JPH05178874A - New transition metallic compound and its use - Google Patents

Abstract

PURPOSE:To obtain a new compound, excellent in polymerization activity and useful as a catalyst, etc., for polymerizing olefins. CONSTITUTION:The objective compound expressed by formula I [M is group IVB transition metal; Cp<1> and Cp<2> are (substituted)cyclopentadienyl, etc.; R<1> is (halogen-substituted)alkyl, aryl, etc.; X is SO3R<1>, R<1>, OR<1>, etc.], e.g. bis (cyclopentadienyl)-zirconium(IV)-bis(methanesulfonato). Furthermore, the compound expressed by formula I is obtained by reacting a compound expressed by formula II (Y<1> is halogen; Y<2> is R<1>, OR<1>, halogen, etc.) and a compound expressed by formula III (Z is Ag, Na, K, etc.) in a solvent such as hexane.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel transition metal compound and its use. More specifically, the present invention relates to a novel transition metal compound which can be a catalyst component for olefin polymerization having excellent polymerization activity, and the transition metal compound. The present invention relates to the following catalyst components.

[0002]

BACKGROUND OF THE INVENTION Conventionally, a method for producing an α-olefin polymer has been carried out in the presence of a titanium catalyst comprising a titanium compound and an organoaluminum compound or a vanadium catalyst comprising a vanadium compound and an organoaluminum compound. , A method of copolymerizing ethylene and α-olefin is known.

Ethylene, which is generally obtained with titanium-based catalysts
The α-olefin copolymer had a broad molecular weight distribution and composition distribution, and was inferior in transparency, surface non-adhesiveness and mechanical properties. In addition, ethylene obtained with vanadium-based catalysts
The α-olefin copolymer has a narrower molecular weight distribution and composition distribution than that obtained with a titanium-based catalyst, and its transparency, surface non-adhesiveness and mechanical properties are considerably improved, but these performances are required. There is still a need for catalysts which are not sufficient for the intended use, and further provide α-olefin polymers having improved performance, particularly ethylene / α-olefin copolymers.

On the other hand, as a new Ziegler type olefin polymerization catalyst, a catalyst comprising a zirconium compound and aluminoxane has been proposed in recent years. For example, JP-A-58-19309, JP-A-60-35006, JP-A-60-35007, and JP-A-60-35.
JP-A-61-130314 and JP-A-2-41303 disclose transition metal compounds having a pentadienyl group such as a cyclopentadienyl group as a ligand, an alkyl group and / or a halogen atom. It is described that the catalyst system in which the metallocene compound and the aluminoxane are combined is highly active in the polymerization of α-olefin, and the properties of the obtained polymer are excellent.

Also, the Journal of Organometallic Chemis
try, 363 (1989) C12-C14 contains Cp ₂ Zr (CF ₃ SO ₃ ) ₂
(THF) and [Cp ₂ Zr (CF ₃ SO ₃ ) (bipy)] ⁺ CF ₃ SO
₃ ^- are disclosed, the two compounds olefin polymerization activity is low compared to the cyclopentadienyl compound as described above. Further, when the concentration of aluminoxane is low, the olefin polymerization activity is remarkably low.

Under these circumstances, it is desired to develop a new transition metal compound which is excellent in olefin polymerization activity and can be an olefin polymerization catalyst component having excellent properties of the obtained olefin.

[0007]

An object of the present invention is to provide a novel transition metal compound which can be an olefin polymerization catalyst component having excellent olefin polymerization activity, and to provide a catalyst component comprising the transition metal compound. I am trying.

[0008]

SUMMARY OF THE INVENTION The transition metal compound according to the present invention is a novel transition metal compound represented by the following general formula [I].

[0009]

[Chemical 3]

(In the formula [I], M is a transition metal of Group IVB, Cp ¹ and Cp ² are groups having a cyclopentadienyl skeleton, and these groups having a cyclopentadienyl skeleton are substituents. Cp ¹ and Cp ² may be bonded to each other through an alkylene group, a substituted alkylene group, a silylene group or a substituted silylene group, wherein R ¹ is substituted with an alkyl group or a halogen atom. Is an alkyl group, an aryl group, an aryl group substituted with a halogen atom or an alkyl group, and X is SO ₃ R ¹ , R ¹ , OR ¹ , N
R ¹ _n, a ^{_{S (O) q R 1,}} SiR 1 3, P (O) q R 1 3 or a halogen atom, n is 1, 2 or 3, q
Is 0, 1 or 2. ) Such a transition metal compound can be used as a catalyst for olefin polymerization in combination with an organoaluminum oxy compound.

[0011]

DETAILED DESCRIPTION OF THE INVENTION The novel transition metal compound according to the present invention and its use are specifically described below.

The transition metal compound according to the present invention is a novel transition metal compound represented by the following general formula [I].

[0013]

[Chemical 4]

(In the formula [I], M is a Group IVB transition metal, Cp ¹ and Cp ² are groups having a cyclopentadienyl skeleton, and these groups having a cyclopentadienyl skeleton are substituents. Cp ¹ and Cp ² may be bonded to each other through an alkylene group, a substituted alkylene group, a silylene group or a substituted silylene group, wherein R ¹ is substituted with an alkyl group or a halogen atom. Is an alkyl group, an aryl group, an aryl group substituted with a halogen atom or an alkyl group, and X is SO ₃ R ¹ , R ¹ , OR ¹ , N
R ¹ _n, a ^{_{S (O) q R 1,}} SiR 1 3, P (O) q R 1 3 or a halogen atom, n is 1, 2 or 3, q
Is 0, 1 or 2. ) In the above formula [I], M
Is a transition metal of Group IVB of the periodic table, and specifically,
Zirconium, titanium or hafnium.

Cp ¹ and Cp ² are groups having a cyclopentadienyl skeleton, and examples of the group having a cyclopentadienyl skeleton include a cyclopentadienyl group, a methylcyclopentadienyl group and an ethylcyclopentadienyl group. Group, n-butylcyclopentadienyl group, dimethylcyclopentadienyl group, trimethylcyclopentadienyl group, pentamethylcyclopentadienyl group and other alkyl-substituted cyclopentadienyl groups, indenyl groups, fluorenyl groups, etc. can do.

Of these, alkyl-substituted cyclopentadienyl groups and indenyl groups are preferred. These groups having a cyclopentadienyl skeleton may be bonded via an alkylene group, a substituted alkylene group, a silylene group or a substituted silylene group.

Examples of the alkylene group include an ethylene group and a propylene group, examples of the substituted alkylene group include an isopropylidene group and diphenylmethylene group, and examples of the substituted silylene group include a dimethylsilylene group.

R ¹ is an alkyl group, an alkyl group substituted with a halogen atom, an aryl group, an aryl group substituted with a halogen atom or an alkyl group, and examples of the alkyl group include a methyl group, an ethyl group, a propyl group and an isopropyl group. Examples thereof include a group and a butyl group, which may be substituted with a halogen atom.

Examples of the aryl group include phenyl group and tolyl group.
Groups, etc., such as a halogen atom or an alkyl group.
It may be substituted with a group. X is SO₃R¹,
R¹, OR¹, NR¹ _n, S (O)_qR¹, SiR¹ ₃, P
(O) _qR¹ ₃Alternatively, it is a halogen atom and n is 1, 2 or
Or 3 and q is 0, 1 or 2.

Examples of the group represented by SO ₃ R ¹ include a methanesulfonato group, a p-toluenesulfonato group, a trifluoromethanesulfonato group, a benzenesulfonato group, a trimethylbenzenesulfonato group, and a triisopropylbenzenesulfonato group. , P-chlorobenzenesulfonato group, pentafluorobenzenesulfonato group and the like.

Examples of the group represented by OR ¹ include a methoxy group, an ethoxy group and a propoxy group. NR
Examples of the group represented by ¹ _n include a dimethylamide group and a diethylamide group.

Examples of the group represented by S (O) _q R ¹ include a methylmercapto group, a thiophenyl group, a methylsulfone group, and a methylsulfoxide group. The group represented by SiR ¹ _3, and the like trimethylsilyl group.

[0023] As the group represented by P (O) _q R ¹ ₃ are trimethylphosphine group, such as triphenyl phosphine groups. Halogen is fluorine, chlorine, bromine, iodine.

Such a transition metal compound represented by the general formula [I] is excellent in stability and, when used as an olefin polymerization catalyst together with an organoaluminum oxy compound or the like, has excellent olefin polymerization activity.

Specific examples of the transition metal compound represented by the above general formula [I] are shown below. Bis (cyclopentadienyl) -zirconium (IV) -bis (methanesulfonato), bis (cyclopentadienyl) -zirconium (I
V) -bis (p-toluenesulfonato), bis (cyclopentadienyl) -zirconium (IV) -bis (trifluoromethanesulfonato), bis (cyclopentadienyl)-
Zirconium (IV) -trifluoromethanesulfonatomonochloride, bis (cyclopentadienyl) -zirconium (IV) -bis (benzenesulfonato), bis (cyclopentadienyl) -zirconium (IV) -bis (2,4 , 6-
Trimethylbenzenesulfonato), bis (cyclopentadienyl) -zirconium (IV) -bis (2,4,6-triisopropylbenzenesulfonato), bis (cyclopentadienyl) -zirconium (IV) -bis (penta Fluorobenzenesulfonato), bis (cyclopentadienyl)-
Zirconium (IV) -benzenesulfonatomonochloride, bis (cyclopentadienyl) -zirconium (I
V) -2,4,6-Trimethylbenzenesulfonatomonochloride, bis (cyclopentadienyl) -zirconium (I
V) -2,4,6-triisopropylbenzenesulfonatomonochloride, bis (cyclopentadienyl) -zirconium (IV) -pentafluorobenzenesulfonatomonochloride, bis (cyclopentadienyl) -zirconium (I
V)-(Ethoxy) (trifluoromethanesulfonato) bis (methylcyclopentadienyl) -zirconium (I
V) -bis (trifluoromethanesulfonato), bis (methylcyclopentadienyl) -zirconium (IV) -trifluoromethanesulfonatomonochloride,

Bis (1,3-dimethylcyclopentadienyl) -zirconium (IV) -bis (trifluoromethanesulfonato), bis (1,3-dimethylcyclopentadienyl) -zirconium (IV) -trifluoromethanesulfo Natomonochloride, bis (1,3-dimethylcyclopentadienyl) -zirconium (IV)-(trifluoromethanesulfonato) (dimethylamide) bis (1,3-dimethylcyclopentadienyl) -zirconium (IV)- Bis (benzenesulfonato), bis (1,3-
Dimethylcyclopentadienyl) -zirconium (IV)-
Bis (p-toluenesulfonato), bis (1,3-dimethylcyclopentadienyl) -zirconium (IV) -bis (2,4,
6-trimethylbenzenesulfonato), bis (1,3-dimethylcyclopentadienyl) -zirconium (IV) -bis (2,4,6-triisopropylbenzenesulfonato), bis (1,3-dimethylcyclopenta) Dienyl) -zirconium (IV) -bis (pentafluorobenzenesulfonato),
Bis (1,3-dimethylcyclopentadienyl) -zirconium (IV) -benzenesulfonatomonochloride, bis (1,3-dimethylcyclopentadienyl) -zirconium (IV) -2,4,6-trimethylbenzene Sulfonatomonochloride, Bis (1,3-dimethylcyclopentadienyl) -zirconium (IV) -2,4,6-triisopropylbenzene Sulfonatomonochloride, Bis (1,3-dimethylcyclopentadienyl)- Zirconium (IV) -pentafluorobenzenesulfonatomonochloride, bis (1,3,5-trimethylcyclopentadienyl) -zirconium (IV) -bis (trifluoromethanesulfonato), bis (1,3,5-trimethyl Cyclopentadienyl) -zirconium (IV) -trifluoromethanesulfonatomonochloride,

Ethylene bis (indenyl) -zirconium (IV) -bis (trifluoromethane sulfonate), ethylene bis (indenyl) -zirconium (IV) -bis (methane sulfonate), ethylene bis (indenyl)-
Zirconium (IV) -bis (p-toluenesulfonato),
Ethylenebis (indenyl) -zirconium (IV) -bis (p-chlorobenzenesulfonato), ethylenebis (indenyl) -zirconium (IV) -trifluoromethanesulfonatomonochloride, ethylenebis (indenyl) -zirconium (IV)- Trifluoromethanesulfonatomonobromide, ethylenebis (indenyl) -zirconium (IV) -trifluoromethanesulfonatomonofluoride,
Ethylenebis (indenyl) -zirconium (IV) -trifluoromethanesulfonatomonoiodide, ethylenebis (indenyl) -zirconium (IV) -methanesulfonatomonochloride, ethylenebis (indenyl) -zirconium (IV) -p-toluenesulfo Nato monochlorid,

Ethylene bis (indenyl) -zirconium (IV)-(trifluoromethanesulfonato) methyl,
Ethylenebis (indenyl) -zirconium (IV)-(methanesulfonato) methyl, ethylenebis (indenyl)
-Zirconium (IV)-(trifluoromethanesulfonato) phenyl, ethylenebis (indenyl) -zirconium (IV)-(methanesulfonato) phenyl, ethylenebis (indenyl) -zirconium (IV)-(trifluoromethanesulfonato) methoxy , Ethylenebis (indenyl) -zirconium (IV)-(methanesulfonato) methoxy, ethylenebis (indenyl) -zirconium (I
V)-(trifluoromethanesulfonato) dimethylamide, ethylenebis (indenyl) -zirconium (IV)-
(Methanesulfonato) dimethylamide, ethylenebis (indenyl) -zirconium (IV)-(trifluoromethanesulfonato) methylmercapto, ethylenebis (indenyl) -zirconium (IV)-(methanesulfonato)
Methyl mercapto, ethylenebis (indenyl) -zirconium (IV)-(trifluoromethanesulfonato) thiophenyl, ethylenebis (indenyl) -zirconium (IV)-(methanesulfonato) thiophenyl, ethylenebis (indenyl) -zirconium (IV) -(Trifluoromethanesulfonato) methyl sulfone, ethylenebis (indenyl) -zirconium (IV)-(methanesulfonato) methylsulfone, ethylenebis (indenyl) -zirconium (IV)-(trifluoromethanesulfonato)
Methyl sulfoxide, ethylenebis (indenyl) -zirconium (IV)-(methanesulfonato) methyl sulfoxide, ethylenebis (indenyl) -zirconium (I
V)-(trifluoromethanesulfonato) trimethylsilyl, ethylenebis (indenyl) -zirconium (IV)-
(Methanesulfonato) trimethylsilyl, ethylenebis (indenyl) -zirconium (IV)-(trifluoromethanesulfonato) trimethylphosphine, ethylenebis (indenyl) -zirconium (IV)-(methanesulfonato) trimethylphosphine, ethylenebis (indenyl) ) -Zirconium (IV)-(trifluoromethanesulfonato) triphenylphosphine, ethylenebis (indenyl) -zirconium (IV)-(methanesulfonato) triphenylphosphine,

Ethylenebis (indenyl) -zirconium (IV) -bis (benzenesulfonato), ethylenebis (indenyl) -zirconium (IV) -bis (2,4,6-trimethylbenzenesulfonato), ethylenebis (indenyl) ) -Zirconium (IV) -bis (2,4,6-triisopropylbenzenesulfonate), ethylenebis (indenyl)
-Zirconium (IV) -bis (pentafluorobenzenesulfonato), ethylenebis (indenyl) -zirconium (IV) -benzenesulfonatomonochloride, ethylenebis (indenyl) -zirconium (IV) -2,4,6-trimethyl Benzenesulfonatomonochloride, ethylenebis (indenyl) -zirconium (IV) -2,4,6-triisopropylbenzenesulfonatomonochloride, ethylenebis (indenyl) -zirconium (IV) -pentafluorobenzenesulfonatomonochloride,

Ethylenebis (indenyl) -hafnium (IV) -bis (trifluoromethanesulfonato), ethylenebis (indenyl) -hafnium (IV) -bis (methanesulfonato), ethylenebis (indenyl) -hafnium (IV) -Bis (p-toluenesulfonato), ethylenebis (indenyl) -hafnium (IV) -bis (p-chlorobenzenesulfonato), ethylenebis (indenyl)-
Hafnium (IV) -trifluoromethanesulfonatomonochloride, ethylenebis (indenyl) -hafnium (I
V) -trifluoromethanesulfonatomonobromide, ethylenebis (indenyl) -hafnium (IV) -trifluoromethanesulfonatomonofluoride, ethylenebis (indenyl) -hafnium (IV) -trifluoromethanesulfonatomonoiodo, ethylenebis ( Indenyl) -hafnium (IV) -methanesulfonatomonochloride, ethylenebis (indenyl) -hafnium (IV) -p-toluenesulfonatomonochloride,

Ethylene bis (indenyl) -titanium (I
V) -bis (trifluoromethanesulfonato), ethylene bis (indenyl) -titanium (IV) -bis (methanesulfonato), ethylene bis (indenyl) -titanium (IV) -bis (p-toluenesulfonato), ethylene Bis (indenyl) -titanium (IV) -bis (p-chlorobenzenesulfonato), ethylenebis (indenyl) -titanium (IV) -trifluoromethanesulfonatomonochloride, ethylenebis (indenyl) -titanium (IV) -trifluoro Romethanesulfonatomonobromide, ethylenebis (indenyl) -titanium (IV) -trifluoromethanesulfonatomonofluoride, ethylenebis (indenyl) -titanium (IV) -trifluoromethanesulfonatomonoiodine, ethylenebis (indenyl) -titanium (IV) -Methanesulfonatomonochloride, ethylenebis (indenyl) -thi Emissions (IV)-p-toluenesulfonate monochloride,

Dimethylsilylbis (indenyl) -zirconium (IV) -bis (trifluoromethanesulfonato), dimethylsilylbis (indenyl) -zirconium (IV) -bis (methanesulfonato), dimethylsilylbis (indenyl) -zirconium (IV) -bis (p-toluenesulfonato), dimethylsilylbis (indenyl)
-Zirconium (IV) -bis (p-chlorobenzenesulfonato), dimethylsilylbis (indenyl) -zirconium (IV) -trifluoromethanesulfonatomonochloride, dimethylsilylbis (indenyl) -zirconium (IV) -trifluoromethanesulfone Natomonobromide,
Dimethylsilylbis (indenyl) -zirconium (I
V) -trifluoromethanesulfonatomonofluoride, dimethylsilylbis (indenyl) -zirconium (IV) -trifluoromethanesulfonatomonoiodide, dimethylsilylbis (indenyl) -zirconium (IV) -methanesulfonatomonochloride, dimethylsilyl Bis (indenyl) -zirconium (IV) -p-toluenesulfonatomonochloride,

Dimethylsilylbis (indenyl) -zirconium (IV) -bis (benzenesulfonato), dimethylsilylbis (indenyl) -zirconium (IV) -bis (2,4,6-trimethylbenzenesulfonato), dimethylsilyl Bis (indenyl) -zirconium (IV) -bis (2,
4,6-triisopropylbenzenesulfonato), dimethylsilylbis (indenyl) -zirconium (IV) -bis (pentafluorobenzenesulfonato), dimethylsilylbis (indenyl) -zirconium (IV) -benzenesulfonatomonochloride, Dimethylsilylbis (indenyl) -zirconium (IV) -2,4,6-trimethylbenzenesulfonatomonochloride, dimethylsilylbis (indenyl) -zirconium (IV) -2,4,6-triisopropylbenzenesulfonatomonochloride , Dimethylsilylbis (indenyl) -zirconium (IV) -pentafluorobenzenesulfonatomonochloride, diphenylsilylbis (indenyl) -zirconium (IV) -bis (benzenesulfonato), diphenylsilylbis (indenyl) -zirconium (IV ) -Bis (2,4,6-trimethyl) Nzensuruhonato), diphenyl silyl bis (indenyl) - zirconium (IV) - bis (2,4,6-triisopropyl benzene sulfonato) diphenyl silyl bis (indenyl) -
Zirconium (IV) -bis (pentafluorobenzenesulfonato), diphenylsilylbis (indenyl) -zirconium (IV) -benzenesulfonatomonochloride,
Diphenylsilylbis (indenyl) -zirconium (I
V) -2,4,6-Trimethylbenzenesulfonatomonochloride, diphenylsilylbis (indenyl) -zirconium (IV) -2,4,6-triisopropylbenzenesulfonatomonochloride, diphenylsilylbis (indenyl)-
Zirconium (IV) -pentafluorobenzenesulfonatomonochloride,

Diphenylmethylene bis (indenyl)-
Zirconium (IV) -bis (trifluoromethanesulfonato), diphenylmethylenebis (indenyl) -zirconium (IV) -bis (methanesulfonato), diphenylmethylenebis (indenyl) -zirconium (IV) -bis (p-toluenesulfo) Nato), diphenylmethylenebis (indenyl) -zirconium (IV) -bis (p-chlorobenzenesulfonato), diphenylmethylenebis (indenyl) -zirconium (IV) -trifluoromethanesulfonatomonochloride, diphenylmethylenebis (indenyl) -Zirconium (IV) -trifluoromethanesulfonatomonobromide, diphenylmethylenebis (indenyl) -zirconium (IV) -trifluoromethanesulfonatomonofluoride, diphenylmethylenebis (indenyl) -zirconium (IV) -trifluoro Methane sulfonato mono- iodo, diphenylmethylene (indenyl)
-Zirconium (IV) -methanesulfonato monochloride,
Diphenylmethylenebis (indenyl) -zirconium (IV) -p-toluenesulfonatomonochloride, etc.

[Production Method] The novel transition metal compound according to the present invention includes, for example, a compound represented by the following general formula [II]:

[0036]

[Chemical 5]

(In the formula [II], M and Cp ¹ , Cp ²
Is the same as in the formula [I], and Cp ¹ and Cp ² may be bonded via an alkylene group, a substituted alkylene group, a silylene group, a substituted silylene group, or the like. Y ¹ is a halogen atom, and Y ² is the same as R ¹ , OR ¹ and N in the formula [I].
R ¹ _n, which is ^{_{S (O) q R 1,}} SiR 1 3, P (O) q R 1 3 or a halogen atom. ) From a sulfonic acid derivative represented by the following general formula [III], R ¹ SO ₃ Z ... [III] (In the formula [III], R ¹ is substituted with the same alkyl group and halogen atom as in the formula [I]. An alkyl group, an aryl group, an aryl group substituted with a halogen atom or an alkyl group, Z is an alkali metal such as Ag or Na or K, or a trialkylammonium group such as triethylammonium or tri (n-octyl) ammonium. It can be produced according to the following reaction formula.

[0038]

[Chemical 6]

In the above formula [I], X is --SO.
₃ R ¹ , or similar to Y ² , R ¹ , OR ¹ ,
NR ¹ _n, which is ^{_{S (O) q R 1,}} SiR 1 3, P (O) q R 1 3 or a halogen atom.

The reaction conditions in this reaction differ depending on the composition of the compound [I] to be obtained, but the compound [III] is usually 1 to 10 times mol, preferably 1 to 3 times the mol of the compound [II]. Used in molar amounts. The reaction temperature is −20 to 180 ° C., preferably 0 to 130 ° C., and the reaction time is 0.5 to 48 hours, preferably 2 to 12 hours.

As the solvent used in the reaction, aliphatic hydrocarbons such as hexane and decane, aromatic hydrocarbons such as benzene, toluene and xylene, halogenated hydrocarbons such as carbon tetrachloride, chloroform and methylene chloride, acetone, Ketones such as methyl isobutyl ketone and acetonitrile are used. Of these, toluene and xylene are particularly preferable. Such a hydrocarbon solvent is usually used in an amount of 1 to 1000 times, preferably 50 to 500 times the amount of the compound [II].

The desired transition metal compound can be produced in good yield by the above-mentioned production method. The transition metal compound thus obtained can be filtered, and the obtained filtrate can be concentrated under reduced pressure for recrystallization, or can be isolated and purified by a method such as sublimation.

[Catalyst] The novel transition metal compound of the present invention represented by the above general formula [I] can be used as an olefin polymerization catalyst in combination with an organoaluminum oxy compound.

In the present invention, the term "polymerization" may be used to mean not only homopolymerization but also copolymerization, and the term "polymer" may refer to homopolymer as well as copolymerization. May be used to mean coalesce.

[A] Used as a catalyst for olefin polymerization together with the novel transition metal compound according to the present invention [B]
The organoaluminum oxy compound may be a conventionally known aluminoxane or a benzene-insoluble organoaluminum oxy compound as exemplified in JP-A-2-78687.

The conventionally known aluminoxane can be produced, for example, by the following method. (1) Compounds containing adsorbed water or salts containing water of crystallization, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, ceric chloride hydrate, etc. A method of recovering a hydrocarbon solution by adding an organoaluminum compound such as trialkylaluminum to the hydrocarbon medium suspension and reacting the same.

(2) A method in which water, ice or steam is directly applied to an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether or tetrahydrofuran to recover it as a hydrocarbon solution.

(3) A method of reacting an organoaluminum compound such as trialkylaluminum with an organotin oxide such as dimethyltin oxide or dibutyltin oxide in a medium such as decane, benzene or toluene.

The aluminoxane may contain a small amount of organic metal component. Alternatively, the solvent or unreacted organoaluminum compound may be removed by distillation from the recovered solution of the aluminoxane, and then redissolved in the solvent.

Specific examples of the organoaluminum compound used in the production of aluminoxane include trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum and triisopropylaluminum.
n-butyl aluminum, triisobutyl aluminum,
Trisec-butylaluminum, tritert-butylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum and other trialkylaluminums; tricyclohexylaluminum, tricyclooctylaluminum and other tricycloalkylaluminums; dimethylaluminum Chloride, diethyl aluminum chloride,
Dialkyl aluminum halides such as diethyl aluminum bromide and diisobutyl aluminum chloride;
Dialkyl aluminum hydrides such as diethyl aluminum hydride and diisobutyl aluminum hydride; dialkyl aluminum alkoxides such as dimethyl aluminum methoxide and diethyl aluminum ethoxide; and dialkyl aluminum aryloxides such as diethyl aluminum phenoxide.

Of these, trialkylaluminum and tricycloalkylaluminum are particularly preferable.
Further, as the organoaluminum compound, the following general formula [I
It is also possible to use isoprenylaluminum represented by V].

[0052] _{(i-C 4 H 9)} X Al y (C 5 H 10) Z ... [IV] in (formula [IV], x, y, z are positive numbers, z ≧
2x. ) The above-mentioned organoaluminum compounds are used alone or in combination.

As the solvent used for the production of aluminoxane, aromatic hydrocarbons such as benzene, toluene, xylene, cumene and cymene, aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane and octadecane. Hydrocarbons, alicyclic hydrocarbons such as cyclopentane, cyclohexane, cyclooctane, and methylcyclopentane, petroleum fractions such as gasoline, kerosene, and light oil, or the above aromatic hydrocarbons, aliphatic hydrocarbons,
Alicyclic hydrocarbon halides, especially hydrocarbon solvents such as chlorinated compounds and brominated compounds are mentioned. In addition, ethers such as ethyl ether and tetrahydrofuran can also be used. Of these solvents, aromatic hydrocarbons are particularly preferable.

The olefin polymerization catalyst containing the novel transition metal compound [A] and the organoaluminum oxy compound [B] is excellent in olefin polymerization activity.
The above-mentioned [A] novel transition metal compound and / or [B] organoaluminum oxy compound may be supported on a carrier for use.

[Polymerization Method] The olefin polymerization method according to the present invention comprises the above-mentioned [A] transition metal compound,
[B] The olefin is polymerized in the presence of the organoaluminum oxy compound.

In the present invention, the polymerization can be carried out by either a liquid phase polymerization method such as solution polymerization or suspension polymerization or a gas phase polymerization method. In the liquid phase polymerization, an inert hydrocarbon solvent or olefin itself can be used as a solvent.

Specifically as the hydrocarbon medium, butane,
Isobutane, pentane, hexane, octane, decane,
Aliphatic hydrocarbons such as dodecane, hexadecane, octadecane; alicyclic hydrocarbons such as cyclopentane, methylcyclopentane, cyclohexane, cyclooctane; aromatic hydrocarbons such as benzene, toluene, xylene; gasoline, kerosene, Examples include petroleum fractions such as light oil.

In the present invention, when carrying out the slurry polymerization method, the polymerization temperature is usually in the range of -50 to 100 ° C, preferably 0 to 90 ° C. When carrying out the liquid phase polymerization method, the polymerization temperature is usually 0 to 250 ° C., preferably 20 to 200 ° C.
When carrying out the gas phase polymerization method, the polymerization temperature is usually 0.
It is desirable to be in the range of 120 to 120 ° C, preferably 20 to 100 ° C.

In the present invention, when the olefin is polymerized by the slurry polymerization method, the solution polymerization method or the gas phase polymerization method,
The transition metal compound [A] has a concentration of the transition metal atom in the polymerization reaction system of usually 10 ^-8 to 10 ^-1 gram atom / liter, preferably 10 ^{-7 to} 5 × 10 ^-2 gram atom / liter. It is preferably used in a quantity. Atomic ratio of transition metal in [A] transition metal compound to aluminum in [B] organoaluminum oxy compound (Al / transition metal)
Is usually 10 to 10,000, preferably 20 to 5,000.
Is desirable.

The polymerization pressure is usually atmospheric pressure to 100 kg.
/ Cm ² , preferably under normal pressure to 50 kg / cm ² , and the polymerization can be carried out in any of batch system, semi-continuous system and continuous system. It is also possible to carry out the polymerization in two or more stages under different reaction conditions.

The molecular weight of the obtained olefin polymer can be adjusted by allowing hydrogen to be present in the polymerization system or by changing the polymerization temperature. The olefins that can be polymerized by the olefin polymerization method according to the present invention include ethylene and α-olefins having 3 to 20 carbon atoms, such as propylene, 1-butene, 1-pentene, 1-hexene and 4-methyl-1. -Penten, 1-octene, 1
-Decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene; 3 to 20 carbon atoms
Cyclic olefins such as cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, 2-methyl-1,4,5,8-dimethano-1,2,
Examples thereof include 3,4,4a, 5,8,8a-octahydronaphthalene. Furthermore, styrene, vinylcyclohexane,
Diene or the like can also be used.

In the present invention, α-olefin may be preliminarily polymerized with the olefin polymerization catalyst in the polymerization of olefin. During the prepolymerization, the olefin polymer is
0.05 to 500 g, preferably 0.1 to 300 g, and more preferably 0.2 to 10 per 1 g of the olefin polymerization catalyst.
It is desirable to prepolymerize in an amount of 0 g.

As olefins for prepolymerization, ethylene and α-olefins having 3 to 20 carbon atoms, such as propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene,
Examples thereof include 1-tetradecene, 3-methyl-1-butene, 3-methyl-1-pentene and the like. Of these, preferred are olefins used during polymerization.

[0064]

INDUSTRIAL APPLICABILITY The novel transition metal compound according to the present invention exhibits excellent polymerization activity when used as an olefin polymerization catalyst together with an organoaluminum oxy compound, and the resulting polymer has excellent properties.

[0065]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

In the present invention, the melt flow rate (MFR), intrinsic viscosity [η], stereoregularity (mm triad fraction), ethylene content and reduced specific viscosity (RSV) are measured as follows.

[Melt Flow Rate (MFR)] ASTM D
According to 785, it was measured under the conditions of 190 ° C. and 2.16 kg load. [Intrinsic viscosity [η]] measured in decalin at 135 ° C, dl
/ G.

[Stereoregularity (mm triad fraction)] The isotactic fraction (mm triad fraction) in the propylene chain was measured by ¹³ C-NMR.

For ¹³ C-NMR, about 150 mg of a sample was dissolved in a mixed solution of hexachlorobutadiene and deuterated benzene (0.5 ml and 0.1 ml, respectively), and was usually analyzed by JEOLGX-50.
Measurement was carried out using a 0 apparatus at a measurement frequency of 125.65 MHz, a spectrum width of 8800 Hz, a pulse repetition time of 4.0 seconds, a pulse angle of 45 ° and a measurement temperature of 95 to 110 ° C.

[Ethylene Content] The ethylene content of the copolymer was determined by measuring the ¹³ C-NMR spectrum of a sample prepared by uniformly dissolving about 200 mg of the copolymer in 1 ml of hexachlorobutadiene in a sample tube of 10 mmφ. Temperature 120
℃, measurement frequency 25.05MHz, spectrum width 1500H
z, pulse repetition time 4.2 seconds, pulse width 6 μsec.

[Reduced Specific Viscosity (RSV)] It was dissolved in decalin at 135 ° C. at a concentration of 0.1 dl / g and measured, and dl / g
It showed with.

[Synthesis of Transition Metal Compound]

[0073]

Example 1 [Bis (cyclopentadienyl) -zirconium (IV)-
Production of bis (methanesulfonato) (Compound No. 100)] A glass reactor having an inner volume of 300 ml, which was sufficiently replaced with nitrogen, was charged with 100 ml of dry acetonitrile and 1.24 g (4.25 mmol) of zirconocene dichloride, Stir at room temperature until uniform. To this reaction solution, 50 ml of a solution of 1.74 g (8.57 mmol) of silver methanesulfonate in acetonitrile was added dropwise at room temperature over 10 minutes, and then the reaction was continued at room temperature for 2 hours. The produced salt was filtered through a glass filter under a nitrogen stream, and the obtained filtrate was concentrated under reduced pressure. The obtained solid was recrystallized from toluene to give 1.04 g of colorless needle crystals (yield: 60%, melting point 14).
5 to 148 ° C).

¹ H-NM of the crystals thus obtained
The results of R spectrum and elemental analysis are shown in Table 1.

[0075]

Example 2 [Bis (cyclopentadienyl) -zirconium (IV)-
Preparation of bis (p-toluenesulfonato) (Compound No. 101)] A glass reactor having an inner volume of 200 ml which had been sufficiently replaced with nitrogen was charged with 50 ml of dry acetonitrile and 1.05 g (3.6 mmol) of zirconocene dichloride. , Stirred at room temperature until uniform. 100 ml of an acetonitrile solution of 2.04 g (7.3 mmol) of silver p-toluenesulfonate was added dropwise to this reaction solution at room temperature over 10 minutes, and then 6
The reaction was continued at 0 ° C for 2 hours. The produced salt was filtered through a glass filter under a nitrogen stream, and the obtained filtrate was concentrated under reduced pressure. When the obtained solid was recrystallized from toluene, 1.39 g of pale yellowish white needle crystals were obtained (yield; 69%,
Melting point 213-216 [deg.] C).

¹ H-NM of the crystals thus obtained
The results of R spectrum and elemental analysis are shown in Table 1.

[0077]

Example 3 [Bis (cyclopentadienyl) -zirconium (IV)-
Bis (trifluoromethanesulfonato) (Compound No. 1
Production of 02)] A glass reactor having an internal volume of 1 liter which had been sufficiently replaced with nitrogen was charged with 250 ml of dry toluene and 0.73 g (2.5 mmol) of zirconocene dichloride,
Stir at room temperature until uniform. 100 ml of a toluene solution containing 1.28 g (5.0 mmol) of silver trifluoromethanesulfonate was added dropwise to this reaction solution at room temperature over 30 minutes. After further stirring at room temperature for 3 hours, the reaction was continued at 60 ° C. for 4 hours. The produced salt was filtered through a glass filter under a nitrogen stream, and the obtained filtrate was concentrated under reduced pressure. The obtained solid is purified by sublimation (1 × 10 ⁻⁴ mmHg / 100 to 120
C.) to give 0.45 g of a white solid (yield; 35%, melting point; 205.degree. C. (decomposition)).

¹ H-of the white solid thus obtained
The results of NMR spectrum and elemental analysis are shown in Table 1.

[0079]

Example 4 [Bis (cyclopentadienyl) -zirconium (IV)-
Production of trifluoromethanesulfonatomonochloride (Compound No. 103)] Example 3 was repeated except that 1.46 g (5 mmol) of zirconocene dichloride and 1.54 g (6 mmol) of silver trifluoromethanesulfonate were used. Carry out the same procedure as in 3 to give 0.96 g of white crystals.
Was obtained (yield; 47%, melting point; 101 ° C. (decomposition)).

¹ H-NM of the crystals thus obtained
The results of R spectrum and elemental analysis are shown in Table 1.

[0081]

Example 5 [Bis (cyclopentadienyl) -zirconium (IV)-
Production of bis (2,4,6-trimethylbenzenesulfonato) (Compound No. 104)] Fully nitrogen-substituted internal volume 500
ml glass reactor, dry acetonitrile 100 m
1 and bis (cyclopentadienyl) -zirconium (IV) -dichloride (1.58 g, 5.4 mmol) were charged and stirred at room temperature until uniform. 2,4,
Silver 6-trimethylbenzenesulfonate 3.70 g (10.8 g
50 ml of acetonitrile solution of (mmol) was added dropwise over 30 minutes. After the dropwise addition was completed, the temperature was raised to 60 ° C., the reaction was continued for 2 hours, then cooled to room temperature, and the produced salt was filtered. Acetonitrile (300 ml) was added to the obtained salt, and the mixture was stirred under reflux for 30 minutes, and then filtered while hot to remove silver chloride. After the filtrate was concentrated under reduced pressure, toluene 100m
When l was added and recrystallized, 1.2 g of needle crystals were obtained (yield; 38%, melting point; 250 to 251 ° C.).

¹ H-NM of the crystals thus obtained
The results of R spectrum and elemental analysis are shown in Table 1.

[0083]

Example 6 [Production of bis (methylcyclopentadienyl) -zirconium (IV) -bis (trifluoromethanesulfonato) (Compound No. 200)] In Example 3, instead of zirconocene dichloride, bis (methylcyclo) was used. 1.60 g (5 mmol) of pentadienyl) -zirconium (IV) -dichloride and silver trifluoromethanesulfonate 2.
The same operation as in Example 3 was carried out except that 59 g (10 mmol) was used to obtain 0.55 g of yellow crystals (yield: 20).
%, Melting point 85 ° C. (decomposition)).

¹ H-NM of the crystals thus obtained
The results of R spectrum and elemental analysis are shown in Table 1.

[0085]

Example 7 [Production of bis (methylcyclopentadienyl) -zirconium (IV) -trifluoromethanesulfonatomonochloride (Compound No. 201)] In Example 3, instead of zirconocene dichloride, bis (methylcyclopentadiene) Dienyl) -zirconium (IV) -dichloride 1.53 g
(4.8 mmol) was used, and the same operation as in Example 3 was carried out except that 1.29 g (5.0 mmol) of silver trifluoromethanesulfonate was used to obtain 1.44 g of yellow crystals (yield; 69%, melting point; 78-79 ° C).

¹ H-NM of the crystals thus obtained
The results of R spectrum and elemental analysis are shown in Table 1.

[0087]

Example 8 [Bis (1,3-dimethylcyclopentadienyl) -zirconium (IV) -bis (trifluoromethanesulfonato)]
Production of (Compound No. 202)] In Example 3, bis (1,3-dimethylcyclopentadienyl) -zirconium (IV) -dichloride 6.9 was used instead of zirconocene dichloride.
The same operation as in Example 3 was performed except that 7 g (20 mmol) was used and 10.53 g (41 mmol) of silver trifluoromethanesulfonate was used. However, the obtained filtrate was concentrated to 20 ml, the precipitated solid was heated at 60 ° C., redissolved and then slowly cooled to room temperature for recrystallization to obtain 7.52 g of a yellow crystal. 25 ml of toluene in this crystal
Was added and dissolved at 50 ° C., gradually cooled to room temperature and recrystallized again to obtain 4.77 g of yellow crystals (yield: 41%,
Melting point; 169-171 ° C).

¹ H-NM of the crystals thus obtained
The results of R spectrum and elemental analysis are shown in Table 1.

[0089]

Example 9 [Production of bis (1,3-dimethylcyclopentadienyl) -zirconium (IV) -trifluoromethanesulfonatomonochloride (Compound No. 203)] In Example 3,
Using 1.60 g (4.6 mmol) of bis (1,3-dimethylcyclopentadienyl) -zirconium (IV) -dichloride instead of zirconocene dichloride, 1.24 g (4.8 mmol) of silver trifluoromethanesulfonate ), Except that the same procedure as in Example 3 was carried out to obtain 0.25 g of yellow crystals.
Was obtained (yield; 12%, melting point; 110 ° C. (decomposition)).

¹ H-NM of the crystals thus obtained
The results of R spectrum and elemental analysis are shown in Table 1.

[0091]

Example 10 [Ethylenebis (indenyl) -zirconium (IV) -bis (trifluoromethanesulfonato) (Compound No. 30
Production of 0)] A glass reactor having an internal volume of 1 liter which had been sufficiently replaced with nitrogen was charged with 600 ml of dry toluene and 1.88 g (4.5 mmol) of ethylenebis (indenyl) -zirconium (IV) -dichloride. , Stirred at room temperature until uniform. To this reaction solution was added a toluene solution 10 containing 2.34 g (9 mmol) of silver trifluoromethanesulfonate.
0 ml was added dropwise at room temperature over 30 minutes. After further stirring at room temperature for 3 hours, the reaction was continued at 60 ° C. for 4 hours. The produced salt was filtered through a glass filter under a nitrogen stream, and the obtained filtrate was concentrated under reduced pressure. The obtained solid is toluene 6
Recrystallized with 0 ml, orange crystals 1.54
g was obtained (yield; 53%, melting point; 180 ° C. (decomposition)).

¹ H-NM of the crystals thus obtained
The results of R spectrum and elemental analysis are shown in Table 1.

[0093]

Example 11 Production of ethylenebis (indenyl) -zirconium (IV) -trifluoromethanesulfonatomonochloride (Compound No. 301) In Example 10, ethylenebis (indenyl) -zirconium (IV) -dichloride 1.88 g
(4.5 mmol) was dissolved in 700 ml of toluene, reacted with 1.17 g (4.5 mmol) of silver trifluoromethanesulfonate, and recrystallized with 60 ml of toluene. Crystal of 0.4
4 g was obtained (yield; 17%, melting point; 235 ° C. (decomposition)).

¹ H-NM of the crystals thus obtained
The results of R spectrum and elemental analysis are shown in Table 1.

[0095]

Example 12 [Ethylenebis (indenyl) -hafnium (IV) -bis (trifluoromethanesulfonato) (Compound No. 40
Preparation of 0)] In Example 10, ethylenebis (indenyl) -hafnium (IV) -dichloride 0.80 g (1.
(58 mmol) was dissolved in 400 ml of toluene, reacted with 0.82 g (3.16 mmol) of silver trifluoromethanesulfonate and recrystallized with 10 ml of toluene. .45 g
Was obtained (yield; 39%, melting point; 225 ° C. (decomposition)).

¹ H-NM of the crystals thus obtained
The results of R spectrum and elemental analysis are shown in Table 1.

[0097]

Example 13 [Bis (cyclopentadienyl) -zirconium (IV)-
Production of (Ethoxy) (trifluoromethanesulfonato) (Compound No. 302)] Fully nitrogen-substituted internal volume 50
In a 0 ml glass reactor, 350 ml of dry toluene and bis (cyclopentadienyl) -zirconium (I
V) -Dichloride (5.27 g) was charged, and the mixture was stirred at room temperature until uniform. Ethyl alcohol 1.16 was added to this reaction solution.
After adding ml, triethylamine (3.77 ml) was added slowly. After heating to 50 ° C and reacting for 1 hour,
It was cooled to room temperature and the salt formed was filtered off. The obtained filtrate was concentrated under reduced pressure, hexane (40 ml) was added, and the mixture was cooled to -20 ° C. As a result, bis (cyclopentadienyl) -zirconium (IV)-(ethoxy) chloride was obtained as a white plate-like product from the hexane layer. 4.00 g of crystals were obtained (yield; 74%).

A glass reactor having an internal volume of 500 ml, which had been sufficiently replaced with nitrogen, was charged with 200 ml of dry toluene and 4.00 g of bis (cyclopentadienyl) -zirconium (IV)-(ethoxy) chloride, and the mixture was homogenized. Up to 6
Stirred at 0 ° C. A toluene solution of silver trifluoromethanesulfonate (0.16 mmol / ml) was added to the reaction solution.
4.4 ml was added dropwise over 1 hour. After continuing the reaction for an additional 1 hour, the mixture was cooled to room temperature, and the produced salt was filtered off.
After concentrating the obtained filtrate under reduced pressure, 50 ml of hexane
Was added and the mixture was cooled to −20 ° C., and 2.40 g of white crystals were obtained from the hexane layer (yield; 44%, melting point; 99-100 ° C. (decomposition)).

¹ H-NM of the crystals thus obtained
The results of R spectrum and elemental analysis are shown in Table 1.

[0100]

[Example 14] [Production of bis (1,3-dimethylcyclopentadienyl) -zirconium (IV)-(trifluoromethanesulfonato) (dimethylamide) (Compound No. 303)] 500 ml of an internal volume sufficiently replaced with nitrogen In a glass reactor at 100 mL of dry hexane and n-butyl thylium (1.62)
15.6 ml of a hexane solution (mol) was added, and -10
Stirred at ° C. Dimethylamine 1.25 is added to this reaction solution.
g was added at -10 ° C and stirred for 30 minutes. After that, 0 ℃
The temperature was raised to 1, and after reacting for 1 hour, nitrogen was blown in to remove residual dimethylamine. Add bis (1,3-
Dimethylcyclopentadienyl) -zirconium (IV)-
200 ml of a toluene solution of 3.66 g of dichloride was added to 30
The solution was added dropwise over 1 minute, and the mixture was stirred at 0 ° C. Subsequently, the temperature was raised to room temperature, the reaction was carried out for 1 hour, and then the mixture was heated at 95 ° C. for 6 hours. The salt formed was filtered off and the resulting filtrate was concentrated under reduced pressure (about 2 ml). The precipitated solid was filtered, and the brown solid was purified by sublimation (200 ° C / 0.5 mmHg).
Crystal of bis (1,3-dimethylcyclopentadienyl) -zirconium (IV)-(dimethylamido) chloride 0.60
g was obtained (yield; 18%).

A glass reactor having an internal volume of 500 ml, which had been sufficiently replaced with nitrogen, was equipped with 100 ml of dry toluene and 1.00 g of bis (1,3-dimethylcyclopentadienyl) -zirconium (IV)-(dimethylamido) chloride. It was charged and stirred at room temperature until uniform. A toluene solution of silver trifluoromethanesulfonate (0.16
1 mmol (mmol / ml) was added dropwise at room temperature over 30 minutes. The temperature was further raised to 60 ° C., the reaction was continued for 1 hour, then cooled to room temperature, and the produced salt was removed by filtration. The obtained filtrate was concentrated under reduced pressure and then recrystallized with a mixed solution of toluene / hexane (5 ml / 10 ml).
0.66 g of crystals were obtained (yield; 50%, melting point; 95-9).
7 ° C).

¹ H-NM of the crystals thus obtained
The results of R spectrum and elemental analysis are shown in Table 1.

[0103]

[Table 1]

[Polymerization of ethylene]

[0105]

Example 15 400 ml of purified toluene was placed in a glass flask having an internal volume of 1 liter which had been sufficiently replaced with nitrogen.
75 ° C while circulating ethylene at 100 liter / hr
For 10 minutes.

Then, 0.8 mg of methylaluminoxane (methylaluminoxane manufactured by Schering Co., Ltd., dried and re-dissolved in toluene) was charged in terms of aluminum atom. Furthermore, bis (cyclopentadienyl) -zirconium (IV) -bis (trifluoromethanesulfonato) obtained in Example 3 (Compound No. 10
2) was charged in an amount of 0.0004 milligram atom in terms of zirconium atom. After carrying out the polymerization at 75 ° C. for 5 minutes, the polymerization was stopped by adding a small amount of isobutanol.

A small amount of dilute hydrochloric acid was added to the obtained polymer suspension and the mixture was filtered through a glass filter to remove n-decane as a solvent, washed with hexane and dried at 80 ° C. for 24 hours.
The amount of polyethylene obtained was 6.37 g, and the polymerization activity was 191100 g / mmol-Zr / hr.

[0108]

[Reference Example 1] Bis (cyclopentadienyl) -zirconium (IV) -bis (trifluoromethanesulfonato)
Ethylene was polymerized in the same manner as in Example 15 except that zirconocene dichloride was used instead of (Compound No. 102).

The amount of polyethylene obtained was 6.30 g, and the polymerization activity was 189000 g / mmol-Zr · hr.
Met.

[0110]

[Reference Example 2] Bis (cyclopentadienyl) -zirconium (IV) -bis (trifluoromethanesulfonate)
Journal of Organomet instead of (Compound No. 102)
allic Chemistry, 363 (1989) was synthesized by the method described in _{C12-C14 [Cp 2 Zr (} CF 3 SO 3) (bipy)] + CF 3 SO
₃ ^- it is obtained by polymerizing ethylene in the same manner as in Example 15 except for using the.

The amount of polyethylene obtained was 0.19 g, and the polymerization activity was 12000 g / mmol-Zr · hr. From this, it is clear that the ethylene polymerization activity of the compound in which 2,2'-dipyridine is coordinated is clearly lower than that of the compound in which 2,2'-dipyridine is not coordinated (Compound No. 102).

[0112]

Example 16 For the purpose of observing the polymerization activity for a long time,
A catalyst preparation method and a polymerization method were adopted so as to obtain a supported catalyst which maintains a good suspension state for a long time.

Fine particle silica (F-94 manufactured by Fuji Davisson Co., Ltd.
8 was calcined at 700 ° C for 7 hours) and 5.5% by weight
Water is adsorbed, and 1/2 mol of silica aluminoxane (methyl aluminoxane manufactured by Schering Co., Ltd. is dried and re-dissolved in toluene) is added to 80 wt.
What was made to react by carrying out the reaction for 3 hours at 0 ° C was used as the aluminoxane component.

1 liter of purified n-decane was placed in a glass flask having an internal volume of 1 liter which had been sufficiently replaced with nitrogen, and hydrogen was flowed at 0.3-2 liter / hr and ethylene was passed at 250 liter / hr to 75 ° C. Hold for 10 minutes.

Next, triisobutylaluminum was converted into aluminum atom at 0.5 mg atom, and the aluminoxane component prepared above was converted into aluminum atom at 5.0 mg atom, and the bis (cyclopentadiene obtained in Example 1 was used. 0.02 mg of zirconium atom-converted (enyl) -zirconium (IV) -bis (methanesulfonato) (Compound No. 100) was charged. 2 at 75 ° C
After carrying out the polymerization for a time, the polymerization was stopped by adding a small amount of isobutanol.

A small amount of dilute hydrochloric acid was added to the obtained polymer suspension and the mixture was filtered through a glass filter to remove n-decane as a solvent, washed with hexane and dried at 80 ° C. for 24 hours.
The polyethylene obtained was 8.8 g and had a polymerization activity of 2
20 g / mmol-Zr / hr, MFR 0.45
It was g / 10 minutes.

[0117]

Examples 17 to 20 Bis (cyclopentadienyl)-
Ethylene was polymerized in the same manner as in Example 16 except that the transition metal compounds shown in Table 2 were used instead of zirconium (IV) -bis (methanesulfonato) (Compound No. 100).

The yield and physical properties of the polymer thus obtained are shown in Table 2.

[0119]

Reference Examples 3 to 6 Example 16 except that the zirconium compounds shown in Table 2 were used in place of bis (cyclopentadienyl) -zirconium (IV) -bis (methanesulfonato) (Compound No. 100). Ethylene was polymerized in the same manner.

The yield and physical properties of the polymer thus obtained are shown in Table 2.

[0121]

[Table 2]

[Polymerization of Propylene]

[0123]

[Example 21] Purified toluene (500 ml) was charged into a glass reactor having an internal volume of 1 liter which had been sufficiently replaced with nitrogen, and propylene (100 liter / hr) was passed through the reactor at 8 minutes per minute.
It was kept at 30 ° C. for 10 minutes while stirring at 00 revolutions. Then, 2.5 mg of methylaluminoxane (methylaluminoxane manufactured by Schering Co., Ltd., dried and redissolved in toluene) was charged in terms of aluminum atom. Further, bis (methylcyclopentadienyl) -zirconium (IV) -bis (trifluoromethanesulfonato) (Compound No. 200) obtained in Example 6 was charged in an amount of 0.01 mg atom in terms of zirconium atom. Three
After polymerization was carried out at 0 ° C. and normal pressure for 2 hours, a small amount of isobutanol was added to terminate the polymerization.

After the reaction, the reaction solution was poured into an aqueous solution of dilute hydrochloric acid to remove the solvent residue, and the toluene layer was concentrated.
It was dried under reduced pressure at 0 ° C overnight. The yield and physical properties of the polymer thus obtained are shown in Table 3.

[0125]

Examples 22 to 24 Except that the transition metal compounds shown in Table 3 were used instead of bis (methylcyclopentadienyl) -zirconium (IV) -bis (trifluoromethanesulfonato) (Compound No. 200). Propylene was polymerized in the same manner as in Example 21.

The yield and physical properties of the polymer thus obtained are shown in Table 3.

[0127]

[Reference Examples 7 to 8] Bis (methylcyclopentadienyl)
-Propylene was polymerized in the same manner as in Example 21 except that zirconium compounds shown in Table 3 were used instead of -zirconium (IV) -bis (trifluoromethanesulfonato) (Compound No. 200).

The yield and physical properties of the polymer thus obtained are shown in Table 3.

[0129]

[Table 3]

[0130]

Examples 25 to 27 Bis (cyclopentadienyl) -zirconium (IV) -bis instead of bis (methylcyclopentadienyl) -zirconium (IV) -bis (trifluoromethanesulfonate) (Compound No. 200) Propylene was polymerized in the same manner as in Example 21 except that (trifluoromethanesulfonato) (Compound No. 102) was used and methylaluminoxane (MAO) was used at the concentration shown in Table 4.

Table 4 shows the yield and physical properties of the polymer thus obtained.

[0132]

[Reference Example 9] Instead of bis (methylcyclopentadienyl) -zirconium (IV) -bis (trifluoromethanesulfonato) (Compound No. 200), Journal of Organ
ometallic Chemistry, 363 (1989) was synthesized by the method described in _{C12-C14 [Cp 2 Zr (} CF 3 SO 3) (bipy)] +
Propylene was polymerized in the same manner as in Example 21 except that CF ₃ SO ₃ ^— was used.

The amount of polypropylene obtained was 0.01 g or less, and since it had almost no polymerization activity, 2,2'-dipyr
The propylene polymerization activity of the compound coordinated with idine is 2,2 '.
-dipyridine uncoordinated compound (Compound No. 10
It can be seen that it is significantly lower than that of 2).

[0134]

[Reference Examples 10 to 12] Bis (cyclopentadienyl)-
Zirconium (IV) -bis (trifluoromethanesulfonato) (Compound No. 102) instead of Journal of Org
Cp ₂ Zr (CF ₃ SO ₃ ) ₂ (THF) synthesized by the method described in Anometallic Chemistry, 363 (1989) C12-C14.
Propylene was polymerized in the same manner as in Examples 25 to 27 except that was used.

The yield and physical properties of the polymer thus obtained are shown in Table 4. From Table 4, it can be seen that the propylene polymerization activity of the compound coordinated with THF is clearly lower than that of the compound without the coordination of THF (Compound No. 102).

[0136]

[Table 4]

[Polymerization of ethylene-propylene]

[0138]

Example 28 500 ml of purified toluene was charged into a glass reactor having an internal volume of 500 liters, which had been sufficiently replaced with nitrogen, and a mixed gas of ethylene and propylene (ethylene / propylene = 40/60 (mol%)) was passed. , 80 per minute
It was kept at 40 ° C. for 10 minutes while stirring at 0 rotation. Next, methylaluminoxane (methylaluminoxane manufactured by Schering Co., Ltd., dried and re-dissolved in toluene)
Was charged in an amount of 1.25 mg atom in terms of aluminum atom. Further, 0.0005 mg of bis (cyclopentadienyl) -zirconium (IV) -bis (p-toluenesulfonato) (Compound No. 101) obtained in Example 2 was charged in terms of zirconium. After polymerization was carried out at 40 ° C. and normal pressure for 30 minutes, a small amount of isobutanol was added to terminate the polymerization.

After the reaction, the reaction solution was poured into an aqueous solution of dilute hydrochloric acid to remove the catalyst residue, and the toluene layer was concentrated.
It was dried under reduced pressure at 0 ° C overnight. The yield and physical properties of the copolymer thus obtained are shown in Table 5.

[0140]

Examples 29 to 30 Bis (cyclopentadienyl)-
Zirconium (IV) -bis (p-toluenesulfonato)
Copolymerization of ethylene and propylene was performed in the same manner as in Example 28 except that the transition metal compounds shown in Table 5 were used instead of (Compound No. 101).

The yield of the copolymer thus obtained,
The physical properties are shown in Table 5.

[0142]

[Reference Examples 13 to 15] Bis (cyclopentadienyl)-
Zirconium (IV) -bis (p-toluenesulfonato)
Copolymerization of ethylene and propylene was conducted in the same manner as in Example 28 except that the zirconium compound shown in Table 5 was used instead of (Compound No. 101).

The yield of the copolymer thus obtained,
The physical properties are shown in Table 5.

[0144]

[Table 5]

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Mitsuaki Mukoyama 1-15-18 Minamiogikubo, Suginami-ku, Tokyo

Claims (2)

[Claims] 1. A novel transition metal compound represented by the following general formula [I]. [Chemical 1] (In the formula [I], M is a group IVB transition metal, and C
p ¹ and Cp ² are groups having a cyclopentadienyl skeleton, and these groups having a cyclopentadienyl skeleton may have a substituent, and Cp ¹ and Cp ² have an alkylene group or a substituted group. They may be bonded via an alkylene group, a silylene group, or a substituted silylene group. R ¹ is an alkyl group, an alkyl group substituted with a halogen atom, an aryl group, an aryl group substituted with a halogen atom or an alkyl group, and X is SO ₃ R ¹ , R ¹ , OR ¹ , NR ¹ _n , S (O) _q
It is _{^{R 1, SiR 1 3, P}} (O) q R 1 3 or a halogen atom, n is 1, 2 or 3, q is 0, 1 or 2. ) 2. A catalyst component for olefin polymerization, comprising a transition metal compound represented by the following general formula [I]. [Chemical 2] (In the formula [I], M is a group IVB transition metal, and C
p ¹ and Cp ² are groups having a cyclopentadienyl skeleton, and these groups having a cyclopentadienyl skeleton may have a substituent, and Cp ¹ and Cp ² have an alkylene group or a substituted group. They may be bonded via an alkylene group, a silylene group, or a substituted silylene group. R ¹ is an alkyl group, an alkyl group substituted with a halogen atom, an aryl group, an aryl group substituted with a halogen atom or an alkyl group, and X is SO ₃ R ¹ , R ¹ , OR ¹ , NR ¹ _n , S (O) _q
It is _{^{R 1, SiR 1 3, P}} (O) q R 1 3 or a halogen atom, n is 1, 2 or 3, q is 0, 1 or 2. )