JPH07216011A - New transition metallic compound, catalyst component for polymerizing olefin composed of the same transition metallic compound, catalyst for polymerizing olefin containing the same catalyst component for polymerizing olefin and method for polymerizing olefin - Google Patents

Abstract

PURPOSE:To obtain a catalyst, comprising a specific transition metal, having excellent polymerization activity for an olefin and capable of producing a polyolefin, having a high molecular weight and a high melting point and excellent in stereoregularity. CONSTITUTION:This transition metallic compound is expressed by the formula (M is a group IVa, Va or VIa transition metal of the Periodic Table; R<1> is H, a halogen, a 1-20C halogenated hydrocarbon, a silicon-containing group, etc.; R<2> is a 1-20C hydrocarbon which may be substituted with a halogen, etc.; Hal is fluorine or chlorine; X and X are each H, a halogen, a 1-20C hydrocarbon, etc.; Y is a 1-20C bivalent hydrocarbon, SO, etc.). Furthermore, the catalyst for polymerizing an olefin comprises the transition metallic compound and is prepared by supporting the transition metallic compound, an organoaluminumoxy compound and a compound, reactive with the metallic compound and forming an ion paxr on a particulate carrier. The method for polymerizing the olefin comprises a reaction in the presence of the catalyst.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel transition metal compound, an olefin polymerization catalyst component comprising the transition metal compound, an olefin polymerization catalyst containing the olefin polymerization catalyst component, and an olefin using the olefin polymerization catalyst. It relates to a polymerization method.

[0002]

BACKGROUND OF THE INVENTION So-called Kaminsky catalysts are well known as homogeneous catalyst systems for olefin polymerization. This catalyst has a feature that a polymer having a very high polymerization activity and a narrow molecular weight distribution can be obtained.

Among the transition metal compound catalyst components used in the Kaminsky catalyst, the transition metal compound catalyst components for producing isotactic polyolefin include ethylene bis (indenyl) zirconium dichloride and ethylene bis (4,5,6,7). -Tetrahydroindenyl) zirconium dichloride (Japanese Patent Laid-Open No. 61-130314) is known. However, a polyolefin produced by using a catalyst containing such a transition metal compound catalyst component usually has a small molecular weight, and therefore an increase in the molecular weight is desired. Further, when it is produced at a low temperature, a highly stereoregular substance and a high molecular weight substance can be obtained, but there are problems such as low polymerization activity.

It is known that a high molecular weight compound can be produced by using a hafnium compound instead of the zirconium compound as described above (Journal of M.
olecular Catalysis, 56 (1989) p.237-247), this method has a problem of low polymerization activity. Further, JP-A-4-268307 discloses an olefin polymerization catalyst comprising a metallocene compound represented by the following formula and an aluminoxane.

[0005]

[Chemical 9]

Further, EP 0 530 648 A1 describes an olefin polymerization catalyst comprising a metallocene compound represented by the following formula and an aluminoxane.

[0007]

[Chemical 10]

(In the formula, A is a lower alkyl group.) The catalyst component in which A is a phenyl group or a naphthyl group in the above formula is 40 YEARS ZIEGLER CATALYSTS IN HONOR.
Published by Hoechst in OF KARL ZIEGER AND WORKSHOP (SEP.1 ~ 3,1993).

However, even the polyolefins obtained by these catalyst components are not always satisfactory in the molecular weight. As a result of diligent studies in view of such conventional techniques, the present inventors have found that a catalyst component composed of a transition metal compound represented by Chemical Formula 9 or Chemical Formula 10 has a polymerization activity depending on the kind of the substituent substituting the indenyl group. The present invention has been completed by finding that the molecular weights of the obtained polyolefins are significantly different.

[0010]

OBJECT OF THE INVENTION The present invention is a novel transition metal compound having excellent olefin polymerization activity, high molecular weight, excellent stereoregularity, and a olefin polymerization catalyst component capable of obtaining a high melting point polyolefin. And to provide a catalyst component for olefin polymerization comprising the transition metal compound. Further, it is an object to provide an olefin polymerization catalyst containing the olefin polymerization catalyst component, and to provide an olefin polymerization method using the olefin polymerization catalyst.

[0011]

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

[0012]

[Chemical 11]

(Where M is IVa, Va, VIa of the periodic table)
Represents a transition metal of Group III, R ¹ is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, an oxygen-containing group, a sulfur-containing group , A nitrogen-containing group or a phosphorus-containing group, R
² represents a hydrocarbon group having 1 to 20 carbon atoms, which is a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms,
It may be substituted with a halogenated hydrocarbon group having 1 to 20 carbon atoms.

Hal represents a fluorine atom or a chlorine atom, and X
¹And X²Is a hydrogen atom, a halogen atom, or a carbon number of 1 to
20 hydrocarbon groups, halogenated hydrocarbons having 1 to 20 carbon atoms
Represents a basic group, an oxygen-containing group or a sulfur-containing group, and Y is charcoal
Divalent hydrocarbon group having a prime number of 1 to 20, 2 having a carbon number of 1 to 20
Divalent halogenated hydrocarbon group, divalent silicon-containing group, divalent
Germanium-containing group, divalent tin-containing group, -O-,-
CO-, -S-, -SO-, -SO₂-, -NR³-,
-P (R³)-, -P (O) (R³)-,-BR³-
Or-AlR³-[However, R ³Is hydrogen atom, halogen
Atom, hydrocarbon group having 1 to 20 carbon atoms, 1 to 20 carbon atoms
Halogenated hydrocarbon group]. ) Oref according to the present invention
The catalyst component for in-polymerization is represented by the above general formula [I].
It is characterized by being composed of a metal transfer compound.

The first olefin polymerization catalyst according to the present invention comprises [A] a transition metal compound represented by the above general formula [I], [B] (B-1) an organoaluminum oxy compound, and (B) -
2) It is characterized by comprising at least one compound selected from the group consisting of compounds which react with the transition metal compound [A] to form an ion pair.

The second olefin polymerization catalyst according to the present invention is [A] a transition metal compound represented by the above general formula [I], [B] (B-1) an organoaluminum oxy compound, and (B) -
2) At least one compound selected from the group consisting of compounds that react with the transition metal compound [A] to form an ion pair, and [C] an organoaluminum compound.

The third olefin polymerization catalyst according to the present invention comprises: [A] a transition metal compound represented by the above general formula [I] and [B] (B-1) an organoaluminum oxy on a particulate carrier. Compound, and (B-
2) It is characterized in that it is loaded with at least one compound selected from the group consisting of compounds that react with the transition metal compound [A] to form an ion pair.

The fourth olefin polymerization catalyst according to the present invention comprises: [A] a transition metal compound represented by the above general formula [I] and [B] (B-1) an organoaluminum oxy on a particulate carrier. Compound, and (B-
2) A solid catalyst component carrying at least one compound selected from the group consisting of compounds that react with the transition metal compound [A] to form an ion pair, and [C] an organoaluminum compound. It is characterized by that.

The fifth olefin polymerization catalyst according to the present invention comprises a fine particle carrier, [A] a transition metal compound represented by the above general formula [I], and [B] (B-1) organoaluminum oxy. Compound, and (B-
2) It is characterized by comprising at least one compound selected from the group consisting of compounds that react with the transition metal compound [A] to form an ion pair, and an olefin polymer formed by prepolymerization.

The sixth olefin polymerization catalyst according to the present invention comprises a fine particle carrier, [A] a transition metal compound represented by the above general formula [I], and [B] (B-1) organoaluminum oxy. Compound, and (B-
2) At least one compound selected from the group consisting of compounds that react with the transition metal compound [A] to form an ion pair, [C] an organoaluminum compound, and an olefin polymer formed by prepolymerization It is characterized by that.

The olefin polymerization method according to the present invention is carried out in the presence of the above-mentioned first to sixth olefin polymerization catalysts, or in the presence of the fifth or sixth olefin polymerization catalyst and an organoaluminum compound. It is characterized by polymerizing or copolymerizing an olefin.

[0022]

DETAILED DESCRIPTION OF THE INVENTION A novel transition metal compound according to the present invention, an olefin polymerization catalyst component comprising the transition metal compound, an olefin polymerization catalyst containing the olefin polymerization catalyst component, and an olefin polymerization catalyst are described below. The olefin polymerization method used will be specifically described.

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

[0024]

[Chemical 12]

In the formula, M represents a transition metal atom of Group IVa, Va or VIa of the Periodic Table, specifically titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum or tungsten, Titanium, zirconium and hafnium are preferable, and zirconium is particularly preferable.

R ¹ is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, an oxygen-containing group, a sulfur-containing group,
Represents a nitrogen-containing group or a phosphorus-containing group, specifically, a halogen atom such as fluorine, chlorine, bromine, or iodine; methyl,
Alkyl groups such as ethyl, propyl, butyl, hexyl, cyclohexyl, octyl, nonyl, dodecyl, eicosyl, norbornyl and adamantyl, alkenyl groups such as vinyl, propenyl and cyclohexenyl, arylalkyl groups such as benzyl, phenylethyl and phenylpropyl, A hydrocarbon group having 1 to 20 carbon atoms such as an aryl group such as phenyl, tolyl, dimethylphenyl, trimethylphenyl, ethylphenyl, propylphenyl, biphenyl, naphthyl, methylnaphthyl, anthracenyl, phenanthryl; and a halogen atom in the hydrocarbon group. Substituted halogenated hydrocarbon group; monohydrocarbon-substituted silyl such as methylsilyl and phenylsilyl, dihydrocarbon-substituted silyl such as dimethylsilyl and diphenylsilyl,
Trihydrocarbyl-substituted silyl such as trimethylsilyl, triethylsilyl, tripropylsilyl, tricyclohexylsilyl, triphenylsilyl, dimethylphenylsilyl, methyldiphenylsilyl, tritolylsilyl, trinaphthylsilyl, and hydrocarbyl-substituted silyl such as trimethylsilyl ether. Silicon-containing groups such as ethers, silicon-substituted alkyl groups such as trimethylsilylmethyl, silicon-substituted aryl groups such as trimethylsilylphenyl; alkoxy groups such as hydroxy group, methoxy, ethoxy, propoxy, butoxy, phenoxy, methylphenoxy, dimethylphenoxy, naphthoxy. An oxygen-containing group such as an aryloxy group such as an arylalkoxy group such as phenylmethoxy or phenylethoxy; A sulfur-containing group such as a substituent substituted with; an amino group, an alkylamino group such as methylamino, dimethylamino, diethylamino, dipropylamino, dibutylamino, dicyclohexylamino, phenylamino, diphenylamino, ditolylamino, dinaphthylamino, methyl A nitrogen-containing group such as an arylamino group such as phenylamino or an alkylarylamino group; a phosphorus-containing group such as a phosphino group such as dimethylphosphino and diphenylphosphino.

Of these, a hydrocarbon group is preferable, and a hydrocarbon group having 1 to 6 carbon atoms such as methyl, ethyl, propyl, butyl, pentyl and hexyl is particularly preferable.

R ² represents a hydrocarbon group having 1 to 20 carbon atoms, and specifically, is an alkyl group, an alkenyl group or an arylalkyl group similar to those exemplified in the item of R ¹ . Alternatively, it is an aryl group such as phenyl, α-naphthyl, β-naphthyl, anthracenyl, phenanthryl, pyrenyl, acenaphthyl, phenalenyl, aceanthrylenyl and the like. Of these, an aryl group is preferable, and phenyl, naphthyl, and phenanthryl are particularly preferable. These hydrocarbon groups have the same structure as R ¹
The same halogen atom and C1-C1 as those exemplified in
It may be substituted with a hydrocarbon group having 20 or a halogenated hydrocarbon group having 1 to 20 carbon atoms.

X ¹ and X ² represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group or a sulfur-containing group. Examples of the halogen atom include the same halogen atom, hydrocarbon group having 1 to 20 carbon atoms, halogenated hydrocarbon group having 1 to 20 carbon atoms, and oxygen-containing group as those exemplified in the item of R ¹ .

As the sulfur-containing group, the same groups as those exemplified in the item of R ¹ above, methyl sulfonate, trifluoromethane sulfonate, phenyl sulfonate, benzyl sulfonate, p-toluene sulfonate, Sulfonate groups such as trimethylbenzene sulfonate, triisobutylbenzene sulfonate, p-chlorobenzene sulfonate, pentafluorobenzene sulfonate, methylsulfinate, phenylsulfinate, benzenesulfinate, p-toluene Sulfinate, trimethylbenzene sulfinate,
Examples thereof include sulfinate groups such as pentafluorobenzene sulfinate.

Of these, a halogen atom and a carbon number of 1 to
It is preferably 20 hydrocarbon groups. Y is the carbon number
1-20 divalent hydrocarbon groups, 1-20 carbon divalent hydrocarbon groups
Halogenated hydrocarbon group, divalent silicon-containing group, divalent gel
Rumanium-containing group, divalent tin-containing group, -O-, -CO
-, -S-, -SO-, -SO₂-, -NR³-, -P
(R³)-, -P (O) (R³)-,-BR³-Or
-AlR³-[However, R ³Is hydrogen atom, halogen atom
Child, hydrocarbon group having 1 to 20 carbon atoms, ha group having 1 to 20 carbon atoms
Rogenated hydrocarbon group], specifically, methylene,
Dimethylmethylene, 1,2-ethylene, dimethyl-1,2-ethyl
Len, 1,3-trimethylene, 1,4-tetramethylene, 1,2-silane
Alkyle such as chlorhexylene and 1,4-cyclohexylene
Group, diphenylmethylene, diphenyl-1,2-ethylene
C1-C20 such as aryl alkylene groups such as
Divalent hydrocarbon group; the above-mentioned carbon number 1 such as chloromethylene
To 20 halogenated divalent hydrocarbon groups
Hydrocarbon group; methylsilylene, dimethylsilylene, di
Ethyl silylene, di (n-propyl) silylene, di (i-p
Ropyr) silylene, di (cyclohexyl) silylene,
Tylphenylsilylene, diphenylsilylene, di (p-to)
Ryl) silylene, di (p-chlorophenyl) silylene, etc.
Alkyl silylenes, alkyl aryl silylenes, ants
Silylsilyl group, tetramethyl-1,2-disilyl, tetra
Alkyldisilyl, such as phenyl-1,2-disilyl, al
Divalent such as cyrylaryldisilyl and aryldisilyl groups
A silicon-containing group of the above;
A divalent germanium-containing group substituted with rumanium;
A divalent sulfur in which silicon in the divalent silicon-containing group is replaced with tin.
Group containing a substituent, such as R,³Is the R¹Example in section
Halogen atoms similar to those shown, carbons with 1 to 20 carbons
A hydrogenated group, a halogenated hydrocarbon group having 1 to 20 carbon atoms
It

Of these, a divalent silicon-containing group, a divalent germanium-containing group and a divalent tin-containing group are preferable, and a divalent silicon-containing group is more preferable, and alkylsilylene and alkylarylsilylene are preferred. More preferably, arylsilylene.

Specific examples of the transition metal compound represented by the above general formula [I] are shown below. rac-Dimethylsilyl-bis {1- (7-fluoro-4-phenylindenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1- (7-
Fluoro-2-methyl-4-phenylindenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1- (7-
Chloro-4-phenylindenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1- (7-fluoro-2,4
-Dimethylindenyl)} zirconium dichloride, rac
-Dimethylsilyl-bis {1- (7-fluoro-2-methyl-4-
Isopropylindenyl)} zirconium dichloride,
rac-Dimethylsilyl-bis {1- (7-fluoro-2-methyl
-4-Cyclohexylindenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1- (7-fluoro-2-
Methyl-4- (α-naphthyl) indenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1- (7-fluoro-2-methyl-4- (β-naphthyl) indenyl)} zirconium dichloride, rac-dimethylsilyl -Bis {1-
(7-Fluoro-2-methyl-4- (1-anthracenyl) indenyl) zirconium dichloride, rac-dimethylsilyl
-Bis {1- (7-fluoro-2-methyl-4- (2-anthracenyl) indenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1- (7-fluoro-2-methyl-4- (9
-Anthracenyl) indenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1- (7-fluoro-2-
Methyl-4- (9-phenanthryl) indenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1- (7-
Fluoro-2-methyl-4- (p-fluorophenyl) indenyl)} zirconium dichloride, rac-dimethylsilyl
-Bis {1- (7-fluoro-2-methyl-4- (pentafluorophenyl) indenyl)} zirconium dichloride,
rac-Dimethylsilyl-bis {1- (4- (p-chlorophenyl) -7-fluoro-2-methylindenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1- (4- (m-
Chlorophenyl) -7-fluoro-2-methylindenyl)} zirconium dichloride, rac-dimethylsilyl-
Bis {1- (4- (o-chlorophenyl) -7-fluoro-2-methylindenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1- (4- (o, p-dichlorophenyl) -7
-Fluoro-2-methylindenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1- (4- (p-bromophenyl) -7-fluoro-2-methylindenyl)} zirconium dichloride, rac-dimethylsilyl -Bis {1- (7
-Fluoro-2-methyl-4- (p-tolyl) indenyl)}
Zirconium dichloride, rac-dimethylsilyl-bis {1
-(7-Fluoro-2-methyl-4- (m-tolyl) indenyl)} zirconium dichloride, rac-dimethylsilyl-
Bis {1- (7-fluoro-2-methyl-4- (o-tolyl) indenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1- (4- (o, o'-dimethylphenyl) -7- Fluoro-2-methylindenyl)} zirconium dichloride,
rac-Dimethylsilyl-bis {1- (4- (p-ethylphenyl) -7-fluoro-2-methylindenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1- (7-fluoro-2-methyl) -4- (pi-propylphenyl) indenyl)} zirconium dichloride, rac-dimethylsilyl-
Bis {1- (4- (p-benzylphenyl) -7-fluoro-2-
Methylindenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1- (4- (p-biphenyl) -7-fluoro-2-methylindenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1- ( 4- (m-biphenyl) -7-fluoro-2-methylindenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1- (7-fluoro-2-methyl-4- (p-trimethylsilylphenyl) indenyl) } Zirconium dichloride, rac-dimethylsilyl-bis {1- (7-fluoro-2-methyl-4- (m-trimethylsilylphenyl) indenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1- (2-ethyl- 7-
Fluoro-4-phenylindenyl)} zirconium dichloride, rac-diphenylsilyl-bis {1- (2-ethyl-7
-Fluoro-4-phenylindenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1- (2-phenyl
-4-Phenyl-7-fluoroindenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1- (7-fluoro-2-n-propyl-4-phenylindenyl)} zirconium dichloride, rac-diethylsilyl- Bis {1- (7-fluoro-2-methyl-4-phenylindenyl)} zirconium dichloride, rac-di- (i-propyl) silyl-bis {1- (7-fluoro-2-methyl-4-phenyl Indenyl)} zirconium dichloride, rac-di- (n-butyl)
Silyl-bis {1- (7-fluoro-2-methyl-4-phenylindenyl)} zirconium dichloride, rac-dicyclohexylsilyl-bis {1- (7-fluoro-2-methyl-4-
Phenylindenyl)} zirconium dichloride, rac-
Methylphenylsilyl-bis {1- (7-fluoro-2-methyl-4-phenylindenyl)} zirconium dichloride, rac-diphenylsilyl-bis {1- (7-fluoro-2-
Methyl-4-phenylindenyl)} zirconium dichloride, rac-di (p-tolyl) silyl-bis {1- (7-fluoro-2-methyl-4-phenylindenyl)} zirconium dichloride, rac-di (p -Chlorophenyl) silyl-bis {1- (7-fluoro-2-methyl-4-phenylindenyl)} zirconium dichloride, rac-methylene-bis {1
-(7-Fluoro-2-methyl-4-phenylindenyl)}
Zirconium dichloride, rac-ethylene-bis {1- (7-
Fluoro-2-methyl-4-phenylindenyl)} zirconium dichloride, rac-dimethylgermyl-bis {1- (7
-Fluoro-2-methyl-4-phenylindenyl)} zirconium dichloride, rac-dimethyltin-bis {1- (7-
Fluoro-2-methyl-4-phenylindenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1- (7-
Fluoro-2-methyl-4-phenylindenyl)} zirconium dibromide, rac-dimethylsilyl-bis {1- (7-
Fluoro-2-methyl-4-phenylindenyl)} zirconium dimethyl, rac-dimethylsilyl-bis {1- (7-fluoro-2-methyl-4-phenylindenyl)} zirconium methyl chloride, rac-dimethylsilyl- Screw {1- (7
-Fluoro-2-methyl-4-phenylindenyl)} zirconium chloride SO ₂ Me, rac-dimethylsilyl-bis {1- (7-fluoro-2-methyl-4-phenylindenyl)} zirconium chloride OSO ₂ Me , Rac-dimethylsilyl-bis {1- (7-fluoro-2-methyl-4-phenylindenyl)} titanium dichloride, rac-dimethylsilyl-bis {1- (7-fluoro-2-methyl-4-phenyl Indenyl)} hafnium dichloride and the like.

In the present invention, a transition metal compound in which zirconium metal, titanium metal, or hafnium metal is replaced with vanadium metal, niobium metal, tantalum metal, chromium metal, molybdenum metal, or tungsten metal in the above compounds may be used. it can.

Such a novel transition metal compound according to the present invention is described in Journal of Organometallic Chem. 288 (1985),
It can be manufactured according to the description of European Patent Application Publication No. 0,320,762 and Examples on pages 63 to 67, for example, as follows.

[0036]

[Chemical 13]

The novel transition metal compound according to the present invention can be used as a catalyst component for olefin polymerization in combination with an organic aluminum oxy compound or the like. The transition metal compound is usually used as a racemate as a catalyst component for olefin polymerization, but R type or S type can also be used.

Next, an olefin polymerization catalyst containing the above-mentioned novel transition metal compound as a catalyst component will be described. FIG. 1 shows a process for preparing an olefin polymerization catalyst according to the present invention.

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 not only homopolymer but also homopolymer. It may be used to include a polymer.

First, the first and second olefin polymerization catalysts according to the present invention will be described. The first olefin polymerization catalyst according to the present invention comprises [A] a transition metal compound represented by the general formula [I] (hereinafter sometimes referred to as "component [A]"), and [B]. (B-1) Organoaluminum oxy compound, and (B-
2) At least one compound selected from the group consisting of compounds that react with the transition metal compound [A] to form an ion pair.

The second olefin polymerization catalyst according to the present invention is [A] a transition metal compound [A] represented by the general formula [I], and [B] (B-1) an organoaluminum oxy compound. , And (B-
2) At least one compound selected from the group consisting of compounds that react with the transition metal compound [A] to form an ion pair, and [C] an organoaluminum compound.

(B-1) Organoaluminumoxy compound (hereinafter referred to as "component") which forms the olefin polymerization catalyst according to the present invention.
(B-1) ”may be described. ) May be a conventionally known aluminoxane, and JP-A-2-78687.
It may be a benzene-insoluble organoaluminum oxy compound as exemplified in the publication.

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 in which an organoaluminum compound such as trialkylaluminum is added to the hydrocarbon medium suspension and reacted. (2) A method in which water, ice, or water vapor is allowed to directly act on an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether, or tetrahydrofuran. (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 an organometallic component. Further, the solvent or the unreacted organoaluminum compound may be removed by distillation from the recovered solution of the aluminoxane, and then redissolved in the solvent or suspended in the poor solvent of the aluminoxane.

Specific examples of the organoaluminum compound used when preparing the aluminoxane include trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum and trisec-butyl. Aluminum, tri-tert-butylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum and other trialkylaluminums; tricyclohexylaluminum, tricyclooctylaluminum and other tricycloalkylaluminums; dimethylaluminum chloride, diethylaluminum Chloride, diethyl aluminum bromide, diisobutyl aluminum chloride, etc. Alkylaluminum halides; diethylaluminum hydride, dialkylaluminum hydride such as diisobutylaluminum hydride; dimethyl aluminum methoxide, dialkylaluminum alkoxides such as diethylaluminum ethoxide; and dialkylaluminum Ally Loki Sid such as diethyl aluminum phenoxide and the like.

Of these, trialkylaluminum and tricycloalkylaluminum are preferable, and trimethylaluminum is particularly preferable. In addition, as the organoaluminum compound used when preparing the aluminoxane, isoprenylaluminum represented by the following general formula [II] can be used.

(I-C ₄ H ₉ ) _x Al _y (C ₅ H ₁₀ ) _z [II] (In the formula, x, y, and z are positive numbers, and z ≧ 2x). Such organoaluminum compounds may be used alone or in combination. For example, trimethylaluminum and triisobutylaluminum are used in combination.

Examples of the solvent used in the aluminoxane solution include aromatic hydrocarbons such as benzene, toluene, xylene, cumene and cymene, and aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane and octadecane. , Cyclopentane, cyclohexane, cyclooctane, methylcyclopentane, and other alicyclic hydrocarbons, petroleum fractions such as gasoline, kerosene, and light oil, or the above aromatic hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbon halides Among these, 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 or aliphatic hydrocarbons are particularly preferable.

Forming the Olefin Polymerization Catalyst of the Present Invention (B-2) A compound that reacts with the transition metal compound [A] to form an ion pair (hereinafter referred to as "component (B-2)". (Japanese Patent Publication No. 1-501950, Japanese Patent Publication No. 1-502036, Japanese Patent Laid-Open No. 3-179).
Examples of Lewis acids, ionic compounds and carborane compounds described in JP-A No. 005, JP-A-3-179006, JP-A-3-207703, JP-A-3-207704, US-547718 and the like. You can

As the Lewis acid, triphenylboron,
Tris (4-fluorophenyl) boron, Tris (p-tolyl) boron, Tris (o-tolyl) boron, Tris (3,5-
Dimethylphenyl) boron, Tris (pentafluorophenyl) boron, MgCl ₂ , Al ₂ O ₃ , SiO ₂ -Al ₂
Examples include O _{3 and the} like.

As the ionic compound, triphenylcarbenium tetrakis (pentafluorophenyl) borate, tri-n-butylammonium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, ferroferrite Examples include cerium tetra (pentafluorophenyl) borate.

The carborane compounds include dodecaborane, 1-carbaundecaborane, bis-n-butylammonium (1-carbedodeca) borate, tri-n-butylammonium (7,8-dicarbaunceca) borate, tri-n-butylammonium. (Trideca hydride-7-carbaundeca) borate etc. can be illustrated.

The compound (B-2) which reacts with the above transition metal compound [A] to form an ion pair can be used as a mixture of two or more kinds. Examples of the [C] organoaluminum compound (hereinafter sometimes referred to as “component [C]”) that forms the olefin polymerization catalyst according to the present invention include, for example, an organoaluminum compound represented by the following general formula [III]. Can be illustrated.

R ⁷ _n AlX _3-n ... [III] (In the formula, R ⁷ is a hydrocarbon group having 1 to 12 carbon atoms, and X
Is a halogen atom or a hydrogen atom, and n is 1 to 3. ) In the above general formula [III], R ⁷ is a hydrocarbon group having 1 to 12 carbon atoms, for example, an alkyl group, a cycloalkyl group or an aryl group, and specifically, a methyl group, an ethyl group, n-propyl group. Group, isopropyl group, isobutyl group,
Examples include a pentyl group, a hexyl group, an octyl group, a cyclopentyl group, a cyclohexyl group, a phenyl group and a tolyl group.

Such an organoaluminum compound [C]
Specifically, the following compounds may be mentioned. Trialkylaluminums such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trioctylaluminum, tri (2-ethylhexyl) aluminum and tridecylaluminum; alkenylaluminums such as isoprenylaluminum; dimethylaluminum chloride and diethylaluminum chloride. Dialkyl aluminum halides such as diisopropyl aluminum chloride, diisobutyl aluminum chloride and dimethyl aluminum bromide; alkyl aluminum such as methyl aluminum sesquichloride, ethyl aluminum sesquichloride, isopropyl aluminum sesquichloride, butyl aluminum sesquibromide and ethyl aluminum sesquibromide. Bromide sesquihalide; methyl aluminum dichloride, ethyl aluminum dichloride, isopropyl aluminum dichloride, alkyl aluminum dihalides such as ethyl aluminum dibromide; diethylaluminum hydride, and alkyl aluminum hydride such as diisobutyl aluminum hydride.

Further, as an organoaluminum compound [C]
It is also possible to use a compound represented by the following general formula [IV]
it can. R⁷ _nAl L_3-n ... [IV] (wherein R⁷Is the same as above, and L is -OR⁸Group,-
OSiR⁹ ₃Group, -OAlR^Ten ₂Group, -NR¹¹ ₂Group,-
SiR¹² ₃Group or -N (R¹³) AlR¹⁴ ₂The base,
n is 1 to 2 and R⁸, R⁹, R^TenAnd R¹⁴Is meth
Group, ethyl group, isopropyl group, isobutyl group, cyclo
Rhexyl group, phenyl group, etc. ¹¹Is hydrogen
Child, methyl group, ethyl group, isopropyl group, phenyl
Group, trimethylsilyl group, etc., R¹²And R¹³Is
Examples include a methyl group and an ethyl group. ) Among such organoaluminum compounds, R is⁷ _nA
l (OAlR^Ten ₂)_3-nA compound represented by, for example, E
t₂ AlOAlEt₂, (Iso-Bu)₂AlOAl (iso
-Bu)₂Are preferred.

[0057] Among the above general formula [III] and an organoaluminum compound represented by the [IV], formula R ⁷ compound represented by ₃ Al are preferred, especially those wherein R ⁷ is an isoalkyl group.

In the present invention, the above component [A] and component (B-1)
In addition to the component (B-2) and the component [C], water may be contained as a catalyst component. As such water, water dissolved in a polymerization solvent as described below, or component (B-1)
Examples thereof include adsorbed water and water of crystallization contained in the compound or salt used in the production of.

The first olefin polymerization catalyst according to the present invention comprises a component [A], a component (B-1) (or a component (B-2)) and, if desired, water as a catalyst component, an inert hydrocarbon. It can be prepared by mixing in a solvent or an olefin solvent.

In this case, the order of mixing the respective components is arbitrary, but the component (B-1) (or the component (B-2)) and water are mixed,
Next, it is preferable to mix the component [A]. The second olefin polymerization catalyst according to the present invention is a component [A], a component
It can be prepared by mixing (B-1) (or component (B-2)), component [C] and optionally water as a catalyst component in an inert hydrocarbon solvent or an olefin solvent.

In this case, the order of mixing the components is arbitrary, but when the component (B-1) is used, the component (B-1) and the component [C] are mixed, and then the component [A]. Are preferably mixed. When using the component (B-2), it is preferable to mix the component [C] and the component [A], and then mix the component (B-2).

When mixing the above components, the components (B-
The atomic ratio (Al / transition metal) between aluminum in 1) and the transition metal in component [A] is usually 10 to 10,000,
It is preferably 20 to 5000, and the concentration of the component [A] is in the range of about 10 ^-8 to 10 ^-1 mol / liter (solvent), preferably 10 ^{-7 to} 5 × 10 ^-2 mol / liter (solvent). Is.

When the component (B-2) is used, the molar ratio of the component [A] to the component (B-2) (component [A] / component (B-2)) is usually 0.01 to 10, It is preferably in the range of 0.1 to 5,
The concentration of the component [A] is in the range of about 10 ⁻⁸ to 10 ⁻¹ mol / liter (solvent), preferably 10 ^{−7 to} 5 × 10 ⁻² mol / liter (solvent).

The aluminum atom (A) in the component [C] forming the second olefin polymerization catalyst according to the present invention is also used.
l _C ) and the aluminum atom (Al _B-1 ) in the component (B-1) have an atomic ratio (Al _C / Al _B-1 ) of usually 0.02 to 20,
It is preferably in the range of 0.2 to 10.

When water is used as the catalyst component, the molar ratio of aluminum atom (Al _B-1 ) and water (H ₂ O) in the component (B-1) (Al _B-1 / H ₂ O) is 0.5-5
The range is 0, preferably 1 to 40.

The above catalyst components may be mixed in the polymerization vessel, or may be mixed in advance and added to the polymerization vessel.
The mixing temperature when mixing in advance is usually -50 to 150 ° C,
It is preferably -20 to 120 ° C, and the contact time is 1 to 1
000 minutes, preferably 5 to 600 minutes. Also,
The mixing temperature may be changed during the mixing contact.

Specific examples of the inert hydrocarbon solvent used for preparing the olefin polymerization catalyst according to the present invention include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; Alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclopentane; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as ethylene chloride, chlorobenzene and dichloromethane, and mixtures thereof. it can.

Next, the third and fourth olefin polymerization catalysts according to the present invention will be described. The third catalyst for olefin polymerization according to the present invention comprises: [A] a transition metal compound represented by the above general formula [I], [B] (B-1) an organoaluminum oxy compound, and (B
-2) At least one compound selected from the group consisting of compounds that react with the transition metal compound [A] to form an ion pair is supported.

The fourth catalyst for olefin polymerization according to the present invention comprises: [A] a transition metal compound represented by the above general formula [I] and [B] (B-1) an organoaluminumoxy compound on a fine particle carrier. Compound, and (B
-2) From a solid catalyst component carrying at least one compound selected from the group consisting of compounds that react with the transition metal compound [A] to form an ion pair, and [C] an organoaluminum compound Has been formed.

The [A] transition metal compound forming the third and fourth olefin polymerization catalysts according to the present invention is the same as the above-mentioned component [A] forming the first and second olefin polymerization catalysts. And a transition metal compound represented by the above general formula [I].

As the organoaluminum oxy compound (B-1) for forming the third and fourth olefin polymerization catalysts according to the present invention, the component (B) for forming the above-mentioned first and second olefin polymerization catalysts (B The same organoaluminum oxy compound as described in -1) can be exemplified.

Forming Third and Fourth Olefin Polymerization Catalysts According to the Present Invention (B-2) The Transition Metal Compound [A]
The compound that reacts with the above to form an ion pair is a component that forms the above-mentioned first and second olefin polymerization catalysts.
The same compounds as (B-2) can be exemplified.

Further, as the [C] organoaluminum compound forming the fourth olefin polymerization catalyst according to the present invention, the same organoaluminum compound as the above-mentioned component [C] forming the second olefin polymerization catalyst can be used. It can be illustrated.

The fine particle carrier for forming the third and fourth olefin polymerization catalysts according to the present invention is an inorganic or organic compound and has a particle size of 10 to 300 μm, preferably 20 to 200 μm. It is a solid in the form of fine particles.

Of these, the inorganic carrier is porous
Oxides are preferred, eg SiO ₂, Al₂O₃Etc.
It can be illustrated. Granular or fine organic compounds
Particulate solids include ethylene, propylene, 1-butene
With α-olefins such as
The polymer or copolymer produced by
Wear.

Further, the third and fourth olefin polymerization catalysts according to the present invention may contain water as a catalyst component as described in the above first and second olefin polymerization catalysts.

The third catalyst for olefin polymerization (solid catalyst component) according to the present invention comprises the above-mentioned particulate carrier, component [A],
It can be prepared by mixing and contacting the component (B-1) (or the component (B-2)) and optionally water as a catalyst component in an inert hydrocarbon solvent or an olefin medium. Further, when the components are mixed and brought into contact with each other, the component [C] can be further added.

The mixing order at this time is selected arbitrarily, but preferably the fine particle carrier and the component (B-1) (or the component (B-2)
), And then component [A] is mixed and contacted, and if desired, water is mixed and contacted, or component (B-
1) a mixture of (or component (B-2)) and component [A],
The particulate carrier is mixed and contacted, and then water is optionally mixed and contacted, or the particulate carrier and the component (B-
It is selected that 1) (or component (B-2)) and water are mixed and contacted, and then component [A] is mixed and contacted.

When the above components are mixed, the component [A] is usually 10 ^{−6 to} 5 × 10 ⁻³ per 1 g of the fine particle carrier in terms of the transition metal atom derived from the component [A].
It is used in a molar amount, preferably 3 × 10 ⁻⁶ to 10 ⁻³ mol, and the concentration of the component [A] is about 5 × 10 ⁻⁶ to the transition metal atom derived from the component [A]. It is in the range of 2 × 10 ^-2 mol / liter (solvent), preferably 10 ^-5 to 10 ^-2 mol / liter (solvent). The atomic ratio of the aluminum in component (B-1) to the transition metal in component [A] (Al / transition metal) is usually 10 to 3000, preferably 20 to 20.
00. When the component (B-2) is used, the molar ratio of the component [A] to the component (B-2) (component [A] / component (B-2)) is usually 0.01 to 10, preferably 0. The range is from .1 to 5.

When water is used as the catalyst component, the molar ratio of aluminum atom (Al _B-1 ) and water (H ₂ O) in the component (B-1) (Al _B-1 / H ₂ O) is 0.5-5
The range is 0, preferably 1 to 40.

The mixing temperature at the time of mixing the above components is usually -50 to 150 ° C, preferably -20 to 120 ° C, and the contact time is 1 to 1000 minutes, preferably 5 to 60 minutes.
0 minutes. Further, the mixing temperature may be changed during the mixing contact.

The fourth olefin polymerization catalyst according to the present invention is the third olefin polymerization catalyst (solid catalyst component).
And [C] organoaluminum compound. The component [C] is desirably used in an amount of 500 mol or less, preferably 5 to 200 mol, per gram atom of the transition metal atom in the component [A].

The inert hydrocarbon medium used for preparing the third and fourth olefin polymerization catalysts according to the present invention is the same as the one used for preparing the first and second olefin polymerization catalysts. Activated hydrocarbon media are mentioned.

Next, the fifth and sixth olefin polymerization catalysts according to the present invention will be described. A fifth olefin polymerization catalyst according to the present invention is a particulate carrier, [A] a transition metal compound represented by the above general formula [I], [B] (B-1) an organoaluminum oxy compound, and (B
-2) At least one compound selected from the group consisting of compounds that react with the transition metal compound [A] to form an ion pair, and an olefin polymer formed by prepolymerization.

The sixth olefin polymerization catalyst according to the present invention comprises a fine particle carrier, [A] a transition metal compound represented by the above general formula [I], and [B] (B-1) organoaluminum oxy. Compound, and (B
-2) At least one compound selected from the group consisting of compounds that react with the transition metal compound [A] to form an ion pair, [C] an organoaluminum compound, and an olefin polymer produced by preliminary polymerization. Are formed from.

Examples of the fine particle carrier for forming the fifth and sixth olefin polymerization catalysts according to the present invention are the same as the above-mentioned fine particle carriers for forming the third and fourth olefin polymerization catalysts. it can.

The [A] transition metal compound forming the fifth and sixth olefin polymerization catalysts according to the present invention is the same as the above-mentioned component [A] forming the first and second olefin polymerization catalysts. And a transition metal compound represented by the above general formula [I].

As the organoaluminum oxy compound (B-1) for forming the fifth and sixth olefin polymerization catalysts according to the present invention, the components (B) for forming the above-mentioned first and second olefin polymerization catalysts can be used. The same organoaluminum oxy compound as described in -1) can be exemplified.

Forming Fifth and Sixth Olefin Polymerization Catalysts of the Present Invention (B-2) The Transition Metal Compound [A]
The compound that reacts with the above to form an ion pair is a component that forms the above-mentioned first and second olefin polymerization catalysts.
The same compounds as (B-2) can be exemplified.

Further, as the [C] organoaluminum compound forming the sixth olefin polymerization catalyst according to the present invention, the same organoaluminum compound as the above-mentioned component [C] forming the second olefin polymerization catalyst can be used. It can be illustrated.

Further, the fifth and sixth olefin polymerization catalysts according to the present invention may contain water as a catalyst component as described in the above first and second olefin polymerization catalysts.

The fifth catalyst for olefin polymerization according to the present invention comprises the above-mentioned particulate carrier, component [A], component (B-1) (or component (B-2)) and optionally water as a catalyst component. It can be prepared by prepolymerizing a small amount of olefin to the solid catalyst component obtained by mixing and contacting with and in an inert hydrocarbon solvent or in an olefin medium. Further, the component [C] can be further added at the time of mixing and contacting.

In this case, the order of mixing the respective components is arbitrarily selected, but it is preferable that the fine particle carrier and the component (B-1) (or the component (B-2)) are mixed and brought into contact with each other, and then the component [A]. Are mixed and contacted with water if desired, or a mixture of the component (B-1) (or component (B-2)) and the component [A] is mixed and contacted with a fine particle carrier, and then, If desired, water may be mixed and contacted, or fine particle carrier and components
It is selected that (B-1) (or component (B-2)) and water are mixed and contacted, and then component [A] is mixed and contacted.

It is desirable that the mixing contact is performed with stirring. In mixing the above components, the component [A] is
The components [A] fine particle carrier 1g per normal 10 ^-6 ~5 × 10 ^-3 mol in terms of transition metal atom derived from, preferably used in an amount of 3 × 10 ^-6 ~10 ^-3 mol, The concentration of the component [A] is about 5 × 10 ⁻⁶ to 2 × 10 ⁻² mol / liter (solvent), preferably 10 ⁻⁵ to 10 ⁻ , in terms of the transition metal atom derived from the component [A]. It is in the range of ² mol / liter (solvent). The atomic ratio of the aluminum in component (B-1) to the transition metal in component [A] (Al / transition metal) is usually 10 to 3000, preferably 20 to 200.
It is 0. When using the component (B-2), the component [A] and the component
The molar ratio with (B-2) (component [A] / component (B-2)) is usually 0.01 to 10, preferably 0.1 to 5.

When water is used as the catalyst component, the aluminum atom (Al _B-1 ) in the component (B-1),
The molar ratio with water (H ₂ O) (Al _B-1 / H ₂ O) is 0.5-5.
The range is 0, preferably 1 to 40.

The mixing temperature for mixing the above components is usually -50 to 150 ° C, preferably -20 to 120 ° C, and the contact time is 1 to 1000 minutes, preferably 5 to 60 minutes.
0 minutes. Further, the mixing temperature may be changed during the mixing contact.

The fifth catalyst for olefin polymerization according to the present invention can be prepared by prepolymerizing an olefin in the presence of each of the above components. Preliminary polymerization can be carried out by introducing an olefin into an inert hydrocarbon solvent in the presence of the above-mentioned components or, if necessary, in the coexistence of the component [C].

In the preliminary polymerization, the amount of the component [A] is usually 10 ⁻⁵ to 2 × 10 ⁻² mol / liter (solvent), preferably 5 × 10 ⁻⁵ to 10 ⁻² mol / liter (solvent). The prepolymerization temperature is -20 to 80 ° C, preferably 0.
˜50 ° C., and the prepolymerization time is 0.5 to 100 hours, preferably 1 to 50 hours.

The olefin used in the prepolymerization is selected from the olefins used in the polymerization,
It is preferably the same monomer as the polymerization or a mixture of the same monomer as the polymerization and an α-olefin.

The olefin polymerization catalyst according to the present invention obtained as described above is about 10 per 1 g of the particulate carrier.
^-6 to 10 ^-3 gram atom, preferably 2 x 10 ^{-6 to} 3 x 1
^0-4 gram atoms of transition metal atoms are supported, about 10 ^-3 〜.
10 ⁻¹ gram atom, preferably 2 × 10 ^{−3 to} 5 × 10 ⁻²
It is desirable to support gram atoms of aluminum atoms. The component (B-2) is supported in an amount of 10 ^{-7 to} 0.1 gram atom, preferably 2 × 10 ^{-7 to} 3 × 10 ^-2 gram atom as a boron atom derived from the component (B-2). It is desirable that

Further, the amount of the polymer produced by the prepolymerization is about 0.1 to 500 g, preferably 0.3 to 300 g, particularly preferably 1 to 100 g, per 1 g of the fine particle carrier.
It is desirable that the range is.

A sixth olefin polymerization catalyst according to the present invention comprises the above-mentioned fifth olefin polymerization catalyst (component),
[C] An organoaluminum compound.
The organoaluminum compound [C] is preferably used in an amount of 500 mol or less, preferably 5 to 200 mol, per 1 gram atom of the transition metal atom in the component [A].

The inert hydrocarbon solvent used in the preparation of the fifth and sixth olefin polymerization catalysts according to the present invention is the same as that used in the preparation of the above-mentioned first and second olefin polymerization catalysts. Inert hydrocarbon solvent of.

The first to sixth olefin polymerization catalysts according to the present invention may contain other components useful for olefin polymerization in addition to the above components. The polyolefin obtained by such an olefin polymerization catalyst according to the present invention has a narrow molecular weight distribution and composition distribution,
High molecular weight and high polymerization activity.

When an olefin having 3 or more carbon atoms is polymerized, a polyolefin having excellent stereoregularity can be obtained.
Next, the olefin polymerization method according to the present invention will be described.

In the present invention, olefin polymerization is carried out in the presence of the above olefin polymerization catalyst. The polymerization can be carried out by either a liquid phase polymerization method such as suspension polymerization or a gas phase polymerization method.

In the liquid phase polymerization method, the same inert hydrocarbon solvent as used in the above catalyst preparation can be used, and the olefin itself can also be used as the solvent.
When carrying out olefin polymerization using the first or second olefin polymerization catalyst of the present invention, the above-mentioned catalyst usually has a concentration of the transition metal atom derived from the component [A] in the polymerization system of 10 ^{− 8-10 -3} gram atom / liter,
It is preferably used in an amount of 10 ⁻⁷ to 10 ⁻⁴ gram atom / liter.

The third or fourth olefin polymerization of the present invention
When carrying out the polymerization of olefins using a catalyst for use
The catalysts such as the above are transitions derived from the component [A] in the polymerization system.
The concentration of metal atoms is usually 10^-8-10^-3Gram atom
/ Liter, preferably 10 ^-7-10^-FourGram atom / Li
It is preferably used in the amount of tottle. At this time, desired
Therefore, aluminoxane may be used.

When the olefin polymerization is carried out by using the olefin polymerization catalyst in which the olefin is prepolymerized like the fifth or sixth olefin polymerization catalyst according to the present invention, the above-mentioned catalyst is The concentration of transition metal atoms derived from the component [A] in the polymerization system is usually 10
^-8 to 10 ^-3 gram atom / liter, preferably 10 ^-7 to
It is preferably used in an amount of 10 ⁻⁴ gram atom / liter. At this time, aluminoxane may be used if desired.

The olefin polymerization temperature is usually in the range of -100 to 100 ° C., preferably -50 to 90 ° C. when carrying out the slurry polymerization method, and when carrying out the liquid phase polymerization method. Is usually in the range of -100 to 250 ° C, preferably -50 to 200 ° C.
Further, when carrying out the gas phase polymerization method, the polymerization temperature is usually −
It is desirable that the temperature is in the range of 47 to 120 ° C, preferably -40 to 100 ° C. The polymerization pressure is usually from atmospheric pressure to 100.
It is under conditions of kg / cm ² , preferably atmospheric pressure to 50 kg / cm ² , and the polymerization reaction can be carried out by any of batch, semi-continuous and continuous methods. 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. Examples of olefins that can be polymerized by the olefin polymerization catalyst 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-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene;
20 cyclic olefins 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 etc. can be mentioned. Further, styrene, vinylcyclohexane, diene and the like can be used.

The olefin polymerization catalyst according to the present invention is particularly suitable for homopolymerization of propylene or copolymerization of propylene with at least one α-olefin selected from the group consisting of ethylene and C 4-20 α-olefins. It is preferably used.

[0113]

The novel transition metal compound according to the present invention is
It can be used as a catalyst component for olefin polymerization.

The olefin polymerization catalyst according to the present invention is highly active and can produce a polyolefin having a narrow molecular weight distribution and compositional distribution and a high molecular weight. A polyolefin obtained by polymerizing an olefin having 3 or more carbon atoms has high stereoregularity and thus has a high melting point and is excellent in heat resistance and rigidity. When a copolymer elastomer containing ethylene or propylene as a main component is produced using the olefin polymerization catalyst of the present invention, a product having a narrow molecular weight distribution can be obtained. Such a copolymer elastomer has high strength,
When used as a modifier, it has an excellent effect of modifying the impact strength and hardness of polyolefin. Furthermore, when used in the production of a block copolymer of propylene, the molecular weight of the copolymer elastomer can be increased, so that an excellent balance between heat resistance, rigidity or transparency and impact strength can be obtained. . Further, even when used in the production of polyethylene, a polyethylene having a high molecular weight can be obtained, and thus polyethylene having excellent mechanical strength such as impact strength, tensile strength and bending strength can be obtained.

[0115]

The present invention will be described in more detail based on the following examples, but the invention is not intended to be limited to these examples.

In this example, the intrinsic viscosity [η] of the obtained polymer was measured in decalin at 135 ° C. M
w / Mn was determined by gel permeation chromatography (GPC). The melting point is measured by a differential scanning calorimeter (D
SC). The composition of the copolymer is ¹³ C-
Obtained by NMR.

[0117]

Example 1 Synthesis of rac-dimethylsilyl-bis {1- (7-fluoro-2-methyl-4-phenylindenyl)} zirconium dichloride [Synthesis of diethyl 2-bromo-5-fluorobenzylmethylmalonate] N-bromosuccinic acid 27. in a 500 ml-4 neck round bottom flask (with stirrer, Dimroth condenser, thermometer).
11 g (152.3 mmol), 2-bromo-5-fluorotoluene 25.04 g (132.5 mmol), carbon tetrachloride 250 ml and benzoyl peroxide 0.64 g (2.6
4 mmol) was added and the mixture was refluxed for 4 hours in a nitrogen atmosphere. The reaction mixture was cooled to room temperature and then filtered. The filter cake was washed with 150 ml of hexane, and the filtrate was concentrated under reduced pressure to obtain 35.9 g of a brown liquid.

Next, 13.7 g (122.4 mmol) of potassium t-butoxide was added to a 500 ml-4 neck round bottom flask (with a stirrer, Dimroth condenser, dropping funnel and thermometer).
Toluene (100 ml) and N-methylpyrrolidone (10 ml) were added, and a solution of diethyl methylmalonate (19.6 g, 112.2 mmol) dissolved in toluene (15 ml) was added dropwise while heating at 60 ° C. in a nitrogen atmosphere. After the dropping was completed, the reaction was carried out at the same temperature for 1 hour. Next, at the same temperature, a solution prepared by dissolving 35.9 g of the brown liquid obtained above in 30 ml of toluene was added dropwise. After completion of dropping, the temperature was raised and the mixture was refluxed for 3.5 hours.
The reaction mixture was cooled to room temperature and then poured into 450 ml of dilute sulfuric acid to make it acidic. The organic phase is separated and the aqueous phase is ether 100m.
It was extracted twice more with l. The combined organic phases were washed 3 times with 150 ml of saturated saline and dried over anhydrous Na ₂ SO ₄ .
The solvent was concentrated under reduced pressure, and the residue was separated and purified by silica gel column chromatography (developed with hexane / ethyl acetate = 20/1 by volume) to give the desired product as a pale yellow liquid 2
8.9 g was obtained (yield: 60%). The physical properties of the obtained product are shown below.

NMR (CDCl ₃ , 90 MHz): δ =
1.27 (t, J = 7.2Hz, 6H); 1.41 (s,
3H); 3.51 (s, 2H) 4.27 (q, J = 7.2)
Hz, 4H) 6.67 to 7.19 (m, 2H); 7.56
(Dd, J = 9.2 Hz, 5.7 Hz, 1 H) IR (neat): 1728 cm ⁻¹ (ν _{c = o} ) [3- (2-bromo-5-fluorophenyl) -2-methylpropionic acid synthesis ] 500 ml-4 neck round bottom flask (with stirrer, Dimroth condenser, dropping funnel, thermometer) 52.63 g (0.797 mol) potassium hydroxide and 158 ml methanol aqueous solution (methanol / H ₂ O = 4/1) (= V
/ V)) was added. 2-Bromo-5- in a nitrogen atmosphere at room temperature
Diethyl meluorobenzyl methyl malonate 28.8g
(79.7 mmol) was added dropwise. After dropping, raise the temperature to 6
Reflux for hours. After the completion of the reaction, methanol was distilled off under reduced pressure, and 100 ml of water was added and dissolved. Dilute sulfuric acid is added and p
H = 2 was set and the precipitated solid was filtered. Next, the filtered material was placed in a 300 ml eggplant-shaped flask equipped with a ball-pulling condenser, and reacted under a nitrogen atmosphere at an oil bath temperature of 180 ° C. for 1 hour. After cooling the reaction solution to room temperature, 50 ml of water and 100 m of ether
l was added and extracted. After separating the organic phase, the aqueous phase was further extracted with 50 ml of ether. The combined organic phase was dried over anhydrous Na ₂
Dried with SO ₄ . The solvent was concentrated under reduced pressure to obtain 10.3 g of an orange-brown liquid (yield: 49%). This carboxylic acid was used in the next reaction without further purification. The physical properties of the obtained product are shown below.

NMR (CDCl ₃ , 90 MHz): δ =
1.26 (d, J = 6.4Hz, 3H, CH 3); 2.66
-3.33 (m, 3H); 6.72-7.20 (m, 2
H); 7.54 (dd, J = 8.9 Hz, 5.7 Hz, 1
H) IR (neat): 1700 cm ^-1 (ν _{c = o} ) [Synthesis of 3- (2-bromo-5-fluorophenyl) -2-methylpropionyl chloride] In a 50 ml eggplant flask (Dimroth condenser, with NaOH trap) 3- (2-Bromo-5-fluorophenyl) -2-methylpropionic acid 1
0.2 g (39.0 mmol) and thionyl chloride (20 ml) were added, and the mixture was heated under reflux in a nitrogen atmosphere for 1 hour. After the reaction was completed, unreacted thionyl chloride was distilled off under reduced pressure, and the residue was distilled under reduced pressure to obtain 10.24 g of a colorless liquid (yield: 94%).

The physical properties of the obtained product are shown below. bp:. 100~103 ℃ / 2.6~2.7mmHg NMR (CDCl 3, 90MHz): δ = 1.36 (d,
_{J = 6.4Hz, 3H, CH 3} ); 2.58~3.47
(M, 3H); 6.68 to 7.13 (m, 2H); 7.5
6 (dd, J = 8.9 Hz, 5.1 Hz, 1H) IR (neat): 1786 cm ⁻¹ (ν _{c = o} ) [Synthesis of 4-bromo-7-fluoro-2-methyl-1-indanone] 100 ml-3 neck round bottom flask (stirrer tip, Dimroth condenser, dropping funnel, thermometer, N
anhydrous aluminum chloride 11.18 with aOH trap)
g (83.9 mmol) and 20 ml of carbon disulfide were added,
At room temperature in a nitrogen atmosphere, 3- (2-bromo-5-fluorophenyl) -2-methylpropionyl chloride 10.2 g (36.
A solution of 5 mmol) dissolved in 10 ml of carbon disulfide was added dropwise. After the dropping was completed, the reaction was further performed for 1 hour. The reaction mixture was poured into 100 ml of ice water to decompose, and 50 m of ether was added.
Extracted twice with 1. The combined organic phases are saturated with NaHCO ₃
It was washed twice with 50 ml of water and then with 50 ml of saturated saline and dried over anhydrous Na ₂ SO ₄ . The solvent was distilled off under reduced pressure to obtain 8.8 g of a light beige solid (yield: 99%). This ketone was used in the next reaction without further purification.

The physical properties of the obtained product are shown below. mp .: 74.6-76.4 ° C. NMR (CDCl ₃ , 90 MHz): δ = 1.34 (d,
_{J = 7.4Hz, 3H, CH 3} ) 2.44~3.01 (m,
2H) 3.15 to 3.62 (m, 1H) 6.98 (dd,
J = 8.9Hz, 8.9Hz, 1H) 7.75 (dd, J
= 8.9 Hz, 4.4 Hz, 1H) IR (KBr disk): 1715 cm ^-1 (ν
_{c = o} ) [Synthesis of 4-bromo-7-fluoro-1-hydroxy-2-methylindan] 100 ml 3-neck round bottom flask (with stirrer chip, Dimroth condenser, dropping funnel, thermometer) sodium borohydride 0.68 g (18.1 mmol) and 8 ml of ethanol were added, and 8.8 g (36.2 mmol) of 4-bromo-7-fluoro-2-methyl-1-indanone was added to 40 ml of ethanol at room temperature under a nitrogen atmosphere. The dissolved solution was added dropwise. After completion of the dropping, the temperature was raised to 50 ° C. and the reaction was further performed for 1 hour. After cooling, unreacted sodium borohydride was decomposed by dropping acetone. The reaction mixture is then concentrated under reduced pressure, 50 ml of water and 5 of ether.
0 ml was added for extraction. After separating the organic phase, the aqueous phase was further extracted with 50 ml of ether. The combined organic phases were washed 4 times with 50 ml of saturated saline and dried over anhydrous Na ₂ SO ₄ . The solvent was distilled off under reduced pressure to obtain 8.6 g of the desired product (a mixture of two isomers) as a pale beige solid (yield: 9
7%). This alcohol was used in the next reaction without further purification. The physical properties of the obtained product are shown below.

[0123]

[Chemical 14]

[4-bromo-7-fluoro-2-methyl-1-to]
Synthesis of Limethylsilyloxyindane] 200 ml-3
Round bottom flask (stirrer tip, dropping funnel, temperature
(With meter)) to 4-bromo-7-fluoro-1-hydroxy-2-me
Cylindane 8.6 g (35.1 mmol), triethyl
6.35 ml (45.6 mmol) amine and methyl chloride
38 ml of ren was added. Me in a nitrogen atmosphere under ice cooling₃S
iCl 5.33 ml (42.1 mmol) methyl chloride
Solution (5 ml) was slowly added dropwise. After the dropping, the chamber
The temperature was raised to room temperature and the reaction was continued for 2 hours. Reaction mixture on ice
After pouring into 100 ml of water / 20 ml of saturated sodium bicarbonate water, the organic phase
Was separated and the aqueous phase was extracted twice more with 50 ml of methylene chloride.
I put it out. Wash the combined organic phases with 50 ml of saturated saline.
And anhydrous Na ₂SO_FourDried in. Evaporate the solvent under reduced pressure
Then, the residue is distilled under reduced pressure to obtain the desired product (mixture of two isomers
As a colorless liquid (10.8 g, yield: 97)
%). The physical properties of the obtained product are shown below.

[0125]

[Chemical 15]

[7-Fluoro-1-hydroxy-2-methyl-
4-Synthesis of Phenylindane] 200 ml-3 neck round bottom flask (with stirrer tip, dropping funnel, thermometer) 4-
Bromo-7-fluoro-2-methyl-1-trimethylsilyloxyindane 10.8 g (34.0 mmol), PdCl
0.12 g (0.17 mmol) ₂ (dppf) and 34 ml anhydrous ether were added. Under a nitrogen atmosphere, 28 ml (68.1 mmol) of an ether solution of 2.43 M phenylmagnesium bromide was slowly added dropwise at room temperature. After the dropping was completed, the reaction was further performed at room temperature for 72 hours.
After the reaction was completed, the reaction mixture was added with saturated NH ₄ Cl water (100 ml).
The mixture was slowly added to a mixture of ice and ice to decompose excess Grignard reagent, and the mixture was extracted twice with 50 ml of ether. The combined organic phase was washed 3 times with 50 ml of saturated saline and dried over anhydrous Na ₂ S.
Dry with O ₄ . The solvent was distilled off under reduced pressure and dark orange-brown liquid 1
2.3 g were obtained. Then, the mixture was diluted with 24.5 ml of tetrahydrofuran, added with 5 ml of 12% hydrochloric acid aqueous solution, and reacted for 3 hours. After the reaction was completed, the mixture was extracted twice with 50 ml of ether. The combined organic phases were washed successively with saturated aqueous sodium hydrogen carbonate and saturated brine and dried over anhydrous Na ₂ SO ₄ . The solvent was distilled off under reduced pressure, and the resulting dark brown liquid residue was subjected to silica gel column chromatography (developed with hexane / ethyl acetate = 20/1 volume part).
The desired product (mixture of two isomers) was obtained as a pale yellow liquid in an amount of 7.72 g (yield: 94%). The physical properties of the obtained product are shown below.

NMR (CDCl ₃ , 90 MHz): δ =
1.17, 1.25 (d for each, J = 7.4H for each)
z, 3H in total, CH ₃ ) 1.69 to 3.67 (m, 4H) 5.01 to 5.40 (m, 1H) 6.67 to 7.90 (m, 7H) IR (neat): 3350 cm ^-1 (ν _oH ) [Synthesis of 7-fluoro-2-methyl-4- _phenylindene ]
200 ml-4 neck round bottom flask (with stirrer tip, dropping funnel, thermometer) 7-fluoro-1-hydroxy-2-
7.71 g (31.8 mmol) of methyl-4-phenylindane, 13.3 ml (95.4 mmol) of triethylamine, 0.19 g (1.6 mmol) of 4-dimethylaminopyridine and 70 ml of methylene chloride were added. below freezing,
4.93 ml of methanesulfonyl chloride under nitrogen atmosphere
A solution of (63.6 mmol) dissolved in 7 ml of methylene chloride was slowly added dropwise. After the dropping, the temperature was raised to room temperature and the reaction was further performed for 2.5 hours. After pouring the reaction mixture into 80 ml of water, the organic phase is separated and the aqueous phase is added with 50 ml of methylene chloride
It was extracted twice more with. The combined organic phase was washed with saturated brine and dried over anhydrous Na ₂ SO ₄ . The solvent was distilled off under reduced pressure to obtain 10.3 g of a dark red liquid.

Then, the liquid obtained above, 7 ml of DBU and 140 ml of acetonitrile were added to a 200 ml-3 neck round bottom flask (with a stirrer tip, Dimroth condenser and thermometer), and the mixture was refluxed for 3 hours in a nitrogen atmosphere. After cooling the reaction solution to room temperature, the solvent was evaporated under reduced pressure, and the residue was separated and purified by silica gel column chromatography (developed with hexane) to obtain 4.62 g of the desired product as a pale yellow liquid (yield 65%).

The physical properties of the obtained product are shown below. NMR (CDCl ₃ , 90 MHz): δ = 2.18 (s,
3H, CH ₃ ); 3.43 (s, 2H); 6.61 (b
s, 1H); 6.77-7.73 (m, 7H) [Synthesis of dimethylsilyl-bis (7-fluoro-2-methyl-4-phenylindene)] 100 ml-3 neck round bottom flask (stirrer tip, 4.6 g of 7-fluoro-2-methyl-4-phenylindene (20.
5 mmol), 72 mg (0.56 mmol) of copper thiocyanate and 46 ml of anhydrous ether were added thereto, and 14.3 ml (22.6 mmol) of a hexane solution of n-butyllithium having a concentration of 1.58 M was slowly added under ice cooling in a nitrogen atmosphere. Dropped.
After the dropping, the temperature was raised to room temperature and the reaction was further performed for 2 hours. Next, 1.37 ml (11.3 mmol) of dimethyldichlorosilane
Was slowly added dropwise to a solution in which 4 ml of anhydrous ether was dissolved. After the dropping was completed, the reaction was continued at room temperature for 4 hours. The reaction mixture was filtered through Celite, and the filtrate was saturated with NH ₄ Cl (50).
poured into ml. After separating the organic phase, the aqueous phase is washed with 50 m of ether.
It was extracted with 1. The combined organic phase was washed with saturated saline,
It was dried over anhydrous Na ₂ SO ₄ . After distilling off the solvent under reduced pressure,
The orange-brown liquid residue was placed in a refrigerator for 2 days to precipitate crystals. Hexane and ether were added to the obtained crystals, followed by reslurry washing, rinsing with ethanol and drying to obtain 3.37 g of the desired product (stereoisomer mixture) as white crystals (yield:
65%). The physical properties of the obtained product are shown below.

[0130]

[Chemical 16]

[Synthesis of rac-dimethylsilyl-bis {1- (7-fluoro-2-methyl-4-phenylindenyl)} zirconium dichloride] 100 ml-3 neck round bottom flask (stirrer tip, ball containing condenser, dropping) Funnel,
Dimethylsilyl-bis (7 with a thermometer) in an argon atmosphere
-Fluoro-2-methyl-4-phenylindene) 1.00 g
(1.98 mmol) and 20 ml of anhydrous ether were added,
At room temperature, 2.64 ml (4.17 mmol) of a hexane solution of 1.58 M concentration n-butyllithium was slowly added dropwise. After the dropping, the reaction was further performed for 4.5 hours. The obtained deep red reaction liquid was cooled to −70 ° C. in a dry ice-acetone bath, and 0.468 g (1.98 mmol) of ZrCl ₄ powder was gradually added. After the addition was completed, the mixture was left overnight while continuing stirring. Then the solvent was distilled off under reduced pressure at room temperature. After adding 20 ml of methylene chloride and 6 ml of anhydrous ether, the insoluble matter was filtered, and the insoluble matter was further diluted with methylene chloride 4
It was washed with 0 ml. The washing solution was concentrated to dryness at room temperature, reslurry-washed with anhydrous ether, and then dried under reduced pressure to obtain 0.1 g of the desired product as an orange-yellow solid (yield 8%).

The physical properties of the obtained product are shown below. NMR (CDCl ₃ , 90 MHz): δ = 1.23 (d,
J = 7.4Hz, 6H, Si- CH 3); 2.23 (s,
_{6H, 2-CH 3);} 6.61~7.71 (m, 16H)

[0133]

Example 2 1 liter of toluene was placed in a gas flow type glass polymerization vessel having an internal volume of 1.5 liter which was sufficiently replaced with nitrogen, and propylene was flowed at 200 liter / hr at 45 ° C. to sufficiently saturate the system. Let Next, 0.35 mmol of triisobutylaluminum and 0.70 mmol of methylaluminoxane converted to Al atoms, rac-dimethylsilyl-bis {1- (7-fluoro-2-methyl-4-phenylindenyl)} Zirconium dichloride was converted to Zr atoms to add 0.001 mmol, and polymerization was carried out at 50 ° C. for 20 minutes. The polymerization was stopped by adding a small amount of methanol. The polymerization suspension was added to 3 liters of methanol containing a small amount of hydrochloric acid, stirred sufficiently, and filtered. The polymer was washed with a large amount of methanol and dried at 80 ° C. for 10 hours.

The amount of the polymer obtained was 10.5 g, and the polymerization activity corresponded to 31.5 kg-PP / mmol-Zr · hr. [Η] is 4.75 dl / g, Mw is 700,0
00, Mw / Mn was 2.35, and the melting point was 153.4 ° C.

[0135]

Comparative Example 1 In Example 2, as a transition metal compound component, rac-dimethylsilyl-bis {1- (7-fluoro-2-
Instead of using methyl-4-phenylindenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1-
Polymerization was performed in exactly the same manner as in Example 2 except that (2-methyl-4-phenylindenyl)} zirconium dichloride was used,
Post-treatment was performed.

The amount of the polymer obtained was 16.8 g, and the polymerization activity corresponded to 50.4 kg-PP / mmol-Zr · hr. [Η] is 1.56 dl / g, Mw is 172,000
0, Mw / Mn was 2.01, and the melting point was 155.8 ° C.

[0137]

Example 3 1 liter of toluene was placed in a gas flow type glass polymerization vessel having an internal volume of 1.5 liter which was sufficiently replaced with nitrogen, and 160 liter / hr of ethylene and 40 liter / hr of ethylene were passed at 45 ° C. The system was fully saturated. Next, 0.35 mmol of triisobutylaluminum and 0.7 mmol of methylaluminoxane converted to Al atoms, rac-dimethylsilyl-bis {1- (7-fluoro-2-methyl-4-phenylindenyl)} Zirconium dichloride was converted to Zr atoms to add 0.001 mmol, and polymerization was carried out at 50 ° C. for 40 minutes. The termination of the polymerization and the post-treatment were carried out in the same manner as in Example 2.

The amount of the polymer obtained was 16.8 g, and the polymerization activity was 25.2 kg-polymer / mmol-Zr · hr.
Was equivalent to. Ethylene content is 9.7 mol%, [η] is 3.
18 dl / g, Mw was 420,000, Mw / Mn was 2.22, and the melting point was 117.6 ° C.

[0139]

Comparative Example 2 In Example 3, as the transition metal compound component, rac-dimethylsilyl-bis {1- (7-fluoro-2-
Instead of using methyl-4-phenylindenyl)} zirconium dichloride, rac-dimethylsilyl-bis {1-
Polymerization and post-treatment were carried out in exactly the same manner as in Example 3 except that 0.0005 mmol of (2-methyl-4-phenylindenyl)} zirconium dichloride was used.

The amount of the polymer obtained was 20.8 g, and the polymerization activity was 62.4 kg-polymer / mmol-Zr · hr.
Was equivalent to. The ethylene content is 7.2 mol% and [η] is 1.
08 dl / g, Mw was 110,000, Mw / Mn was 1.96, and the melting point was 118.5 ° C.

[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) Terutaka Fujita, Inventor 6-1-2 Waki, Waki-machi, Kuga-gun, Yamaguchi Prefecture Mitsui Petrochemical Industries Ltd. (72) Takashi Tashiro, Kuga-gun, Yamaguchi Prefecture 6-1-2 Waki, Waki Town Mitsui Petrochemical Industry Co., Ltd. (72) Inventor Koji Kawago 6-1-2 Waki Town, Waki Town, Kuga District, Yamaguchi Prefecture Mitsui Petrochemical Industry Co., Ltd. (72) Inventor Masaru Yoshida Yasushi Yamaguchi 6-1-2 Waki, Waki-cho, Yamaguchi Prefecture Mitsui Petrochemical Industry Co., Ltd. (72) Takashi Ueda 6-1-2 Waki, Waki-cho, Yamaguchi Prefecture Mitsui Within Petrochemical Industry Co., Ltd. (72) Inventor Yoshihisa Kiso 6-1-2 Waki, Waki Town, Kuga District, Yamaguchi Prefecture Mitsui Petrochemical Industry Co., Ltd.

Claims (10)

[Claims] 1. A novel transition metal represented by the following general formula [I]:
Genus compound;(In the formula, M is a transition metal of Group IVa, Va or VIa of the periodic table.
Indicates R¹Is a hydrogen atom, a halogen atom, or a carbon atom having 1 to 20 carbon atoms.
Hydrogenated groups, halogenated hydrocarbon groups having 1 to 20 carbon atoms,
Ion-containing groups, oxygen-containing groups, sulfur-containing groups, nitrogen-containing groups
Or a phosphorus-containing group, R²Represents a hydrocarbon group having 1 to 20 carbon atoms.
The hydrogen group is a halogen atom or a hydrocarbon having 1 to 20 carbon atoms.
Substituted with a halogenated hydrocarbon group having 1 to 20 carbon atoms
May be. Hal represents a fluorine atom or a chlorine atom, X¹And X²Is a hydrogen atom, halogen atom, carbon number 1
~ 20 hydrocarbon groups, C1-20 halogenated carbonization
Represents a hydrogen group, an oxygen-containing group or a sulfur-containing group, Y is a divalent hydrocarbon group having 1 to 20 carbon atoms, 1 to 1 carbon atoms
20 divalent halogenated hydrocarbon groups, divalent silicon containing
Group, divalent germanium-containing group, divalent tin-containing group,
O-, -CO-, -S-, -SO-, -SO₂-, -N
R³-, -P (R³)-, -P (O) (R³)-, -B
R³-Or-AlR³-[However, R ³Is a hydrogen atom,
Halogen atom, hydrocarbon group having 1 to 20 carbon atoms, 1 carbon atom
20 halogenated hydrocarbon groups]. ) 2. A transition metal compound represented by the following general formula [I]:
Catalyst composition for olefin polymerization characterized by comprising
Min;(In the formula, M is a transition metal of Group IVa, Va or VIa of the periodic table.
Indicates R¹Is a hydrogen atom, a halogen atom, or a carbon atom having 1 to 20 carbon atoms.
Hydrogenated groups, halogenated hydrocarbon groups having 1 to 20 carbon atoms,
Ion-containing groups, oxygen-containing groups, sulfur-containing groups, nitrogen-containing groups
Or a phosphorus-containing group, R²Represents a hydrocarbon group having 1 to 20 carbon atoms.
The hydrogen group is a halogen atom or a hydrocarbon having 1 to 20 carbon atoms.
Substituted with a halogenated hydrocarbon group having 1 to 20 carbon atoms
May be. Hal represents a fluorine atom or a chlorine atom, X¹And X²Is a hydrogen atom, halogen atom, carbon number 1
~ 20 hydrocarbon groups, C1-20 halogenated carbonization
Represents a hydrogen group, an oxygen-containing group or a sulfur-containing group, Y is a divalent hydrocarbon group having 1 to 20 carbon atoms, 1 to 1 carbon atoms
20 divalent halogenated hydrocarbon groups, divalent silicon containing
Group, divalent germanium-containing group, divalent tin-containing group,
O-, -CO-, -S-, -SO-, -SO₂-, -N
R³-, -P (R³)-, -P (O) (R³)-, -B
R³-Or-AlR³-[However, R ³Is a hydrogen atom,
Halogen atom, hydrocarbon group having 1 to 20 carbon atoms, 1 carbon atom
20 halogenated hydrocarbon groups]. ) 3. [A] Transition gold represented by the following general formula [I]:
A genus compound, and(In the formula, M is a transition metal of Group IVa, Va or VIa of the periodic table.
Indicates R¹Is a hydrogen atom, a halogen atom, or a carbon atom having 1 to 20 carbon atoms.
Hydrogenated groups, halogenated hydrocarbon groups having 1 to 20 carbon atoms,
Ion-containing groups, oxygen-containing groups, sulfur-containing groups, nitrogen-containing groups
Or a phosphorus-containing group, R²Represents a hydrocarbon group having 1 to 20 carbon atoms.
The hydrogen group is a halogen atom or a hydrocarbon having 1 to 20 carbon atoms.
Substituted with a halogenated hydrocarbon group having 1 to 20 carbon atoms
May be. Hal represents a fluorine atom or a chlorine atom, X¹And X²Is a hydrogen atom, halogen atom, carbon number 1
~ 20 hydrocarbon groups, C1-20 halogenated carbonization
Represents a hydrogen group, an oxygen-containing group or a sulfur-containing group, Y is a divalent hydrocarbon group having 1 to 20 carbon atoms, 1 to 1 carbon atoms
20 divalent halogenated hydrocarbon groups, divalent silicon containing
Group, divalent germanium-containing group, divalent tin-containing group,
O-, -CO-, -S-, -SO-, -SO₂-, -N
R³-, -P (R³)-, -P (O) (R³)-, -B
R³-Or-AlR³-[However, R ³Is a hydrogen atom,
Halogen atom, hydrocarbon group having 1 to 20 carbon atoms, 1 carbon atom
20 halogenated hydrocarbon groups]. ) [B] (B-1) organoaluminum oxy compound, and (B-
2) Reaction with the transition metal compound [A] to form an ion pair
At least one compound selected from the group consisting of compounds
A catalyst for olefin polymerization characterized by comprising a compound
Medium. 4. [A] Transition gold represented by the following general formula [I]:
A genus compound, and(In the formula, M is a transition metal of Group IVa, Va or VIa of the periodic table.
Indicates R¹Is a hydrogen atom, a halogen atom, or a carbon atom having 1 to 20 carbon atoms.
Hydrogenated groups, halogenated hydrocarbon groups having 1 to 20 carbon atoms,
Ion-containing groups, oxygen-containing groups, sulfur-containing groups, nitrogen-containing groups
Or a phosphorus-containing group, R²Represents a hydrocarbon group having 1 to 20 carbon atoms.
The hydrogen group is a halogen atom or a hydrocarbon having 1 to 20 carbon atoms.
Substituted with a halogenated hydrocarbon group having 1 to 20 carbon atoms
May be. Hal represents a fluorine atom or a chlorine atom, X¹And X²Is a hydrogen atom, halogen atom, carbon number 1
~ 20 hydrocarbon groups, C1-20 halogenated carbonization
Represents a hydrogen group, an oxygen-containing group or a sulfur-containing group, Y is a divalent hydrocarbon group having 1 to 20 carbon atoms, 1 to 1 carbon atoms
20 divalent halogenated hydrocarbon groups, divalent silicon containing
Group, divalent germanium-containing group, divalent tin-containing group,
O-, -CO-, -S-, -SO-, -SO₂-, -N
R³-, -P (R³)-, -P (O) (R³)-, -B
R³-Or-AlR³-[However, R ³Is a hydrogen atom,
Halogen atom, hydrocarbon group having 1 to 20 carbon atoms, 1 carbon atom
20 halogenated hydrocarbon groups]. ) [B] (B-
1) Organoaluminum oxy compound, and (B-2) transition
A compound that reacts with a metal transfer compound [A] to form an ion pair
At least one compound selected from the group consisting of compounds, and [C] an organoaluminum compound.
Olefin polymerization catalyst. 5. A fine particle carrier, [A] a transition metal compound represented by the following general formula [I], and(In the formula, M is a transition metal of Group IVa, Va or VIa of the periodic table.
Indicates R¹Is a hydrogen atom, a halogen atom, or a carbon atom having 1 to 20 carbon atoms.
Hydrogenated groups, halogenated hydrocarbon groups having 1 to 20 carbon atoms,
Ion-containing groups, oxygen-containing groups, sulfur-containing groups, nitrogen-containing groups
Or a phosphorus-containing group, R²Represents a hydrocarbon group having 1 to 20 carbon atoms.
The hydrogen group is a halogen atom or a hydrocarbon having 1 to 20 carbon atoms.
Substituted with a halogenated hydrocarbon group having 1 to 20 carbon atoms
May be. Hal represents a fluorine atom or a chlorine atom, X¹And X²Is a hydrogen atom, halogen atom, carbon number 1
~ 20 hydrocarbon groups, C1-20 halogenated carbonization
Represents a hydrogen group, an oxygen-containing group or a sulfur-containing group, Y is a divalent hydrocarbon group having 1 to 20 carbon atoms, 1 to 1 carbon atoms
20 divalent halogenated hydrocarbon groups, divalent silicon containing
Group, divalent germanium-containing group, divalent tin-containing group,
O-, -CO-, -S-, -SO-, -SO₂-, -N
R³-, -P (R³)-, -P (O) (R³)-, -B
R³-Or-AlR³-[However, R ³Is a hydrogen atom,
Halogen atom, hydrocarbon group having 1 to 20 carbon atoms, 1 carbon atom
20 halogenated hydrocarbon groups]. ) [B] (B-1) organoaluminum oxy compound, and (B-
2) Reaction with the transition metal compound [A] to form an ion pair
At least one compound selected from the group consisting of compounds
Olefin weight, which is characterized in that
Combined catalyst. 6. A fine particle carrier, [A] a transition metal compound represented by the following general formula [I], and(In the formula, M is a transition metal of Group IVa, Va or VIa of the periodic table.
Indicates R¹Is a hydrogen atom, a halogen atom, or a carbon atom having 1 to 20 carbon atoms.
Hydrogenated groups, halogenated hydrocarbon groups having 1 to 20 carbon atoms,
Ion-containing groups, oxygen-containing groups, sulfur-containing groups, nitrogen-containing groups
Or a phosphorus-containing group, R²Represents a hydrocarbon group having 1 to 20 carbon atoms.
The hydrogen group is a halogen atom or a hydrocarbon having 1 to 20 carbon atoms.
Substituted with a halogenated hydrocarbon group having 1 to 20 carbon atoms
May be. Hal represents a fluorine atom or a chlorine atom, X¹And X²Is a hydrogen atom, halogen atom, carbon number 1
~ 20 hydrocarbon groups, C1-20 halogenated carbonization
Represents a hydrogen group, an oxygen-containing group or a sulfur-containing group, Y is a divalent hydrocarbon group having 1 to 20 carbon atoms, 1 to 1 carbon atoms
20 divalent halogenated hydrocarbon groups, divalent silicon containing
Group, divalent germanium-containing group, divalent tin-containing group,
O-, -CO-, -S-, -SO-, -SO₂-, -N
R³-, -P (R³)-, -P (O) (R³)-, -B
R³-Or-AlR³-[However, R ³Is a hydrogen atom,
Halogen atom, hydrocarbon group having 1 to 20 carbon atoms, 1 carbon atom
20 halogenated hydrocarbon groups]. ) [B] (B-1) organoaluminum oxy compound, and (B-
2) Reaction with the transition metal compound [A] to form an ion pair
At least one compound selected from the group consisting of compounds
A solid catalyst component supporting a compound and [C] an organoaluminum compound.
Olefin polymerization catalyst. 7. A fine particle carrier, [A] a transition metal compound represented by the following general formula [I], and(In the formula, M is a transition metal of Group IVa, Va or VIa of the periodic table.
Indicates R¹Is a hydrogen atom, a halogen atom, or a carbon atom having 1 to 20 carbon atoms.
Hydrogenated groups, halogenated hydrocarbon groups having 1 to 20 carbon atoms,
Ion-containing groups, oxygen-containing groups, sulfur-containing groups, nitrogen-containing groups
Or a phosphorus-containing group, R²Represents a hydrocarbon group having 1 to 20 carbon atoms.
The hydrogen group is a halogen atom or a hydrocarbon having 1 to 20 carbon atoms.
Substituted with a halogenated hydrocarbon group having 1 to 20 carbon atoms
May be. Hal represents a fluorine atom or a chlorine atom, X¹And X²Is a hydrogen atom, halogen atom, carbon number 1
~ 20 hydrocarbon groups, C1-20 halogenated carbonization
Represents a hydrogen group, an oxygen-containing group or a sulfur-containing group, Y is a divalent hydrocarbon group having 1 to 20 carbon atoms, 1 to 1 carbon atoms
20 divalent halogenated hydrocarbon groups, divalent silicon containing
Group, divalent germanium-containing group, divalent tin-containing group,
O-, -CO-, -S-, -SO-, -SO₂-, -N
R³-, -P (R³)-, -P (O) (R³)-, -B
R³-Or-AlR³-[However, R ³Is a hydrogen atom,
Halogen atom, hydrocarbon group having 1 to 20 carbon atoms, 1 carbon atom
20 halogenated hydrocarbon groups]. ) [B] (B-1) organoaluminum oxy compound, and (B-
2) Reaction with the transition metal compound [A] to form an ion pair
At least one compound selected from the group consisting of compounds
Compound and olefin polymer produced by prepolymerization
An olefin polymerization catalyst comprising: 8. A particulate support, [A] a transition metal compound represented by the following general formula [I], and(In the formula, M is a transition metal of Group IVa, Va or VIa of the periodic table.
Indicates R¹Is a hydrogen atom, a halogen atom, or a carbon atom having 1 to 20 carbon atoms.
Hydrogenated groups, halogenated hydrocarbon groups having 1 to 20 carbon atoms,
Ion-containing groups, oxygen-containing groups, sulfur-containing groups, nitrogen-containing groups
Or a phosphorus-containing group, R²Represents a hydrocarbon group having 1 to 20 carbon atoms.
The hydrogen group is a halogen atom or a hydrocarbon having 1 to 20 carbon atoms.
Substituted with a halogenated hydrocarbon group having 1 to 20 carbon atoms
May be. Hal represents a fluorine atom or a chlorine atom, X¹And X²Is a hydrogen atom, halogen atom, carbon number 1
~ 20 hydrocarbon groups, C1-20 halogenated carbonization
Represents a hydrogen group, an oxygen-containing group or a sulfur-containing group, Y is a divalent hydrocarbon group having 1 to 20 carbon atoms, 1 to 1 carbon atoms
20 divalent halogenated hydrocarbon groups, divalent silicon containing
Group, divalent germanium-containing group, divalent tin-containing group,
O-, -CO-, -S-, -SO-, -SO₂-, -N
R³-, -P (R³)-, -P (O) (R³)-, -B
R³-Or-AlR³-[However, R ³Is a hydrogen atom,
Halogen atom, hydrocarbon group having 1 to 20 carbon atoms, 1 carbon atom
20 halogenated hydrocarbon groups]. ) [B] (B-1) organoaluminum oxy compound, and (B-
2) Reaction with the transition metal compound [A] to form an ion pair
At least one compound selected from the group consisting of compounds
Compound, [C] organoaluminum compound, and prepolymerized
And an olefin polymer that
Reffin polymerization catalyst. 9. A method for polymerizing an olefin, which comprises polymerizing or copolymerizing an olefin in the presence of the catalyst for olefin polymerization according to claim 3. 10. A method for polymerizing an olefin, which comprises polymerizing or copolymerizing an olefin in the presence of the catalyst for olefin polymerization according to claim 7 and an organoaluminum compound.