JPH09278823A - Olefin polymerization catalyst and method of polymerization of olefin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an olefin polymerization catalyst which has a high polymerization activity and can give an olefin (co)polymer with a wide molecular weight distribution by combining specified transition metal compounds and other compounds. SOLUTION: This catalyst is obtained from a group 4 transition metal compound (A), a transition metal compound (B) of formula I wherein M is any one of groups 8 to 10 transition metal atoms; X<1> and X<2> are each N or P; R<1> and R<2> are each H or a hydrocarbon group; m and n are each 1 or 2; R<3> is a group of formula II (wherein R<6> , R<7> , R<61> , R<62> , R<71> and R<72> are the same as R<1> ); and R<4> and R<5> are each H, halogeno, a hydrocarbon group, -OR<8> , -SR<9> , -N(R<10> )2 or -P(R<11> )2 [wherein R<8> to R<11> are each (cyclo)alkyl, aryl, aralkyl or an organic silyl group]}, at least one compound (C) selected among organoaluminumoxy impounds, alkyl borate derivatives and compounds that react with a transition metal compound to form an ion pair, and if necessary an organometal compound (D).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a catalyst for olefin polymerization and a method for polymerizing olefin using the catalyst. More specifically, an olefin (co) polymer having a high polymerization activity and a wide molecular weight distribution can be obtained. Such a novel olefin polymerization catalyst and a method for polymerizing olefins using the catalyst.

[0002]

BACKGROUND OF THE INVENTION Conventionally, as a catalyst for producing an olefin polymer such as an ethylene polymer or an ethylene / α-olefin copolymer, a titanium-based catalyst comprising a titanium compound and an organoaluminum compound, and a vanadium compound There is known a vanadium-based catalyst comprising an organic aluminum compound.

A Ziegler catalyst comprising a metallocene compound such as zirconocene and an organic aluminum oxy compound (aluminoxane) is known as a catalyst capable of producing an olefin polymer with high polymerization activity.

Recently, as a new olefin polymerization catalyst, an olefin polymerization catalyst comprising a nickel compound or a palladium compound and a cocatalyst such as an aluminoxane or an ionic compound has been proposed (J. Am. Chem. Soc. 1995, 1
17,6414-6415).

By the way, polyolefins such as ethylene polymers are excellent in mechanical strength and chemical resistance.
It is used as various molding materials. However, a catalyst composed of the above nickel compound or palladium compound and a co-catalyst has a high polymerization activity, but an olefin polymer obtained by using this has a narrow molecular weight distribution and does not necessarily have good moldability. is not. Therefore, there has been a demand for improvement of a catalyst comprising a nickel compound or a palladium compound and a cocatalyst so that an olefin polymer having a wide molecular weight distribution and excellent moldability can be obtained without impairing high polymerization activity.

[0006]

DISCLOSURE OF THE INVENTION The object of the present invention is to provide an olefin (co) polymer having a high polymerization activity, a wide molecular weight distribution and excellent moldability. It is intended to provide such an olefin polymerization catalyst.

Another object of the present invention is to provide a method for polymerizing olefins using a catalyst having such good properties.

[0008]

SUMMARY OF THE INVENTION An olefin polymerization catalyst according to the present invention comprises (A) a transition metal compound of Group 4 of the periodic table, and (B) a transition metal compound of Group 8-10 of the periodic table represented by the following general formula (I). At least a compound selected from a transition metal compound, (C) (C-1) organoaluminum oxy compound, (C-2) alkylboronic acid derivative, and (C-3) transition metal compound to form an ion pair. It is characterized by comprising one kind of compound and, if necessary, (D) an organometallic compound.

[0009]

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(In the formula, M represents a transition metal atom of Groups 8 to 10 of the periodic table, X ¹ and X ² may be the same or different from each other, represent a nitrogen atom or a phosphorus atom, and R 1
¹ and R ² may be the same or different from each other,
Represents a hydrogen atom or a hydrocarbon group, m and n may be the same or different from each other, and 1 or 2,
R is a number satisfying the valences of X ¹ and X ² , respectively, and R
³ is

[0011]

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(However, R ⁶ , R ⁷ , R ⁶¹ , R ⁶² , R ⁷¹
And R ^{72, which} may be the same or different, each represents a hydrogen atom or a hydrocarbon group. ), R ⁴ and R ^{5, which} may be the same or different, are each a hydrogen atom, a halogen atom, a hydrocarbon group, —OR ⁸ , —SR ⁹ ,
-N (R ¹⁰⁾ ₂ or -P (R ¹¹⁾ ₂ (provided that, R ⁸ ~
R ¹¹ represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an organic silyl group, and R ^{10 s} or R ^{11 s} may be linked to each other to form a ring. )
And R ⁴ and R ⁵ may be linked to each other to form a ring, and R ¹ , R ² , R ⁶ (or R ⁶¹ ,
Two or more of R ⁶² ) and R ⁷ (or R ⁷¹ , R ⁷² ) may be linked to each other to form a ring. In the present invention, the transition metal compound represented by the general formula (I) is preferably a compound represented by the following general formula (I ′).

[0013]

[Chemical 6]

(In the formula, M represents a transition metal atom of Groups 8 to 10 of the periodic table, X ¹ and X ² may be the same or different from each other, represent a nitrogen atom or a phosphorus atom, and R 1
¹ and R ² may be the same or different from each other,
A hydrogen atom or a hydrocarbon group, R ⁶ and R ⁷ are
They may be the same or different from each other and represent a hydrogen atom or a hydrocarbon group, and R ⁴ and R ⁵ may be the same or different from each other, and are a hydrogen atom, a halogen atom, a hydrocarbon group, —OR ⁸ , —SR. ^9, -N (R ¹⁰⁾ ₂ or -P
(R ¹¹ ) ₂ (wherein R ^{8 to} R ¹¹ represent an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an organic silyl group, and R ^{10 s} or R ^{11 s} are linked to each other to form a ring. R ⁴ and R ^4
5 may combine with each other to form a ring, and R ¹ , R
^Two or more of ² , R ⁶ and R ⁷ may be linked to each other to form a ring. The olefin polymerization catalyst of the present invention has a high polymerization activity, a wide molecular weight distribution, and an olefin (co) polymer having a narrow composition distribution when two or more olefins are polymerized.

The olefin polymerization method according to the present invention is characterized in that the olefin is polymerized or copolymerized in the presence of the above-mentioned catalyst.

[0016]

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

In the present specification, the term "polymerization" is sometimes used to mean not only homopolymerization but also copolymerization, and the term "polymer" means not only homopolymer but also homopolymer. , May also be used in a meaning including a copolymer.

The olefin polymerization catalyst according to the present invention comprises (A) a transition metal compound of Group 4 of the periodic table, (B) a transition metal compound of Groups 8 to 10 of the periodic table, and (C) (C-1 ) At least one compound selected from the group consisting of an organoaluminum oxy compound, a (C-2) alkylboronic acid derivative and a compound (C-3) which forms an ion pair by reacting with a transition metal compound, and optionally (D ) Formed from an organometallic compound.

First, each catalyst component forming the olefin polymerization catalyst of the present invention will be described. (A) Transition metal compound of Group 4 of the periodic table The transition metal compound of Group 4 (A) of the periodic table used in the present invention has a cyclopentadienyl skeleton represented by the following general formula (II-1). It is a transition metal compound containing a ligand.

M ¹ L _x (II-1) In the formula, M ¹ represents a transition metal atom selected from Group 4 of the periodic table, specifically zirconium, titanium or hafnium, preferably zirconium. is there.

[0021] x is the valence of the transition metal atom M ^1, illustrating a coordinated number of ligands L to the transition metal atom M ^1. L represents a ligand coordinated to a transition metal atom, and at least one L is a ligand having a cyclopentadienyl skeleton, and L other than a ligand having a cyclopentadienyl skeleton.
Is a hydrocarbon group having 1 to 20 carbon atoms, 1 carbon atom
To 20 halogenated hydrocarbon groups, oxygen-containing groups, sulfur-containing groups, silicon-containing groups, halogen atoms or hydrogen atoms.

Examples of the ligand having a cyclopentadienyl skeleton include cyclopentadienyl group, methylcyclopentadienyl group, dimethylcyclopentadienyl group, trimethylcyclopentadienyl group, tetramethylcyclopentadienyl group. Group, pentamethylcyclopentadienyl group, ethylcyclopentadienyl group, methylethylcyclopentadienyl group, propylcyclopentadienyl group, methylpropylcyclopentadienyl group, butylcyclopentadienyl group, methylbutylcyclo Examples thereof include an alkyl-substituted cyclopentadienyl group such as a pentadienyl group and a hexylcyclopentadienyl group or an indenyl group, a 4,5,6,7-tetrahydroindenyl group, and a fluorenyl group. These groups may be substituted with a (halogenated) hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group, a sulfur-containing group, a silicon-containing group, a halogen atom, or the like.

When the compound represented by the general formula (II-1) contains two or more ligands having a cyclopentadienyl skeleton, a ligand having two cyclopentadienyl skeletons among them Are (substituted) alkylene groups, (substituted)
It may be bonded via a divalent bonding group such as a silylene group. As such a transition metal compound in which a ligand having two cyclopentadienyl skeletons is bonded via a divalent bonding group, a transition represented by the following general formula (II-3) is used. Metal compounds.

Specific examples of the ligand L other than the ligand having a cyclopentadienyl skeleton include the following. Examples of the hydrocarbon group having 1 to 20 carbon atoms include an alkyl group, a cycloalkyl group, an alkenyl group, an arylalkyl group, and an aryl group. More specifically, methyl, ethyl, propyl, butyl, and hexyl Alkyl groups such as octyl, nonyl, dodecyl and eicosyl; cycloalkyl groups such as cyclopentyl, cyclohexyl, norbornyl and adamantyl; vinyl,
Alkenyl groups such as propenyl and cyclohexenyl; arylalkyl groups such as benzyl, phenylethyl and phenylpropyl; phenyl, tolyl, dimethylphenyl, trimethylphenyl, ethylphenyl, propylphenyl, biphenyl, naphthyl, methylnaphthyl, anthryl and phenanthryl Aryl groups.

Examples of the halogenated hydrocarbon group having 1 to 20 carbon atoms include groups in which the aforementioned hydrocarbon group having 1 to 20 carbon atoms is substituted with halogen. A hydroxy group as the oxygen-containing group; methoxy, ethoxy, propoxy,
Alkoxy groups such as butoxy; aryloxy groups such as phenoxy, methylphenoxy, dimethylphenoxy and naphthoxy; and arylalkoxy groups such as phenylmethoxy and phenylethoxy.

As the sulfur-containing group, a substituent in which oxygen of the oxygen-containing group is replaced with sulfur, and methyl sulfonate, trifluoromethane sulfonate, phenyl sulfonate, benzyl sulfonate, p-toluene sulfonate. , Trimethylbenzene sulfonate,
Sulfonate groups such as triisobutylbenzene sulfonate, p-chlorobenzene sulfonate and pentafluorobenzene sulfonate; methylsulfinate, phenylsulfinate, benzenesulfinate, p-toluenesulfinate, trimethylbenzene Examples thereof include sulfinate groups such as sulfinate and pentafluorobenzene sulfinate.

As the silicon-containing group, monohydrocarbon-substituted silyl such as methylsilyl and phenylsilyl; dihydrocarbon-substituted silyl such as dimethylsilyl and diphenylsilyl;
Trihydrosilyl substituted silyls such as trimethylsilyl, triethylsilyl, tripropylsilyl, tricyclohexylsilyl, triphenylsilyl, dimethylphenylsilyl, methyldiphenylsilyl, tritolylsilyl, and trinaphthylsilyl; silyls of hydrocarbon substituted silyls such as trimethylsilyl ether Ether; a silicon-substituted alkyl group such as trimethylsilylmethyl; and a silicon-substituted aryl group such as trimethylphenyl.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Such a transition metal compound has, for example, a transition metal valence of 4
Is more specifically represented by the following general formula (II-2).

R ³¹ R ³² R ³³ R ³⁴ M ¹ (II-2) In the formula, M ¹ represents a transition metal atom selected from Group 4 of the periodic table as described above, and preferably a zirconium atom. .

R ³¹ represents a group (ligand) having a cyclopentadienyl skeleton, and R ³² , R ³³ and R ³⁴ may be the same or different from each other and are groups having a cyclopentadienyl skeleton. (Ligand), a (halogenated) hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group, a sulfur-containing group, a silicon-containing group, a halogen atom or a hydrogen atom.

In the present invention, represented by the above general formula (II-3)
In the transition metal compound, R³², R ³³And R³⁴Out of
Group having at least one cyclopentadienyl skeleton
A compound which is a (ligand), eg R³¹And R³²But
A group (ligand) having a clopentadienyl skeleton
Compounds are preferably used. Also, R³¹And R³²But
When it is a group (ligand) having a clopentadienyl skeleton
If R³³And R³⁴Has a cyclopentadienyl skeleton
Groups, alkyl groups, cycloalkyl groups, alkenyl groups,
Arylalkyl group, aryl group, alkoxy group, ant
-Roxy group, trialkylsilyl group, sulfonate
Preferably a group, a halogen atom or a hydrogen atom
Yes.

The following is represented by the general formula (II-1) and M
^A specific compound is illustrated about the transition metal compound whose ¹ is zirconium. Bis (indenyl) zirconium dichloride, bis (indenyl) zirconium dibromide, bis (indenyl) zirconium bis (p-toluenesulfonate), bis (4,5,6,7-tetrahydroindenyl) zirconium dichloride, bis (fluorenyl) )
Zirconium dichloride, bis (cyclopentadienyl) zirconium dichloride, bis (cyclopentadienyl) zirconium dibromide, bis (cyclopentadienyl) methylzirconium monochloride, bis (cyclopentadienyl) ethylzirconium monochloride,
Bis (cyclopentadienyl) cyclohexyl zirconium monochloride, Bis (cyclopentadienyl) phenyl zirconium monochloride, Bis (cyclopentadienyl) benzyl zirconium monochloride, Bis (cyclopentadienyl) zirconium monochloride, Bis (Cyclopentadienyl) methylzirconium monohydride, bis (cyclopentadienyl) dimethylzirconium, bis (cyclopentadienyl) diphenylzirconium, bis (cyclopentadienyl) dibenzylzirconium, bis (cyclopentadienyl) zirconium Methoxy chloride, bis (cyclopentadienyl) zirconium ethoxy chloride, bis (cyclopentadienyl) zirconium bis (methanesulfonate), Bis (cyclopentadienyl) zirconium bis (p-toluene sulfonate), bis (cyclopentadienyl) zirconium bis (trifluoromethane sulfonate), bis (methylcyclopentadienyl) zirconium dichloride, bis (dimethylcyclo) Pentadienyl) zirconium dichloride, bis (dimethylcyclopentadienyl) zirconium ethoxy chloride, bis (dimethylcyclopentadienyl) zirconium bis (trifluoromethanesulfonate), bis (ethylcyclopentadienyl) zirconium dichloride, bis ( Methylethylcyclopentadienyl) zirconium dichloride, bis (propylcyclopentadienyl) zirconium dichloride, bis (methylpropylcyclopentadienyl) zirconium dichloride Chloride, bis (butylcyclopentadienyl) zirconium dichloride, bis (methylbutylcyclopentadienyl) zirconium dichloride, bis (methylbutylcyclopentadienyl) zirconium bis (methanesulfonate),
Bis (trimethylcyclopentadienyl) zirconium dichloride, bis (tetramethylcyclopentadienyl) zirconium dichloride, bis (pentamethylcyclopentadienyl) zirconium dichloride, bis (hexylcyclopentadienyl) zirconium dichloride, bis (trimethylsilylcyclo) Pentadienyl) zirconium dichloride and the like.

In the above examples, the di-substituted cyclopentadienyl ring includes 1,2- and 1,3-substituted compounds, and the tri-substituted compound is 1,2,3- and 1,2,4. -Includes substitutions. Alkyl groups such as propyl and butyl are n-, i-, sec-, tert.
-Including isomers such as.

Further, in the zirconium compound as described above, a compound in which zirconium is replaced with titanium or hafnium can also be mentioned. Examples of the transition metal compound compound in which a ligand having two cyclopentadienyl skeletons are bonded via a divalent bonding group include, for example, a compound represented by the following formula (II-3).

[0035]

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In the formula, M ¹ represents a transition metal atom of Group 4 of the periodic table, specifically zirconium, titanium or hafnium, preferably zirconium.
R ³⁵ , R ³⁶ , R ³⁷ and R ³⁸ may be the same or different from each other, and may be a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, or an oxygen-containing group. Group, sulfur-containing group, silicon-containing group, nitrogen-containing group, phosphorus-containing group, halogen atom or hydrogen atom. R ³⁵ ,
Of the groups represented by R ³⁶ , R ³⁷ and R ³⁸ , some of the groups adjacent to each other may be bonded to form a ring together with the carbon atoms to which those groups are bonded. Note that R ³⁵ , R ³⁶ ,
Although R ³⁷ and R ³⁸ are displayed on each two positions, etc. Each example R ³⁵ and R ^35, may be well also different radicals in the same group. The same suffixes among the groups represented by R indicate preferred combinations in the case where they are joined to form a ring.

Examples of the hydrocarbon group having 1 to 20 carbon atoms include the same alkyl group, cycloalkyl group, alkenyl group, arylalkyl group and aryl group as those described above for L.

The ring formed by combining these hydrocarbon groups is a benzene ring, a naphthalene ring, an acenaphthene ring,
Examples thereof include a condensed ring group such as an indene ring, and a group in which a hydrogen atom on the condensed ring group is substituted with an alkyl group such as methyl, ethyl, propyl and butyl.

Examples of the halogenated hydrocarbon group having 1 to 20 carbon atoms include a group obtained by substituting the above hydrocarbon group having 1 to 20 carbon atoms with halogen. As the oxygen-containing group, a hydroxy group and an alkoxy group similar to the aforementioned L,
Examples include an aryloxy group and an arylalkoxy group.

Examples of the sulfur-containing group include a substituent in which oxygen of the oxygen-containing group is replaced with sulfur. Examples of the silicon-containing group include the same mono-hydrocarbon-substituted silyl, di-hydrocarbon-substituted silyl, tri-hydrocarbon-substituted silyl,
Examples include a silyl ether of a hydrocarbon-substituted silyl, a silicon-substituted alkyl group, and a silicon-substituted aryl group.

As the nitrogen-containing group, an amino group; an alkylamino group such as methylamino, dimethylamino, diethylamino, dipropylamino, dibutylamino, dicyclohexylamino; phenylamino, diphenylamino,
Examples thereof include arylamino groups such as ditolylamino, dinaphthylamino and methylphenylamino, and alkylarylamino groups.

Examples of the phosphorus-containing group include phosphino groups such as dimethylphosphino and diphenylphosphino. As the halogen atom, those similar to the aforementioned L can be mentioned.

Of these, a hydrocarbon group having 1 to 20 carbon atoms or a hydrogen atom is preferable, and a hydrocarbon group having 1 to 4 carbon atoms such as methyl, ethyl, propyl and butyl, and a hydrocarbon group are particularly preferable. A benzene ring formed by bonding with, a hydrogen atom on the benzene ring formed by bonding with a hydrocarbon group is methyl, ethyl, n-propyl, iso-propyl,
It is preferably a group substituted with an alkyl group such as n-butyl, iso-butyl and tert-butyl.

X ³ and X ⁴ may be the same or different from each other, and are a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group,
It represents a sulfur-containing group, a silicon-containing group, a hydrogen atom or a halogen atom.

Examples of the hydrocarbon group having 1 to 20 carbon atoms include the same alkyl group, cycloalkyl group, alkenyl group, arylalkyl group and aryl group as those described above for L.

Examples of the halogenated hydrocarbon group having 1 to 20 carbon atoms include groups obtained by substituting the above hydrocarbon group having 1 to 20 carbon atoms with halogen. Examples of the oxygen-containing group include a hydroxy group and the same alkoxy group, aryloxy group, and arylalkoxy group as those described above for L.

Examples of the sulfur-containing group include a substituent in which oxygen of the oxygen-containing group is substituted with sulfur, and a sulfonate group and a sulfinate group similar to the above L. Examples of the silicon-containing group include a silicon-substituted alkyl group and a silicon-substituted aryl group as described above for L.

As the halogen atom, the same groups and atoms as the above L can be mentioned. Of these, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a sulfonate group is preferable.

Y¹Is a divalent carbon having 1 to 20 carbon atoms
Hydrogenated group, divalent halogenated carbon having 1 to 20 carbon atoms
Hydrogen-containing group, divalent silicon-containing group, divalent germanium-containing group
Group, divalent tin-containing group, -O-, -CO-, -S-,
-SO-, -SO_Two-, -Ge-, -Sn-, -NR³⁹
-, -P (R³⁹)-, -P (O) (R³⁹)-, -BR ³⁹
-Or-AlR³⁹-[However, R³⁹Are identical to each other
Hydrocarbon water having 1 to 20 carbon atoms
Elementary groups, halogenated hydrocarbon groups having 1 to 20 carbon atoms,
A hydrogen atom or a halogen atom].

Specific examples of the divalent hydrocarbon group having 1 to 20 carbon atoms include methylene, dimethylmethylene and 1,2-
Ethylene, dimethyl-1,2-ethylene, 1,3-trimethylene, 1,4-tetramethylene, 1,2-cyclohexylene, 1,4-
Examples include alkylene groups such as cyclohexylene; arylalkylene groups such as diphenylmethylene and diphenyl-1,2-ethylene.

Specific examples of the divalent halogenated hydrocarbon group having 1 to 20 carbon atoms include a group obtained by halogenating the above divalent hydrocarbon group having 1 to 20 carbon atoms such as chloromethylene. Is mentioned.

As the divalent silicon-containing group, silylene,
Methyl silylene, dimethyl silylene, diethyl silylene, di (n-propyl) silylene, di (i-propyl) silylene, di (cyclohexyl) silylene, methylphenyl silylene, diphenyl silylene, di (p-tolyl) silylene, di (p- Alkylsilylylene groups such as chlorophenyl) silylene; Alkylarylsilylene groups; Arylsilylene groups; Tetramethyl-1,2-disilirene, tetraphenyl-1,2-disilylene and other alkyldisilylene groups; Alkylaryldisilylene groups; Aryldiyl Examples thereof include a silylene group.

Examples of the divalent germanium-containing group include groups obtained by substituting germanium for silicon in the divalent silicon-containing group. Examples of the divalent tin-containing group include groups obtained by substituting tin for silicon in the divalent silicon-containing group.

R ³⁹ is a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms or a halogen atom similar to L. Of these, substituted silylene groups such as dimethylsilylene, diphenylsilylene, and methylphenylsilylene are particularly preferable.

Specific examples of the transition metal compound represented by the formula (II-3) are shown below. ethylene
-Bis (indenyl) dimethyl zirconium, ethylene-
Bis (indenyl) zirconium dichloride, ethylene
-Bis (indenyl) zirconium bis (trifluoromethanesulfonate), ethylene-bis (indenyl) zirconium bis (methanesulfonate), ethylene-bis (indenyl) zirconium bis (p-toluenesulfonate), ethylene-bis (Indenyl) zirconium bis (p-chlorobenzene sulfonate),
Ethylene-bis (4,5,6,7-tetrahydroindenyl) zirconium dichloride, isopropylidene-bis (cyclopentadienyl) (fluorenyl) zirconium dichloride, isopropylidene-bis (cyclopentadienyl) (methylcyclopentadiene Enyl) zirconium dichloride, dimethylsilylene-bis (cyclopentadienyl) zirconium dichloride, dimethylsilylene-bis (methylcyclopentadienyl) zirconium dichloride, dimethylsilylene-bis (dimethylcyclopentadienyl) zirconium dichloride, dimethylsilylene-
Bis (trimethylcyclopentadienyl) zirconium dichloride, dimethylsilylene-bis (indenyl) zirconium dichloride, dimethylsilylene-bis (indenyl) zirconium bis (trifluoromethanesulfonate), dimethylsilylene-bis (4,5,6,7 -Tetrahydroindenyl) zirconium dichloride, dimethylsilylene-bis (cyclopentadienyl) (fluorenyl) zirconium dichloride, diphenylsilylene-bis (indenyl) zirconium dichloride, methylphenylsilylene-bis (indenyl) zirconium dichloride, rac-dimethylsilylene- Bis (2,3,5-trimethylcyclopentadienyl) zirconium dichloride, rac-
Dimethylsilylene-bis (2,4,7-trimethylcyclopentadienyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4-tert-butylcyclopentadienyl) zirconium dichloride, isopropylidene-
(Cyclopentadienyl) (fluorenyl) zirconium dichloride, dimethylsilylene- (3-tert-butylcyclopentadienyl) (indenyl) zirconium dichloride, isopropylidene- (4-methylcyclopentadienyl) (3-methylindenyl ) Zirconium dichloride, isopropylidene- (4-tert-butylcyclopentadienyl) (3-methylindenyl) zirconium dichloride, isopropylidene- (4-tert-butylcyclopentadienyl) (3-tert-butylindenyl) ) Zirconium dichloride, dimethylsilylene- (4-methylcyclopentadienyl) (3-methylindenyl) zirconium dichloride, dimethylsilylene- (4-tert-butylcyclopentadienyl) (3-methylindenyl) zirconium dichloride, Dimethylsilylene- (4-tert-butylcycline Lopentadienyl) (3-tert-butylindenyl) zirconium dichloride, dimethylsilylene- (3-tert-butylcyclopentadienyl) (fluorenyl) zirconium dichloride, isopropylidene- (3-tert-butylcyclopentadienyl) (fluorenyl ) Zirconium dichloride and the like.

Further, a compound in which zirconium in the above compound is replaced with titanium or hafnium can also be mentioned. In the present invention, as the transition metal compound represented by the formula (II-3), more specifically, the following general formula (II)
-4) or (II-5).

[0057]

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In the formula, M ¹ represents a transition metal atom of Group 4 of the periodic table, specifically titanium, zirconium or hafnium, preferably zirconium. R
⁴¹ may be the same or different and each represents a hydrocarbon group having 1 to 6 carbon atoms, and specifically, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl Alkyl groups such as tert-butyl, n-pentyl, neopentyl, n-hexyl, cyclohexyl;
Examples thereof include alkenyl groups such as vinyl and propenyl.

Of these, an alkyl group having a primary carbon atom bonded to an indenyl group is preferable, an alkyl group having 1 to 4 carbon atoms is more preferable, and a methyl group and an ethyl group are particularly preferable.

R ⁴² , R ⁴⁴ , R ⁴⁵ and R ^{46, which} may be the same or different, each represents a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 6 carbon atoms similar to R ⁴¹ . R ⁴³ may be the same or different, and represent a hydrogen atom or an aryl group having 6 to 16 carbon atoms;
Specifically, phenyl, α-naphthyl, β-naphthyl, anthryl, phenanthryl, pyrenyl, acenaphthyl,
Examples include phenalenyl, aceanthrylenyl, tetrahydronaphthyl, indanyl, biphenylyl and the like. Of these, phenyl, naphthyl, anthryl, and phenanthryl are preferable.

These aryl groups include halogen atoms such as fluorine, chlorine, bromine and iodine; methyl, ethyl, propyl, butyl, hexyl, cyclohexyl, octyl,
Alkyl groups such as nonyl, dodecyl, eicosyl, norbornyl and adamantyl; alkenyl groups such as vinyl, propenyl and cyclohexenyl; arylalkyl groups such as benzyl, phenylethyl, phenylpropyl; phenyl, tolyl, dimethylphenyl, trimethylphenyl, ethylphenyl , Propylphenyl, biphenyl,
Hydrocarbon group having 1 to 20 carbon atoms such as an aryl group such as α- or β-naphthyl, methylnaphthyl, anthryl, phenanthryl, benzylphenyl, pyrenyl, acenaphthyl, phenalenyl, aceanthrylenyl, tetrahydronaphthyl, indanyl and biphenylyl. It may be substituted with an organic silyl group such as trimethylsilyl, triethylsilyl and triphenylsilyl.

[0062] X ³ and X ⁴ may be the same or different from each other, X ³ and X ⁴ in the general formula (II-3)
Is the same as Of these, a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms is preferable.

[0063] Y ¹ is the same as Y ¹ in the general formula (II-3). Of these, a divalent silicon-containing group, a divalent germanium-containing group are preferable, a divalent silicon-containing group is more preferable, and an alkylsilylene, alkylarylsilylene or arylsilylene is more preferable. preferable.

Specific examples of the transition metal compound represented by the general formula (II-4) are shown below. rac-dimethylsilylene
-Bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2
-Methyl-4- (α-naphthyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-methyl-4- (β-naphthyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛ 1- (2-methyl-
4- (1-anthryl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-methyl-4- (2
-Anthryl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-methyl-4- (9-
Anthryl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-methyl-4- (9-phenanthryl) indenyl)} zirconium dichloride,
rac-Dimethylsilylene-bis {1- (2-methyl-4- (p-fluorophenyl) indenyl)} zirconium dichloride, rac-Dimethylsilylene-bis {1- (2-methyl-4- (pentafluorophenyl) indenyl) )} Zirconium dichloride, rac-dimethylsilylene-bis {1- (2-methyl-
4- (p-chlorophenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-methyl-
4- (m-chlorophenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-methyl-
4- (o-chlorophenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-methyl-
4- (o, p-dichlorophenyl) phenylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1
-(2-Methyl-4- (p-bromophenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1
-(2-Methyl-4- (p-tolyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-methyl-4- (m-tolyl) indenyl)} zirconium dichloride, rac-dimethylsilylene -Bis {1- (2-methyl-4- (o
-Tolyl) indenyl)} zirconium dichloride, rac
-Dimethylsilylene-bis {1- (2-methyl-4- (o, o'-dimethylphenyl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis {1- (2-methyl-4- (p -
Ethylphenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-methyl-4- (pi
-Propylphenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-methyl-4-)
(p-benzylphenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-methyl-
4- (p-biphenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-methyl-4- (m
-Biphenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-methyl-4- (p-
Trimethylsilylenephenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-
Methyl-4- (m-trimethylsilylenephenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2-phenyl-4-phenylindenyl)} zirconium dichloride, rac-diethylsilylene-bis {1-
(2-Methyl-4-phenylindenyl)} zirconium dichloride, rac-di- (i-propyl) silylene-bis {1- (2
-Methyl-4-phenylindenyl) zirconium dichloride, rac-di- (n-butyl) silylene-bis {1- (2-methyl-4-phenylindenyl) zirconium dichloride, rac-dicyclohexylsilylene-bis} 1- (2-methyl-4-phenylindenyl)｝ zirconium dichloride, rac-methylphenylsilylene-bis ｛1- (2-methyl-
4-phenylindenyl)} zirconium dichloride, ra
c-diphenylsilylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride, rac-di (p-tolyl) silylene-bis {1- (2-methyl-4-phenylindenyl)} Zirconium dichloride, rac-di (p-chlorophenyl) silylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride, rac-methylene-bis {1- (2-methyl-4-phenylindenyl) )} Zirconium dichloride, rac-ethylene-bis {1- (2-methyl-4-)
Phenylindenyl) zirconium dichloride, rac-
Dimethylgermylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride, rac-Dimethylstanylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride, rac- Dimethyl silylene
-Bis {1- (2-methyl-4-phenylindenyl)} zirconium dibromide, rac-dimethylsilylene-bis {1- (2
-Methyl-4-phenylindenyl)} zirconium dimethyl, rac-dimethylsilylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium methyl chloride, rac-
Dimethylsilylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium chloride SO ₂ Me, rac-Dimethylsilylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium chloride OSO ₂ Me, rac-dimethylsilylene-bis {1- (2-ethyl-4-phenylindenyl)} zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2-ethyl-4- (α-naphthyl) indenyl)} zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2-ethyl-4- (β-naphthyl) indenyl)} zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2-ethyl-4- (2-methyl-1-naphthyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-ethyl-4- (5-acenaphthyl) indenyl) ｝ Zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-ethyl-4- (9-anthryl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2-ethyl-4- (9-phenanthryl) indenyl)} zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2-ethyl-4- (o-methylphenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2-ethyl-4- (m-methylphenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2-ethyl-4- (p-methylphenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2-ethyl-4- (2,3-dimethylphenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-ethyl-4- (2,4-dimethylphenyl)
Indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-ethyl-4- (2,5-dimethylphenyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-ethyl- 4- (2,4,6-trimethylphenyl) indenyl)｝ zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-ethyl-4- (o-chlorophenyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-ethyl-4- (m-chlorophenyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-ethyl-4- (p-chlorophenyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-ethyl-4- (2,3-dichlorophenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-ethyl-4- (2,6
-Dichlorophenyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-ethyl-4-
(3,5-dichlorophenyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-ethyl
-4- (2-bromophenyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-ethyl
-4- (3-bromophenyl) indenyl) zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-ethyl
-4- (4-bromophenyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-ethyl
-4- (4-biphenylyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-ethyl-4
-(4-trimethylsilylphenyl) indenyl) zirconium dichloride, rac-dimethylsilylene-bis
(2-n-propyl-4-phenylindenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-n-propyl-4- (α-naphthyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene -Bis {1- (2-n-propyl-4- (β-naphthyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-n-propyl
-4- (2-methyl-1-naphthyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-n-propyl-4- (5-acenaphthyl) indenyl)｝ zirconium dichloride, rac-dimethyl Silylene-bis ｛1- (2-n-
Propyl-4- (9-anthryl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-n-
Propyl-4- (9-phenanthryl) indenyl) {zirconium dichloride, rac-dimethylsilylene-bis} 1-
(2-i-propyl-4-phenylindenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-i-propyl-4- (α-naphthyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene -Bis {1- (2-i-propyl-4- (β-naphthyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-i-propyl
-4- (8-methyl-9-naphthyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-i-propyl-4- (5-acenaphthyl) indenyl)｝ zirconium dichloride, rac-dimethyl Silylene-bis ｛1- (2-i-
Propyl-4- (9-anthryl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-i-
Propyl-4- (9-phenanthryl) indenyl) {zirconium dichloride, rac-dimethylsilylene-bis} 1-
(2-s-butyl-4-phenylindenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-s-butyl
-4- (α-naphthyl) indenyl) zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-s-butyl-4-
(Β-naphthyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-s-butyl-4- (2
-Methyl-1-naphthyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-s-butyl-4)
-(5-acenaphthyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-s-butyl-4)
-(9-anthryl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-s-butyl-4-
(9-phenanthryl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-n-pentyl)
-4-Phenylindenyl)} zirconium dichloride, r
ac-dimethylsilylene-bis ｛1- (2-n-pentyl-4- (α-
Naphthyl) indenyl) zirconium dichloride, ra
c-dimethylsilylene-bis {1- (2-n-butyl-4-phenylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-n-butyl-4- (α-naphthyl) indenyl) )｝ Zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-n-butyl-4- (β-naphthyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2-n-butyl-4- (2-methyl-1-naphthyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-n-butyl-4- (5- Acenaphthyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-n-butyl-4- (9-anthryl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-n -Butyl-4- (9-phenanthryl) indenyl) {zirconium dichloride, rac-dimethylsilylene-bis {1- (2-i-butyl-4-phenylindenyl)}
Zirconium dichloride, rac-dimethylsilylene-bis {1- (2-i-butyl-4- (α-naphthyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis
-(2-i-butyl-4- (β-naphthyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-
i-butyl-4- (2-methyl-1-naphthyl) indenyl) {zirconium dichloride, rac-dimethylsilylene-bis} 1
-(2-i-butyl-4- (5-acenaphthyl) indenyl) {zirconium dichloride, rac-dimethylsilylene-bis} 1
-(2-i-butyl-4- (9-anthryl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1-
(2-i-butyl-4- (9-phenanthryl) indenyl) {zirconium dichloride, rac-dimethylsilylene-bis} 1
-(2-neopentyl-4-phenylindenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-neopentyl-4- (α-naphthyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛ 1- (2-n-
Hexyl-4-phenylindenyl) zirconium dichloride, rac-dimethylsilylene-bis {1- (2-n-hexyl)
-4- (α-naphthyl) indenyl) zirconium dichloride, rac-methylphenylsilylene-bis ｛1- (2-ethyl
-4-Phenylindenyl)} zirconium dichloride, r
ac-methylphenylsilylene-bis ｛1- (2-ethyl-4- (α
-Naphthyl) indenyl)} zirconium dichloride, r
ac-methylphenylsilylene-bis {1- (2-ethyl-4- (9-
Anthryl) indenyl)} zirconium dichloride,
rac-methylphenylsilylene-bis {1- (2-ethyl-4- (9
-Phenanthryl) indenyl)｝ zirconium dichloride, rac-diphenylsilylene-bis ｛1- (2-ethyl-4-
Phenylindenyl) zirconium dichloride, rac-
Diphenylsilylene-bis {1- (2-ethyl-4- (α-naphthyl) indenyl)} zirconium dichloride, rac-diphenylsilylene-bis {1- (2-ethyl-4- (9-anthryl) indenyl)} zirconium Dichloride, rac-diphenylsilylene-bis {1- (2-ethyl-4- (9-phenanthryl) indenyl)} zirconium dichloride, rac-diphenylsilylene-bis {1- (2-ethyl-4- (4-biphenylyl) Indenyl) {zirconium dichloride, rac-methylene-bis {1- (2-ethyl-4-phenylindenyl)}
Zirconium dichloride, rac-methylene-bis {1- (2-ethyl-4- (α-naphthyl) indenyl)} zirconium dichloride, rac-ethylene-bis {1- (2-ethyl-4-phenylindenyl)} zirconium Dichloride, rac-ethylene-bis {1- (2-ethyl-4- (α-naphthyl) indenyl)} zirconium dichloride, rac-ethylene-bis
-(2-n-propyl-4- (α-naphthyl) indenyl)｝ zirconium dichloride, rac-dimethylgermyl-bis ｛1-
(2-ethyl-4-phenylindenyl) zirconium dichloride, rac-dimethylgermyl-bis ｛1- (2-ethyl-4-
(Α-naphthyl) indenyl)｝ zirconium dichloride, rac-dimethylgermyl-bis ｛1- (2-n-propyl-4-)
Phenylindenyl) zirconium dichloride.

Further, there may be mentioned compounds in which zirconium in the above compounds is replaced with titanium or hafnium. Further, meso forms of these compounds can be used as well.

In the present invention, the racemic body of the transition metal compound represented by the above general formula (II-4) is usually used as the catalyst component, but R type or S type can also be used. Such a transition metal compound represented by the general formula (II-4) is
urnal of Organometallic Chem. 288 (1985), Nos. 63-67
Page, European Patent Application Publication No. 0,320,762, and Examples.

Next, the transition metal compound represented by the general formula (II-5) will be described.

[0068]

Embedded image

In the formula, M ¹ represents a transition metal atom of Group 4 of the periodic table, specifically titanium, zirconium or hafnium, preferably zirconium. R
⁵¹ and R ⁵² may be the same or different from each other;
Hydrocarbon group having 1 to 20 carbon atoms, 1 to 1 carbon atoms
20 halogenated hydrocarbon group, oxygen-containing group, a sulfur-containing group, a silicon-containing group, a nitrogen-containing group, a phosphorus-containing group, a halogen atom or a hydrogen atom, specifically, the R ³⁵ to R
The same atoms or groups as those described in ³⁸ are mentioned.

Of these, R ⁵¹ has 1 to 2 carbon atoms.
It is preferably a hydrocarbon group having 0, and particularly preferably a hydrocarbon group having 1 to 3 carbon atoms such as methyl, ethyl and propyl.

R ⁵² has a hydrogen atom or a carbon atom number of 1 to
20 hydrocarbon groups are preferred, and particularly hydrogen atom or methyl, ethyl, propyl having 1 to 10 carbon atoms.
It is preferably a hydrocarbon group of 3.

R ⁵³ and R ^{54, which} may be the same or different, each represents an alkyl group having 1 to 20 carbon atoms, specifically, methyl, ethyl, n-propyl, isopropyl, n-butyl, Examples thereof include alkyl groups such as isobutyl, sec-butyl, tert-butyl, n-pentyl, neopentyl, n-hexyl, cyclohexyl, octyl, nonyl, dodecyl and eicosyl; and cycloalkyl groups such as norbornyl and adamantyl.

Of these, R ⁵³ is preferably a secondary or tertiary alkyl group. X ³ and X ⁴ may be the same or different from each other is the same as X ³ and X ⁴ in the general formula (II-3).

[0074] Y ¹ is the same as Y ¹ in the general formula (II-3). Specific examples of the transition metal compound represented by the general formula (II-5) are shown below. rac-dimethyl silylene-
Bis ｛1- (2,7-dimethyl-4-ethylindenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1-
(2,7-dimethyl-4-n-propylindenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2,7
-Dimethyl-4-i-propylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2,7-dimethyl-4-n-butylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis { 1- (2,7-dimethyl-4-
sec-Butylindenyl)} zirconium dichloride, ra
c-Dimethylsilylene-bis {1- (2,7-dimethyl-4-t-butylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2,7-dimethyl-4-n-pentylindene) Nil)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2,7-dimethyl-4-n-hexylindenyl)} zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2,7-dimethyl-4-cyclohexylindenyl)} zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2,7-dimethyl-4-methylcyclohexylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2,7-dimethyl-4-phenylethylindenyl)} zirconium dichloride, rac-Dimethylsilylene-bis {1- (2,7-dimethyl-4-phenyldichloromethylindenyl)} zirconium dichloride, rac-Dimethylsilylene-bis {1- (2,7-dimethyl-4-chloromethylindenyl) )} Zirconium dichloride, rac-dimethylsilylene-bis {1- (2,7-dimethyl-4-trimethylsilylmethylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2,7-dimethyl-4-) Trimethylsiloxymethylindenyl)} zirconium dichloride, ra
c-Diethylsilylene-bis {1- (2,7-dimethyl-4-i-propylindenyl)} zirconium dichloride, rac-di (i-propyl) silylene-bis {1- (2,7-dimethyl-4) -i-
Propylindenyl) zirconium dichloride, rac-
Di (n-butyl) silylene-bis {1- (2,7-dimethyl-4-i-
Propylindenyl) zirconium dichloride, rac-
Di (cyclohexyl) silylene-bis {1- (2,7-dimethyl-4-i-propylindenyl)} zirconium dichloride, rac-methylphenylsilylene-bis {1- (2,7-dimethyl-4-i- Propylindenyl)} zirconium dichloride, rac-methylphenylsilylene-bis {1- (2,7-dimethyl-4-t-butylindenyl)} zirconium dichloride, rac-diphenylsilylene-bis {1- (2,7 -Dimethyl-4-t-butylindenyl)} zirconium dichloride, rac-diphenylsilylene-bis {1- (2,7-dimethyl-
4-i-propylindenyl)} zirconium dichloride,
rac-diphenylsilylene-bis {1- (2,7-dimethyl-4-ethylindenyl)} zirconium dichloride, rac-di (p-tolyl) silylene-bis {1- (2,7-dimethyl-4-i -Propylindenyl)} zirconium dichloride, rac-di (p-chlorophenyl) silylene-bis {1- (2,7-dimethyl-4-i-propylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1 -(2-Methyl-4-i-propyl-7-ethylindenyl)} zirconium dibromide rac-dimethylsilylene-bis {1- (2,3,7-trimethyl-
4-Ethylindenyl)} zirconium dichloride, rac-
Dimethylsilylene-bis {1- (2,3,7-trimethyl-4-n-propylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2,3,7-trimethyl-4-i- Propylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2,3,7-trimethyl-4-n-butylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2, 3,7-Trimethyl-4-sec-butylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2,3,7-trimethyl-4-t-butylindenyl)} zirconium dichloride, rac- Dimethylsilylene-bis {1- (2,3,7-trimethyl-4-n-pentylindenyl)} zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2,3,7-trimethyl-4-n-hexylindenyl)} zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2,3,7-trimethyl-4-cyclohexylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2,3,7-trimethyl-4-methylcyclohexylindenyl)} Zirconium dichloride, rac-dimethylsilylene-bis {1- (2,3,7-trimethyl-4-trimethylsilylmethylindenyl)} zirconium dichloride,
rac-Dimethylsilylene-bis {1- (2,3,7-trimethyl-4-
Trimethylsiloxymethylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2,3,7-
Trimethyl-4-phenylethylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2,
3,7-Trimethyl-4-phenyldichloromethylindenyl)} zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2,3,7-trimethyl-4-chloromethylindenyl)} zirconium dichloride, rac-diethylsilylene
-Bis {1- (2,3,7-trimethyl-4-i-propylindenyl)} zirconium dichloride, rac-di (i-propyl)
Silylene-bis {1- (2,3,7-trimethyl-4-i-propylindenyl)} zirconium dichloride, rac-di (n-butyl) silylene-bis {1- (2,3,7-trimethyl- 4-i-Propylindenyl)} zirconium dichloride, rac-di (cyclohexyl) silylene-bis {1- (2,3,7-trimethyl-
4-i-propylindenyl)} zirconium dichloride,
rac-Methylphenylsilylene-bis {1- (2,3,7-trimethyl-4-i-propylindenyl)} zirconium dichloride, rac-methylphenylsilylene-bis {1- (2,3,7-
Trimethyl-4-t-butylindenyl)} zirconium dichloride, rac-diphenylsilylene-bis {1- (2,3,7-
Trimethyl-4-t-butylindenyl)} zirconium dichloride, rac-diphenylsilylene-bis {1- (2,3,7-
Trimethyl-4-i-propylindenyl)} zirconium dichloride, rac-diphenylsilylene-bis {1- (2,3,7
-Trimethyl-4-ethylindenyl)} zirconium dichloride, rac-di (p-tolyl) silylene-bis {1- (2,3,7
-Trimethyl-4-i-propylindenyl)} zirconium dichloride, rac-di (p-chlorophenyl) silylene-bis {1- (2,3,7-trimethyl-4-i-propylindenyl)} zirconium dichloride, rac-dimethyl silylene
-Bis {1- (2-methyl-4-i-propyl-7-methylindenyl)} zirconium dimethyl, rac-dimethylsilylene-
Bis {1- (2-methyl-4-i-propyl-7-methylindenyl)} zirconium methyl chloride, rac-dimethylsilylene-bis {1- (2-methyl-4-i-propyl-7-methylindene Nyl)} zirconium-bis (methanesulfonate), rac-dimethylsilylene-bis {1- (2-methyl-4-i-
Propyl-7-methylindenyl)} zirconium-bis (p-phenylsulfinato), rac-dimethylsilylene-
Bis {1- (2-methyl-3-methyl-4-i-propyl-7-methylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-methyl-4,6-di-i -Propylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-ethyl-4-i-propyl-7-methylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2 -Phenyl-4-i-propyl-7-methylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-methylindenyl)} zirconium dichloride, rac-ethylene-bis {1- (2, 4,7-Trimethylindenyl)} zirconium dichloride, rac-isopropylidene-bis {1- (2,4,7-trimethylindenyl)} zirconium dichloride and the like.

In addition, compounds in which zirconium in the above compounds is replaced by titanium or hafnium can also be mentioned. Furthermore, meso forms of these compounds can also be used.

Among these, those having a branched alkyl group such as i-propyl, sec-butyl, tert-butyl group at the 4-position are particularly preferred. In the present invention, the general formula (II
The racemic body of the transition metal compound represented by -5) is used as the catalyst component, but R type or S type can also be used.

The transition metal compound represented by the general formula (II-5) as described above can be synthesized from an indene derivative by a known method, for example, the method described in JP-A-4-268307.

Further, in the present invention, a compound represented by the following formula (III-1) can be used as the transition metal compound of Group 4 of the periodic table (A). L ² M ¹ X ⁵² ₂ (III-1) In the formula, M ¹ represents a transition metal atom belonging to Group 4 of the periodic table.

L ² is a derivative of a delocalized π-bonding group, which imparts a constrained geometric shape to the metal M ¹ active site, and X ^{5 s} may be the same or different from each other. A hydrocarbon group, a silyl group or a germyl group containing a halogen atom or 20 or less carbon atoms, a silicon atom or a germanium atom.

Among the compounds represented by the general formula (III-1), the compound represented by the following formula (III-2) is preferable.

[0081]

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In the formula, M ¹ represents a transition metal atom of Group 4 of the periodic table, specifically zirconium, titanium or hafnium, preferably zirconium. Cp is
A substituted cyclopentadienyl group having a π bond to M ¹ and having a substituent Z or a derivative thereof.

Z¹Is an oxygen atom, sulfur atom, boron atom
A child or a ligand containing an element of Group 14 of the periodic table
For example -Si (R⁵⁵ _Two)-, -C (R⁵⁵ _Two)-, -Si
(R⁵⁵ _Two) Si (R⁵⁵ _Two)-, -C (R⁵⁵ _Two) C (R⁵⁵ _Two)
-, -C (R⁵⁵ _Two) C (R⁵⁵ _Two) C (R⁵⁵ _Two)-, -C
(R⁵⁵) = C (R⁵⁵)-, -C (R⁵⁵ _Two) Si (R⁵⁵ _Two)
-, -Ge (R⁵⁵ _Two)-.

Y ² represents a ligand containing a nitrogen atom, a phosphorus atom, an oxygen atom or a sulfur atom, for example, --N (R
⁵² )-, -O-, ^-S- , -P ( ^R52 )-and the like.
Further, Z ¹ and Y ² may form a condensed ring.

R ⁵⁵ is a hydrogen atom or a group selected from an alkyl group having up to 20 non-hydrogen atoms, an aryl group, a silyl group, an alkyl halide group, an aryl halide group or a combination thereof, and R ⁵² is a carbon atom Alkyl having 1 to 10 atoms, aryl group having 6 to 10 carbon atoms or aralkyl group having 7 to 10 carbon atoms, or condensation of one or more R ⁵⁵ with up to 30 non-hydrogen atoms. It may form a ring system.

Specific examples of the transition metal compound represented by the above general formula (III-2) are shown below. (Tert-butylamide) (tetramethyl-η ⁵ -cyclopentadienyl) -1,2-
Ethanediylzirconium dichloride, (tert-butylamide) (tetramethyl-η ⁵ -cyclopentadienyl)-
1,2-ethanediyl titanium dichloride, (methyl amide)
(Tetramethyl-η ⁵ -cyclopentadienyl) -1,2-ethanediylzirconium dichloride, (methylamide)
(Tetramethyl-η ⁵ -cyclopentadienyl) -1,2-ethanediyltitanium dichloride, (ethylamide) (tetramethyl-η ⁵ -cyclopentadienyl) -methylenetitanium dichloride, (tert-butylamido) dimethyl (tetra Methyl-η ⁵ -cyclopentadienyl) silanetitanium dichloride, (tert-butylamido) dimethyl (tetramethyl-
η ⁵ -cyclopentadienyl) silane zirconium dichloride, (benzylamido) dimethyl- (tetramethyl-η
⁵ -cyclopentadienyl) silane titanium dichloride,
(Phenyl phosphide) dimethyl (tetramethyl-η ^5-
Cyclopentadienyl) silane zirconium dibenzyl and the like.

(B) Transition metal compounds of Groups 8 to 10 of the periodic table
Objects (B) used in the present invention the periodic table transition metal compound of Groups 8-10 is a transition metal compound represented by the following general formula (I).

[0088]

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In the formula, M represents a transition metal atom of Groups 8 to 10 of the periodic table, preferably nickel, palladium or platinum. X ¹ and X ² may be the same or different from each other and represent a nitrogen atom or a phosphorus atom.

R ¹ and R ^{2, which} may be the same or different, each represents a hydrogen atom or a hydrocarbon group. Specific examples of the hydrocarbon group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group,
sec-Butyl group, tert-butyl group, pentyl group, hexyl group, etc., linear or branched alkyl group having 1 to 20 carbon atoms; phenyl group, naphthyl group, etc., having 6 to 20 carbon atoms Group; these aryl groups have 1 to 5 substituents such as an alkyl group having 1 to 20 carbon atoms.
Examples thereof include a substituted aryl group substituted with an individual.

M and n, which may be the same or different, are 1 or 2 and are numbers which satisfy the valences of X ¹ and X ² , respectively. R ³ is

[0092]

[Chemical 12]

Is shown. However, R ⁶ , R ⁷ , R ⁶¹ ,
R ⁶² , R ⁷¹ and R ^{72, which} may be the same or different, each represents a hydrogen atom or a hydrocarbon group similar to R ¹ and R ² .

The above R ¹ , R ² , R ⁶ (or R ⁶¹ ,
R ⁶² ) and R ⁷ (or R ⁷¹ , R ⁷² ) may form a ring by connecting two or more of them, preferably adjacent groups, to each other.

R ⁴ and R ^{5, which} may be the same or different, each represents a hydrogen atom, a halogen atom or a hydrocarbon group. Examples of the halogen atom include fluorine, chlorine, bromine and iodine.

Specific examples of the hydrocarbon group include alkyl groups having 1 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, and benzyl groups such as R ¹ and R ² described above. 7 to 20 aralkyl groups and the like can be mentioned. One or more substituents such as the alkyl group having 1 to 20 carbon atoms may be substituted on the aryl group and the aralkyl group.

Further, as R ⁴ and R ⁵ , —OR ⁸ ,
-SR ^9, a group represented by -N (R ¹⁰⁾ ₂ or -P (R ¹¹⁾ ₂ is also shown. R ^{8 to} R ¹¹ are the same as R ¹ and R ² described above.
Similarly, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms such as a cyclohexyl group, and a carbon number 7 to 7 such as a benzyl group. 20 aralkyl groups; organic silyl groups such as methylsilyl group, dimethylsilyl group, trimethylsilyl group, ethylsilyl group, diethylsilyl group and triethylsilyl group. The aryl group and the aralkyl group may be substituted with one or more substituents such as the alkyl group having 1 to 20 carbon atoms. And R
^10's or R ^11's may be linked to each other to form a ring.

R ⁴ and R ⁵ may be linked to each other to form a ring. The transition metal compound represented by the general formula (I) is preferably a compound represented by the following general formula (I ′).

[0099]

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(Wherein M, X ¹ , X ² , R ¹ , R ² and R
⁴ , R ⁵ , R ⁶ and R ⁷ are the same as in the general formula (I). ) Specific examples of the transition metal compound represented by the general formula (I ′) include the following compounds.
In the following formula, iPr represents an isopropyl group.

[0101]

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[0102]

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[0103]

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[0104]

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[0105]

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[0106]

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[0107]

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[0108]

[Chemical 21]

[0109]

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[0110]

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In addition to the above, examples of the transition metal compound represented by the general formula (I ') include compounds in which palladium or nickel in the above compounds is replaced by platinum.

Examples of the compound represented by the above general formula (I) include the following compounds other than the above. In the following formula, iPr represents an isopropyl group.

[0113]

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[0114]

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In addition to the above, examples of the transition metal compound represented by the general formula (I) include compounds in which palladium or nickel in the above compounds is replaced by platinum.

The above transition metal compounds may be used alone or in combination of two or more. (C-1) Organoaluminum Oxy Compound The (C-1) organoaluminum oxy compound used in the present invention may be a conventionally known aluminoxane, or as exemplified in JP-A-2-78687. It may be a benzene-insoluble organoaluminum oxy compound.

The conventionally known aluminoxane can be produced, for example, by the following method and is usually obtained as a solution of a hydrocarbon solvent. (1) Compounds containing water of adsorption or salts containing water of crystallization such as hydrated magnesium chloride, hydrated copper sulfate, hydrated aluminum sulfate, hydrated nickel sulfate, hydrated cerium chloride A method of adding an organoaluminum compound such as a trialkylaluminum to a suspension of a hydrocarbon medium of the above, and reacting the water of adsorption or water of crystallization with the organoaluminum compound. (2) A method in which water, ice or steam 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 organometallic component. The solvent or unreacted organoaluminum compound may be removed from the recovered solution of the aluminoxane by distillation, and then redissolved in a solvent or suspended in a poor solvent for the aluminoxane.

Specific examples of the organoaluminum compound used when preparing the aluminoxane include trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum and tri-n-.
Butylaluminum, triisobutylaluminum, trisec-butylaluminum, tritert-butylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum, etc., trialkylaluminum, tricyclohexylaluminum, tricyclooctylaluminum, etc. Dialkylaluminum halides such as tricycloalkylaluminum, dimethylaluminum chloride, diethylaluminum chloride, diethylaluminum bromide and diisobutylaluminum chloride, dialkylaluminum hydrides such as diethylaluminum hydride and diisobutylaluminum hydride, dimethylaluminum methoxide, diethylaluminum ethoxy And dialkylaluminum aryloxides such as diethylaluminum alkoxide and diethylaluminum phenoxide.

Of these, trialkylaluminum and tricycloalkylaluminum are preferable, and trimethylaluminum is particularly preferable. Further, as an organoaluminum compound used for preparing aluminoxane, isoprenylaluminum represented by the following general formula can also be used.

(I-C ₄ H ₉ ) _x Al _y (C ₅ H ₁₀ ) _z (IV) (wherein x, y, and z are positive numbers, and z ≧ 2x). Such organoaluminum compounds may be used alone or in combination of two or more.

As the solvent used for the preparation of aluminoxane, 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. Further, ethers such as ethyl ether and tetrahydrofuran can also be used. Among these solvents, aromatic hydrocarbons and aliphatic hydrocarbons are particularly preferred.

In the benzene-insoluble organoaluminum oxy compound used in the present invention, the Al component dissolved in benzene at 60 ° C. is usually 10% or less, preferably 5% or less, particularly preferably 2% or less in terms of Al atom. Yes, it is insoluble or sparingly soluble in benzene.

The above (C-1) organoaluminum oxy compounds may be used alone or in combination of two or more. (C-2) Alkylboronic Acid Derivative Examples of the alkylboronic acid derivative (C-2) used in the present invention include compounds represented by the following general formula (V).

[0125]

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In the formula, R ¹² represents a hydrocarbon group having 1 to 10 carbon atoms. R < ¹³ >, which may be the same or different, each represents a hydrogen atom, a halogen atom, a siloxy group, a lower alkyl group-substituted siloxy group or a hydrocarbon group having 1 to 10 carbon atoms.

The alkylboronic acid derivative (B-2) represented by the general formula (V) includes an alkylboronic acid represented by the following general formula (VI) and R ¹² -B- (OH) ₂ (VI) (In the formula, R ¹² represents the same group as described above.) A reaction with an organoaluminum compound in an inert solvent in an inert gas atmosphere at a temperature of −80 ° C. to room temperature for 1 minute to 24 hours. Can be manufactured by

Specific examples of the alkylboronic acid represented by the general formula (VI) include methylboronic acid, ethylboronic acid, isopropylboronic acid, n-propylboronic acid, n-butylboronic acid, isobutylboronic acid, n. -Hexylboronic acid, cyclohexylboronic acid, phenylboronic acid, 3,5-difluoroboronic acid, pentafluorophenylboronic acid, 3,5-bis (trifluoromethyl) phenylboronic acid and the like. Of these, methylboronic acid, n-butylboronic acid, isobutylboronic acid, 3,5-difluorophenylboronic acid, and pentafluorophenylboronic acid are preferable. These may be used alone or in combination of two or more.

The organoaluminum compound to be reacted with the alkylboronic acid is represented by the following general formula (VII-
Examples thereof include organoaluminum compounds represented by 1), (VII-2) and (VII-3).

(R ¹³ ) _3-p -Al-Y _p ... (VII-1) (R ¹³ ) _3-p -Al- [OSi (R ¹⁴ ) ₃ ] _p ... (VII-2) (R ¹³ ) _{2 -Al-O-Al- (R} 13) 2 ... (VII-3) ( in the formula, Y is a hydrogen atom or a halogen atom, R ¹⁴ is
A hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 10 carbon atoms, p is 0 ≦ p <3, and R ¹³ is the same group as described above. ) Specific examples of the organoaluminum compounds represented by the general formulas (VII-1), (VII-2) and (VII-3) include trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum and triisopropylaluminum.
n-butyl aluminum, triisobutyl aluminum,
Trialkylalkyl such as trisec-butylaluminum, tritert-butylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum, etc., tricycloalkylaluminum such as tricyclohexylaluminum, tricyclooctylaluminum, dimethylaluminum Chloride, diethylaluminum chloride,
Dialkylaluminum halides such as diethylaluminum bromide and diisobutylaluminum chloride;
Dialkylaluminum hydrides such as diethylaluminum hydride and diisobutylaluminum hydride; dialkylaluminum alkoxides such as dimethylaluminum methoxide and diethylaluminum ethoxide; and dialkylaluminum aryloxides such as diethylaluminum phenoxide.

Of these, trialkyl aluminum and tricycloalkyl aluminum are preferable, and trimethyl aluminum, triethyl aluminum and triisobutyl aluminum are particularly preferable. These may be used alone or in combination of two or more.

The above-mentioned (C-2) alkylboronic acid derivative may be used alone or in combination of two or more kinds. (C-3) Reaction to form an ion pair by reacting with a transition metal compound
The compound (C-3) (hereinafter, referred to as “ionized ionic compound”) that reacts with the transition metal compound used in the present invention to form an ion pair is the transition metal compound (A) and / or the transition metal compound. A compound which reacts with the metal compound (B) to form an ion pair, and examples of such a compound include JP-A-1-501950, JP-A-1-502036, and JP-A-3-179005. Kaihei 3-17
Examples thereof include Lewis acids, ionic compounds, borane compounds and carborane compounds described in JP-A-9006, JP-A-3-207703, JP-A-3-207704, US-547718 and the like.

Specifically, as the Lewis acid, BR is
₃ (R is a phenyl group which may have a substituent such as fluorine, a methyl group, a trifluoromethyl group or fluorine), and examples thereof include trifluoroboron, triphenylboron, Tris (4-fluorophenyl) boron, Tris (3,5-difluorophenyl) boron, Tris (4-fluoromethylphenyl) boron, Tris (pentafluorophenyl) boron, Tris (p-tolyl) boron, Tris (o- Trily) boron, tris (3,5-dimethylphenyl) boron and the like.

Examples of the ionic compound include compounds represented by the following general formula (VIII).

[0135]

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In the formula, examples of R ¹⁵ include H ⁺ , carbonium cation, oxonium cation, ammonium cation, phosphonium cation, cycloheptyltrienyl cation, and ferrocenium cation having a transition metal.

R ^{16 to} R ^{19, which} may be the same or different, are organic groups, preferably aryl groups or substituted aryl groups. Specific examples of the carbonium cation include triphenylcarbonium cation, tri (methylphenyl) carbonium cation, tri (dimethylphenyl) carbonium cation, and other trisubstituted carbonium cations.

Specific examples of the ammonium cations include trimethylammonium cations, triethylammonium cations, tripropylammonium cations, tributylammonium cations, tri (n-butyl) ammonium cations and other trialkylammonium cations; N, N-diethylaniline. Nium cation, N,
N, N- such as N-2,4,6-pentamethylanilinium cation
Dialkylanilinium cation; di (isopropyl)
Examples thereof include dialkylammonium cations such as ammonium cation and dicyclohexylammonium cation.

Specific examples of the phosphonium cation include triarylphosphonium cations such as triphenylphosphonium cation, tri (methylphenyl) phosphonium cation and tri (dimethylphenyl) phosphonium cation.

R ¹⁵ is preferably a carbonium cation, an ammonium cation or the like, particularly preferably a triphenylcarbonium cation or an N, N-diethylanilinium cation.

As the ionic compound, a boron compound represented by the following formula (IX) is preferable.

[0142]

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(In the formula, Et represents an ethyl group.) Examples of the ionic compound include trialkyl-substituted ammonium salts, N, N-dialkylanilinium salts, dialkylammonium salts, and triarylphosphonium salts. You can also

Specific examples of the trialkyl-substituted ammonium salt include, for example, triethylammonium tetra (phenyl) boron, tripropylammonium tetra (phenyl) boron, tri (n-butyl) ammonium tetra (phenyl) boron and trimethylammonium tetra (p). -Tolyl) boron, trimethylammonium tetra (o-tolyl) boron, tri (n-butyl) ammonium tetra (pentafluorophenyl) boron, tripropylammonium tetra (o, p-dimethylphenyl) boron,
Tri (n-butyl) ammonium tetra (m, m-dimethylphenyl) boron, tri (n-butyl) ammonium tetra (p-trifluoromethylphenyl) boron, tri (n-butyl) ammonium tetra (3,5-ditri Fluoromethylphenyl) boron, tri (n-butyl) ammonium tetra (o-tolyl) boron and the like.

Specific examples of the N, N-dialkylanilinium salt include, for example, N, N-dimethylanilinium tetra (phenyl) boron, N, N-diethylanilinium tetra (phenyl) boron, N, N-2, Examples include 4,6-pentamethylanilinium tetra (phenyl) boron.

Specific examples of the dialkyl ammonium salt include di (1-propyl) ammonium tetra (pentafluorophenyl) boron and dicyclohexylammonium tetra (phenyl) boron.

Further, as an ionic compound, triphenylcarbenium tetrakis (pentafluorophenyl)
Borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, ferrocenium tetra (pentafluorophenyl) borate, triphenylcarbenium pentaphenylcyclopentadienyl complex,
Examples also include N, N-diethylanilinium pentaphenylcyclopentadienyl complex and a boron compound represented by the following formula (X).

[0148]

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Specific examples of the borane compound include decaborane (14); bis [tri (n-butyl) ammonium] nonaborate, bis [tri (n-butyl) ammonium] decaborate and bis [tri (n-butyl) ammonium]. ] Undecaborate, bis [tri (n-butyl) ammonium] dodecaborate, bis [tri (n-butyl) ammonium] decachlorodecaborate, bis [tri (n-
Salts of anions such as butyl) ammonium] dodecachlorododecaborate; tri (n-butyl) ammonium bis (dodecahydride dodecaborate) cobaltate (III), bis [tri (n-butyl) ammonium] bis (dodecahydride dodecaborate) Borate) salts of metal borane anions such as nickelate (III).

Specific examples of the carborane compound include 4-carbanonaborane (14), 1,3-dicarbanonaborane (13), 6,9-dicarbadecaborane (14) and dodecahydride-1-phenyl- 1,3-dicarbanonaborane,
Dodeca hydride-1-methyl-1,3-dicarbanonaborane, undecahydride-1,3-dimethyl-1,3-dicarbanonaborane, 7,8-dicarbaundecaborane (13), 2,
7-dicarbaundecaborane (13), undecahydride-7,8-dimethyl-7,8-dicarbaundecaborane, dodecahydride-11-methyl-2,7-dicarbaundecaborane, tri (n-butyl) ) Ammonium 1-carbadecaborate, tri (n-butyl) ammonium 1-carbaundecaborate, tri (n-butyl) ammonium 1-carbadodecaborate, tri (n-butyl) ammonium 1-trimethylsilyl-1-carbadeca Borate, tri (n-butyl) ammonium bromo-1-carbadodecaborate, tri (n-butyl) ammonium 6-carbadecaborate (14), tri (n-butyl) ammonium 6-carbadecaborate (1
2), tri (n-butyl) ammonium 7-carbaundecaborate (13), tri (n-butyl) ammonium 7,8-
Dicarbaundecaborate (12), tri (n-butyl)
Ammonium 2,9-dicarbaundecaborate (12),
Tri (n-butyl) ammonium dodeca hydride-8-
Methyl-7,9-dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-8-ethyl-7,9-
Dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-8-butyl-7,9-dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-8-allyl-7,9-dicarbaun Decaborate, tri (n-butyl) ammonium undecahydride-9-trimethylsilyl-7,8-dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-4,6-dibromo-7-carbaundecaborate Salts of anions such as; tri (n-butyl) ammonium bis (nonahydride-1,3-dicarbanonaborate) cobaltate (III), tri (n-butyl) ammonium bis (undecahydride-7,8 -Dicarbaundecaborate) ferrate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarbaundecaborate) co Belt salt (III), tri (n- butyl) ammonium bis (undecapeptide 7,8-dicarbaundecaborate deca borate)
Nickelate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarbaundecaborate) cuprate (III), tri (n-butyl) ammonium bis (undecahydride-7) , 8-Dicarbaundecaborate) aurate (III), tri (n-butyl) ammonium bis (nonahydride-7,8-dimethyl-7,8-dicarbaundecaborate) ferrate (III), tri (N-Butyl) ammonium bis (nonahydride-7,8-dimethyl-7,8-dicarbaundecaborate) chromate (III), tri (n-butyl) ammonium bis (tribromooctahydride-7,8 -Dicarbaundecaborate) cobaltate (II
I), tris [tri (n-butyl) ammonium] bis (undecahydride-7-carboundecaborate) chromate (III), bis [tri (n-butyl) ammonium]
Bis (undecahydride-7-carboundecaborate) manganate (IV), bis [tri (n-butyl) ammonium] bis (undecahydride-7-carboundecaborate) cobaltate (III), Bis [tri (n-butyl) ammonium] bis (undecahydride-7-
Examples thereof include salts of metal carborane anions such as carbaundecaborate) nickelate (IV).

The above (C-3) ionized ionic compound may be used alone or in combination of two or more. Further, the olefin polymerization catalyst according to the present invention is a transition metal compound (A) of Group 4 of the above periodic table, and 8 to 10 of the periodic table.
Group transition metal compounds (B), (C-1) organoaluminum oxy compounds, (C-2) alkylboronic acid derivatives and (C-
3) At least one selected from ionized ionic compounds
In addition to the seed compound (C), an organometallic compound (D), a particulate carrier (E), etc., which will be described later, can be used, if necessary.

(D) Organometallic Compound As the (D) organometallic compound used as necessary in the invention, specifically, the following organometallic compounds of Groups 1, 2 and 12 and 13 of the periodic table. A compound is used.

[0153] (D-1) In the general formula _{^{R a m Al (OR b)}} n H p X q ( wherein, R ^a and R ^b may be the same or different from each other, the number of carbon atoms from 1 to 15 , Preferably 1 to 4 hydrocarbon groups, X is a halogen atom, and m is 0 <
m ≦ 3, n is 0 ≦ n <3, p is 0 ≦ p <3, q is 0 ≦ q
<3, and m + n + p + q = 3. The organoaluminum compound represented by).

(D-2) General formula M ² AlR ^a ₄ (In the formula, M ² represents Li, Na and K, and R ^a is a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms. A complex alkylated product of a Group 1 metal and aluminum.

(D-3) Formula R ^a R ^b M ³ (wherein R ^a and R ^b may be the same or different from each other, and have 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms). A dialkyl compound of a Group 2 or Group 12 metal, which represents a hydrocarbon group, and M ³ is Mg, Zn or Cd).

Examples of the organoaluminum compound belonging to the above (D-1) include the following compounds. In the general formula _{^{R a m Al (OR b)}} 3-m ( wherein, R ^a and R ^b may be the same or different, 1 to 15, preferably 1 to 4 hydrocarbon group having carbon atoms are shown, m is preferably a number 1.5 ≦ m ≦ 3.) an organoaluminum compound represented by the general formula R ^a _m AlX _3-m (wherein, R ^a is 1 to carbon atoms 15, preferably 1 to
4 represents a hydrocarbon group, X represents a halogen atom, and m is preferably 0 <m <3. An organoaluminum compound represented by), the general formula R ^a _m AlH _3-m (wherein, R ^a is the number of carbon atoms 1 to 15, preferably 1 to
4 represents a hydrocarbon group, and m is preferably 2 ≦ m <3. An organoaluminum compound represented by), the general formula _{^{R a m Al (OR b)}} n X q ( wherein, R ^a and R ^b may be the same or different from each other, the number of carbon atoms 1 to 15, Preferably, it represents a hydrocarbon group of 1 to 4, X represents a halogen atom, and m represents 0 <
m ≦ 3, n is 0 ≦ n <3, q is a number 0 ≦ q <3,
And m + n + q = 3. The organoaluminum compound represented by).

Specific examples of the aluminum compound belonging to (D-1) include tri-n-alkylaluminum such as triethylaluminum and tri-n-butylaluminum; triisopropylaluminum, triisobutylaluminum, trisec-butylaluminum, tritert-aluminum. -Butyl aluminum, tri 2-methylbutyl aluminum, tri 3-
Methyl butyl aluminum, tri 2-methyl pentyl aluminum, tri 3-methyl pentyl aluminum, tri 4-
Methylpentylaluminum, tri-2-methylhexylaluminum, tri-3-methylhexylaluminum, tri
Tri-branched alkyl aluminum such as 2-ethylhexyl aluminum; tricycloalkyl aluminum such as tricyclohexyl aluminum; triaryl aluminum such as triphenyl aluminum and tritolyl aluminum; dialkyl aluminum hydride such as diisobutyl aluminum hydride; triisoprenyl aluminum and the like Trialkenyl aluminum; alkyl aluminum alkoxides such as isobutyl aluminum methoxide, isobutyl aluminum ethoxide, isobutyl aluminum isopropoxide;
Dialkyl aluminum alkoxides such as diethyl aluminum ethoxide and dibutyl aluminum butoxide; alkyl aluminum sesqui alkoxides such as ethyl aluminum sesquiethoxide and butyl aluminum sesquibutoxide; parts having an average composition represented by R ^a _2.5 Al (OR ^b ) _0.5 Alkyloxylated aluminum; Dialkyl aluminum halides such as diethyl aluminum chloride, dibutyl aluminum chloride, diethyl aluminum bromide;
Alkyl aluminum sesquihalides such as ethyl aluminum sesquichloride, butyl aluminum sesquichloride and ethyl aluminum sesquibromide; partially halogenated alkyl aluminum such as alkyl aluminum dihalides such as ethyl aluminum dichloride, propyl aluminum dichloride and butyl aluminum dibromide Diethyl aluminum hydride;
Dialkyl aluminum hydrides such as dibutyl aluminum hydride; Other partially hydrogenated alkyl aluminums such as ethyl aluminum dihydride, alkyl aluminum dihydrides such as propyl aluminum dihydride; ethyl aluminum ethoxy chloride, butyl aluminum butoxycyclolide, ethyl aluminum ethoxy Mention may be made of partially alkoxylated and halogenated alkylaluminum such as bromide.

A compound similar to (D-1) can also be used, and examples thereof include an organoaluminum compound in which two or more aluminum compounds are bonded via a nitrogen atom. Specific examples of such a compound include (C ₂ H ₅ ) ₂ AlN (C ₂ H ₅ ) Al (C ₂ H ₅ ) _{2 and the} like.

Examples of compounds belonging to the above (D-2) include LiAl (C ₂ H ₅ ) ₄ LiAl (C ₇ H ₁₅ ) ₄ .

[0160] Besides, as the organic metal compound (D), the general formula _{(i-C 4 H 9)} x Al y (C 5 H 10) z ( wherein, x, y and z are positive numbers And z ≧ 2x), it is also possible to use isoprenylaluminum.

In addition to the above, the organometallic compound (D)
As, methyllithium, ethyllithium, propyllithium, butyllithium, methylmagnesium bromide, methylmagnesium chloride, ethylmagnesium bromide, ethylmagnesium chloride, propylmagnesium bromide, propylmagnesium chloride, butylmagnesium bromide, butylmagnesium chloride, dimethylmagnesium, It is also possible to use diethyl magnesium, dibutyl magnesium, butyl ethyl magnesium and the like.

It is also possible to use a compound capable of forming the organoaluminum compound in the polymerization system, for example, a combination of aluminum halide and alkyllithium, or a combination of aluminum halide and alkylmagnesium.

As the organometallic compound (D) used in the present invention, a metal compound having a branched alkyl group is preferable, and a metal compound having an isobutyl group is particularly preferable, and a triisobutyl metal compound is particularly preferable. Aluminum is preferable as the metal, and triisobutylaluminum is most preferable.

The organometallic compound (D) acts as an alkylating agent, and R bonded to the transition metal (M) in the transition metal compound (B) represented by the general formula (I).
^{When 4} and / or R ⁵ is an atom or group other than an alkyl group, for example, a halogen atom such as chlorine or bromine; a group such as an alkoxy group such as a methoxy group, an ethoxy group or a butoxy group, these are substituted with an alkyl group. To do. Such an alkyl group-substituted transition metal compound (B) is (C)
Reacts with components, especially component (C-3) to form ionic complexes with high catalytic activity.

The (D) organometallic compound is a scavenger.
It also acts as a jar and removes water and other impurities from the system.
Since the reaction system is removed to keep the system clean, the catalyst activity is stable and highly active.
The effect of being able to express is obtained. this
Action binds to transition metal (M) in transition metal compound (B)
Doing R^FourAnd / or R^FiveIs an alkyl group
Is also expressed. Therefore, the organometallic compound (D) is
Transition gold in transition metal compound (B) represented by general formula (I)
R bound to genus (M)^FourAnd / or R ^FiveIs al
When used together with a transition metal compound (B) which is a kill group
Also, the same effect as described above can be obtained.

The (D) organometallic compound as described above is 1
They may be used alone or in combination of two or more.(E) Fine particle carrier (E) Fine particle carrier used as necessary in the present invention
Is an inorganic or organic compound having a particle size of 10 to 3
00 μm, preferably 20-200 μm granular or
Is used as a fine solid. Of these, inorganic compounds
Is preferably a porous oxide, specifically, SiO 2_Two,
Al_TwoO_Three, MgO, ZrO, TiO_Two, B_Two O_Three, Ca
O, ZnO, BaO, ThO_TwoOr a mixture of these
Compound, eg SiO_Two-MgO, SiO_Two-Al_Two O_Three,
SiO_Two-TiO_Two, SiO_Two-V_TwoO_Five, SiO_Two-Cr
_TwoO_Three, SiO_Two-TiO_Two-It is possible to exemplify MgO
Wear. Among these SiO_TwoAnd Al_Two O_ThreeConsists of
Mainly contains at least one component selected from the group
Is preferred.

A small amount of Na ₂ C is contained in the above inorganic oxide.
O ₃ , K ₂ CO ₃ , CaCO ₃ , MgCO ₃ , Na ₂ S
O ₄ , Al ₂ (SO ₄ ) ₃ , BaSO ₄ , KNO ₃ , Mg
(NO ₃ ) ₂ , Al (NO ₃ ) ₃ , Na ₂ O, K ₂ O, L
It may contain carbonate, sulfate, nitrate and oxide components such as i ₂ O.

The properties of the (A) particulate carrier differ depending on the type and production method, but the carrier preferably used in the present invention has a specific surface area of 50 to 1000 m ² / g.
It is preferably in the range of 100 to 700 m ² / g, and the pore volume is preferably in the range of 0.3 to 2.5 cm ³ / g. The carrier may be 100 to 1000 ° C. if necessary,
Preferably, it is used by firing at 150 to 700 ° C.

Further, as the fine particle carrier (A) which can be used in the present invention, a granular or fine particle solid of an organic compound having a particle diameter in the range of 10 to 300 μm can be mentioned. As these organic compounds, ethylene, propylene, 1-butene, 4-methyl-1-pentene and other (co) polymers mainly composed of α-olefins having 2 to 14 carbon atoms or vinylcyclohexane, A polymer or copolymer formed mainly with styrene can be exemplified.

The olefin polymerization catalyst according to the present invention comprises a transition metal compound (A) of Group 4 of the periodic table, a transition metal compound (B) of Groups 8 to 10 of the periodic table, (C- 1) at least one compound (C) selected from an organoaluminum oxy compound, a (C-2) alkylboronic acid derivative and a (C-3) ionized ionic compound, and optionally an organometallic compound (D), It comprises a fine particle carrier (E).

At the time of polymerization, the method of using each component and the order of addition are arbitrarily selected, but the following methods are exemplified. (1) A method in which the component (A), the component (B) and the component (C) are added to a polymerization vessel in an arbitrary order. (2) A method in which the catalyst component in which the component (A) is supported on the carrier (E), the component (B) and the component (C) are added to the polymerization vessel in any order. (3) A method in which the catalyst component in which the component (B) is supported on the carrier (E), the component (A) and the component (C) are added to the polymerization vessel in any order. (4) A method of adding the catalyst component in which the component (C) is supported on the carrier (E), the component (A) and the component (B) to the polymerization vessel in any order. (5) A method of adding a catalyst component in which the component (A) and the component (B) are supported on a carrier (E), and the component (C) to the polymerization vessel in any order. (6) A method in which the catalyst component in which the component (A) is supported on the carrier (E), the catalyst component in which the component (B) is supported on the carrier (E), and the component (C) are added to the polymerization vessel in any order. (7) A method in which the catalyst component in which the component (A) and the component (C) are supported on the carrier (E) and the component (B) are added in any order to the polymerization vessel. (8) A method of adding a catalyst component in which components (B) and (C) are supported on a carrier (E), and component (A) to a polymerization vessel in any order. (9) A method of adding a catalyst component in which a component (A), a component (B) and a component (C) are supported on a carrier (E) to a polymerization vessel.

In each of the above methods (1) to (9), the component (D) may be used if necessary. Further, the solid catalyst component in which the component (A) and the component (C) are supported on the above component (E), and the component (B) and the component (C) on the component (E).
A solid catalyst component on which component (A) is added to component (E),
Olefin may be prepolymerized in the above solid catalyst component on which the component (B) and the component (C) are supported.

Further, in the present invention, after the component (B) and the component (C) and, if necessary, the component (D) are brought into contact with each other in advance, the contact product and the component (A) are added to a polymerization vessel. Good. Ingredient (B) and ingredient (C), and optionally ingredient (D)
It is presumed that the ionic coordination compound represented by the following general formula (XI-1) is formed by previously contacting with.

[0174]

Embedded image

(Wherein M, X ¹ , X ² , R ¹ , R ² ,
m and n are the same as those in the general formula (I), R ²¹ represents a hydrocarbon group, and Z is (C-1) an organoaluminumoxy compound, (C-2) an alkylboronic acid derivative and ( C-3) A molecule formed of at least one compound (C) selected from ionized ionic compounds. ) In the general formula (XI-1), R ²¹ represents the general formula (I).
A hydrocarbon group of R ⁴ or R ⁵ (for example, an alkyl group)
Or an alkyl group introduced by the (D) organometallic compound.

In the above general formula (XI-1), Z is a molecule formed from the component (C) upon contact between the component (B) and the component (C) and, if necessary, the component (D). , For example, an anion forming the above-mentioned (C-3) ionized ionic compound, and specific examples thereof include the following formula (XII)
A boron compound represented by

[0177]

Embedded image

The boron compound represented by the formula (XII) is a molecule formed from the boron compound represented by the formula (IX). Specific examples of Z other than the above include tetrakis (pentafluorophenyl) borate, tetra (phenyl) boron, and the like.

The ionic coordination compound represented by the general formula (XI-1) is an ether compound formed from the component (C) upon contact between the transition metal compound (B) and the component (C). (Ether molecule) may coordinate with the transition metal represented by M. Such an ionic coordination compound is represented by the following general formula (XI-2).

[0180]

Embedded image

(Wherein M, X ¹ , X ² , R ¹ , R ² ,
m and n are the same as those in the general formula (I), R ²¹ and Z are the same as those in the general formula (XI-1), and R ²² is the transition metal compound (B) and component (C). With contact with (C)
The ether compound (ether molecule) formed from the components is shown. ) Specific examples of the ether compound (ether molecule) represented by R ²² in the general formula (XI-2) include dimethyl ether, diethyl ether, dipropyl ether,
Dibutyl ether and the like.

Specific examples of the ionic coordination compound represented by the above general formula (XI-2) include ionic coordination compounds represented by the following formula.

[0183]

Embedded image

(In the formula, iPr represents an isopropyl group and Et represents an ethyl group.) The component (B) and the component (C) and, if necessary, the component (D) are brought into contact with each other in advance, and the general formula (XI- 1) or (XI-2) to form an ionic coordination compound, component (B) and component (C), and optionally (D) in the reaction medium at -120 to + 20 ° C. , Preferably -80 to -20 ° C
The reaction is conducted for 5 minutes to 100 hours, preferably 30 minutes to 5 hours.

As the reaction medium, inert hydrocarbons such as hexane, heptane, octane, cyclohexane, mineral oil, benzene, toluene and xylene; halogenated hydrocarbons such as chloroform, methylene chloride, dichloroethane and chlorobenzene can be used. .

Further, in the present invention, when the component (B) and the component (C) and, if necessary, the component (D) are brought into contact with each other in advance, a (meth) acrylic acid alkyl ester may be allowed to coexist. In this case, it is preferable to use the (C-3) ionized ionic compound as the component (C).

Examples of the (meth) acrylic acid alkyl ester include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate and the like can be mentioned.

The component (B) and the component (C), and optionally the component (D) are brought into contact with each other in the presence of an alkyl (meth) acrylic acid ester to obtain a compound represented by the following general formula (XI-3). It is speculated that an ionic coordination compound is formed.

[0189]

Embedded image

(Wherein M, X ¹ , X ² , R ¹ , R ² ,
m and n are the same as in the general formula (I), Z is the same as in the general formula (XI-1), R ²³ represents a residue of a hydrocarbon group, and R ²⁴ and R ²⁵ Shows a part of the residue of (meth) acrylic acid alkyl ester. In the general formula (XI-3), R ²³ is the hydrocarbon group (for example, the residue of an alkyl group) of R ⁴ or R ^{5 in} the general formula (I), or the organic metal (D). It is the residue of an alkyl group introduced by a compound.

Specific examples of the group represented by R ²³ include the following:

[0192]

Embedded image

And the like. In the general formula (XI-3), R ²⁴ and R ²⁵ are residues formed by the (meth) acrylic acid alkyl ester upon contact between the transition metal compound (B) and the (meth) acrylic acid alkyl ester. Is part of.

Specific examples of the group represented by R ²⁴ include

[0195]

Embedded image

And the like. Specific examples of the group represented by R ²⁵ include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group and ter.
Number of carbon atoms such as t-butyl and 2-ethylhexyl is 1
~ 20 alkyl groups and the like.

Specific examples of the ionic coordination compound represented by the general formula (XI-3) include ionic coordination compounds represented by the following formula.

[0198]

Embedded image

(In the formula, iPr represents an isopropyl group.) The component (B) and the component (C) and, if necessary, the component (D) are brought into contact with each other in the presence of the (meth) acrylic acid alkyl ester in the above-mentioned manner. In order to form the ionic coordination compound represented by the general formula (XI-3), the component (B) and the component (C) in the coexistence of the (meth) acrylic acid alkyl ester, and optionally the component (D) ) In the same reaction medium as described above, from -120 to
+ 40 ° C, preferably -80 to 0 ° C for 5 minutes to 100
The reaction is carried out under the condition of time, preferably 30 to 5 hours.

The amount of the (meth) acrylic acid alkyl ester used is such that the molar ratio of the (meth) acrylic acid alkyl ester to the component (B) is usually 0.3 to 3, preferably 0.8.
It is preferable to set to 1.1.

In the olefin polymerization method according to the present invention,
An olefin polymer is obtained by polymerizing or copolymerizing an olefin in the presence of the above olefin polymerization catalyst.

In the present invention, the polymerization can be carried out by either a liquid phase polymerization method such as solution polymerization or suspension polymerization or a gas phase polymerization method. As the inert hydrocarbon medium used in the liquid phase polymerization method, specifically, propane, butane, pentane,
Aliphatic hydrocarbons such as hexane, heptane, octane, decane, dodecane, and kerosene; Alicyclic hydrocarbons such as cyclopentane, cyclohexane, methylcyclopentane; Aromatic hydrocarbons such as benzene, toluene, xylene; Ethylene chloride, chlorine Examples thereof include halogenated hydrocarbons such as benzene and dichloromethane, or a mixture thereof, and the olefin itself can be used as a solvent.

When the olefin polymerization is carried out using the above olefin polymerization catalyst, the component (A) is
It is generally used in an amount of 10 ^-8 to 10 ^-3 mol, preferably 10 ^-7 to 10 ^-4 mol, per 1 liter of reaction volume, and the component (B) is usually 10 ^-8 to 10 ^-3 mol, It is preferably used in an amount such that it is 10 ⁻⁷ to 10 ⁻³ mol. Component (B) is used in an amount such that the molar ratio of component (B) to component (A) [(B) / (A)] is usually 0.02 to 100, preferably 0.05 to 50. Used in

The component (C-1) and the component (C-2) are the components (C-
1) or the molar ratio of aluminum atoms in the component (C-2) to all transition metal atoms (M) in the components (A) and (B) [(C-1) / M or (C -2) / M] is usually 1
It is used in an amount of 0 to 5000, preferably 20 to 2000. The component (C-3) has a molar ratio [(C-3) / M] of the component (C-3) to all the transition metal atoms (M) in the components (A) and (B) is usually 1-10, preferably 1
Used in an amount such that

The component (D) used as necessary is a molar ratio [(D) / M] of the component (D) and all transition metal atoms (M) in the components (A) and (B). But usually 0.0
It is used in an amount of 1 to 5000, preferably 0.05 to 2000.

The olefin polymerization temperature using such an olefin polymerization catalyst is usually -50 to 200 ° C.
It is preferably in the range of 0 to 170 ° C. The polymerization pressure is usually atmospheric pressure to 100 kg / cm ² , preferably atmospheric pressure to 50 k.
It is under the condition of g / cm ² , and the polymerization reaction can be carried out by any of a batch system, a semi-continuous system and a continuous system. Further, the polymerization can be performed in two or more stages having 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 the olefin that can be polymerized by such an olefin polymerization catalyst include α-olefins having 2 to 20 carbon atoms, for example, ethylene, propylene, 1-butene, 1-pentene,
3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, 1-decene, 1-
Dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene; a cyclic olefin having 3 to 20 carbon atoms, for example, cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, 2-methyl-1,4,5,8-dimethano-1,2,3,4,4
Examples include a, 5,8,8a-octahydronaphthalene. Further, styrene, vinylcyclohexane, diene and the like can be used.

[0208]

The olefin polymerization catalyst according to the present invention has a high polymerization activity, a wide molecular weight distribution, and an olefin (co) polymer having a narrow composition distribution when two or more olefins are copolymerized. be able to.

The olefin polymerization method of the present invention can provide an olefin polymer having a high polymerization activity, a wide molecular weight distribution, and a narrow composition distribution when two or more olefins are copolymerized. The olefin (co) polymer obtained by the method of the present invention has excellent moldability because of its wide molecular weight distribution.

[0210]

EXAMPLES Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to these examples.

In this example, the molecular weight distribution (Mw
/ Mn) is 140% with o-dichlorobenzene as a solvent.
It measured and determined by gel permeation chromatography (GPC) at ° C.

[0212]

Example 1 250 ml of toluene was charged into a glass autoclave having an internal volume of 500 ml which had been sufficiently replaced with nitrogen.
A mixed gas of ethylene and propylene (120 liters / hour, 80 liters / hour, respectively) was passed through, and the temperature was 25 ° C.
For 10 minutes. After that, 1.25 mmol of methylaluminoxane in terms of aluminum atoms,
Polymerization was initiated by adding a mixture of 0.0005 mmol of bis (1,2,4-trimethylcyclopentadienyl) zirconium dichloride and 0.005 mmol of a transition metal compound represented by the following formula (A). Continuously supply a mixed gas of ethylene and propylene, and under normal pressure at 25 ° C for 30
Polymerization was performed for minutes. After the completion of the polymerization, a small amount of methanol was added to stop the polymerization. The polymer solution was added to a large excess of methanol to precipitate the polymer, which was dried under reduced pressure at 130 ° C. for 12 hours. As a result, the weight average molecular weight (Mw)
Was 1.2 × 10 ⁵ , and 14.4 g of a polymer having Mw / Mn of 4.3 was obtained.

[0213]

Embedded image

[0214]

Comparative Example 1 In Example 1, bis (1,2,4-trimethylcyclopentadienyl) zirconium dichloride 0.
Instead of a mixture of 0005 mmol and 0.005 mmol of the transition metal compound represented by the formula (A), 0.0005 mmol of bis (1,2,4-trimethylcyclopentadienyl) zirconium dichloride alone was used. Except for the above, ethylene and propylene were polymerized in the same manner as in Example 1. As a result, Mw was 1.9 × 10 ⁵ , and Mw
8.2 g of a polymer with a / Mn of 2.1 were obtained.

[0215]

Comparative Example 2 In Example 1, bis (1,2,4-trimethylcyclopentadienyl) zirconium dichloride 0.
Instead of using a mixture of 0005 mmol and 0.005 mmol of the transition metal compound represented by the formula (A), only 0.005 mmol of the transition metal compound represented by the formula (A) was used. Ethylene and propylene were polymerized in the same manner as in Example 1. As a result, Mw is 4.3 × 1
0 is ^4, polymer 7.9 Mw / Mn is 1.8
g was obtained.

[0216]

Example 2 240 ml of toluene was charged into a glass autoclave having an internal volume of 500 ml which had been sufficiently replaced with nitrogen.
Then 10 ml of 1-octene was charged. Ethylene was passed through this at a rate of 200 liters / hour and left at 25 ° C. for 10 minutes. Thereafter, 1.25 mmol of methylaluminoxane in terms of aluminum atom was added, followed by bis (1,
Polymerization was initiated by adding a mixture of 0.0005 mmol of 2,4-trimethylcyclopentadienyl) zirconium dichloride and 0.005 mmol of the transition metal compound represented by the formula (A). 200 liters of ethylene gas /
It was continuously fed in an amount of time, and polymerization was carried out at 25 ° C. for 10 minutes under normal pressure. After the completion of the polymerization, a small amount of methanol was added to stop the polymerization. The polymer solution was added to a large excess of methanol to precipitate the polymer, which was dried under reduced pressure at 130 ° C. for 12 hours. As a result, 3.9 g of a polymer having Mw of 1.5 × 10 ⁵ and Mw / Mn of 4.6 was obtained.

[0219]

COMPARATIVE EXAMPLE 3 In Example 3, bis (1,2,4-trimethyi) was used.
Rucyclopentadienyl) zirconium dichloride
Transition metallization represented by the above formula (A)
Instead of a mixture with 0.005 mmol of compound
(1,2,4-Trimethylcyclopentadienyl) zirconium
Since only 0.0005 mmol of mudic chloride was used,
Other than that, ethylene was polymerized in the same manner as in Example 1. The result
As a result, Mw is 2.5 × 10 ^FiveAnd Mw / Mn is 2.0
2.2 g of a polymer of

[0218]

Comparative Example 4 In Example 3, bis (1,2,4-trimethylcyclopentadienyl) zirconium dichloride.
Instead of using a mixture of 0005 mmol and 0.005 mmol of the transition metal compound represented by the formula (A), 0.005 mmol of only the transition metal compound represented by the formula (A) was used. Ethylene was polymerized in the same manner as in Example 1. As a result, Mw was 5.2 × 10 ⁴ , and Mw
1.8 g of a polymer with a w / Mn of 1.9 was obtained.

[Brief description of drawings]

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

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Satoshi Hayashi 6-12 Waki, Waki-cho, Kuga-gun, Yamaguchi Mitsui Petrochemical Industry Co., Ltd.

Claims (3)

[Claims] 1. A transition metal compound of Group 4 of the periodic table (A), (B) a transition metal compound of Groups 8 to 10 of the periodic table represented by the following general formula (I), and (C) (C -1) At least one compound selected from an organoaluminum oxy compound, a (C-2) alkylboronic acid derivative and a compound which reacts with a (C-3) transition metal compound to form an ion pair, and, if necessary, (D) An olefin polymerization catalyst comprising an organometallic compound; (In the formula, M represents a transition metal atom of Groups 8 to 10 of the periodic table, X ¹ and X ² may be the same or different from each other, represent a nitrogen atom or a phosphorus atom, and R ¹ and R ² May be the same or different from each other and represent a hydrogen atom or a hydrocarbon group, and m and n may be the same or different from each other, 1
Or 2 which are each a number satisfying the valences of X ¹ and X ² , and R ³ is (However, R ⁶ , R ⁷ , R ⁶¹ , R ⁶² , R ⁷¹ and R
⁷² may be the same or different from each other and represent a hydrogen atom or a hydrocarbon group. ), R ⁴ and R ⁵ may be the same or different from each other, and are a hydrogen atom, a halogen atom, a hydrocarbon group, —OR ⁸ ,
-SR ⁹ , -N (R ¹⁰ ) ₂ or -P (R ¹¹ ) ₂ (wherein R ^{8 to} R ¹¹ represent an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an organic silyl group, and R ¹⁰
Or between R ¹¹ each other may be bonded to form a ring. And R ⁴ and R ⁵ may combine with each other to form a ring, and R ¹ , R ² , R ⁶ (or R ⁶¹ and R ⁶² ) and R ⁷ (or R ⁷¹ and R ⁷²⁾ ), Two or more of these may be linked to each other to form a ring. ) 2. The catalyst for olefin polymerization according to claim 1, wherein the transition metal compound represented by the general formula (I) is a compound represented by the following general formula (I ′); (In the formula, M represents a transition metal atom of Groups 8 to 10 of the periodic table, X ¹ and X ² may be the same or different from each other, represent a nitrogen atom or a phosphorus atom, and R ¹ and R ² R ⁶ and R ⁷ may be the same or different from each other and represent a hydrogen atom or a hydrocarbon group, R ⁶ and R ⁷ may be the same or different and represent a hydrogen atom or a hydrocarbon group, R ⁴ and R ⁵ May be the same or different from each other, and are a hydrogen atom, a halogen atom, a hydrocarbon group, —OR ⁸ , or
-SR ⁹ , -N (R ¹⁰ ) ₂ or -P (R ¹¹ ) ₂ (wherein R ^{8 to} R ¹¹ represent an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an organic silyl group, and R ¹⁰
Or between R ¹¹ each other may be bonded to form a ring. ), R ⁴ and R ⁵ may be linked to each other to form a ring, and R ¹ , R ² , R ⁶ and R ⁷ are ring groups in which two or more of them are linked to each other. May be formed. ) 3. 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 1.