JPH11199592A - Transition metal compound, catalyst for olefin polymerization and polymerization - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject new compound having excellent polymerizaltion activity for olefin, useful as a catalytic component for olefin polymerization, providing a polymer having excellent properties, comprising a specific transition metal compound containing an aromatic amino compound as a ligand. SOLUTION: This new transition metal compound is shown by formula I [M is a transition metal atom of the group 3-11 of the periodic table; (m) is 1-6; R<1> to R<12> are each H, a halogen, a hydrocarbon, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a sulfur- containing group, a silicon-containing group or the like; A is O, S, Se or N-R<5> ; B is R<9> and R<10> or =(R<11> )R<12> as a bond group of N; (n) is a number for satisfying the valence of M; X is H, a halogen, a hydrocarbon, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group or the like] and is useful as a catalytic component for olefin polymerization, etc. The compound is obtained by reacting an aromatic amino compound of formula II with a base to form a salt and reacting the salt with a transition metal halide.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel transition metal compound, a catalyst for olefin polymerization comprising the transition metal compound, and a method for polymerizing olefins using the catalyst for olefin polymerization.

[0002]

2. Description of the Related Art As a catalyst for olefin polymerization, a so-called Kaminski catalyst is well known. This catalyst is characterized by a very high polymerization activity and a polymer having a narrow molecular weight distribution. As a transition metal compound used for such a Kaminsky catalyst, for example, bis (cyclopentadienyl) zirconium dichloride (Japanese Patent Laid-Open No.
8-19309), ethylene bis (4,5,6,
7-tetrahydroindenyl) zirconium dichloride (see Japanese Patent Application Laid-Open No. Sho 61-130314) and the like are known. Also, if the transition metal compound used for polymerization is different,
It is also known that the olefin polymerization activity and the properties of the obtained polyolefin differ greatly. Furthermore, a transition metal compound having a ligand having a diimine structure (see International Publication No. WO9623010) has recently been proposed as a new catalyst for olefin polymerization.

[0003] Incidentally, polyolefins are generally used in various fields, such as for various molded articles, because of their excellent mechanical properties. However, in recent years, the demand for physical properties of polyolefins has been diversified, and polyolefins having various properties have been developed. Is desired. Another challenge is to improve productivity. Under such circumstances, the emergence of an olefin polymerization catalyst which is excellent in olefin polymerization activity and can produce a polyolefin having excellent properties is desired.

[0004]

DISCLOSURE OF THE INVENTION The present invention provides a novel transition metal compound, a catalyst for olefin polymerization comprising the transition metal compound and having excellent olefin polymerization activity, and a method for polymerizing olefins using the catalyst. The purpose is to provide.

[0005]

Means for Solving the Problems The first transition metal compound according to the present invention is a compound represented by the following general formula (I).

Embedded image (Wherein, M represents a transition metal atom of Groups 3 to 11 of the periodic table, m represents an integer of 1 to 6, and A represents an oxygen atom, a sulfur atom, a selenium atom, or a bonding group- R represents a nitrogen atom having R ⁵ , and B represents —R ⁹ and —R ¹⁰ , or ＣC (R ¹¹ ) R ¹² as a bonding group of N (where — represents a single bond, and ＝ represents a double bond). And R ^{1 to} R ¹² may be the same or different, and each represents a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, or a boron-containing group. , A sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group, two or more of which may be linked to each other to form a ring (R ¹ and R ⁹ Or R ¹ and R ¹⁰
Are linked to form an aromatic ring), and when m is 2 or more, one group of R ^{1 to} R ¹² contained in one ligand and another group of may have been bonded with one of the radicals R ¹ to R ¹² contained in the child, R ¹ each other, R ² together, R ³ together, R ⁴ together, R ⁵ each other, R ⁹ together,
R ¹⁰ , R ¹¹ , and R ¹² may be the same or different, and n is a number satisfying the valence of M;
Represents a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, a halogen-containing group, a heterocyclic compound residue, and a silicon-containing group. Represents a germanium-containing group or a tin-containing group, and when n is 2 or more, a plurality of groups represented by X may be the same or different from each other, and a plurality of groups represented by X are bonded to each other A ring may be formed. )

[0006] The second transition metal compound according to the present invention is a compound represented by the following general formula (II).

Embedded image (Wherein, M represents a transition metal atom belonging to Groups 3 to 11 of the periodic table, m represents an integer of 1 to 6, and A represents a bonding group —R ⁵
An oxygen atom, a sulfur atom, a selenium atom, or
As bonding group, -R ⁵ and -R ⁶ or ^{= C (R 7), R} 8
(Where - is a single bond, = represents a double bond) represents nitrogen atom having, B represents a -R ⁹ as binding group N, R ¹ to R ⁹ may be the same or different from each other May be, a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group,
A sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group;
Or more may be connected to each other to form a ring, and when m is 2 or more, R ¹ contained in one ligand
To one group of R ⁹ and R ¹ to R ⁹ contained in another ligand.
One of R ⁹ may be bonded to R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ ,
R ⁷ , R ⁸ , and R ⁹ may be the same or different from each other, n is a number satisfying the valence of M, and X is
Hydrogen atom, halogen atom, hydrocarbon group, oxygen-containing group, sulfur-containing group, nitrogen-containing group, boron-containing group, aluminum-containing group, phosphorus-containing group, halogen-containing group, heterocyclic compound residue, silicon-containing group, germanium When n is 2 or more, a plurality of groups represented by X may be the same or different from each other, and a plurality of groups represented by X are bonded to each other to form a ring. It may be formed. )

[0007] The third transition metal compound according to the present invention is a compound represented by the following general formula (III).

Embedded image (Wherein, M represents a transition metal atom of Groups 3 to 11 of the periodic table, m represents an integer of 1 to 3, and A represents an oxygen atom, a sulfur atom, a selenium atom, or a bonding group. represents nitrogen atom with -R ^5, B is, -R a binding group N ⁹
Wherein R ^{1 to} R ⁹ may be the same or different from each other, and represent a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group,
A sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group;
Or more may be connected to each other to form a ring, and when m is 2 or more, R ¹ contained in one ligand
To one group of R ⁹ and R ¹ to R ⁹ contained in another ligand.
One group of R ⁹ may be bonded, and R ^{1 s} , R ^{2 s} , R ^{3 s} , R ^{4 s} , R ^{5 s} , and R ^{9 s} may be the same or different. , N is a number satisfying the valence of M, and X is a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group. Represents a halogen-containing group, a heterocyclic compound residue, a silicon-containing group, a germanium-containing group or a tin-containing group, and when n is 2 or more, a plurality of groups represented by X may be the same or different from each other Also, a plurality of groups represented by X may combine with each other to form a ring. )

The fourth transition metal compound according to the present invention is a compound represented by the following general formula (IV).

Embedded image (Wherein, M represents the periodic table 3 to 11 transition metal atom of Group, m represents an integer of 1 to 3, A is a bond group -R ⁵
An oxygen atom, a sulfur atom, a selenium atom, or
As bonding group, -R ⁵ and -R ⁶ or ^{= C (R 7), R} 8
(Where-represents a single bond and = represents a double bond), and B represents -R ⁹
And -R ¹⁰ or = C (R ^11), shows the R ^12, R ¹ ~R
¹² may be the same or different from each other, and represent a hydrogen atom,
Halogen atom, hydrocarbon group, heterocyclic compound residue, oxygen-containing group, nitrogen-containing group, boron-containing group, sulfur-containing group,
A phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group, two or more of which may be connected to each other to form a ring, and when m is 2 or more, One of R ^{1 to} R ¹² contained in one ligand
Groups and one of R ^{1 to} R ¹⁴ contained in the other ligand.
May be bonded with each number of groups, R ¹ each other, R ² to each other,
R ³ together, R ⁴ together, R ⁵ each other, R ⁶ to each other, each other R ^7, together R ^8, together R ^9, R ¹⁰ together, R ¹¹ together, R ¹² to each other may be the same or different, n Is a number that satisfies the valence of M, and X is a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, and a halogen atom. A containing group, a heterocyclic compound residue, a silicon-containing group, a germanium-containing group or a tin-containing group, and when n is 2 or more, a plurality of groups represented by X may be the same or different from each other; A plurality of groups represented by X may be bonded to each other to form a ring. )

In the transition metal compound of the present invention, in the general formulas (I) to (IV), M is a transition metal atom preferably selected from Groups 3 to 5 and 8 to 10 of the periodic table. .

The olefin polymerization catalyst according to the present invention comprises:
(A-1) one or more transition metal compounds of the above general formulas (I) to (IV), (B) (B-1) an organometallic compound, (B-2) an organoaluminum oxy compound, and (B-
3) It is characterized by comprising at least one compound selected from the group consisting of compounds that form an ion pair by reacting with a transition metal compound.

In the present invention, the transition metal compound (A) is preferably a compound in which A is an oxygen atom in the general formulas (I) to (IV).

In the present invention, the transition metal compound (A) is preferably a compound in which A is a sulfur atom in the general formulas (I) to (IV).

In the present invention, the transition metal compound (A) is preferably a compound in which A is a selenium atom in the general formulas (I) to (IV).

In the present invention, the transition metal compound (A) is represented by the general formulas (I) to (IV),
Preferably, the compound is a nitrogen atom having a bonding group of R ⁵ , —R ⁵ and —R ⁶ , or ＣC (R ⁷ ) R ⁸ .

The catalyst for olefin polymerization according to the present invention comprises the above transition metal compound (A), (B-1): an organometallic compound, (B
-2): at least one compound (B) selected from the group consisting of an organoaluminum oxy compound and (B-3): a compound which reacts with the transition metal compound (A) to form an ion pair.
In addition, a carrier (C) may be included.

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

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the transition metal compound of the present invention,
An olefin polymerization catalyst comprising the transition metal compound and a method for polymerizing an olefin using the catalyst will be specifically described. In this specification, the term "polymerization" may be used to mean not only homopolymerization but also copolymerization, and the term "polymer" means not only homopolymer but also copolymer. It is sometimes used in a sense that also includes coalescence.

The transition metal compound according to the present invention is represented by the general formulas (I) to (IV). Further, the catalyst for olefin polymerization according to the present invention comprises (A) the above general formulas (I) to (I)
(B) (B-1) an organometallic compound, (B-2) an organoaluminum oxy compound, and (B-3) a transition metal compound And at least one compound selected from the group consisting of compounds that form an ion pair by reacting with the compound. First, the transition metal compound (A) of the present invention and each catalyst component of the olefin polymerization catalyst comprising the compound will be described.

[0019](A) Transition metal compound  The first transition metal compound used in the present invention has the following general formula:
It is a compound represented by the formula (I).

Embedded image (In this case, N ... M indicates coordination,
This compound also includes those in which N... M is not coordinated. )

In the formula (I), M represents a transition metal atom of Groups 3 to 11 of the periodic table (Group 3 also includes lanthanoids), and preferably Group 3 to Group 10 (Group 3 also includes lanthanoids). ), More preferably a metal atom of groups 3 to 5 and 8 to 10, and particularly preferably a metal atom of group 4 or 5. Specifically, scandium, yttrium, lanthanoid, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, rhenium,
Iron, ruthenium, cobalt, rhodium, nickel, palladium and the like, preferably scandium, lanthanoid, titanium, zirconium, hafnium, vanadium, niobium, tantalum, iron, cobalt, rhodium, nickel, palladium, and more preferably, Titanium, zirconium, hafnium, vanadium, niobium,
Tantalum, iron, cobalt, rhodium and the like are particularly preferable, and titanium, zirconium and hafnium are particularly preferable.

M represents an integer of 1 to 6, preferably 1 to 4, and more preferably 1 to 2. A represents an oxygen atom, a sulfur atom, a selenium atom or represents a nitrogen atom having a bonding group -R ^5, B is a linking group N, -R ⁹ and -R ¹⁰ or = C, (R ¹¹⁾ R ¹² (where-represents a single bond and = represents a double bond), and R ^{1 to} R ¹² may be the same or different from each other and represent a hydrogen atom, a halogen atom, a hydrocarbon group, A cyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group; two or more of these May be linked to form a ring (R ¹ and R ⁹ or R ¹ and R ¹⁰
Are linked to form an aromatic ring).

Here, R ^{1 to} R ¹² represent a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, a hydrocarbon-substituted silyl group, a hydrocarbon-substituted siloxy group, an alkoxy group,
Alkylthio group, aryloxy group, arylthio group, acyl group, ester group, thioester group, amide group, imide group, amino group, imino group, sulfone ester group, sulfonamide group, cyano group, nitro group, carboxyl group,
Sulfo, mercapto or hydroxy groups are preferred.

Also, at least one of R ⁵ , R ⁹ and R ¹⁰ is a sulfo group, a silyl group or an amide group, or B is ＢC (R ¹¹ ) R ¹² Is preferred. In particular, at least one of R ⁵ , R ⁹ and R ¹⁰
Preferably, each is a sulfo group or B is ＝ C (R ¹¹ ) R ¹² .

Examples of the halogen atom include fluorine, chlorine, bromine and iodine. Specific examples of the hydrocarbon group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, neopentyl, and n-hexyl having 1 to 30 carbon atoms, preferably A linear or branched alkyl group having 1 to 20 carbon atoms; a linear or branched alkenyl group having 2 to 30 carbon atoms, preferably 2 to 20 carbon atoms, such as vinyl, allyl and isopropenyl; ethynyl , A linear or branched alkynyl group having 2 to 30, preferably 2 to 20 carbon atoms, such as propargyl; cyclopropyl, cyclobutyl,
A cyclic saturated hydrocarbon group having 3 to 30, preferably 3 to 20 carbon atoms such as cyclopentyl, cyclohexyl and adamantyl; a cyclic unsaturated hydrocarbon group having 5 to 30 carbon atoms such as cyclopentadienyl, indenyl and fluorenyl; Aryl having 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms, such as phenyl, benzyl, naphthyl, biphenyl, terphenyl, phenanthryl and anthracenyl.
l) groups; and alkyl-substituted aryl groups such as tolyl, iso-propylphenyl, t-butylphenyl, dimethylphenyl, and di-t-butylphenyl.

The hydrocarbon group may have a hydrogen atom substituted with a halogen atom. For example, a halogenated carbon atom having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms such as trifluoromethyl, pentafluorophenyl and chlorophenyl. And a hydrogen group. The hydrocarbon group may have a hydrogen atom substituted with another hydrocarbon group, and examples thereof include an aryl-substituted alkyl group such as benzyl and cumyl.

Further, the hydrocarbon group may be a heterocyclic compound residue; an alkoxy group, an aryloxy group, an ester group, an ether group, an acyl group, a carboxyl group, a carbonate group, a hydroxy group, a peroxy group, and a carboxylic acid anhydride. Oxygen-containing groups such as groups; amino groups, imino groups, amide groups, imide groups, hydrazino groups, hydrazono groups, nitro groups, nitroso groups, cyano groups, isocyano groups, cyanate ester groups, amidino groups, diazo groups, amino groups A boron-containing group such as a boranediyl group, a borantoriyl group, a diboranyl group, etc .; a mercapto group, a thioester group, a dithioester group, an alkylthio group, an arylthio group, a thioacyl group;
A sulfur-containing group such as a thioether group, a thiocyanate ester group, an isothiocyanate ester group, a sulfone ester group, a sulfonamide group, a thiocarboxyl group, a dithiocarboxyl group, a sulfo group, a sulfonyl group, a sulfinyl group, and a sulfenyl group; It may have a phosphorus-containing group such as a phosphoryl group, a thiophosphoryl group, a phosphato group, a silicon-containing group, a germanium-containing group, or a tin-containing group.

Of these, methyl, ethyl, n-
Propyl, isopropyl, n-butyl, isobutyl, sec-
Butyl, t-butyl, neopentyl, n-hexyl and other linear or branched alkyl groups having 1 to 30, preferably 1 to 20 carbon atoms; phenyl, naphthyl, biphenyl, terphenyl, phenanthryl, anthracenyl and the like. Aryl groups having 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms; halogen atoms, alkyl or alkoxy groups having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, 6 to 30 carbon atoms, Preferably, 6 to 20 substituents such as an aryl group or an aryloxy group have 1 to 5 substituents.
A monosubstituted substituted aryl group is preferred.

Examples of the heterocyclic compound residues include nitrogen-containing compounds such as pyrrole, pyridine, pyrimidine, quinoline, and triazine; oxygen-containing compounds such as furan and pyran;
Residues such as sulfur-containing compounds such as thiophene, and groups in which these heterocyclic compound residues are further substituted with a substituent such as an alkyl group or an alkoxy group having 1 to 30, preferably 1 to 20 carbon atoms. Is mentioned.

The oxygen-containing group, nitrogen-containing group, boron-containing group, sulfur-containing group and phosphorus-containing group represented by R ^{1 to} R ¹² include those exemplified as the substituents which may be contained in the hydrocarbon group. Similar ones can be mentioned.

Examples of the silicon-containing group include a silyl group, a siloxy group, a hydrocarbon-substituted silyl group and a hydrocarbon-substituted siloxy group. Specific examples include methylsilyl, dimethylsilyl, trimethylsilyl, ethylsilyl, diethylsilyl, triethylsilyl, and diphenylmethyl. Silyl, triphenylsilyl, dimethylphenylsilyl, dimethyl-t-butylsilyl, dimethyl (pentafluorophenyl) silyl and the like. Among them, methylsilyl, dimethylsilyl, trimethylsilyl, ethylsilyl, diethylsilyl, triethylsilyl, dimethylphenylsilyl, triphenylsilyl and the like are preferable. Particularly, trimethylsilyl, triethylsilyl, triphenylsilyl and dimethylphenylsilyl are preferred. Specific examples of the hydrocarbon-substituted siloxy group include trimethylsiloxy. Examples of the germanium-containing group and the tin-containing group include those in which silicon of the silicon-containing group is replaced with germanium and tin.

Next, examples of R ^{1 to} R ¹² described above will be described more specifically. Among the oxygen-containing groups, alkoxy groups include methoxy, ethoxy, n-propoxy,
Isopropoxy, n-butoxy, isobutoxy, tert-butoxy, etc., and aryloxy groups such as phenoxy,
2,6-dimethylphenoxy, 2,4,6-trimethylphenoxy and the like, as an acyl group, formyl group, acetyl group,
Preferred examples include a benzoyl group, a p-chlorobenzoyl group, a p-methoxybenzoyl group, and examples of the ester group include acetyloxy, benzoyloxy, methoxycarbonyl, phenoxycarbonyl, and p-chlorophenoxycarbonyl.

Among the nitrogen-containing groups, amide groups include acetamido, N-methylacetamido, N-methylbenzamide, etc., amino groups include dimethylamino, ethylmethylamino, diphenylamino, etc., and imide groups include Preferred examples of the imino group include methylimino, ethylimino, propylimino, butylimino, and phenylimino.

Among the sulfur-containing groups, alkylthio groups include methylthio and ethylthio, arylthio groups include phenylthio, methylphenylthio, and naphthylthio, and thioester groups include acetylthio, benzoylthio, methylthiocarbonyl, and phenylthio. Carbonyl and the like, and sulfonate groups such as methyl sulfonate, ethyl sulfonate and phenyl sulfonate; Are preferred.

When A is an oxygen atom, a sulfur atom or a selenium atom, R ⁴ is preferably a substituent other than hydrogen. That is, R ⁴ is a halogen atom, a hydrocarbon group,
Heterocyclic compound residues, oxygen-containing groups, boron-containing groups, sulfur-containing groups, silicon-containing groups, germanium-containing groups or tin-containing groups are preferred. In particular, R ⁴ is a halogen atom,
Hydrocarbon group, heterocyclic compound residue, hydrocarbon-substituted silyl group, hydrocarbon-substituted siloxy group, alkoxy group, alkylthio group, aryloxy group, arylthio group, acyl group, ester group, thioester group, amide group, amino group, It is preferably an imide group, an imino group, a sulfone ester group, a sulfonamide group, a cyano group, a nitro group or a hydroxy group.

When A is an oxygen atom, a sulfur atom or a selenium atom, preferred hydrocarbon groups for R ⁴ include:
Methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, thiopentyl, n-hexyl, etc. having 1 to 30, preferably 1 to 20 linear or branched carbon atoms Alkyl group; a cyclic saturated hydrocarbon group having 3 to 30, preferably 3 to 20 carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and adamantyl; carbon atoms such as phenyl, benzyl, naphthyl, biphenylyl and triphenylyl An aryl group having 6 to 30, preferably 6 to 20; and an alkyl or alkoxy group having 1 to 30, preferably 1 to 20, carbon atoms in these groups, and having 1 to 30, preferably 1 to 30 carbon atoms. Is a halogenated alkyl group of 1 to 20, having 6 to 30 carbon atoms, preferably 6 to 2 carbon atoms.
A group further substituted with a substituent such as an aryl group or an aryloxy group of 0, a halogen, a cyano group, a nitro group, a hydroxy group and the like are preferable.

When A is an oxygen atom, a sulfur atom or a selenium atom, preferred hydrocarbon-substituted silyl groups for R ⁴ include methylsilyl, dimethylsilyl, trimethylsilyl, ethylsilyl, diethylsilyl, triethylsilyl, diphenylmethylsilyl, Triphenylsilyl, dimethylphenylsilyl, dimethyl-t-butylsilyl, dimethyl (pentafluorophenyl) silyl and the like. Particularly preferred are trimethylsilyl, triethylphenyl, diphenylmethylsilyl, isophenylsilyl, dimethylphenylsilyl, dimethyl-t-butylsilyl, dimethyl (pentafluorophenyl) silyl and the like.

R ^{1 to} R ¹² represent two or more of these groups, preferably adjacent groups, being linked to each other to form an aliphatic ring, an aromatic ring, or a hydrocarbon ring containing a heteroatom such as a nitrogen atom. (Excluding those in which R ¹ and R ⁹ or R ¹ and R ¹⁰ are linked to form an aromatic ring), and these rings may further have a substituent.

Further, when m is 2 or greater, and one of the radicals R ¹ to R ¹² contained in one ligand of R ¹ to R ¹² contained in other ligands One of the groups may be bonded. When R ^{9 s} , R ^{10 s} , R ^{11 s,} or R ^{12 s} are bonded, it is preferable that the main chain of the bond is formed by three or more atoms. Furthermore, R ¹ each other, R ² together, R ³ together, R ⁴ together, R ⁵ each other, R ⁶ to each other,
R ⁷ together, R ⁸ together, R ⁹ together, R ¹⁰ together, R ¹¹ s, R
¹² may be the same or different from each other.

X represents a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, a halogen-containing group, or a heterocyclic compound residue. , A silicon-containing group, a germanium-containing group, or a tin-containing group. n is a number that satisfies the valence of M, and is specifically 0 to 5, preferably 1 to
4, more preferably an integer of 1 to 3. Note that n is 2
In the above case, the plurality of Xs may be the same or different.

Here, as the halogen atom, fluorine,
Chlorine, bromine and iodine. Examples of the hydrocarbon group include the same groups as those described above for R ^{1 to} R ¹² . Specifically, alkyl groups such as methyl, ethyl, propyl, butyl, hexyl, octyl, nonyl, dodecyl and eicosyl; and those having 3 carbon atoms such as cyclopentyl, cyclohexyl, norbornyl and adamantyl
To 30 cycloalkyl groups; alkenyl groups such as vinyl, propenyl and cyclohexenyl; arylalkyl groups such as benzyl, phenylethyl and phenylpropyl;
Examples include, but are not limited to, aryl groups such as phenyl, tolyl, dimethylphenyl, trimethylphenyl, ethylphenyl, propylphenyl, biphenyl, naphthyl, methylnaphthyl, anthryl, and phenanthryl. In addition, these hydrocarbon groups include halogenated hydrocarbons, specifically, having 1 to 2 carbon atoms.
A group in which at least one hydrogen atom of the hydrocarbon group 0 is substituted with a halogen is also included. Among them, the number of carbon atoms is 1 to
Twenty are preferred.

As the heterocyclic compound residue, R ¹
It includes the same as those exemplified in to R ^12.

Examples of the oxygen-containing group include the same ones as those described above for R ^{1 to} R ^12. Specific examples include a hydroxy group; an alkoxy group such as methoxy, ethoxy, propoxy and butoxy; phenoxy, methyl Phenoxy,
Examples include, but are not limited to, aryloxy groups such as dimethylphenoxy and naphthoxy; arylalkoxy groups such as phenylmethoxy and phenylethoxy; acetoxy groups; and carbonyl groups.

Examples of the sulfur-containing group include the same ones as those described above for R ^{1 to} R ¹² , and specifically, methyl sulfonate, trifluoromethane sulfonate, phenyl sulfonate, benzyl sulfonate and the like. Sulfonate groups such as phonate, p-toluenesulfonate, trimethylbenzenesulfonate, triisobutylbenzenesulfonate, p-chlorobenzenesulfonate, and pentafluorobenzenesulfonate; methylsulfinate, phenylsulfate Sulfonate groups such as carboxylate, benzylsulfinate, p-toluenesulfinate, trimethylbenzenesulfinate, pentafluorobenzenesulfinate; alkylthio; arylthio; and the like, but are not limited thereto. .

Specific examples of the nitrogen-containing group include the aforementioned R ¹ to
The same as those exemplified in R ¹² can be mentioned, specifically, amino group, methylamino, dimethylamino, diethylamino, dipropylamino, dibutylamino, alkylamino groups such as dicyclohexyl amino; phenylamino, diphenylamino , Ditolylamino, dinaphthylamino, an arylamino group such as methylphenylamino or an alkylarylamino group.
It is not limited to these.

Specific examples of the boron-containing group include BR
₄ (R represents hydrogen, an alkyl group, an aryl group which may have a substituent, a halogen atom, or the like). Specific examples of the phosphorus-containing group include trialkylphosphine groups such as trimethylphosphine, tributylphosphine, and tricyclohexylphosphine; triphenylphosphine;
Triarylphosphine groups such as tolylphosphine; phosphite groups (phosphide groups) such as methyl phosphite, ethyl phosphite and phenyl phosphite; phosphonic acid groups; phosphinic acid groups, and the like, but are not limited thereto. is not.

Specific examples of the silicon-containing group include the aforementioned R ¹
It includes the same ones as exemplified to R ^12, specifically, phenyl silyl, diphenyl silyl, trimethylsilyl, triethylsilyl, tripropylsilyl, tricyclohexylsilyl silyl, triphenyl silyl, methyl diphenyl silyl, tritolylsilyl A hydrocarbon-substituted silyl group such as trinaphthylsilyl; a hydrocarbon-substituted silyl ether group such as trimethylsilyl ether; a silicon-substituted alkyl group such as trimethylsilylmethyl; a silicon-substituted aryl group such as trimethylsilylphenyl.

Specific examples of the germanium-containing group include the same as those exemplified above for R ^{1 to} R ¹² .
Specifically, a group in which silicon of the silicon-containing group is substituted with germanium is exemplified.

Examples of the tin-containing group include the same ones as those exemplified for R ^{1 to} R ¹² above, and more specifically,
And a group in which silicon of the silicon-containing group is substituted with tin.

Specific examples of the halogen-containing group include P
Examples include, but are not limited to, fluorine-containing groups such as F ₆ and BF ₄ , chlorine-containing groups such as ClO ₄ and SbCl _6, and iodine-containing groups such as IO ₄ .

Specific examples of the aluminum-containing group include A
lR ₄ (R represents a hydrogen, an alkyl group, an aryl group which may have a substituent, a halogen atom, or the like), but is not limited thereto.

When n is 2 or more, a plurality of groups represented by X may be the same or different from each other.
May be bonded to each other to form a ring.

The transition metal compound represented by the general formula (I)
Wherein m is 2 and R contained in one ligand
¹~ R¹²And the R contained in the other ligand¹
~ R ¹²The compound linked to one of the groups is
For example, it is a compound represented by the following general formula (Ia).

Embedded imageIn the formula (I-a), M, A, R¹~ R¹², X are respectively
As in the case of the general formula (I), A ′ is the same as A
Oxygen atom, sulfur atom, selenium atom which may be different
Or a bonding group -R^FiveIndicates a nitrogen atom having a '.
B ′ may be the same as or different from B, and
And -R⁹'And -R^Ten', Or = C (R ¹¹') R¹²'
Is shown. R¹'~ R¹²'Is R¹~ R¹²Same as
Particularly preferred are the following groups.

R ¹ ′ to R ¹² ′ may be the same or different, and each represents a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, It indicates a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group, and specifically, the same atoms or groups as those exemplified for R ^{1 to} R ¹² . Two or more groups of R ¹ ′ to R ¹² ′, preferably adjacent groups, are linked to each other to form an aliphatic ring, an aromatic ring or a hydrocarbon ring containing a hetero atom such as a nitrogen atom. (In the case of the above formula (Ia), R ¹ ′ and R ⁹ ′ or R ¹ ′ and R ¹⁰ ′ are linked to form an aromatic ring).

Y is at least one group selected from R ^{1 to} R ¹² and at least one group selected from R ¹ ′ to R ¹² ′
It is a bonding group or a single bond bonding to the above groups. The bonding group is not particularly limited, but preferably has a structure in which the main chain is composed of 3 or more atoms, more preferably 4 to 20 atoms, and particularly preferably 4 to 10 atoms. In addition, this bonding group may have a substituent.

As the bonding group represented by Y, oxygen, ion
C, carbon, nitrogen, phosphorus, silicon, selenium, tin, boron
Group containing at least one element selected from
And specifically, -O-, -S-, -Se- and the like.
Chalcogen atom-containing group; -NH-, -N (CH_Three)_Two−, −
PH-, -P (CH_Three)_TwoContaining nitrogen or phosphorus atoms such as-
Group; -CH_Two-, -CH_Two-CH_Two-, -C (CH_Three)_Two−
Which hydrocarbon group has 1 to 20 carbon atoms; benzene, na
Phthalene, anthracene and the like having 6 to 20 carbon atoms
Cyclic unsaturated hydrocarbon residue; pyridine, quinoline, thiof
3 to 3 carbon atoms including heteroatoms such as
20 heterocyclic compound residues; -SiH _Two-, -Si (C
H_Three)_TwoA silicon-containing group such as -SnH_Two-, -Sn
(CH_Three)_Two-BH-, -B (C
H_Three)-, A boron atom-containing group such as -BF-, or the like, or
A single bond.

Hereinafter, specific examples of the transition metal compound represented by the general formula (I) will be shown, but the invention is not limited thereto. In the following specific examples, M is a transition metal atom belonging to Groups 3 to 11 of the periodic table. Specific examples include scandium, yttrium, lanthanoid, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, and tungsten. , Manganese, rhenium, iron, ruthenium, cobalt, rhodium, nickel, palladium and the like, preferably scandium,
Lanthanoids, titanium, zirconium, hafnium, vanadium, niobium, tantalum, iron, cobalt, rhodium, nickel, palladium, etc., more preferably titanium, zirconium, hafnium, vanadium,
Niobium, tantalum, iron, cobalt, rhodium and the like are particularly preferable, and titanium, zirconium and hafnium are particularly preferable.

X represents a halogen such as Cl or Br, or an alkyl group such as methyl, but is not limited thereto. When there are a plurality of Xs, these may be the same or different.

N is determined by the valence of the metal M. For example, if two monoanion species are bound to a metal,
N = 0 for a divalent metal, n = 1 for a trivalent metal, n = 2 for a tetravalent metal, and n = 3 for a pentavalent metal. The metal is Ti (IV)
, N = 2, Zr (IV), n = 2, and Hf (IV), n = 2. In the examples of the compounds, Me is a methyl group, Et is an ethyl group, and iPr is
i-propyl group, tBu represents a tert-butyl group, and Ph represents a phenyl group.

[0059]

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[0061]

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[0062]

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[0063]

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[0064]

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[0065]

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The second transition metal compound used in the present invention is a compound represented by the following general formula (II).

Embedded image (Note that A ... M indicates coordination,
This compound also includes those in which A... M is not coordinated. )

In the formula (II), M represents a transition metal atom of Groups 3 to 11 of the periodic table (Group 3 includes lanthanoids), preferably Group 3 to Group 10 (Group 3 includes lanthanoids). ), More preferably a metal atom of groups 3 to 5 and 8 to 10, and particularly preferably a metal atom of group 4 or 5. Specifically, the metal represented by the formula (I) can be given.

M represents an integer of 1 to 6, preferably 1 to 4, and more preferably 1 to 2. A is an oxygen atom having a bonding group -R ^5, sulfur atom, selenium atom or, as a binding group, the nitrogen atom having a -R ⁵ and -R ⁶ or ^{= C (R 7) R 8} ,, B Is -R ⁹ as a linking group for N.
Is shown.

R ^{1 to} R ⁹ may be the same or different from each other and include a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, and a sulfur-containing group. A group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group, and two or more of these may be connected to each other to form a ring.
Specific examples include the same groups as R ^{1 to} R ^{12 in the} above formula (I).

Further, at least one of R ⁵ , R ⁶ and R ⁹ is a sulfo group, a silyl group or an amide group, or A is ＣC (R ⁷ ) R ⁸ Is preferred. In particular, it is preferable that at least one of R ⁵ , R ⁶ and R ⁹ is a sulfo group, or A is ＝ C (R ⁷ ) R ⁸ .

X is the same as in the above formula (I). When n is 2 or more, a plurality of Xs may be the same or different, and a plurality of groups represented by X may be bonded to each other to form a ring.

In the transition metal compound represented by the above general formula (II), m is 2, and R is contained in one ligand.
^{One of} R ^{1 to} R ⁹ and R ¹ contained in another ligand;
The compound in which one of R ⁹ to R ⁹ is linked is
Examples having the same structure as in the case of the above formula (Ia) can be given.

Hereinafter, specific examples of the transition metal compound represented by the general formula (II) will be shown, but the invention is not limited thereto. In the following specific examples, M is a transition metal atom of Groups 3 to 11 of the periodic table, and specific examples include scandium, yttrium, lanthanoid, titanium,
Zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese,
Rhenium, iron, ruthenium, cobalt, rhodium, nickel, palladium and the like, preferably scandium, lanthanoid, titanium, zirconium, hafnium, vanadium, niobium, tantalum, iron, cobalt, rhodium, nickel, palladium and the like, more preferably Is titanium, zirconium, hafnium, vanadium, niobium, tantalum, iron, cobalt, rhodium and the like, and particularly preferably titanium, zirconium and hafnium.

X represents a halogen such as Cl or Br, or an alkyl group such as methyl, but is not limited thereto. When there are a plurality of Xs, these may be the same or different. n is determined by the valence of the metal M, similarly to the first transition metal compound.

[0075]

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The third transition metal compound used in the present invention is a compound represented by the following general formula (III).

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In the formula (III), M represents a transition metal atom of Groups 3 to 11 of the periodic table (Group 3 also includes lanthanoids), preferably Group 3 to Group 10 (Group 3 also includes lanthanoids). ), More preferably a metal atom of groups 3 to 5 and 8 to 10, and particularly preferably 4
Group 5 or 5 metal atoms. Specifically, the formula (I)
Metal.

M represents an integer of 1 to 3, preferably 1 to 2. A represents an oxygen atom, a sulfur atom, a selenium atom, or a nitrogen atom having a -R ⁵ as the binding group, B
Shows -R ⁹ as binding group N.

R ^{1 to} R ⁹ may be the same or different from each other and include a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, and a sulfur-containing group. A group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group, and two or more of these may be connected to each other to form a ring.
Specific examples include the same groups as R ^{1 to} R ^{12 in the} above formula (I).

It is preferable that at least one of R ⁵ and R ⁹ is a sulfo group, a silyl group, or an amide group. In particular, at least one of R ⁵ and R ⁹
Preferably, each is a sulfo group. X represents the same as in the above formula (I). When n is 2 or more, a plurality of Xs may be the same or different, and a plurality of groups represented by X may be bonded to each other to form a ring.

In the transition metal compound represented by the general formula (III), m is 2, and one group of R ^{1 to} R ⁹ contained in one ligand and the other R contained in the child
Compounds in which ^{one of} R ^{1 to} R ⁹ is linked are
Examples having the same structure as in the case of the above formula (Ia) can be given.

The following are specific examples of the transition metal compound represented by the general formula (III), but the invention is not limited thereto. In the following specific examples, M is a transition metal atom of Groups 3 to 11 of the periodic table, and specific examples thereof include scandium, yttrium, lanthanoid, titanium, zirconium, hafnium, vanadium, niobium,
Tantalum, chromium, molybdenum, tungsten, manganese, rhenium, iron, ruthenium, cobalt, rhodium,
Nickel, palladium and the like, preferably scandium, lanthanoid, titanium, zirconium, hafnium, vanadium, niobium, tantalum, iron, cobalt, rhodium, nickel, palladium, and more preferably, titanium, zirconium, hafnium, vanadium, Niobium, tantalum, iron, cobalt, rhodium and the like are particularly preferable, and titanium, zirconium and hafnium are particularly preferable.

X represents a halogen such as Cl or Br, or an alkyl group such as methyl, but is not limited thereto. When there are a plurality of Xs, they may be the same or different. n is determined by the valence of the metal M, similarly to the first transition metal compound.

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The fourth transition metal compound used in the present invention is a compound represented by the following general formula (IV).

Embedded image (Here, N ... M and A ... M indicate that they are coordinated together.)

In the formula (IV), M represents a transition metal atom belonging to Groups 3 to 11 of the periodic table (Group 3 also includes lanthanoids), and preferably Group 3 to Group 10 (Group 3 also includes lanthanoids). ), More preferably a metal atom of groups 3 to 5 and 8 to 10, and particularly preferably 8 to
It is a Group 10 metal atom. Specifically, the metal represented by the formula (I) can be given.

M represents an integer of 1 to 3, preferably 1 to 2. A is an oxygen atom having a bonding group -R ^5, sulfur atom, selenium atom or, as a binding group, the nitrogen atom having a -R ⁵ and -R ⁶ or ^{= C (R 7) R 8} ,,
B represents -R ⁹ and -R ¹⁰ or ＣC (R ¹¹ ) R ¹² as a bonding group for N.

R ^{1 to} R ¹² may be the same or different from each other and include a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, and a sulfur-containing group. A group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group, and two or more of these may be connected to each other to form a ring. Specific examples include the same groups as R ^{1 to} R ^{12 in the} above formula (I).

Further, at least one of R ⁵ , R ⁶ , R ⁹ and R ¹⁰ is any one of a sulfo group, a silyl group and an amide group, or A is ＣC (R ⁷ ) R ⁸ Or
Alternatively, B is preferably ＝ C (R ¹¹ ) R ¹² . In particular, R ^5, R ^6, or at least one of R ⁹ and R ^{1 0} is a sulfo group, or, A is = C (R ⁷⁾ or a R ^8, or, B is = C (R ¹¹⁾ is preferably R ^12.

X is the same as in the above formula (I). When n is 2 or more, a plurality of Xs may be the same or different, and a plurality of groups represented by X may be bonded to each other to form a ring.

The transition metal compound represented by the general formula (IV)
Wherein m is 2 and R contained in one ligand
¹~ R¹²And the R contained in the other ligand¹
~ R ¹²The compound linked to one of the groups is
An example of a structure similar to that of the above formula (I-a) is shown.
Can be

Hereinafter, specific examples of the transition metal compound represented by the general formula (IV) will be shown, but the invention is not limited thereto. In the following specific examples, M is a transition metal atom belonging to Groups 3 to 11 of the periodic table. Specific examples include scandium, yttrium, lanthanoid, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, and tungsten. , Manganese, rhenium, iron, ruthenium, cobalt, rhodium, nickel, palladium and the like, preferably scandium,
Lanthanoids, titanium, zirconium, hafnium, vanadium, niobium, tantalum, iron, cobalt, rhodium, nickel, palladium, etc., more preferably titanium, zirconium, hafnium, vanadium,
Niobium, tantalum, iron, cobalt, rhodium, nickel, palladium and the like are particularly preferable, and iron, cobalt, rhodium, nickel and palladium are particularly preferable.

X represents a halogen such as Cl or Br, or an alkyl group such as methyl, but is not limited thereto. When there are a plurality of Xs, they may be the same or different. n is determined by the valence of the metal M, similarly to the first transition metal compound.

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The transition metal compound (A) as described above has 1
These are used alone or in combination of two or more. Also,
It can be used in combination with a transition metal compound other than the above transition metal compound (A), for example, a known transition metal compound comprising a ligand containing a hetero atom such as nitrogen, oxygen, sulfur, boron or phosphorus. Hereinafter, other transition metal compounds that can be used in combination will be described.

[0100]Other transition metal compounds  A transition metal compound other than the above transition metal compound (A)
Specifically, the following transition metal compounds are used.
be able to. However, it is not limited to these.
No.

(A-1) Transition metal imide compound represented by the following formula:

Embedded image In the formula, M represents a transition metal atom belonging to Groups 8 to 10 of the periodic table, and is preferably nickel, palladium or platinum.

R ^{21 to} R ²⁴ may be the same or different from each other, and may have 1 to 50 carbon atoms.
Represents a halogenated hydrocarbon group, a hydrocarbon-substituted silyl group, or a hydrocarbon group substituted with a substituent containing at least one element selected from nitrogen, oxygen, phosphorus, sulfur and silicon. Groups represented by R ²¹ to R ²⁴ is two or more of these, preferably may form a ring adjacent groups together.

X represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group, a sulfur-containing group, a silicon-containing group or a nitrogen-containing group. A q is an integer of 0 to 4; When q is 2 or more, a plurality of groups represented by X may be the same or different.

(A-2) Transition metal amide compound represented by the following formula:

Embedded image In the formula, M represents a transition metal atom belonging to Groups 3 to 6 of the periodic table;
It is preferably titanium, zirconium or hafnium.

R ′ and R ″ may be the same or different, and each represents a hydrogen atom, a hydrocarbon group having 1 to 50 carbon atoms, a halogenated hydrocarbon group having 1 to 50 carbon atoms, a hydrocarbon-substituted silyl group, Or a substituent having at least one element selected from nitrogen, oxygen, phosphorus, sulfur, and silicon.

A represents an atom belonging to Groups 13 to 16 of the periodic table, and specifically includes boron, carbon, nitrogen, oxygen, silicon,
Examples thereof include phosphorus, sulfur, germanium, selenium, and tin, and are preferably carbon or silicon. m is 0
And n is an integer of 1 to 5. n is 2
In the above case, the plurality of A may be the same or different from each other.

E is a substituent having at least one element selected from carbon, hydrogen, oxygen, halogen, nitrogen, sulfur, phosphorus, boron and silicon. When m is 2, two Es may be the same or different from each other;
Alternatively, they may be connected to each other to form a ring.

X is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group, a sulfur-containing group, a silicon-containing group or A nitrogen-containing group is shown, and p is an integer of 0-4. When p is 2 or more, a plurality of groups represented by X may be the same or different from each other. Of these,
X is preferably a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a sulfonate group.

(A-3) Transition metal diphenoxy compound represented by the following formula:

Embedded image In the formula, M represents a transition metal atom of Groups 3 to 11 of the periodic table, l and m are each an integer of 0 or 1, and A
And A ′ is a hydrocarbon group having 1 to 50 carbon atoms, a halogenated hydrocarbon having 1 to 50 carbon atoms, a hydrocarbon group having a substituent containing oxygen, sulfur or silicon, or 1 carbon atom. To 50 halogenated hydrocarbon groups, and A and A ′ may be the same or different.

B is a hydrocarbon group having 0 to 50 carbon atoms,
A halogenated hydrocarbon group having 1 to 50 carbon atoms, R ¹ R ² Z
Wherein R ¹ and R ² are a hydrocarbon group having 1 to 20 carbon atoms or a hydrocarbon group having 1 to 20 carbon atoms containing at least one hetero atom. And Z represents carbon, nitrogen, sulfur, phosphorus or silicon.

N is a number satisfying the valence of M. X is
A hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group, a sulfur-containing group, a silicon-containing group or a nitrogen-containing group; In the case of two or more, a plurality of groups represented by X may be the same or different from each other, or may be bonded to each other to form a ring.

(A-4) A transition metal compound containing a ligand having a cyclopentadienyl skeleton containing at least one hetero atom represented by the following formula:

Embedded image In the formula, M represents a transition metal atom of Groups 3 to 11 of the periodic table.
X represents an atom belonging to Group 13, 14 or 15 of the periodic table, and at least one of X is an element other than carbon.

R represents a hydrogen atom, a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a hydrocarbon-substituted silyl group, which may be the same or different, nitrogen, oxygen,
A hydrocarbon group substituted with a substituent containing at least one element selected from phosphorus, sulfur and silicon,
Two or more Rs may be connected to each other to form a ring.
a is 0 or 1, b is an integer of 1 to 4,
When b is 2 or more, each [((R) a) ₅ -X ₅ ] group may be the same or different, and R may be cross-linked.

C is a number satisfying the valence of M. Y is
It represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group, a sulfur-containing group, a silicon-containing group or a nitrogen-containing group. When c is 2 or more, a plurality of groups represented by Y may be the same or different, and a plurality of groups represented by Y may be bonded to each other to form a ring.

(A-5) Transition metal compound represented by the formula RB (Pz) ₃ MXn: In the formula, M represents a transition metal compound belonging to Groups 3 to 11 of the periodic table, R represents a hydrogen atom, and a carbon atom having 1 carbon atom. Represents a hydrocarbon group having from 20 to 20 or a halogenated hydrocarbon group having from 1 to 20 carbon atoms, and Pz represents a pyrazoyl group or a substituted pyrazoyl group.

N is a number satisfying the valence of M. X is
A hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group, a sulfur-containing group, a silicon-containing group or a nitrogen-containing group; In the case of two or more, a plurality of groups represented by X may be the same or different from each other, or may be bonded to each other to form a ring.

(A-6) Transition metal compound represented by the following formula:

Embedded image In the formula, Y ¹ and Y ³ are elements of Group 15 of the periodic table, which may be the same or different, and Y ² is an element of Group 16 of the periodic table. R ^{21 to} R ²⁸ may be the same or different, and may be a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group, sulfur, Represents a containing group or a silicon-containing group, and two or more of these may be connected to each other to form a ring.

(A-7) Compound of a compound represented by the following formula and a Group VIII transition metal atom:

Embedded image In the formula, R ^{31 to} R ³⁴ are a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group having 1 to 20 carbon atoms, which may be the same or different from each other, Two or more of these may be connected to each other to form a ring.

(A-8) A transition metal compound represented by the following formula:

Embedded image In the formula, M represents a transition metal atom of Groups 3 to 11 of the periodic table, m is an integer of 0 to 3, n is an integer of 0 or 1, and p is 1 to 3 Q is an integer satisfying the valence of M.

[0120] R ⁴¹ to R ^{4 8} are each optionally hydrogen atoms be the same or different, a halogen atom, carbon atom 20
Hydrocarbon group, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group, a sulfur-containing group, a silicon-containing group or a nitrogen-containing group, two or more of which are connected to each other to form a ring. It may be formed.

X is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group, a sulfur-containing group, a silicon-containing group or a nitrogen-containing group. A group, and when q is 2 or more, X
May be the same as or different from each other, or the groups represented by X may be bonded to each other to form a ring.

Y is a group for bridging the borata benzene ring, and represents carbon, silicon or germanium. A is
Shows an element belonging to Group 14, 15, or 16 of the periodic table.

(A-9) A transition metal compound containing a ligand having a cyclopentadienyl skeleton other than (a-4). (a-10) Compound containing magnesium, titanium and halogen as essential components.

Next, each compound of the component (B) will be described.
I do.(B-1) Organometallic compound  Specific examples of the (B-1) organometallic compound used in the present invention include:
Specifically, Periodic Tables 1 and 2 and 12
Group 13 organometallic compounds are used.

[0125] (B-1a) In the formula _{^{R a m Al (OR b)}} n H p X q ( wherein, R ^a and R ^b, a good number of carbon atoms may be the same or different 1 to 15, It preferably represents 1 to 4 hydrocarbon groups, X represents a halogen atom, and m represents 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).

[0126] (B-1b) In the general formula M ² AlR ^a ₄ (wherein, M ² represents a Li, Na or K, R ^a is the number of carbon atoms 1 to 15, preferably 1 to 4 hydrocarbon groups A complex alkylated product of a Group 1 metal and aluminum represented by the formula: (B-1c) a general formula R ^a R ^b M ³ (where R ^a and R ^b each represent a hydrocarbon group having 1 to 15, preferably 1 to 4 carbon atoms which may be the same or different from each other) And M ³ is Mg, Zn or Cd.)
A dialkyl compound of a Group 2 or Group 12 metal represented by the formula:

As the organoaluminum compound belonging to the above (B-1a), the following compounds can be exemplified. In the general formula _{^{R a m Al (OR b)}} 3-m ( wherein, R ^a and R ^b, a good number of carbon atoms may be the same or different 1 to 15, preferably 1 to 4 hydrocarbon groups indicates, m is preferably a number of 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
4 represents a hydrocarbon group, X represents a halogen atom, and m is preferably 0 <m <3. An organoaluminum compound represented by

[0128] 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, a good number of carbon atoms may be the same or different 1 to 15, preferably Represents a hydrocarbon group of 1 to 4, X represents a halogen atom, and m represents 0 <m ≦
3, n is a number satisfying 0 ≦ n <3, q is a number satisfying 0 ≦ q <3, and m + n + q = 3. The organoaluminum compound represented by).

As the organoaluminum compound belonging to (B-1a), more specifically, trimethylaluminum, triethylaluminum, trin-butylaluminum, tripropylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum,
Tri-n-alkyl aluminums such as tridecyl aluminum; triisopropyl aluminum, triisobutyl aluminum, tri sec-butyl aluminum, tri tert
-Butylaluminum, tri2-methylbutylaluminum, tri3-methylbutylaluminum, tri2-methylpentylaluminum, tri3-methylpentylaluminum, tri4-methylpentylaluminum, tri2-methylhexylaluminum, tri3-methyl Tri-branched alkyl aluminum such as hexyl aluminum and tri 2-ethylhexyl aluminum;

Tricycloalkylaluminum such as tricyclohexylaluminum and tricyclooctylaluminum; triarylaluminum such as triphenylaluminum and tritolylaluminum; dialkylaluminum hydride such as diisobutylaluminum hydride and diisobutylaluminum hydride; (i-C ₄ H ₉ ) _x Al _y (C ₅ H ₁₀ ) _z (where x, y,
z is a positive number and z ≧ 2x. ) And other trialkenyl aluminums such as triisoprenyl aluminum;

Alkyl aluminum alkoxides such as isobutylaluminum methoxide, isobutylaluminum ethoxide and isobutylaluminum isopropoxide; dialkylaluminum alkoxides such as dimethylaluminum methoxide, diethylaluminum ethoxide and dibutylaluminum butoxide; ethylaluminum sesquiethoxide and butyl Alkyl aluminum sesquialkoxides such as aluminum sesquibutoxide;

Partially alkoxylated alkyl aluminum having an average composition represented by ^Ra _2.5 Al (OR ^b ) _{0.5 and the} like; diethyl aluminum phenoxide, diethyl aluminum (2,6-di-t-butyl-4- Methylphenoxide), ethyl aluminum bis (2,6-di-t-butyl-4-methylphenoxide), diisobutyl aluminum (2,6-
Dialkylaluminum aryloxides such as di-t-butyl-4-methylphenoxide) and isobutylaluminum bis (2,6-di-t-butyl-4-methylphenoxide); dimethylaluminum chloride, diethylaluminum chloride, dibutylaluminum chloride Dialkylaluminum halides such as ethylaluminum sesquichloride, butylaluminum sesquichloride and ethylaluminum sesquibromide; alkyls such as ethylaluminum dichloride, propylaluminum dichloride and butylaluminum dibromide Partially halogenated alkylaluminums such as aluminum dihalide;

Dialkylaluminum hydrides such as diethylaluminum hydride and dibutylaluminum hydride; other partially hydrogenated alkylaluminums such as alkylaluminum dihydrides such as ethylaluminum dihydride and propylaluminum dihydride; ethylaluminum ethoxychloride, butyl Partially alkoxylated and halogenated alkylaluminums such as aluminum butoxycyclolide, ethylaluminum ethoxybromide and the like can be mentioned.

Also, compounds similar to (B-1a) can be used, and examples thereof include an organic aluminum compound in which two or more aluminum compounds are bonded via a nitrogen atom. As such a compound, specifically, (C ₂ H
₅ ) ₂ AlN (C ₂ H ₅ ) Al (C ₂ H ₅ ) ₂ .

Compounds belonging to the above (B-1b) include Li
_{Al (C 2 H 5) 4} , LiAl (C 7 H 15) 4 and the like.

In addition, as the organometallic compound (B-1), methyl lithium, ethyl lithium, propyl lithium, butyl lithium, methyl magnesium bromide, methyl magnesium chloride, ethyl magnesium bromide, ethyl magnesium chloride, propyl magnesium bromide , Propyl magnesium chloride, butyl magnesium bromide, butyl magnesium chloride, dimethyl magnesium, diethyl magnesium, dibutyl magnesium, butyl ethyl magnesium and the like can also be used.

Further, a compound which forms the above-mentioned organoaluminum compound in the polymerization system, for example, a combination of aluminum halide and alkyl lithium, or a combination of aluminum halide and alkyl magnesium can also be used. (B-1) Among the organometallic compounds, an organoaluminum compound is preferred. The organometallic compounds (B-1) as described above are used alone or in combination of two or more.

[0138](B-2) Organoaluminum oxy compound  (B-2) the organic aluminum oxy compound used in the present invention
The product may be a conventionally known aluminoxane,
Japanese Patent Application Laid-Open No. 2-78687 discloses a battery pack.
An organic aluminum oxy compound insoluble in benzene
Is also good.

A 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) In a medium such as benzene, toluene, ethyl ether, tetrahydrofuran, etc., water,
A method of applying ice or water vapor. (3) A method of reacting an organoaluminum compound such as trialkylaluminum with an organotin oxide such as dimethyltin oxide or dibutyltin oxide in a medium such as decane, benzene or toluene.

The aluminoxane may contain a small amount of an organic metal 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 in preparing the aluminoxane include those described in the above (B-1a).
The same organoaluminum compounds as those exemplified as the organoaluminum compounds belonging to the above. Of these, trialkylaluminum and tricycloalkylaluminum are preferred, and trimethylaluminum is particularly preferred. The organoaluminum compound as described above,
One type is used alone, or two or more types are used in combination.

Solvents used for the preparation of aluminoxane include aromatic hydrocarbons such as benzene, toluene, xylene, cumene and cymene, and aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane and octadecane. , Cyclopentane, cyclohexane, cyclooctane, methylcyclopentane and other alicyclic hydrocarbons, petroleum fractions such as gasoline, kerosene and gas oil, or halides of the above aromatic hydrocarbons, aliphatic hydrocarbons and alicyclic hydrocarbons Among them, hydrocarbon solvents such as chlorinated products and brominated products are exemplified. 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 soluble in benzene at 60 ° C. is usually 10% or less, preferably 5% or less, particularly preferably 2% or less in terms of Al atom. Certain, ie, those that are insoluble or poorly soluble in benzene, are preferred.

Examples of the organic aluminum oxy compound used in the present invention include an organic aluminum oxy compound containing boron represented by the following general formula (i).

Embedded image In the formula, R ²⁰ represents a hydrocarbon group having 1 to 10 carbon atoms. R ²¹ represents a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 10 carbon atoms which may be the same or different from each other.

The organoaluminum oxy compound containing boron represented by the general formula (i) is represented by the following general formula (ii)
And R ²⁰ —B— (OH) ₂ ... (Ii) (wherein R ²⁰ represents the same group as above) under an inert gas atmosphere. In an inert solvent at a temperature of -80 ° C to room temperature for 1 minute to 24 hours.

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

Specific examples of such an organoaluminum compound to be reacted with an alkylboronic acid include those described in (B-1a) above.
The same organoaluminum compounds as those exemplified as the organoaluminum compounds belonging to the above. Of these, trialkylaluminum and tricycloalkylaluminum are preferable, and trimethylaluminum, triethylaluminum and triisobutylaluminum are particularly preferable. These are used alone or in combination of two or more.

The above (B-2) organoaluminum oxy compounds are used alone or in combination of two or more.

[0150](B-3) Reaction with transition metal compound (A)
Compounds that form pairs  Reaction with the transition metal compound (A) used in the present invention
Compound (B-3) forming an on-pair (hereinafter referred to as “ionized ion
Compounds ". ) Is the transition metal compound (A)
Is a compound that reacts with to form an ion pair. Therefore,
Contacting at least the transition metal compound (A)
Those that form a pair are included in this compound. This
As such compounds, JP-A-1-501950,
JP-A-1-502036, JP-A-3-17900
No. 5, JP-A-3-179006, JP-A-3-179006
207703, JP-A-3-207704,
Lewis acids described in USP-5321106 and the like,
Ionic compounds, borane compounds and carborane compounds
And the like. In addition, heteropoly compounds and
Sopoly compounds can also be mentioned.

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

Examples of the ionic compound include a compound represented by the following general formula (VI).

Embedded image In the formula, R ²² includes H ⁺ , carbonium cation, oxonium cation, ammonium cation, phosphonium cation, cycloheptyltrienyl cation, and ferrocenium cation having a transition metal. R ^{23 to} R ²⁶ are an organic group which may be the same or different, preferably an aryl group or a substituted aryl group.

Specific examples of the carbonium cation include trisubstituted carbonium cations such as triphenylcarbonium cation, tri (methylphenyl) carbonium cation, and tri (dimethylphenyl) carbonium cation. Specifically, as the ammonium cation, a trimethylammonium cation,
Trialkylammonium cations such as triethylammonium cation, tripropylammonium cation, tributylammonium cation, tri (n-butyl) ammonium cation; N, N-dimethylanilinium cation, N, N-diethylanilinium cation, N, N- 2,4,
N, N-dialkylanilinium cations such as 6-pentamethylanilinium cation; dialkylammonium cations such as di (isopropyl) 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.

As R ²² , a carbonium cation, an ammonium cation and the like are preferable, and a triphenylcarbonium cation, an N, N-dimethylanilinium cation and an N, N-diethylanilinium cation are particularly preferable.

As the ionic compound, a trialkyl-substituted ammonium salt, an N, N-dialkylanilinium salt,
Dialkylammonium salts, triarylphosphonium salts and the like are also included.

Specific examples of the trialkyl-substituted ammonium salts include, for example, triethylammonium tetra (phenyl) boron, tripropylammonium tetra (phenyl) boron, tri (n-butyl) ammonium tetra (phenyl) boron, trimethylammonium tetra (p -Tolyl) boron, trimethylammoniumtetra (o-tolyl) boron, tri (n-butyl) ammoniumtetra (pentafluorophenyl) boron, tripropylammoniumtetra (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-dimethylaniliniumtetra (phenyl) boron, N, N-diethylaniliniumtetra (phenyl) boron, N, N-2, 4,6-pentamethylanilinium tetra (phenyl) boron and the like. 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,
N, N-diethylanilinium pentaphenylcyclopentadienyl complex, and a boron compound represented by the following formula (VII) or (VIII) are also included.

Embedded image (In the formula, Et represents an ethyl group.)

Embedded image

Specific examples of the borane compound include, for example, 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, for example, 4-carbanonaborane (14), 1,3-dicarbanonaborane (13), 6,9-dicarbadecaborane (14), dodecahydride-1-phenyl- 1,3-dicarbanonaborane, dodeca hydride-1-methyl-1,3-dicarbanona borane, undeca hydride-1,3-dimethyl-1,3-dicarbanona borane, 7,8-dicarban Decaborane (13),
2,7-dicarboundecaborane (13), undecahydride-7,8-dimethyl-7,8-dicarboundecaborane, dodecahydride-11-methyl-2,7-dicarboundecaborane, tri (n -Butyl) ammonium 1-carbadecaborate, tri (n-butyl) ammonium 1-carboundecaborate, tri (n-butyl) ammonium 1-carbadodecaborate, tri (n-butyl) ammonium 1-trimethylsilyl-1- Carbadecaborate, tri (n-butyl) ammonium bromo-1-carbadodecaborate, tri (n-butyl
Butyl) ammonium 6-carbadecaborate (14),
Tri (n-butyl) ammonium 6-carbadecaborate (12), tri (n-butyl) ammonium 7-carboundecaborate (13), tri (n-butyl) ammonium
7,8-dicarboundecaborate (12), tri (n-butyl) ammonium 2,9-dicarboundecaborate (1
2), tri (n-butyl) ammonium dodecahydride-8-methyl-7,9-dicarboundecaborate, tri (n-butyl
Butyl) ammonium undecahydride-8-ethyl
-7,9-Dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-8-butyl-7,9-dicarbaundecaborate, tri (n-butyl) ammoniumundecahydride-8-allyl-7 , 9-Dicarboundecaborate, tri (n-butyl) ammonium undecahydride-9-trimethylsilyl-7,8-dicarboundecaborate, tri (n-butyl) ammoniumundecahydride-4,6-dibromo-7 -Salts of anions such as carbaundecaborates;

Tri (n-butyl) ammonium bis (nonahydride-1,3-dicarbanonaborate) cobaltate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarbaun Decaborate) ferrate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarbaundecaborate) cobaltate (III), tri (n-butyl) ammonium bis (undecarate) Hydride-7,8-dicarboundecaborate) nickelate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarboundecaborate) cuprate (III), tri (n -Butyl) ammonium bis (undecahydride-7,8-dicarboundecaborate) aurate (III), tri (n-butyl) ammonium bis (nonahydride-7,8-dimethyl-7,8-dica Ruboundecaborate) ferrate (III), tri (n-butyl)
Ammonium bis (nonahydride-7,8-dimethyl-
7,8-dicarboundecaborate) chromate (III), tri (n-butyl) ammonium bis (tribromooctahydride-7,8-dicarboundecaborate) cobaltate (III), 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-carbaun Decaborate) nickelate (IV)
And the like, and salts of metal carborane anions.

The heteropoly compound is composed of atoms consisting of silicon, phosphorus, titanium, germanium, arsenic or tin and one or more atoms selected from vanadium, niobium, molybdenum and tungsten. Specifically, phosphorus vanadic acid, germanovanadate, arsenic vanadate, phosphorus niobate, germanoniobate, siliconomolybdate, phosphomolybdate, titanium molybdate, germanomolybdate, arsenic molybdate, tin molybdate, phosphorus molybdate, phosphorus Tungstic acid, germanotungstic acid, tin tungstic acid, phosphomolybdovanadic acid, phosphorus tungstovanadic acid, germanotangostovanadate acid, phosphomolybdatovantovanadate acid, germanomolybdatovantovanadate acid, phosphomolybdine Tungstic acid, phosphomolybdniobic acid, salts of these acids, for example, metals of Group Ia or IIa of the Periodic Table, specifically
Salts with lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium and the like, and organic salts such as triphenylethyl salt, and isopoly compounds can be used,
This is not the case.

The heteropoly compound and isopoly compound are not limited to one of the above compounds, and two or more of them can be used. The above (B-3) ionized ionic compounds are used alone or in combination of two or more.

When the transition metal compound according to the present invention is used as a catalyst, when a co-catalyst component is used in combination with an organoaluminum oxy compound (B-2) such as methylaluminoxane,
Shows very high polymerization activity for olefin compounds.
When an ionized ionic compound (B-3) such as triphenylcarbonium tetrakis (pentafluorophenyl) borate is used as a cocatalyst component, an olefin polymer having excellent activity and a very high molecular weight can be obtained.

Further, the catalyst for olefin polymerization according to the present invention comprises the above-mentioned transition metal compound (A), (B-1) organometallic compound, (B-2) organoaluminum oxy compound, and (B-3)
A carrier (C) as described later can be used together with at least one compound (B) selected from ionized ionic compounds, if necessary.

[0167](C) Carrier  The carrier (C) used in the present invention is an inorganic or organic compound.
The compound is a granular or particulate solid.
Of these, inorganic compounds include porous oxides and inorganic chlorides.
Materials, clays, clay minerals or ion-exchange layered compounds are preferred.
Good.

As the porous oxide, specifically, Si
O ₂ , Al ₂ O ₃ , MgO, ZrO, TiO ₂ , B ₂ O ₃ , C
aO-, ZnO, BaO, etc. ThO _2, or using a composite or mixture containing them, for example, natural or synthetic _{zeolites, SiO 2 -MgO, SiO 2 -Al} 2 O 3, S
_{iO 2 -TiO 2, SiO 2 -V} 2 O 5, SiO 2 -Cr
₂ O ₃ , SiO ₂ —TiO ₂ —MgO or the like can be used. Of these, SiO ₂ and / or Al ₂ O
Those containing ₃ as a main component are preferred.

The above-mentioned inorganic oxide is prepared by adding a small amount of Na ₂ C
O ₃ , K ₂ CO ₃ , CaCO ₃ , MgCO ₃ , Na ₂ SO ₄ ,
Al ₂ (SO ₄ ) ₃ , BaSO ₄ , KNO ₃ , Mg (NO ₃ )
₂ , carbonates such as Al (NO ₃ ) ₃ , Na ₂ O, K ₂ O, and Li ₂ O, sulfates, nitrates, and oxide components may be contained.

Although such porous oxides have different properties depending on the kind and the production method, the carrier preferably used in the present invention has a particle size of 10 to 300 μm, preferably 20 to 300 μm.
And a specific surface area of 50 to 1000 m ^2.
/ G, preferably in the range of 100 to 700 m ² / g, and the pore volume is desirably in the range of 0.3 to 3.0 cm ³ / g. Such a carrier may be used, if necessary, for 10 hours.
It is used by firing at 0 to 1000 ° C, preferably 150 to 700 ° C.

Examples of inorganic chlorides include MgCl ₂ , MgB
r ₂ , MnCl ₂ , MnBr ₂ or the like is used. The inorganic chloride may be used as it is, or may be used after being pulverized by a ball mill or a vibration mill. In addition, after dissolving an inorganic chloride in a solvent such as alcohol, a material obtained by precipitating into fine particles with a precipitant can also be used.

The clay used as a carrier in the present invention is usually composed mainly of a clay mineral. Further, the ion-exchangeable layered compound used as a carrier in the present invention is a compound having a crystal structure in which surfaces formed by ionic bonds and the like are stacked in parallel with weak bonding force to each other, and the contained ions are exchangeable. It is. Most clay minerals are ion-exchangeable layered compounds. In addition, as these clays, clay minerals and ion-exchangeable layered compounds, not only natural ones but also artificially synthesized ones can be used. As the clay, clay mineral or ion-exchangeable layered compound, clay, clay mineral, ionic crystalline compound having a layered crystal structure such as hexagonal dense packing type, antimony type, CdCl ₂ type, CdI ₂ type, and the like. Examples can be given.

[0173] Such clays and clay minerals include kao.
Phosphorus, bentonite, Kibushi clay, Gairome clay, Alof
Ene, hischingelite, pyrophyllite, plum group, mo
Nmorillonite group, vermiculite, ryokudeite
Flock, palygorskite, kaolinite, nacrite, de
Ion exchange, hallucite, ion exchange
Α-Zr (HAsO)_Four)_Two・ H_Two
O, α-Zr (HPO_Four) _Two, Α-Zr (KPO_Four)_Two・ 3
H_TwoO, α-Ti (HPO_Four)_Two, Α-Ti (HAsO_Four)
_Two・ H_TwoO, α-Sn (HPO_Four)_Two・ H_TwoO, γ-Zr
(HPO_Four)_Two, Γ-Ti (HPO_Four)_Two, Γ-Ti (NH
_FourPO_Four)_Two・ H_TwoCrystalline acid salts of polyvalent metals such as O
No.

Such a clay, clay mineral or ion-exchangeable layered compound preferably has a pore volume of at least 20 angstroms and a pore volume of at least 0.1 cc / g, as measured by a mercury intrusion method, and is preferably from 0.3 to 5 cc / g. g are particularly preferred. Here, the pore volume is measured by a mercury intrusion method using a mercury porosimeter in a range of pore radius of 20 to 3 × 10 ⁴ Å. When a carrier having a radius of 20 Å or more and a pore volume of less than 0.1 cc / g is used as a carrier, a high polymerization activity tends to be hardly obtained.

The clays and clay minerals used in the present invention include:
It is also preferable to perform a chemical treatment. As the chemical treatment, any of a surface treatment for removing impurities adhering to the surface, a treatment for affecting the crystal structure of clay, and the like can be used. Specific examples of the chemical treatment include acid treatment, alkali treatment, salt treatment, and organic substance treatment. Acid treatment removes impurities on the surface, and removes Al, Fe, Mg in the crystal structure.
The surface area is increased by eluting cations such as. Alkaline treatment destroys the crystal structure of clay,
This results in a change in the structure of the clay. In the salt treatment and the organic substance treatment, an ion complex, a molecular complex, an organic derivative, and the like are formed, and the surface area and the interlayer distance can be changed.

The ion-exchangeable layered compound used in the present invention
The material uses ion exchange properties to separate exchangeable ions between layers.
By exchanging with large bulky ions, the interlayer can be expanded.
It may be a layered compound in a large state. Such bulk
High ions play the role of pillars supporting the layered structure
And are usually called pillars. Also layered like this
Introducing another substance between compound layers
Is called a solution. Guest compound to intercalate
As a material, TiCl_Four, ZrCl_FourSuch as cationic
Compound, Ti (OR)_Four, Zr (OR)_Four, PO (O
R)_Three, B (OR)_ThreeSuch as metal alkoxide (R is carbonized
Hydrogen group), [Al₁₃O_Four(OH)_{twenty four}] ⁷⁺, [Zr
_Four(OH)₁₄]²⁺, [Fe_ThreeO (OCOCH_Three)₆]⁺Such
And the like.

These compounds are used alone or in combination of two or more. When intercalating these compounds, Si (OR) ₄ , Al (O
A polymer obtained by hydrolyzing a metal alkoxide (R is a hydrocarbon group or the like) such as R) ₃ , Ge (OR) ₄ , SiO
A colloidal inorganic compound such as _2, etc. may be allowed to coexist. Examples of the pillars include oxides formed by intercalating the metal hydroxide ions between layers and then heating and dehydrating the layers.

The clay, clay mineral, and ion-exchange layered compound used in the present invention may be used as they are, or may be used after performing a treatment such as ball milling or sieving. Further, it may be used after water is newly added and adsorbed or subjected to heat dehydration treatment. Further, they may be used alone or in combination of two or more.

Of these, preferred are clay or clay minerals, and particularly preferred are montmorillonite, vermiculite, hectorite, teniolite and synthetic mica.

The organic compound has a particle size of 10 to 300.
Granular or particulate solids in the range of μm can be mentioned. Specifically, ethylene, propylene, 1-
Butene, 4-methyl-1-pentene, etc. having 2 to 2 carbon atoms
Produced mainly with α-olefin of 14 (co)
Examples thereof include polymers or (co) polymers formed mainly of vinylcyclohexane and styrene, and modified products thereof.

The olefin polymerization catalyst according to the present invention comprises the above-mentioned transition metal compound (A), (B-1) an organometallic compound, (B-2)
At least one compound (B) selected from an organoaluminum oxy compound and (B-3) an ionized ionic compound, and optionally a carrier (C), and if necessary, a specific organic compound as described later. (D) can also be included.

[0182](D) Organic compound component  In the present invention, (D) the organic compound component may be
To improve polymerization performance and physical properties of the produced polymer
Used for Such organic compounds include al
Coals, phenolic compounds, carboxylic acids, phosphorus compounds
Substances and sulfonates, but are not limited thereto.
Not something.

Alcohols and phenolic compounds
In general, R³¹-OH is used
(Where R³¹Is a hydrocarbon group having 1 to 50 carbon atoms or
Represents a halogenated hydrocarbon group having 1 to 50 carbon atoms.
You. ), Alcohols such as R ³¹Is halogenated carbonized
Hydrogen is preferred. Also, as a phenolic compound
A hydrocarbon having 1 to 20 carbon atoms in the α, α'-position of the hydroxyl group
Those substituted with element are preferable.

As the carboxylic acid, R is usually³²-COO
The one represented by H is used. R ³²Represents 1 to 1 carbon atoms
50 hydrocarbon groups or halogens having 1 to 50 carbon atoms
A halo group having 1 to 50 carbon atoms.
Genated hydrocarbon groups are preferred. Phosphorus compounds include P
Phosphoric acid having -OH bond, P-OR, P = O bond
Phosphate and phosphine oxide compounds having
Used well.

As the sulfonate, the following general formula (IX)
Is used.

Embedded image In the formula, M is an element belonging to Groups 1 to 14 of the periodic table. R ³³ is hydrogen, a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group having 1 to 20 carbon atoms. X is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon group having 1 to 20 carbon atoms. m is an integer of 1 to 7, and n is 1 ≦ n ≦ 7.

FIG. 1 shows a process for preparing the olefin polymerization catalyst according to the present invention.

Next, the olefin polymerization method will be described. The olefin polymerization method according to the present invention comprises (co) polymerizing olefin in the presence of the above-mentioned catalyst.
At the time of polymerization, the method of use and the order of addition of each component are arbitrarily selected, and the following methods are exemplified. (1) Component (A) and at least one component (B) selected from the group consisting of (B-1) an organometallic compound, (B-2) an organoaluminum oxy compound, and (B-3) an ionized ionic compound Simply referred to as "component (B)") in any order. (2) A method in which the catalyst in which the component (A) and the component (B) are brought into contact in advance is added to the polymerization reactor.

(3) A method in which the catalyst component in which the component (A) and the component (B) are brought into contact in advance and the component (B) are added to the polymerization reactor in an arbitrary order. In this case, the components (B) may be the same or different. (4) A method in which the catalyst component in which the component (A) is supported on the carrier (C) and the component (B) are added to the polymerization reactor in any order. (5) A method in which a catalyst in which the component (A) and the component (B) are supported on a carrier (C) is added to a polymerization reactor. (6) A method in which the catalyst component in which the component (A) and the component (B) are supported on the carrier (C) and the component (B) are added to the polymerization reactor in an arbitrary order. In this case, the components (B) may be the same or different.

(7) A method in which the catalyst component in which the component (B) is supported on the carrier (C) and the component (A) are added to the polymerization reactor in any order. (8) A method in which the catalyst component in which the component (B) is supported on the carrier (C), the component (A), and the component (B) are added to the polymerization reactor in an arbitrary order. In this case, the components (B) may be the same or different. (9) A method in which a component in which the component (A) is supported on the carrier (C) and a component in which the component (B) is supported on the carrier (C) are added to the polymerization vessel in an arbitrary order. (10) Component (A) supported on carrier (C), component (B) supported on carrier (C), and component (B)
To the polymerization vessel in any order. In this case, the components (B) may be the same or different.

(11) A method in which the component (A), the component (B), and the organic compound component (D) are added to the polymerization vessel in any order. (12) A method in which the component (B) and the component (D) are brought into contact in advance, and the component (A) is added to the polymerization reactor in an arbitrary order. (13) A method in which the component (B) and the component (D) supported on the carrier (C) and the component (A) are added to the polymerization vessel in an arbitrary order. (14) A method in which the catalyst component in which the component (A) and the component (B) are brought into contact in advance and the component (D) are added to the polymerization reactor in an arbitrary order.

(15) A method in which the catalyst component in which the component (A) and the component (B) are brought into contact in advance, and the component (B) and the component (D) are added to the polymerization reactor in any order. (16) A method in which the catalyst component in which the component (A) and the component (B) are brought into contact in advance and the component in which the component (B) and the component (D) are brought into contact in advance are added to the polymerization reactor in an arbitrary order. (17) A method in which the component in which the component (A) is carried on the carrier (C), the component (B), and the component (D) are added to the polymerization vessel in an arbitrary order. (18) A method in which the component in which the component (A) is supported on the carrier (C) and the component in which the component (B) and the component (D) are brought into contact in advance are added to the polymerization reactor in an arbitrary order.

(19) A method in which the component (A), the component (B), and the component (D) are brought into contact in advance in an arbitrary order, and a catalyst component is added to the polymerization reactor. (20) A method in which the catalyst component in which the component (A), the component (B) and the component (D) are brought into contact in advance, and the component (B) are added to the polymerization reactor in an arbitrary order. In this case, the components (B) may be the same or different. (21) A method in which a catalyst in which the components (A), (B) and (D) are supported on a carrier (C) is added to a polymerization reactor. (22) A method in which the catalyst component in which the component (A), the component (B) and the component (D) are supported on the carrier (C), and the component (B) are added to the polymerization reactor in an arbitrary order. In this case, component (B)
May be the same or different. The solid catalyst component in which the component (A) and the component (B) are supported on the carrier (C) may be prepolymerized with olefin.

In the olefin polymerization method according to the present invention,
An olefin polymer is obtained by polymerizing or copolymerizing olefin in the presence of the olefin polymerization catalyst as described above. In the present invention, the polymerization can be carried out by any of a liquid phase polymerization method such as solution polymerization and suspension polymerization or a gas phase polymerization method.

Specific examples of the inert hydrocarbon medium used in the liquid phase polymerization include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane and kerosene; cyclopentane, cyclopentane, and the like. Aliphatic hydrocarbons such as hexane and methylcyclopentane; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as ethylene chloride, chlorobenzene and dichloromethane, and mixtures thereof; It may itself be used as a solvent.

In carrying out the polymerization of olefin using the olefin polymerization catalyst as described above, the component (A)
Usually 10 ^-12 to 10 ^-2 mol per liter of reaction volume,
Preferably, it is used in such an amount that it becomes 10 ^-10 to 10 ^-3 mol. In the present invention, olefin can be polymerized with high polymerization activity even when the component (A) is used at a relatively low concentration.

The component (B-1) has a molar ratio [(B-1) / M] of the component (B-1) to the transition metal atom (M) in the component (A) of usually 0.01%. ~ 100,000, preferably 0.05 ~ 50
000 is used. The component (B-2) has a molar ratio [(B-2) / M] of the aluminum atom in the component (B-2) to the transition metal atom (M) in the component (A) of usually 10%.
It is used in such an amount that it becomes ５００500,000, preferably 20-100,000. The component (B-3) is obtained by a molar ratio of the component (B-3) to the transition metal atom (M) in the component (A) [(B-3) /
M] is usually used in an amount such that it becomes 1 to 10, preferably 1 to 5.

Component (D) is the same as component (B)
In the case of (B-1), the molar ratio [(D) / (B-1)] is usually 0.01.
Component, in an amount such that it is
In the case of (B-2), the molar ratio [(D) / (B-2)] between the component (D) and the aluminum atom in the component (B-2) is usually 0.001 to 0.001.
2, preferably in an amount such that 0.005-1
In the case of (B-3), the molar ratio [(D) / (B-3)] is usually 0.01.
-10, preferably 0.1-5.

The polymerization temperature of an olefin using such an olefin polymerization catalyst is usually from -50 to 200.
° C, preferably in the range of 0 to 170 ° C. The polymerization pressure is usually from normal pressure to 100 kg / cm ² , preferably from normal pressure to 50 kg / cm ² , and the polymerization reaction can be performed in any of a batch system, a semi-continuous system, and a continuous system. it can. 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. Furthermore, it can be adjusted by the difference of the component (B) used.

The olefin that can be polymerized with such an olefin polymerization catalyst is one having 2 carbon atoms.
Α-20 olefins such as 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-1,2,3,4,4a, 5,8,8a-octahydronaphthalene;

Polar monomers such as acrylic acid, methacrylic acid, fumaric acid, maleic anhydride, itaconic acid,
Α, β-unsaturated carboxylic acids such as itaconic anhydride, bicyclo [2.2.1] -5-heptene-2,3-dicarboxylic acid, and sodium, potassium, lithium, zinc, and magnesium salts thereof; Metal salts such as calcium salts; methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate Α, β-unsaturated carboxylate esters such as methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate; vinyl acetate, vinyl propionate, vinyl caproate, vinyl caprate , Vinyl laurate, vinyl stearate, vinyl trifluoroacetate Glycol ester compounds;
And unsaturated glycidyl such as glycidyl acrylate, glycidyl methacrylate, and monoglycidyl itaconate.

Further, vinylcyclohexane, diene or polyene may be used. The diene or polyene is a cyclic or chain compound having 4 to 30, preferably 4 to 20 carbon atoms and having two or more double bonds. Specifically, butadiene, isoprene,
4-methyl-1,3-pentadiene, 1,3-pentadiene, 1,4-
Pentadiene, 1,5-hexadiene, 1,4-hexadiene,
1,3-hexadiene, 1,3-octadiene, 1,4-octadiene, 1,5-octadiene, 1,6-octadiene, 1,7-octadiene, ethylidene norbornene, vinyl norbornene, dicyclopentadiene; 7-methyl- 1,6-octadiene, 4-ethylidene-8-methyl-1,7-nonadiene, 5,9-dimethyl-1,4,8-decatriene;

Further, aromatic vinyl compounds such as styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o, p-dimethylstyrene, o-ethylstyrene, m
Mono- or polyalkylstyrenes such as ethylstyrene and p-ethylstyrene; methoxystyrene, ethoxystyrene, vinylbenzoic acid, methyl vinylbenzoate, vinylbenzyl acetate, hydroxystyrene, o-chlorostyrene, p-chlorostyrene, divinylbenzene Functional group-containing styrene derivatives; and 3-phenylpropylene, 4-phenylpropylene, α-methylsterene, and the like.

The olefin polymerization catalyst according to the present invention exhibits a high polymerization activity and can obtain a polymer having a narrow molecular weight distribution. Furthermore, when two or more olefins are copolymerized, an olefin copolymer having a narrow composition distribution can be obtained.

The olefin polymerization catalyst according to the present invention can be used for copolymerizing an α-olefin and a conjugated diene. As the α-olefin used herein, the same number of carbon atoms as described above is 2 to 30, preferably 2
To 20 linear or branched α-olefins. Among them, ethylene, propylene, 1-butene, 1
-Pentene, 1-hexene, 4-methyl-1-pentene and 1-octene are preferred, and ethylene and propylene are particularly preferred. These α-olefins can be used alone or in combination of two or more.

Examples of the conjugated diene include 1,3
-Butadiene, isoprene, chloroprene, 1,3-cyclohexadiene, 1,3-pentadiene, 4-methyl-1,3-pentadiene, 1,3-hexadiene, 1,
Examples thereof include aliphatic conjugated dienes having 4 to 30 carbon atoms, preferably 4 to 20 carbon atoms, such as 3-octadiene. These conjugated dienes can be used alone or in combination of two or more.

In the present invention, an α-olefin and a non-conjugated diene or polyene can be further copolymerized. As the non-conjugated diene or polyene used,
1,4-pentadiene, 1,5-hexadiene, 1,4
-Hexadiene, 1,4-octadiene, 1,5-octadiene, 1,6-octadiene, 1,7-octadiene, ethylidene norbornene, vinylnorbornene, dicyclopentadiene, 7-methyl-1,6-octadiene, 4-ethylidene Examples thereof include -8-methyl-1,7-nonadiene and 5,9-dimethyl-1,4,8-decatriene.

Next, a method for producing a transition metal compound will be described.
explain.Method for producing transition metal compound  Transitions represented by general formulas (I), (II), (III) and (IV)
The metal compound is not particularly limited.
It can be manufactured as follows.

The ligand constituting the transition metal compound according to the present invention includes, for example, an o-aminophenol compound when A is an oxygen atom, and an o-aminophenol compound when A is a sulfur atom.
Aminothiophenol compounds, when A contains nitrogen o-
It can be obtained by using a phenylenediamine compound or the like as a raw material and then introducing a substituent into the amine moiety. Specifically, first, both starting compounds are dissolved in a solvent. As the solvent, those commonly used in such reactions can be used, and among them, an aqueous solvent is preferable. The resulting solution is then stirred from 0 ° C. under reflux for about 1 to 48 hours to give the corresponding ligand in good yield.

Thereafter, the ligand thus obtained is reacted with a compound containing a transition metal M, whereby a corresponding transition metal compound can be synthesized. Specifically, the synthesized ligand is dissolved in a solvent, and if necessary, contacted with a base to prepare a phenoxide salt, and then mixed with a metal compound such as a metal halide or a metal alkylate at a low temperature. -7
The mixture is stirred at 8 ° C. to room temperature or under reflux conditions for about 1 to 48 hours. As the solvent, those commonly used in such reactions can be used, and among them, polar solvents such as ether and tetrahydrofuran (THF), and hydrocarbon solvents such as toluene are preferably used. Further, as the base used when preparing the phenoxide salt, lithium salts such as n-butyllithium, metal salts such as sodium salts such as sodium hydride, and organic bases such as triethylamine and pyridine are preferable. However, the present invention is not limited to this. The number of ligands that react can be adjusted by changing the charge ratio of the transition metal M-containing compound to the ligand.

Further, depending on the properties of the compound, the corresponding transition metal compound can be synthesized by directly reacting the ligand with the metal compound without going through the preparation of the phenoxide salt. For example, a compound of the following formulas (I ′) to (III ′) (corresponding to the transition metal compounds (I) to (III), respectively) is reacted with a base to form a salt, and then reacted with a transition metal halide. And prepared. In addition, the following formula (I
The compound of V ′) (corresponding to the transition metal compound (IV)) is prepared by directly reacting with a transition metal halide.

Embedded image

Furthermore, the metal M in the synthesized transition metal compound can be exchanged for another transition metal by a conventional method. Further, for example, when any of R ^{1 to} R ¹² is a hydrogen atom, a substituent other than a hydrogen atom can be introduced at any stage of the synthesis.

[0213]

According to the present invention, a novel transition metal complex useful as a catalyst for olefin polymerization is provided. Further, the olefin polymerization catalyst according to the present invention has high polymerization activity for olefins. Furthermore, according to the olefin polymerization method of the present invention, an olefin (co) polymer can be produced with high polymerization activity.

[0214]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited to these Examples. The structure of the compound obtained in the synthesis example is 270M
Hz ¹ H-NMR (JEOL GSH-270), FT
-IR (SHIMAZU FTIR-8200D type),
FD-mass spectrometry (JEOL SX-102A type), metal content analysis (analysis by ICP method after dry incineration and dissolution of diluted nitric acid, equipment: SHIMAZU ICPS-8000 type),
Analysis of carbon, hydrogen and nitrogen contents (Heraus CHNO
Type) and the like. The intrinsic viscosity [η] is 1
Measured in decalin at 35 ° C.

Hereinafter, specific synthetic examples of the transition metal compound according to the present invention will be described. (Synthesis Example 1) <Synthesis of ligand represented by the following formula (L1)> 1 sufficiently substituted with nitrogen
In a 00 ml reactor, α-naphthyl aldehyde 3.22 was added.
g (20 mmol) of molecular sieve 3A and 5 ml of ethanol, and o-aminophenol2.
18 g (20 mmol) of ethanol solution (20 ml)
Was added dropwise. After completion of the dropwise addition, stirring was continued at room temperature for 8 hours. The reaction solution was filtered, and the filtrate was concentrated under reduced pressure to remove the solvent. Then, 40 ml of ethyl acetate and 40 ml of water were added again to carry out liquid separation. The oil layer was dried over sodium sulfate, concentrated under reduced pressure, and purified by column (developing solvent: hexane / ethyl acetate system) to obtain 3.3 g of a compound as a fluorescent yellow oil represented by the following formula (L1).
(67% yield).

Embedded image FD-mass spectrometry: (M ⁺ ) 247 ¹ H-NMR (CDCl ₃ ): 7.0-8.2 (m, 11H) 8.50 (s, 1H) 12.64 (s,
1H)

<Synthesis of Transition Metal Compound of the Following Formula (A-1)>
0.742 g (3.0 mmol) of the compound (L1) obtained above was placed in a 100 ml reactor sufficiently purged with argon.
And 15 ml of anhydrous diethyl ether, and the mixture was cooled to -78 ° C and stirred. 2.1 ml of n-butyl lithium
(N-hexane solution, 1.54 N, 3.3 mmol) in 5
The mixture was dropped over a period of minutes, and then slowly heated to room temperature.
After stirring at room temperature for 4 hours, the mixture was cooled again to -78 ° C and
₄ in 3.0 ml (decane solution, 0.5 N, 1.50 mm
ol) was added slowly. After the addition, the temperature was slowly raised to room temperature, and the mixture was heated under reflux for 6 hours. This reaction solution was concentrated under reduced pressure, and the precipitated solid was dried over 30 m of anhydrous dichloromethane.
1 to remove insolubles. The obtained dichloromethane solution was concentrated under reduced pressure, and the precipitated solid was dissolved in anhydrous diethyl ether / anhydrous methylene chloride solution (anhydrous diethyl ether:
After washing with 30 ml of anhydrous methylene chloride = 30 ml, further washing with 50 ml of hexane, and drying under reduced pressure, 0.31 g of a compound of an orange powder represented by the following formula (A-1) (34% yield) )Obtained.

Embedded image FD- Mass ^{spectrometry: (M +) 611 1 H} -NMR (CDCl 3): 7.0-8.4 (m, 24H) Elemental analysis: Ti 8.1% (calculated value 7.8%)

(Synthesis Example 2) <Synthesis of Transition Metal Compound of the Following Formula (B-1)> The compound (L1) obtained above was placed in a 100 ml reactor sufficiently purged with argon; 0.742 g (3.0 mmol) And THF1
5 ml was charged, cooled to -78 ° C, and stirred. to this
2.0 ml of n-butyllithium (n-hexane solution, 1.5 ml
4N, 3.10 mmol) was added dropwise over 5 minutes and then slowly warmed to room temperature. After stirring at room temperature for 4 hours, the mixture was cooled again to −78 ° C. and 0.35 g of ZrCl ₄ (1.0 g
0 mmol) was added slowly. After the addition, the temperature was slowly raised to room temperature, and stirring was continued for 8 hours. The reaction solution was concentrated under reduced pressure, and the precipitated solid was washed with 30 ml of dichloromethane to remove insolubles. The obtained methylene chloride solution was concentrated under reduced pressure, and the precipitated solid was dissolved in diethyl ether / methylene chloride solution (diethyl ether: methylene chloride = 10:
1) After washing with 30 ml, further washing with 50 ml of hexane and drying under reduced pressure, 0.15 g of an orange powder compound represented by the following formula (B-1) (yield: 15%)
Obtained.

Embedded image FD- Mass ^{spectrometry: (M +) 655 1 H} -NMR (CDCl 3): 7.0-8.1 (m, 24H) Elemental analysis: Zr 14.2% (calculated value 13.9%)

(Synthesis Example 3) <Synthesis of ligand represented by formula (L2)>
In a 00 ml reactor, 2,4-di-t-butylphenol 9.
Nitration of 18 g (30.0 mmol) with copper nitrate in acetic anhydride gave 2.12 g of 2-nitro-4,6-di-t-butylphenol (yield 28%). This was hydrogenated in an ethyl acetate solution in the presence of a palladium / carbon catalyst to give 2-amino-4,6-di-t-butylphenol.
84 g were obtained. (Yield 98%) Using 0.81 g (3.66 mmol) of 2-amino-4,6-di-t-butylphenol obtained here and 0.38 g (3.6 mmol) of benzaldehyde, the system of Synthesis Example 1 was used. In the same manner as in the synthesis of the ligand L1, 0.52 g of the compound of the following formula (L2) as a green-white crystal was obtained. (Yield 47%)

Embedded image FD-mass spectroscopy: (M ⁺ ) 309 ¹ H-NMR (CDCl ₃ ): 1.40 (s, 9H) 1.62 (s, 9H) 7.3-8.0 (m, 7
H) 8.75 (s, 1H) 12.10 (s, 1H)

<Synthesis of Transition Metal Compound of the Following Formula (A-2)>
Using 0.50 g of the ligand (L2), a transition metal compound (A-2) represented by the following formula was synthesized in the same manner as in Synthesis Example 1.
(Brown powder; yield 24%)

Embedded image FD-mass spectroscopy: (M ⁺ ) 735 ¹ H-NMR (CDCl ₃ ): 0.8-2.0 (m, 36H) 6.8-7.8 (m, 14H) 8.0
(brs, 2H) Elemental analysis: Ti 6.7% (calculated value 6.5%)

(Synthesis Example 4) <Synthesis of transition metal compound of the following formula (B-2)> Using 0.52 g (1.62 mmol) of ligand L2, the following formula (B- 0.4% of the transition metal compound shown in 2)
3 g (0.55 mmol) was synthesized. (Green powder; yield
67%)

Embedded image FD-mass spectroscopy: (M ⁺ ) 779 ¹ H-NMR (CDCl ₃ ): 0.7-1.8 (m, 36H) 6.8-7.8 (m, 14H) 8.0
(brs, 2H) Elemental analysis: Zr 11.2% (calculated value 11.7%)

(Synthesis Example 5) <Synthesis of Ligand of the Following Formula (L3)> Similarly, under an argon atmosphere, 1.00 g of 2-methyl-7-aminobenzothiazole was used.
(6.10 mmol) was dissolved in 15 ml of diethyl ether and, under ice-cooling, 0.66 g of trimethylsilyl chloride.
A solution of (6.10 mmol) in 10 ml of diethyl ether is added dropwise. After heating to room temperature, the mixture was stirred for 8 hours. The insolubles were removed by filtration, and the filtrate was concentrated under reduced pressure to obtain a crude compound of the following formula (L3).

Embedded image FD-Mass Spec: (M ⁺ ) 236

<Synthesis of Transition Metal Compound (C-3)> The compound (L3) obtained above; 0.71 g (converted to 3.0 mmol) and 15 ml of diethyl ether were charged into a 100 ml reactor sufficiently purged with argon. , Cooled to -78 ° C and stirred. 2.0 ml of n-butyl lithium (n-butyl lithium)
(Hexane solution, 1.54 N, 3.10 mmol) was added dropwise over 5 minutes, and then the temperature was slowly raised to 0 ° C. 0
After stirring at 1 ° C. for 1 hour, it was cooled again to −78 ° C. and VCl ₄ ;
A solution of 0.29 g (1.50 mmol) in 10 ml diethyl ether was slowly added. After the addition, the temperature was slowly raised to room temperature, and stirring was continued for 8 hours. The reaction solution was concentrated under reduced pressure, and the precipitated solid was washed with 30 ml of dichloromethane to remove insolubles. The obtained methylene chloride solution was concentrated under reduced pressure, and the precipitated solid was dissolved in diethyl ether / methylene chloride solution (diethyl ether: methylene chloride = 10:
1) After washing with 30 ml, further washing with 50 ml of hexane and drying under reduced pressure, 0.08 g (yield 9%) of a black-green powder represented by the following formula (C-3) was obtained.

Embedded image FD-mass spectroscopy: (M ⁺ ) 592 ¹ H-NMR (CDCl ₃ ): 7.0-7.5 (m, 7H) Elemental analysis: V 8.8% (calculated 8.6%)

(Synthesis Example 6) <Synthesis of Ligand of the Following Formula (L4)> 1.84 g (8.3 mmol) of 2-amino-4,6-di-t-butylphenol;
F in 60 ml, and p-toluenesulfonyl chloride; 1.69 g (8.7 mmol) in 15 ml aqueous solution
Was added. 1.85 g of potassium carbonate was added to the reaction solution.
(13.3 mmol), and the mixture was stirred for 5 hours under reflux. After cooling to room temperature, ethyl acetate was added to separate oil and water, and the oil layer was concentrated and purified by silica gel column to obtain 1.74 g of a compound of the following formula (L4) as a white solid. (Yield 5
6%)

Embedded image FD-Mass Spectroscopy: (M ⁺ ) 375 ¹ H-NMR (CDCl ₃ ): 1.01 (s, 9H) 1.38 (s, 9H) 2.38 (s, 3H)
5.90 (s, 1H) 6.15 (s, 1H) 6.62 (s, 1H) 7.1-7.7 (m, 4H) 13.
34 (s, 1H)

<Synthesis of Transition Metal Compound (A-4)> The following formula (A-4) was prepared in the same manner as in Synthesis Example 1 using 0.56 g (1.5 mmol) of the ligand (L4). 0.12 g of a transition metal compound was synthesized. (Dark brown powder; yield 16%)

Embedded image FD-mass spectroscopy: (M ⁺ ) 492 ¹ H-NMR (CDCl ₃ ): 1.00 (s, 18H) 1.25 (s, 18H) 2.35 (s, 3H)
6.1-6.7 (m, 4H) 7.1-7.7 (m, 8H) Elemental analysis: Ti 9.9% (calculated 9.7%)

(Synthesis Example 7) <Synthesis of Transition Metal Compound of the Following Formula (B-4)> Ligand (L4)
Using 0.56 g (1.50 mmol) of the transition metal compound 0.2 represented by the following formula (B-4) in the same manner as in Synthesis Example 2.
0 g was synthesized. (Brown powder; 25% yield)

Embedded image FD-mass spectroscopy: (M ⁺ ) 535 ¹ H-NMR (CDCl ₃ ): 1.11 (s, 18H) 1.33 (s, 18H) 2.32 (s, 3H)
6.0-6.7 (m, 4H) 7.0-7.8 (m, 8H) Elemental analysis: Zr 17.0% (calculated 17.0%)

(Synthesis Example 8) <Synthesis of Ligand: Formula (L5)> 8-Aminoquinoline
0 g (6.9 mmol) and 1.34 g (10.0 mmol) of 2,5-dimethylbenzaldehyde in 20 m of ethanol
After stirring at room temperature for 4 hours, the solvent was distilled off, and the residue was purified by a silica gel column to give 1.61 g of a compound (L5) shown below as a red-orange oil. (Yield 90%)

Embedded image FD-mass spectroscopy: (M ⁺ ) 260 ¹ H-NMR (CDCl ₃ ): 2.10 (s, 3H) 2.44 (s, 3H) 6.5-7.8 (m, 9
H) 8.56 (s, 1H)

<Synthesis of Transition Metal Compound of the Following Formula (D-5)>
0.47 g (3.6 mmol) of cobalt dichloride and 15 ml of THF are placed in a 100 ml reactor which is sufficiently purged with argon.
And 1.00 g (3.8 g) of compound (L5) was added at room temperature.
(mmol) in 10 ml of THF, a yellow precipitate was deposited. The mixture was further stirred for 1 hour, and the precipitate was filtered off with a glass filter. The obtained solid was reprecipitated with a diethyl ether / methylene chloride solution, washed with 50 ml of hexane, and dried under reduced pressure to obtain the following formula (D-5) 1.10 g (yield 78%) of a brown powder represented by was obtained.

Embedded image FD-mass spectrometry: (M ⁺ ) 390 Elemental analysis: Co 15.0% (calculated value 15.1%) Note that all operations in the above synthesis were performed under an argon or nitrogen atmosphere, and a commercially available anhydrous solvent was used as a solvent.

Next, examples of the polymerization method according to the present invention will be described. (Example 1) 250 ml of toluene was charged into a 500 ml-volume glass autoclave sufficiently purged with nitrogen,
The liquid and gas phases were saturated with ethylene. Thereafter, methylaluminoxane was added in an amount of 1.25 mmol in terms of aluminum atoms, and subsequently, 0.005 mmol of the titanium compound (A-1) obtained in Synthesis Example 1 was added, and polymerization was started. The reaction was carried out at 25 ° C. for 30 minutes in an atmosphere of ethylene gas at normal pressure. After completion of the polymerization, the reaction product was poured into a large amount of methanol to precipitate the entire polymer, and hydrochloric acid was added, followed by filtration through a glass filter. After drying the polymer under reduced pressure at 80 ° C. for 10 hours, 0.03 g of polyethylene (PE) was obtained. The polymerization activity was 12 g / mmol-Ti · hr, and the intrinsic viscosity [η] of the obtained polyethylene was 7.5 dl / g.

(Example 2) Under the same conditions as in Example 1, 0.005 mmol of compound (B-1) was added to initiate polymerization. After reacting at 25 ° C. for 30 minutes in an atmosphere of ethylene gas at normal pressure, the same post-treatment as in Example 1 was performed to obtain 0.11 g of polyethylene (PE). Polymerization activity is 44 g / mmol
-Zr · hr, the intrinsic viscosity of the obtained polyethylene [η]
Was 9.0 dl / g.

(Example 3) Under the same conditions as in Example 1, 0.005 mmol of compound (A-2) was added to initiate polymerization. After a reaction at 25 ° C. for 30 minutes in an atmosphere of ethylene gas at normal pressure, the same post-treatment as in Example 1 was performed to obtain 0.08 g of polyethylene (PE). Polymerization activity is 32 g / mmol
-Ti · hr, the intrinsic viscosity of the obtained polyethylene [η]
Was 9.1 dl / g.

(Example 4) Under the same conditions as in Example 1, 0.005 mmol of compound (B-2) was added to initiate polymerization. After reacting at 25 ° C. for 30 minutes in an atmosphere of ethylene gas at normal pressure, the same post-treatment as in Example 1 was performed to obtain 0.10 g of polyethylene (PE). Polymerization activity is 40 g / mmol
-Zr · hr, the intrinsic viscosity of the obtained polyethylene [η]
Was 3.3 dl / g.

(Example 5) Internal volume 5 sufficiently purged with nitrogen
250 ml of toluene in a 00 ml glass autoclave
and the liquid and gaseous phases in 100 liters of ethylene
/ hr saturated. Thereafter, 0.25 mmol of triisobutylaluminum (TIBA) was added, followed by compound (C
-3) in 0.005 mmol of triphenylcarbenium tetrakis (pentafluorophenyl) borate (Tr
0.006 mmol of B) was added to initiate polymerization. After reacting for 1 hour at 25 ° C under ethylene gas atmosphere at normal pressure,
The polymerization was stopped by adding a small amount of isobutanol. After completion of the polymerization, the reaction product was poured into a large amount of methanol to precipitate the entire amount of the polymer, and hydrochloric acid was added, followed by filtration through a glass filter. After drying the polymer under reduced pressure at 80 ° C. for 10 hours, 0.03 g of polyethylene (PE) was obtained. The polymerization activity was 12 g / mmol-V · hr, and the intrinsic viscosity [η] was 5.0 dl / g.

(Example 6) Under the same conditions as in Example 1, 0.005 mmol of compound (A-4) was added to initiate polymerization. After reacting at 25 ° C. for 60 minutes in an atmosphere of ethylene gas at normal pressure, the same post-treatment as in Example 1 was performed to obtain 0.62 g of polyethylene (PE). Polymerization activity is 124 g / mm
ol-Ti · hr, and the intrinsic viscosity [η] of the obtained polyethylene was 18.3 dl / g.

(Example 7) Under the same conditions as in Example 5, 0.005 mmol of compound (A-4) was added to initiate polymerization. After reacting at 25 ° C. for 30 minutes in an atmosphere of ethylene gas at normal pressure, the same post-treatment as in Example 1 was performed to obtain 0.25 g of polyethylene (PE). Polymerization activity is 100 g / mm
ol-Ti · hr, and the intrinsic viscosity [η] of the obtained polyethylene was 8.3 dl / g.

(Example 8) Under the same conditions as in Example 1, 0.005 mmol of compound (A-4) was added to initiate polymerization. After a reaction at 25 ° C. for 30 minutes in an atmosphere of ethylene gas at normal pressure, the same post-treatment as in Example 1 was performed to obtain 0.03 g of polyethylene (PE). Polymerization activity is 12 g / mmol
-Zr · hr, the intrinsic viscosity of the obtained polyethylene [η]
Was 7.6 dl / g.

(Example 9) Internal volume 5 sufficiently purged with nitrogen
250 ml of toluene in a 00 ml glass autoclave
and the liquid and gaseous phases in 100 liters of ethylene
Saturated with / hr. Thereafter, 0.25 mmol of triisobutylaluminum (TIBA) was added, followed by compound (C
The polymerization was started by adding 0.005 mmol of -3). After reacting at 25 ° C. for 30 minutes under an atmosphere of ethylene gas at normal pressure, the polymerization was stopped by adding a small amount of isobutanol. After completion of the polymerization, the reaction product was poured into a large amount of methanol to precipitate the entire amount of the polymer, and hydrochloric acid was added, followed by filtration through a glass filter. After drying the polymer under reduced pressure at 80 ° C. for 10 hours, 0.03 g of polyethylene (PE)
Obtained. The polymerization activity was 12 g / mmol-Co · hr, and the intrinsic viscosity [η] of the obtained polyethylene was 3.1 dl / g.

[Brief description of the drawings]

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

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Makoto Mitani 6-1-2, Waki, Waki-cho, Kuga-gun, Yamaguchi Prefecture Within Mitsui Chemicals, Inc. (72) Inventor Terunori Fujita Wakoku, Waki-cho, Kuga-gun, Yamaguchi Prefecture 1-2 Chome, Mitsui Chemicals, Inc.

Claims (12)

[Claims] 1. A transition metal compound represented by the following general formula (I): (Wherein, M represents a transition metal atom of Groups 3 to 11 of the periodic table, m represents an integer of 1 to 6, and A represents an oxygen atom, a sulfur atom, a selenium atom, or a bonding group- R represents a nitrogen atom having R ⁵ , and B represents —R ⁹ and —R ¹⁰ , or ＣC (R ¹¹ ) R ¹² as a bonding group for N, and R ^{1 to} R
¹² may be the same or different from each other, and represent a hydrogen atom,
Halogen atom, hydrocarbon group, heterocyclic compound residue, oxygen-containing group, nitrogen-containing group, boron-containing group, sulfur-containing group,
A phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group, two or more of which may be connected to each other to form a ring (R ¹ and R ⁹ or R ¹
And R ¹⁰ are connected to form an aromatic ring), and when m is 2 or more, R ¹ contained in one ligand
To R ¹² and R ¹ contained in another ligand.
To one group of R ¹² may be bonded;
R ¹ each other, R ² together, R ³ together, R ⁴ together, R ⁵ each other, each other R ^9, R ¹⁰ together, R ¹¹ together, R ¹² to each other may be the same or different, n is the M A number that satisfies the valence,
X represents a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, a halogen-containing group, a heterocyclic compound residue, or a silicon-containing residue. A group, a germanium-containing group or a tin-containing group, and when n is 2 or more, a plurality of groups represented by X may be the same or different from each other, and a plurality of groups represented by X are bonded to each other To form a ring. ) 2. A transition metal compound represented by the following general formula (II): (Wherein, M represents a transition metal atom belonging to Groups 3 to 11 of the periodic table, m represents an integer of 1 to 6, and A represents a bonding group —R ⁵
An oxygen atom, a sulfur atom, a selenium atom, or
As bonding group, -R ⁵ and -R ⁶ or ^{= C (R 7), R} 8
And B represents -R as a bonding group for N.
^And R ^{1 to} R ⁹ may be the same or different from each other, and represent a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, A containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group, and two or more of these may be connected to each other to form a ring,
Further, when m is 2 or more, R contained in one ligand
^{One of} R ^{1 to} R ⁹ and R ¹ contained in another ligand;
And one of R ⁹ to R ⁹ may be bonded to R ¹
, R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ may be the same or different, and n is the valence of M Is a number that satisfies
Represents a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, a halogen-containing group, a heterocyclic compound residue, and a silicon-containing group. Represents a germanium-containing group or a tin-containing group, and when n is 2 or more, a plurality of groups represented by X may be the same or different from each other, and a plurality of groups represented by X are bonded to each other A ring may be formed. ) 3. A transition metal compound represented by the following general formula (III): (Wherein, M represents a transition metal atom of Groups 3 to 11 of the periodic table, m represents an integer of 1 to 3, and A represents an oxygen atom, a sulfur atom, a selenium atom, or a bonding group. represents nitrogen atom with -R ^5, B is, -R a binding group N ⁹
Wherein R ^{1 to} R ⁹ may be the same or different from each other, and represent a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group,
A sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group;
Or more may be connected to each other to form a ring, and when m is 2 or more, R ¹ contained in one ligand
To one group of R ⁹ and R ¹ to R ⁹ contained in another ligand.
One group of R ⁹ may be bonded, and R ^{1 s} , R ^{2 s} , R ^{3 s} , R ^{4 s} , R ^{5 s} , and R ^{9 s} may be the same or different. , N is a number satisfying the valence of M, and X is a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group. Represents a halogen-containing group, a heterocyclic compound residue, a silicon-containing group, a germanium-containing group or a tin-containing group, and when n is 2 or more, a plurality of groups represented by X may be the same or different from each other Also, a plurality of groups represented by X may combine with each other to form a ring. ) 4. A transition metal compound represented by the following general formula (IV): (Wherein, M represents the periodic table 3 to 11 transition metal atom of Group, m represents an integer of 1 to 3, A is a bond group -R ⁵
An oxygen atom, a sulfur atom, a selenium atom, or
As bonding group, -R ⁵ and -R ⁶ or ^{= C (R 7), R} 8
A nitrogen atom having the following formula:
Shows the R ⁹ and -R ¹⁰ or ^{= C (R 11) R 12} ,, R 1 ~
R ¹² may be the same or different from each other, and represent a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, A silicon-containing group, a germanium-containing group, or a tin-containing group, two or more of which may be linked to each other to form a ring, and when m is 2 or more, one coordination well and one of the radicals R ¹ to R ¹² contained in the child, be binding and one of the radicals R ¹ to R ¹² contained in other ligands, R ¹ together ,
R ² together, R ³ together, with R ⁴ together, R ⁵ each other, R ⁶ to each other, each other R ^7, R ⁸ together, R ⁹ together, R ¹⁰ together, R ¹¹ together, R ¹² together are mutually the same or different And n is a number that satisfies the valence of M, and X is a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group. Represents a containing group, a halogen-containing group, a heterocyclic compound residue, a silicon-containing group, a germanium-containing group or a tin-containing group. When n is 2 or more, a plurality of groups represented by X are the same or different. And a plurality of groups represented by X may be bonded to each other to form a ring. ) 5. The method according to claim 1, wherein in the formulas (I) to (IV), M is a transition metal atom selected from Groups 3 to 5 and 8 to 10 of the periodic table. The transition metal compound as described. 6. (A) any one or more of the transition metal compounds according to claim 1 and (B) (B-1) an organometallic compound, (B-2) an organoaluminum oxy compound, and (B-3) An olefin polymerization catalyst comprising at least one compound selected from the group consisting of compounds which react with the transition metal compound (A) to form an ion pair. 7. The olefin polymerization catalyst according to claim 6, wherein the (A) transition metal compound is a compound in which A is an oxygen atom in the general formulas (I) to (IV). 8. The catalyst for olefin polymerization according to claim 6, wherein the transition metal compound (A) is a compound in which A is a sulfur atom in the general formulas (I) to (IV). 9. The catalyst for olefin polymerization according to claim 6, wherein the (A) transition metal compound is a compound in which A is a selenium atom in the general formulas (I) to (IV). 10. The transition metal compound (A) in the above general formulas (I) to (IV), wherein A is -R ⁵ , -R ⁵ and -R ⁶ , or ＝ C (R ⁷ ) R ⁸ The olefin polymerization catalyst according to claim 6, which is a compound having a bonding group represented by the following formula: 11. The transition metal compound (A), and (B-1):
At least one compound selected from the group consisting of an organometallic compound, (B-2): an organoaluminum oxy compound, and (B-3): a compound which reacts with the transition metal compound (A) to form an ion pair ( The catalyst for olefin polymerization according to any one of claims 6 to 10, comprising B) and a carrier (C). 12. A method for polymerizing olefins, comprising polymerizing or copolymerizing olefins in the presence of the catalyst for olefin polymerization according to claim 6. Description: