JPH05178926A - Catalyst for polymerization of olefin and polymerization of olefin - Google Patents

Abstract

PURPOSE:To obtain an olefin polymer of a narrow molecular weight distribution at a high polymerization activity by using a catalyst comprising a specified transition metal complex component and an organoaluminumoxy compound component. CONSTITUTION:A transition metal complex component is obtained by bringing 1mol of a transition metal compound of formula I [wherein M is a group IVB metal; Cp<1> and Cp<2> are each a cyclopentadienyl group which may have a substituent and may be combined with each other through (substituted) alkylene or (substituted) silylene; X is H, halogen, alkyl or aryl] into contact with 1-10mol of an organic compound of formula II (wherein R<1> and R<3> are each a 1-20C alkyl, aryl or alkoxyl group which may have a substituent; R<2> is H, halogen or R1) at -20 to 180 deg.C for 0.5-48hr. An olefin is polymerized at -50 to 100 deg.C under atmospheric pressure to 100kg/cm<2> in the presence of a catalyst comprising the above component and an organoaluminumoxy compound.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel catalyst for olefin polymerization and a method for polymerizing an olefin in the presence of this catalyst, and more specifically, a catalyst comprising a specific transition metal complex component and an organoaluminum oxy compound component. And a method for polymerizing olefins in the presence of this catalyst.

[0002]

BACKGROUND OF THE INVENTION Conventionally, as a method for producing an olefin polymer, ethylene has been used in the presence of a titanium catalyst composed of a titanium compound and an organoaluminum compound or a vanadium catalyst composed of a vanadium compound and an organoaluminum compound. There is known a method of copolymerizing α-olefin with α-olefin.

Generally, an ethylene / α-olefin copolymer obtained with a titanium catalyst has a broad molecular weight distribution and composition distribution, and is inferior in transparency, surface non-adhesiveness and mechanical properties. On the other hand, the ethylene / α-olefin copolymer obtained with the vanadium catalyst has a narrower molecular weight distribution and composition distribution than those obtained with the titanium catalyst,
Further, the transparency, surface non-adhesiveness and mechanical properties are considerably improved, but they are still insufficient for the applications requiring these performances. -A catalyst that can obtain an α-olefin copolymer is required.

Recently, as a new Ziegler type olefin polymerization catalyst, a catalyst comprising a zirconium compound and aluminoxane has been proposed. For example, JP-A-58
-19309, JP-A-60-35006,
JP-A-60-35007, JP-A-60-3500
No. 8, JP 61-130314 A, JP 2
No. 41303 discloses a catalyst system in which a metallocene compound of a transition metal compound having a pentadienyl group such as a cyclopentadienyl group as a ligand, an alkyl group and / or a halogen atom is combined with aluminoxane. -It is described that they are highly active in the polymerization of olefins and the properties of the obtained polymers are excellent.

Also, the Journal of Organometallic Chemis
try, 363 (1989) C12-C14 has Cp ₂ Zr (CF ₃ SO ₃ ).
₂ (THF) and [Cp ₂ Zr (CF ₃ SO ₃ ) (bipy)] ⁺ CF ₃ S
Although O ₃ ⁻ is disclosed, these two compounds have lower olefin polymerization activity than the above-mentioned cyclopentadienyl compound. Further, when the concentration of aluminoxane is low, the olefin polymerization activity is remarkably low.

Under these circumstances, it has been desired to develop a new olefin polymerization catalyst which is excellent in olefin polymerization activity and excellent in properties of the obtained polyolefin.

[0007]

OBJECT OF THE INVENTION It is an object of the present invention to provide a catalyst for olefin polymerization which has excellent polymerization activity, and a method for polymerizing olefins in the presence of a catalyst having such excellent properties.

[0008]

SUMMARY OF THE INVENTION A catalyst for olefin polymerization according to the present invention comprises (A) [a-I] a transition metal compound represented by the following general formula [I]:

[0009]

[Chemical 3]

(In the formula, 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. It may be bonded via an alkylene group, a silylene group, or a substituted silylene group. X is a hydrogen atom, a halogen atom, an alkyl group or an aryl group. ) [A-II] An organic compound represented by the following general formula [II]

[0011]

[Chemical 4]

(Wherein R ¹ and R ³ are an alkyl group having 1 to 20 carbon atoms, an aryl group or an alkoxy group,
These groups may have a substituent. R ¹ and R ³ may be the same or different. R ² is a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group or an aralkyl group, and these groups may have a substituent. R ¹ and R ² may combine with each other to form a ring. And (B) an organoaluminum oxy compound component.

The olefin polymerization method according to the present invention is characterized in that the olefin is polymerized in the presence of the above catalyst. According to the olefin polymerization catalyst and the olefin polymerization method of the present invention, an olefin polymer having high activity and a narrow molecular weight distribution can be obtained. Further, when two or more kinds of monomers are copolymerized, a copolymer having a narrow composition distribution can be obtained.

[0014]

DETAILED DESCRIPTION OF THE INVENTION The olefin polymerization catalyst and the olefin polymerization method according to the present invention will be specifically described below.

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

The olefin polymerization catalyst according to the present invention comprises a transition metal compound represented by the following general formula [I] (hereinafter sometimes referred to as "compound [I]").

[0017]

[Chemical 5]

Where 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. It may be bonded via an alkylene group, a silylene group, or a substituted silylene group. X is a hydrogen atom, a halogen atom, an alkyl group or an aryl group. ) An organic compound represented by the following general formula [II] (hereinafter referred to as "compound [I
I] ”. )

[0019]

[Chemical 6]

(Wherein R ¹ and R ³ are an alkyl group having 1 to 20 carbon atoms, an aryl group or an alkoxy group,
These groups may have a substituent. R ¹ and R ³ may be the same or different. R ² is a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group or an aralkyl group, and these groups may have a substituent. R ¹ and R ² may combine with each other to form a ring. (A) transition metal complex component and (B) organoaluminum oxy compound component.

In the above-mentioned general formula [I], M is a transition metal of Group IVB, specifically zirconium, titanium or hafnium. Examples of the group having a cyclopentadienyl skeleton include a cyclopentadienyl group; methylcyclopentadienyl group, ethylcyclopentadienyl group, n-butylcyclopentadienyl group, dimethylcyclopentadienyl group, trimethylcyclopentadienyl group Examples include an alkyl-substituted cyclopentadienyl group such as a pentadienyl group and a pentamethylcyclopentadienyl group; an indenyl group, a fluorenyl group, and the like.

Of these, alkyl-substituted cyclopentadienyl groups and indenyl groups are preferred. Examples of the alkylene group include ethylene group and propylene group, examples of the substituted alkylene group include isopropylidene group and diphenylmethylene group, and examples of the substituted silylene group include dimethylsilylene group.

Examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, etc., examples of the aryl group include phenyl group, tolyl group, etc., and halogen includes fluorine, chlorine, bromine. , Iodine.

In the general formula [II], R ¹ and R ³
Is a C1-C20 alkyl group such as methyl group, ethyl group, propyl group, isopropyl group, t-butyl group, aryl group such as phenyl group, alkoxy group such as methoxy group, ethoxy group, R ¹ and R ³ may have a substituent, and examples thereof include a halogenated alkyl group such as a trifluoromethyl group and a heptafluoropropyl group, or a methoxyphenyl group.

R ¹ and R ³ may be the same or different. R ² is a hydrogen atom, a halogen atom such as chlorine, bromine, or fluorine, an alkyl group having 1 to 20 carbon atoms such as a methyl group or an ethyl group, an aryl group such as a phenyl group, or an aralkyl group such as a benzyl group.

R ² may have a substituent, for example, o-, m- or p-methoxyphenyl group, 3,4- or 3,5-dimethoxyphenyl group, 3,4,5-triphenyl group. A methoxyphenyl group etc. are mentioned.

Further, R ¹ and R ² may be bonded to each other to form a ring. For example, R ¹ and R ² are bonded to each other to form a ring such as a 5-membered ring or a 6-membered ring. You may have. Specific examples of the transition metal compound represented by the general formula [I] are shown below.

Bis (cyclopentadienyl) -zirconium (IV) -dihydride, bis (cyclopentadienyl) -zirconium (IV) -methyl hydride, bis (cyclopentadienyl) -zirconium (IV) -ethyl hydride, Bis (cyclopentadienyl) -zirconium (I
V) -propyl hydride, bis (cyclopentadienyl)
-Zirconium (IV) -hydride monochloride, bis (cyclopentadienyl) -zirconium (IV) -hydride monobromide, bis (methylcyclopentadienyl) -zirconium- (IV) dihydride, bis (methylcyclopentadienyl) ) -Zirconium- (IV) ethyl hydride,
Bis (methylcyclopentadienyl) -zirconium-
(IV) Isopropyl hydride, bis (methylcyclopentadienyl) -zirconium- (IV) hydride monochloride, bis (1,3-dimethylcyclopentadienyl) -zirconium (IV) -dihydride, bis (1,3- Dimethylcyclopentadienyl) -zirconium (IV) -methylhydrido, bis (1,3-dimethylcyclopentadienyl) -zirconium (IV) -hydridomonochloride, bis (1,3-dimethylcyclopentadienyl)- Zirconium (IV) -butyl hydride, bis (1,3,5-trimethylcyclopentadienyl) -zirconium (IV) dihydride, bis (1,3,5
-Trimethylcyclopentadienyl) -zirconium (I
V) Methyl hydride, bis (1,3,5-trimethylcyclopentadienyl) -zirconium (IV) hydridomonoiodide, ethylene bis (indenyl) -zirconium (IV)
Dihydride, ethylene bis (indenyl) -zirconium (IV) methyl hydride, ethylene bis (indenyl)
-Zirconium (IV) ethyl hydride, ethylene bis (indenyl) -zirconium (IV) propyl hydride, ethylene bis (indenyl) -zirconium (IV)
Hydride monochloride, ethylene bis (indenyl)-
Zirconium (IV) hydride monofluoride, ethylenebis (indenyl) -hafnium (IV) -dihydride, ethylenebis (indenyl) -hafnium (IV) -methylhydride, ethylenebis (indenyl) -hafnium (IV)-
Propyl hydride, ethylene bis (indenyl) -hafnium (IV) -isopropyl hydride, ethylene bis (indenyl) -hafnium (IV) -hydride monobromide, ethylene bis (indenyl) -hafnium (IV) -te
rt-Butyl hydride, ethylene bis (indenyl) -titanium (IV) -dihydride, ethylene bis (indenyl) -titanium (IV) -methyl hydride, ethylene bis (indenyl) -titanium (IV) -ethyl hydride, ethylene bis (indenyl) ) -Titanium (IV) -propyldihydride, ethylenebis (indenyl) -titanium (IV) -hydride fluoride, ethylenebis (indenyl) -titanium (IV) -hydride chloride, dimethylsilylbis (indenyl) -zirconium (IV) ) Dihydride, dimethylsilylbis (indenyl) -zirconium (IV) methyl hydride, dimethylsilylbis (indenyl) -zirconium (IV) butyl hydride, dimethylsilylbis (indenyl) -zirconium (IV) isopropyl hydride, dimethylsilylbis (indenyl) ) -Zirconium (IV) Dori de monobromide, dimethylsilyl bis (indenyl) - zirconium (IV) hydride mono iodo, diphenylmethylene-bis (indenyl) - zirconium (IV) dihydride,
Diphenylmethylenebis (indenyl) -zirconium (IV) methyl hydride, diphenylmethylenebis (indenyl) -zirconium (IV) ethyl hydride, diphenylmethylenebis (indenyl) -zirconium (IV)
Propyl hydride, diphenylmethylene bis (indenyl) -zirconium (IV) hydrido monochloride, diphenyl methylene bis (indenyl) -zirconium (I
V) Hydride monobromide and the like These transition metal compounds represented by the general formula [I] may be obtained by any method and are not particularly limited. Moreover, you may use a commercial item.

Specific examples of the organic compound represented by the general formula [II] include compounds represented by the following formulas [II-A] to [II-N].

[0030]

[Chemical 7]

(In the formula, Me is a methyl group, Et is an ethyl group, t-Bu is a tert-butyl group, and Ph is a phenyl group.) These organic compounds represented by the general formula [II] are
It may be obtained by any method and is not particularly limited. Moreover, you may use a commercial item.

[Production of Transition Metal Complex Component] The transition metal complex component (A) used in the present invention is represented by the transition metal compound represented by the above general formula [I] and the above general formula [II]. It can be prepared by bringing an organic compound into contact with a solvent.

When the compound [I] and the compound [II] are brought into contact with each other, the compound [II] is usually used in an amount of 1 to 10 times, preferably 1 to 3 times the mol of the compound [I]. used. The contact temperature is −20 to 180 ° C., preferably 0.
~ 130 ° C is desirable, contact time is 0.5-
Desirably, it is 48 hours, preferably 2 to 12 hours.

Examples of the solvent (A) used in the production of the transition metal complex component include aliphatic hydrocarbons such as hexane and decane, aromatic hydrocarbons such as benzene, toluene and xylene, carbon tetrachloride, chloroform and chloride. Halogenated hydrocarbons such as methylene, ketones such as acetone and methyl isobutyl ketone, acetonitrile and the like are used. Of these, benzene, toluene and xylene are particularly preferable.
Such a hydrocarbon solvent is generally used in an amount of 1 to 1000 times, preferably 50 to 500 times the amount of the compound [I].

The desired (A) is obtained by the above-mentioned production method.
A transition metal complex component can be obtained. The (A) transition metal complex component thus obtained may be, for example, concentrated by filtration under reduced pressure for recrystallization, or may be isolated and purified by a method such as sublimation. You can

The transition metal complex component (A) obtained by contacting the compound [I] with the compound [II] is
When used as an olefin polymerization catalyst together with an organoaluminum oxy compound described below, the olefin polymerization activity is excellent.

[Catalyst] The transition metal complex component (A) according to the present invention can be used as an olefin polymerization catalyst in combination with the component (B) organoaluminum oxy compound component.

The organoaluminum oxy compound component (B) used together with the transition metal complex component (A) in the present invention may be a conventionally known aluminoxane, and is exemplified in JP-A-2-78687. Such a benzene-insoluble organoaluminum oxy compound may be used.

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, and ceric chloride hydrate 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 producing the aluminoxane solution include trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, trisec. -Butyl aluminum, tri-tert-butyl aluminum, tripentyl aluminum, trihexyl aluminum, trioctyl aluminum, tridecyl aluminum, tricyclohexyl aluminum,
Trialkyl aluminum such as tricyclooctyl aluminum; dimethyl aluminum chloride, diethyl aluminum chloride, diethyl aluminum bromide,
Dialkyl aluminum halides such as 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; Dialkyl aluminum aryloxides such as diethyl aluminum phenoxide. To be

Of these, trialkylaluminum is particularly preferable. Also, as an organoaluminum compound,
Isoprenylaluminum represented by the following general formula [III] can also be used.

(I-C ₄ H ₉ ) _x Al _y (C ₅ H ₁₀ ) _z ... [III] (where x, y and z are positive numbers, and z ≧ 2x). Such organoaluminum compounds are used alone or in combination.

Solvents used in the production of the aluminoxane solution include benzene, toluene, xylene,
Aromatic hydrocarbons such as cumene and cymene, aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane and octadecane, alicyclic hydrocarbons such as cyclopentane, cyclohexane, cyclooctane and methylcyclopentane Examples thereof include petroleum fractions such as gasoline, kerosene, and light oil, or halides of the above aromatic hydrocarbons, aliphatic hydrocarbons, and alicyclic hydrocarbons, particularly hydrocarbon solvents such as chlorinated compounds and brominated compounds. Other,
Ethers such as ethyl ether and tetrahydrofuran can also be used. Of these solvents, aromatic hydrocarbons are particularly preferable.

In the present invention, together with (A) a transition metal complex component and (B) an organoaluminum oxy compound component, (C)
An organoaluminum compound component may be used. The organoaluminum compound component (C) optionally used in the present invention is an organoaluminum compound used in producing a solution of aluminoxane, and preferably trimethylaluminum, triethylaluminum, or triisobutylaluminum.

The organoaluminum compound component (C) is generally diluted with a hydrocarbon solvent such as hexane or decane before use. The olefin polymerization catalyst according to the present invention comprises, for example, (A) transition metal complex component, (B) organoaluminum oxy compound component, and (C) organoaluminum compound component in an inert hydrocarbon solvent or in an olefin medium. It can be prepared by mixing. The mixing order at this time is arbitrarily selected.

FIG. 1 shows the steps for preparing the olefin polymerization catalyst according to the present invention. When mixing the components (A) and (B), and optionally the component (C), the atomic ratio of the aluminum in the components (B) and (C) to the transition metal in the component (A) (Al / Transition metal) is usually 10
The concentration of component (A) is in the range of about 10 ^-8 to 10 ^-1 mol / liter, preferably 10 ^{-7 to} 5 × 10 ^-2 mol / liter.

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

In the present invention, the polymerization can be carried out by either a liquid phase polymerization method such as a slurry polymerization method, a solution polymerization method or a suspension polymerization method, 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 complex component (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. Is preferably used in an amount of The atomic ratio (Al / transition metal) between the transition metal in the component (A) and the aluminum in the component (B) and the component (C) is usually 10 to 1.
It is desirable that it is 0000, preferably 20 to 5000.

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, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene,
1-octadecene, 1-eicosene; cyclic olefins having 3 to 20 carbon atoms, such as cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, 2-methyl-1,4,5,8- Dimethano-1,2,3,4,
4a, 5,8,8a-octahydronaphthalene and the like can be mentioned. Further, styrene, vinylcyclohexane, diene and the like can be used.

In the present invention, it is also possible to carry out copolymerization of two or more components using the above-mentioned olefins.
For example, ethylene / propylene, ethylene / 1-butene,
Examples are ethylene / propylene / diene and ethylene / tetracyclododecene.

In the present invention, the above-mentioned (A) transition metal complex component, (B) organoaluminum oxy compound component, (C).
At least one of the organoaluminum compound components may be used by supporting it on a carrier such as silica, alumina, silica-alumina or zirconia.

In the present invention, the olefin may be prepolymerized with the olefin polymerization catalyst during the polymerization of the olefin. In the prepolymerization, the olefin polymer is 0.05 to 500 g, preferably 0.1 to 300 g, and more preferably 0.2 to 100 g per 1 g of the olefin polymerization catalyst.
Is preferably prepolymerized in an amount of.

The olefins to be prepolymerized include 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, 1-tetradecene, 3-methyl-1-butene, 3-methyl-1-
A penten etc. can be illustrated. Of these, preferred are the same olefins as those used in the main polymerization.

[0061]

According to the olefin polymerization catalyst and the olefin polymerization method of the present invention, an olefin polymer having high activity and a narrow molecular weight distribution can be obtained. Further, when two or more kinds of monomers are copolymerized, a copolymer having a narrow composition distribution can be obtained.

[0062]

EXAMPLES The catalyst for olefin polymerization and the method for polymerizing olefins according to the present invention will be described in more detail below with reference to Examples, but the present invention is not limited to these Examples.

In the present invention, the intrinsic viscosity [η] is
It was measured in decalin at 135 ° C. and expressed in dl / g. [Preparation of transition metal complex component]

[0064]

Preparation Example 1 Biscyclopentadienylzirconium dihydride (345.8 mg, 1.549 mmol) was added to 100 m.
The mixture was placed in a 2-necked eggplant flask (1), the atmosphere was replaced with nitrogen, and benzene (20 ml) was added. Acetoneacetone (310.2 mg, 3.098 mmol) benzene (10
ml) solution was added dropwise. The reaction was carried out at room temperature for 3 hours. Generation of hydrogen gas was confirmed during the reaction.

[0065]

Preparation Example 2 100 ml of biscyclopentadienylzirconium dihydride (109.4 mg, 0.49 mmol)
The flask was placed in a 2-necked eggplant flask, the atmosphere was replaced with nitrogen, and benzene (20 ml) was added. A solution of acetylacetone (49 mg, 0.49 mmol) in benzene (20 ml) was added dropwise to this mixed system. The reaction was carried out at room temperature for 3 hours. Generation of hydrogen gas was confirmed during the reaction.

[0066]

Preparation Example 3 Biscyclopentadienylzirconium dihydride (176.8 mg, 0.792 mmol) was added to 100 m.
The mixture was placed in a 2-necked eggplant flask (1), the atmosphere was replaced with nitrogen, and benzene (20 ml) was added. Dipivaloylmethane (292 mg, 1.58 mmol) benzene (20 m
l) The solution was added dropwise. The reaction was carried out at room temperature for 1 day. Generation of hydrogen gas was confirmed during the reaction.

[0067]

Preparation Example 4 Biscyclopentadienylzirconium dihydride (199.2 mg, 0.892 mmol) was added to 100 m.
The mixture was placed in a 2-necked eggplant flask (1), the atmosphere was replaced with nitrogen, and benzene (20 ml) was added. Dipivaloylmethane (164 mg, 0.892 mmol) of benzene (20 mg) was added to this mixed system.
ml) solution was added dropwise. The reaction was carried out at room temperature for 2 days. Generation of hydrogen gas was confirmed during the reaction.

[0068]

Preparation Example 5 Biscyclopentadienylzirconium dihydride (144.4 mg, 0.647 mmol) was added to 100 m.
The mixture was placed in a 2-necked eggplant flask (1), the atmosphere was replaced with nitrogen, and benzene (20 ml) was added. To this mixed system, a solution of hexafluoroacetylacetone (0.183 ml, 1.294 mmol) in benzene (20 ml) was added dropwise. The reaction was carried out at room temperature for 3 hours. Generation of hydrogen gas was confirmed during the reaction.

[0069]

Preparation Example 6 Biscyclopentadienylzirconium dihydride (165.8 mg, 0.743 mmol) was added to 100 m.
The mixture was placed in a 2-necked eggplant flask (1), the atmosphere was replaced with nitrogen, and benzene (20 ml) was added. A solution of hexafluoroacetylacetone (0.105 ml, 0.743 mmol) in benzene (20 ml) was added dropwise to this mixed system. The reaction was carried out at room temperature for 2 hours. Generation of hydrogen gas was confirmed during the reaction.

[0070]

Preparation Example 7 Biscyclopentadienylzirconium dihydride (137.9 mg, 0.618 mmol) was added to 100 m.
The mixture was placed in a 2-necked eggplant flask (1), the atmosphere was replaced with nitrogen, and benzene (20 ml) was added. A solution of trifluoroacetylacetone (0.150 ml, 1.236 mmol) in benzene (20 ml) was added dropwise to this mixed system. The reaction was carried out at room temperature for 3 hours. Generation of hydrogen gas was confirmed during the reaction.

[0071]

Preparation Example 8 Biscyclopentadienylzirconium dihydride (121.9 mg, 0.546 mmol) was added to 100 m.
The mixture was placed in a 2-necked eggplant flask (1), the atmosphere was replaced with nitrogen, and benzene (20 ml) was added. A solution of trifluoroacetylacetone (0.066 ml, 0.546 mmol) in benzene (20 ml) was added dropwise to this mixed system. The reaction was carried out at room temperature for 2 hours. Generation of hydrogen gas was confirmed during the reaction.

[0072]

Preparation Example 9 Biscyclopentadienylzirconium dihydride (281.5 mg, 1.261 mmol) was added to 100 m.
The mixture was placed in a 2-necked eggplant flask (1), the atmosphere was replaced with nitrogen, and benzene (20 ml) was added. Add heptafluorobutanoyl pivaloyl methane (747 mg, 2.522 m
Mol) in benzene (10 ml) was added dropwise. The reaction was carried out at room temperature for 3 hours. Generation of hydrogen gas was confirmed during the reaction.

[0073]

Preparation Example 10 Biscyclopentadienylzirconium dihydride (110.7 mg, 0.496 mmol) was added to 100 parts.
The mixture was placed in a 2-necked round-bottomed flask having a capacity of 2 ml, nitrogen substitution was performed, and benzene (20 ml) was added. Add heptafluorobutanoyl pivaloyl methane (147 mg, 0.49) to this mixture.
A solution of 6 mmol of benzene (20 ml) was added dropwise. The reaction was carried out at room temperature for 3 hours. Generation of hydrogen gas was confirmed during the reaction.

[Polymerization of ethylene]

[0075]

Example 1 200 ml of purified toluene was placed in a glass flask having an inner volume of 500 ml that had been sufficiently replaced with nitrogen, and ethylene was passed at 100 liters / hr at 60 ° C.
I kept it for 10 minutes.

Next, methylaluminoxane (manufactured by Schling) was charged in an amount of 0.6 mg atom in terms of aluminum atom. Further, with the temperature kept at 60 ° C., the transition metal complex component obtained in Preparation Example 1 was converted into zirconium atom,
Charged 0.0008 mg atom. After performing the polymerization at 60 ° C. for 10 minutes, the polymerization was stopped by adding a large amount of methanol.

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 toluene as a solvent, washed with acetone and dried under reduced pressure. The results of the polymerization are shown in Table 1.

[0078]

Examples 2 to 10 Ethylene was polymerized in the same manner as in Example 1 except that the transition metal complex components shown in Table 1 were used and the polymerization time was changed as shown in Table 1.

The results of the polymerization are shown in Table 1.

[0080]

[Table 1]

[Brief description of drawings]

FIG. 1 is an explanatory view showing a process for preparing an olefin polymerization catalyst according to the present invention.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Shuji Minami 580-2 32 Takuji Nagaura, Sodegaura, Chiba Prefecture Mitsui Petrochemical Industry Co., Ltd.

Claims (2)

[Claims] 1. A transition metal compound represented by the following general formula [I]: (In the formula, M is a group IVB transition metal, and Cp ¹ and Cp ²
Is a group having a cyclopentadienyl skeleton, and these groups having a cyclopentadienyl skeleton may have a substituent, and Cp ¹ and Cp ² are an alkylene group, a substituted alkylene group or a silylene group. , May be bonded via a substituted silylene group. X is a hydrogen atom, a halogen atom, an alkyl group or an aryl group. ) [A-II] An organic compound represented by the following general formula [II] and (In the formula, R ¹ and R ³ are alkyl groups having 1 to 20 carbon atoms,
Alternatively, it is an aryl group or an alkoxy group, and these groups may have a substituent. R ¹ and R ³ may be the same or different. R ² is a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group,
It is an aralkyl group, and these groups may have a substituent. R ¹ and R ² may combine with each other to form a ring. And a transition metal complex component obtained by bringing them into contact with each other, and (B) an organoaluminum oxy compound component. 2. A method for polymerizing an olefin, which comprises polymerizing an olefin in the presence of the catalyst according to claim 1.