylene powder.

Example 2 Synthesis of transition metal compound [1,4-dicyclopentadienyl-1,4-bisfluorenylcyclohexane] Fluorene 1 was placed in a 500 ml glass flask purged with nitrogen.
6.6 g was dissolved in tetrahydrofuran and lithiated with methyllithium to obtain a fluorenyllithium tetrahydrofuran solution. A solution obtained by diluting 10.4 g of 1,4-biscyclopentadienylidenecyclohexane synthesized in Example 1 with 200 ml of tetracodrofuran was added to this solution.
It was added dropwise at 10 ° C. over 30 minutes. After the completion of the dropwise addition, the reaction temperature was raised to room temperature, and the stirring was further continued for 15 hours. The reaction was stopped by charging 200 ml of 3.6% hydrochloric acid, and the resulting solid was separated by filtration, washed with ether, and dried to give 1,4-dicyclopentadienyl-1,4-bisfluene as a white powder. 18.5 g of oleenylcyclohexane was obtained. The analytical values of this compound are shown below.

Elemental analysis C ₄₂ H ₃₆ C H Calculated (%) 93.33 6.67 Found (%) indicated 93.19 6.54 ¹ H-NMR Figure 1.

[1,4-cyclohexanediylidenebis [(dicyclopentadienyl-9-fluorenyl) zirconium dichloride] The above synthesized 1,4-biscyclopentadienyl 1,4-bifluorenylcyclohexane is converted to n-butyllithium. Thus, a tetralithium salt of 1.4-biscyclopentadienyl-1,4-bifluorenylcyclohexane was prepared. Next, 6.1 g of zirconium tetrachloride in methylene chloride was placed in a 500 ml glass flask purged with nitrogen.
It was suspended in 100 ml. Dissolved in this suspension at -78 ° C
300 ml of a 0.013 mol solution of tetralithium salt of 1,4-biscyclopentadienyl-1,4-bifluorenylcyclohexane in methylene chloride were introduced. After stirring at −78 ° C. for 4 hours, the temperature was raised to room temperature, and the reaction was continued at that temperature for another 15 hours. The red-brown solution containing a white precipitate of lithium chloride was filtered off, concentrated, and cooled at -30 ° C for 24 hours to give orange 1,4-cyclohexanediylidenebis [(cyclopentadienyl-9-fluorenyl) zirconium chloride. 3.1 g was obtained.

 The elemental analysis values of the product are shown below.

Cwt% Hwt% Clwt% Zrwt% Analytical value 58.6 3.72 16.5 21.2 Calculated value 58.1 3.78 16.7 20.4 The measurement result of the compound ¹ H-NMR spectrum is shown in FIG.

Polymerization test 2 l of a SUS autoclave were replaced with nitrogen, and then charged with 1 of toluene. 3.0 mg of the above-prepared 1,4-cyclohexanediylidenebis [(dicyclopentadienyl-9-fluorenyl) zirconium dichloride], Tosoh Akzo 0.4 g of a methylaluminoxane (polymerization degree: 17.7) manufactured by the Company was added.
Add propylene and maintain the system at 3kg / cm ² G at 20 ℃
For 1 hour.

After the polymerization, the slurry was taken out and filtered. After drying, 100.0 g of syndioctatic polypropylene powder was obtained. Further, the toluene soluble in the filtrate is distilled off under reduced pressure to remove toluene.
1 g was obtained.

The ultimate precision (hereinafter abbreviated as η) measured with a 135 ° C. tetralin solution of the powder was 0.60 dl / g, and the molecular weight distribution index (Mw / Mn) measured by GPC (gel permeation chromatography) was 2.7. Was. Measure ¹³ C-NMR, about
The syndiotactic pentad fraction determined from the peak attributed to the methyl group at 20.2 ppm was 0.91.

Example 3 Synthesis of Transition Metal Compound 5 g of 1,4-biscyclopentadienyl-1,4-bifluorenylcyclohexane synthesized in Example 1 was lithiated with n-butyllithium to give 1,4-bis. The tetralithium salt of biscyclopentadienyl-1,4-bifluorenylcyclohexane was prepared.

Next, a mixture of 2.2 g of zirconium tetrachloride and 3.0 g of hafnium tetrachloride was suspended in 100 ml of a methylene chloride solution in a 500-ml glass flask sufficiently purged with nitrogen. This suspension was mixed with 1,4-biscyclopentadienyl-1,4- synthesized above.
300 ml of a methylene chloride solution of tetralithium salt of bifluorenylcyclohexane was charged at -78 ° C, and the mixture was stirred at -78 ° C for 4 hours, heated to room temperature, and further reacted at room temperature for 15 hours.

Filtering the reddish-brown solution containing a white precipitate of lithium chloride,
The filtrate was concentrated and cooled at −30 ° C. for 24 hours to precipitate a solid. After filtration and drying, 2.6 g of an orange solid was obtained.

 The elemental analysis of the orange solid was 52.16% for C, 3.21% for Hf, 14.33% for Cl, 9.04% for Zr, and 20.50% for Hr.

Polymerization test After replacing the 2 l SUS autoclave with nitrogen, 2.0 mg of the orange solid synthesized above and 0.2 g of methylaluminoxane were added, and then 400 g of liquefied propylene was charged into the autoclave and polymerized at 50 ° C for 1 hour. .

Unreacted propylene was purged, and the resulting polymer was dried under reduced pressure to obtain 116.2 g of syndiotactic polypropylene powder.

The η of this powder was 0.93 dl / g, (Mw / Mn) was 6.8, and the syndiotactic pentad fraction was 0.82.

[Brief description of the drawings]

FIG. 1 shows the ¹ H-NMR measurement results of 1,4-dicyclopentadienyl-1,4-bisfluorenylcyclohexane obtained in Example 1 of the present invention. FIG. 2 shows the result of ¹ H-NMR measurement of 1,4-cyclohexanediylidenebis [(cyclopentadienyl-9-fluorenyl) zirconium dichloride] obtained in Example 1 of the present invention. [Effect of the Invention] The transition metal compound of the present invention is a novel transition metal compound having two transition metals in one molecule, and is useful for α-olefin polymerization.

Continuation of front page (58) Field surveyed (Int.Cl. ⁶ , DB name) C07F 17/00 C07C 13/15 C07C 13/465 C07C 13/567

Claims (2)

(57) [Claims] 1. The compound of the general formula (I) (However, A ¹ , A ² , A ³ , A ⁴ represent a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, a fluorenyl group, a substituted fluorenyl group,
A ⁵ represents a hydrocarbon diylidene group having 4 to 30 carbon atoms. Then, each of A ¹ and A ^2, A ³ and A ⁴ are bonded to the same carbon in the A ^5, results in a crosslinked structure. R ¹ and R ² are a halogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group,
R ¹ and R ² may be the same or different from each other.
M ¹ and M ² are selected from titanium, zirconium, and hafnium, and may be the same or different from each other. The novel transition metal compound represented by). 2. A compound of the general formula (II) (However, A ¹ , A ² , A ³ , A ⁴ represent a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, a fluorenyl group, a substituted fluorenyl group,
A ⁵ represents a hydrocarbon diylidene group having 4 to 30 carbon atoms. Then, A ¹ and A ^2, A ³ and A ⁴ are attached to the same carbon in the A ^5, respectively. An organic compound represented by).