JP2000119313A - Polymerization of olefin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain high molecular weight olefin polymers having narrow distributions of the molecular weights and the compositions in high polymerization reactivity by reacting a transition metal compound and an organometallic compound in a specific condition. SOLUTION: In the (co)polymerization of an olefin in the presence of an olefin polymerization catalyst comprising (A) a transition metal compound expressed by the formula (M is a transition metal selected from the third to eleventh groups of the periodic table; (m) is an integer of 1 to 6; R1 to R6 are each H, a halogen, a hydrocarbon or the like; (n) is an integer satisfying the valency of M; X is H, a halogen, a hydrocarbon or the like), (B) an organometallic compound (e.g.; trimethyl aluminum or the like), and (C) a compound forming an ion pair by reaction with the component (A) (e.g.; a Lewis acid or the like), the component (A) and the component (B) are brought into contact in the practical absence of the olefin, and then the olefin polymerization catalyst is contacted with the olefin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an olefin polymerization method, and more particularly, to a catalyst comprising a specific transition metal compound, an organometallic compound and a compound which reacts with the transition metal compound to form an ion pair. The present invention relates to an olefin polymerization method for polymerizing or copolymerizing an olefin using the method.

[0002]

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

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

Further, as a recently new olefin polymerization catalyst, the present applicant has filed Japanese Patent Application No. 10-132706,
A transition metal compound having a salicylaldimine ligand represented by the following general formula has been proposed. This complex shows high olefin polymerization activity.

[0005]

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However, an olefin polymerization catalyst comprising the transition metal compound, an organometallic compound, and a compound which reacts with the transition metal compound to form an ion pair has a high polymerization activity, but has a high molecular weight. There is a disadvantage that it is difficult to obtain.

Under these circumstances, the present inventors have conducted intensive studies and found that a transition metal compound having a salicylaldimine ligand, an organometallic compound, and an ion pair are formed by reacting with the transition metal compound. When the olefin is polymerized in the presence of an olefin polymerization catalyst comprising the compound to be reacted with the olefin polymerization catalyst, the transition metal compound and the organometallic compound are brought into contact with each other in a state where the olefin is not substantially present. The present inventors have found that an olefin polymer can be obtained with a high polymerization activity by contacting with, and completed the present invention.

[0008]

An object of the present invention is to provide a high-molecular-weight olefin (co) polymer having a high polymerization activity, a narrow molecular weight distribution and a narrow composition distribution when polymerizing using a transition metal compound having a salicylaldimine ligand. It aims to provide a way to generate.

[0009]

SUMMARY OF THE INVENTION An olefin polymerization method according to the present invention comprises:
(A) a transition metal compound represented by the following general formula (I);
(B) an organometallic compound and (C) a transition metal compound (A)
When the olefin is polymerized or copolymerized in the presence of an olefin polymerization catalyst comprising a compound which forms an ion pair by reacting with the above, the above-mentioned transition metal compound (A) and organometallic compound (B) are substantially After the olefin is contacted in the absence of olefin, the olefin polymerization catalyst is contacted with the olefin;

[0010]

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(Wherein, M represents a transition metal atom selected from Groups 3 to 11 of the periodic table, m represents an integer of 1 to 6,
R ^{1 to} R ⁶ 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, a sulfur-containing group, A 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, R ¹ To R ⁶ , two of which may be linked, n is a number satisfying the valency 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, a halogen-containing group, a heterocyclic compound residue, a silicon-containing group, a germanium-containing group or a tin-containing group, and n is 2 or more. In the case of, the groups represented by X are 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. )

[0012]

DETAILED DESCRIPTION OF THE INVENTION The olefin polymerization method of the present invention will be specifically described below. In this specification, the term "polymerization" means not only homopolymerization,
The term “polymer” may be used in a sense that encompasses not only a homopolymer but also a copolymer in some cases.

The olefin polymerization method according to the present invention comprises:
(A) a transition metal compound represented by the general formula (I),
(B) an organometallic compound and (C) a transition metal compound (A)
Are polymerized or copolymerized in the presence of an olefin polymerization catalyst comprising a compound which forms an ion pair by reacting with an olefin. First, each catalyst component forming the olefin polymerization catalyst of the present invention will be described.

(A) Transition metal compound The (A) transition metal compound used in the present invention is a compound represented by the following general formula (I).

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(Note that N ... M generally indicates coordination, but in the present invention, it may or may not be coordinated.) In the general formula (I), M represents a transition metal atom of Groups 3 to 11 of the periodic table (Group 3 also includes lanthanoids), preferably a metal atom of Groups 3 to 9 (Group 3 also includes lanthanoids), more preferably Is a metal atom of groups 3 to 5 and 9 and particularly preferably a metal atom of group 4 or 5. Specifically, scandium, titanium, zirconium, hafnium, vanadium, niobium, tantalum,
Cobalt, rhodium, yttrium, chromium, molybdenum, tungsten, manganese, rhenium, iron, ruthenium and the like, preferably scandium, titanium, zirconium, hafnium, vanadium, niobium, tantalum, cobalt, rhodium, and more preferably,
Titanium, zirconium, hafnium, cobalt, rhodium, vanadium, niobium, tantalum 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. R ^{1 to} R ⁶ 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 connected to each other to form a ring;

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, such as vinyl, allyl, and isopropenyl;
30, preferably 2 to 20 linear or branched alkenyl groups; ethynyl, propargyl and the like having 2 carbon atoms
A linear or branched alkynyl group having a carbon number of 3 to 30, preferably 2 to 20; a cyclic saturated hydrocarbon group having a carbon number of 3 to 30, preferably 3 to 20, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and adamantyl. A cyclic unsaturated hydrocarbon group having 5 to 30 carbon atoms such as cyclopentadienyl, indenyl, and fluorenyl; and 6 carbon atoms such as phenyl, benzyl, naphthyl, biphenylyl, terphenyl, phenanthryl and anthryl.
To 30, preferably 6 to 20 aryl groups; tolyl, is
Examples include alkyl-substituted aryl groups such as o-propylphenyl, t-butylphenyl, dimethylphenyl, di-t-butylphenyl, and the like.

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 be substituted with another hydrocarbon group, for example, an aryl-substituted alkyl group such as benzyl and cumyl. Furthermore, the hydrocarbon group is a heterocyclic compound residue;
Alkoxy groups, aryloxy groups, ester groups, ether groups, acyl groups, carboxyl groups, carbonate groups, hydroxy groups, peroxy groups, oxygen-containing groups such as carboxylic anhydride groups; amino groups, imino groups, amide groups, imide groups,
Hydrazino group, hydrazono group, nitro group, nitroso group,
A nitrogen-containing group such as a cyano group, an isocyano group, a cyanate ester group, an amidino group, a diazo group, or an amino group having an ammonium salt; a boron-containing group such as a borandiyl group, a borantriyl group, or a diboranyl group; a mercapto group;
Thioester group, dithioester group, alkylthio group,
Arylthio group, thioacyl group, thioether group, thiocyanate group, isothiocyanate group, sulfone ester group, sulfonamide group, thiocarboxyl group, dithiocarboxyl group, sulfo group, sulfonyl group,
Sulfur-containing groups such as a sulfinyl group and a sulfenyl group;
It may have a phosphorus-containing group such as a phosphide group, 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, etc., a linear or branched alkyl group having 1 to 30, preferably 1 to 20 carbon atoms; phenyl, naphthyl, biphenylyl, terphenyl, phenanthryl, anthryl, etc. Aryl groups having 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms;
And a substituted aryl group in which 1 to 5 substituents such as an aryl group or an aryloxy group having 6 to 30 carbon atoms, preferably an aryl group or an aryloxy group having 6 to 30 carbon atoms, and preferably 6 to 20 carbon atoms are preferable. .

Oxygen-containing groups, nitrogen-containing groups, boron-containing groups,
Examples of the sulfur-containing group and the phosphorus-containing group include the same as those exemplified above. Heterocyclic compound residues include pyrrole, pyridine, pyrimidine, quinoline, nitrogen-containing compounds such as triazine, furans, oxygen-containing compounds such as pyran, residues such as sulfur-containing compounds such as thiophene, and heterocyclic compounds thereof. Examples include groups in which the compound residue is further substituted with a substituent such as an alkyl group or an alkoxy group having 1 to 30, preferably 1 to 20 carbon atoms.

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 the silicon of the silicon-containing group is replaced with germanium and tin. Next, the examples of R ^{1 to} R ⁶ 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 and the like, and aryloxy groups include phenoxy and 2,6-dimethylphenoxy. , 2,4,6-trimethylphenoxy and the like; acyl groups include formyl group, acetyl group, benzoyl group, p-chlorobenzoyl group, p-methoxybensoyl group and the like; and ester groups include acetyloxy and benzoyl groups. Preferred are oxy, methoxycarbonyl, phenoxycarbonyl, p-chlorophenoxycarbonyl and the like.

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, ethylthio, etc., arylthio groups include phenylthio, methylphenylthio, naltylthio, etc., and thioester groups include acetylthio, benzoylthio, methylthiocarbonyl, and phenylthio groups. Carbonyl and the like, and sulfonate groups such as methyl sulfonate, ethyl sulfonate and phenyl sulfonate; and sulfonamide groups such as phenylsulfonamide, N-methylsulfonamide, and N-methyl-p-toluenesulfonamide. Are preferred.

Preferably, R ⁶ is a substituent other than hydrogen. That is, R ⁶ is preferably a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a boron-containing group, a sulfur-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group. In particular, R ⁶ is a halogen atom, a hydrocarbon group, a heterocyclic compound residue, a hydrocarbon-substituted silyl group, a hydrocarbon-substituted siloxy group, an alkoxy group, an alkylthio group, an aryloxy group, an arylthio group, an acyl group, an ester group, a thioester. Group, an amide group, an amino group, an imide group, an imino group, a sulfone ester group, a sulfonamide group, a cyano group, a nitro group or a hydroxy group, and more preferably a halogen atom, a hydrocarbon group, or a hydrocarbon-substituted silyl group. Preferably, there is.

Preferred hydrocarbon groups for R ⁶ include:
Methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, neopentyl, 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.

Preferred hydrocarbon-substituted silyl groups for R ⁶ 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.

In the present invention, R ⁶ has 3 to 30 carbon atoms, preferably 3 to 2 carbon atoms, such as isopropyl, isobutyl, sec-butyl, tert-butyl and neopentyl.
A branched alkyl group of 0, a group in which a hydrogen atom of these groups is substituted with an aryl group having 6 to 30, preferably 6 to 20 carbon atoms (such as a cumyl group), adamantyl, cyclopropyl, cyclobutyl, cyclopentyl, Cyclohexyl or the like having 3 to 30, preferably 3 to 2 carbon atoms.
0 is preferably a group selected from cyclic saturated hydrocarbon groups, or phenyl, naphthyl, fluorenyl,
6 to 3 carbon atoms such as anthryl and phenanthryl
It is also preferably 0, preferably 6 to 20 aryl groups or hydrocarbon-substituted silyl groups.

R ^{1 to} R ⁶ 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 hetero atom such as a nitrogen atom. And these rings may further have a substituent.

When m is 2 or more, R ^{1 to} R ⁶
And two groups may be linked to each other.
Further, when m is 2 or more, R ¹ and R ² , R ² and R ^2
3 together, R ⁴ together, R ⁵ each other, R ⁶ to each other may be the same or different from each other.

N is a number that satisfies the valence of M, and is specifically 0 to 5, preferably 1 to 4, and more preferably 1 to 3.
Is an integer. 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. Group, germanium-containing group, or tin-containing group. When n is 2 or more, they may be the same or different.

Examples of the halogen atom include fluorine, chlorine, bromine and iodine. As the hydrocarbon group, the aforementioned R
^{The same} ones as exemplified for ^{1 to} R ⁶ can be mentioned. Specifically, alkyl groups such as methyl, ethyl, propyl, butyl, hexyl, octyl, nonyl, dodecyl, and eicosyl; cycloalkyl groups having 3 to 30 carbon atoms such as cyclopentyl, cyclohexyl, norbornyl, and adamantyl; vinyl, Alkenyl groups such as propenyl and cyclohexenyl; arylalkyl groups such as benzyl, phenylethyl and phenylpropyl; phenyl, tolyl, dimethylphenyl, trimethylphenyl, ethylphenyl, propylphenyl, biphenylyl, naphthyl, methylnaphthyl, anthryl and phenanthryl Examples include, but are not limited to, aryl groups. These hydrocarbon groups also include halogenated hydrocarbons, specifically, groups in which at least one hydrogen of a hydrocarbon group having 1 to 20 carbon atoms has been replaced with halogen.

Of these, those having 1 to 20 carbon atoms are preferred. As the heterocyclic compound residue, the aforementioned R
^{The same} ones as exemplified for ^{1 to} R ⁶ can be mentioned.

Examples of the oxygen-containing group include the same ones as those described above for R ^{1 to} R ^6. Specific examples include a hydroxy group; an alkoxy group such as methoxy, ethoxy, propoxy, and butoxy; phenoxy, methyl Aryloxy groups such as phenoxy, dimethylphenoxy and naphthoxy;
Arylalkoxy groups such as phenylmethoxy and phenylethoxy; acetoxy groups; carbonyl groups, and the like, but are not limited thereto.

Examples of the sulfur-containing group include the same as those exemplified above in R ^{1 to} R ⁶ , 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 catenate, benzylsulfinate, p-toluenesulfinate, trimethylbenzenesulfinate, and 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 ones as those exemplified for R ⁶ can be mentioned, and specifically, an amino group; an alkylamino group such as methylamino, dimethylamino, diethylamino, dipropylamino, dibutylamino, dicyclohexylamino; 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 ^6, 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 groups as those exemplified above for R ^{1 to} R ⁶ , and specific examples include a group in which silicon of the silicon-containing group is replaced with germanium. .

Specific examples of the tin-containing group include the aforementioned R ^1-
The same groups as those exemplified for R ⁶ can be mentioned, and more specifically, a group in which silicon of the silicon-containing group is substituted with tin is mentioned.

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 .

As the aluminum-containing group, specifically, 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. As such a transition metal compound represented by the general formula (I), there is a compound represented by the following general formula (Ia) in which R ¹ is not bonded to each other.

[0047]

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(Wherein M represents a transition metal atom selected from Groups 3 to 11 of the periodic table, m represents an integer of 1 to 6,
R ^{1 to} R ⁶ 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, a sulfur-containing group, A silicon-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, R Two of the groups represented by ^{1 to} R ⁶ may be linked (however, R ¹ is not bonded to each other), and n is a number satisfying the valence of M; 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, a silicon-containing group, a germanium-containing group or a tin-containing group; May be the same or different from each other, and the groups represented by X may be bonded to each other to form a ring. In the formula (Ia), M, m, R ^{1 to} R ⁶ , n and X have the same meanings as in the above formula (I).

In the transition metal compound represented by the general formula (Ia), m is 2, and two of the groups represented by R ^{1 to} R ⁶ (excluding R ¹ ) are linked. The compound described is, for example, a compound represented by the following general formula (Ia ′).

[0050]

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In the formula (Ia ′), M, R ^{1 to} R ⁶ and X are the same as those in the general formula (I), and R ^{11 to} R
¹⁶ is the same as R ^{1 to} R ⁶ . M, R ^{1 to} R ⁶ , R ¹¹ to
The following groups are particularly preferred as R ¹⁶ and X.

R ^{1 to} R ⁶ and R ^{11 to} R ¹⁶ 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, It indicates a boron-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, a tin-containing group, or the like. Two or more groups, preferably adjacent groups, of R ^{1 to} R ⁶ and R ^{11 to} R ¹⁶ are connected to each other to form an aliphatic ring, an aromatic ring, or a hydrocarbon ring containing a hetero atom such as a nitrogen atom. May be formed.

Y ′ bonds at least one or more groups selected from R ^{1 to} R ⁶ and at least one or more groups selected from R ^{11 to} R ¹⁶ (provided that R ¹ and R ¹¹ are Excluding the case where is bonded.) It is a bonding group or a single bond.

Examples of the bonding group represented by Y ′ include groups containing at least one element selected from oxygen, sulfur, carbon, nitrogen, phosphorus, silicon, selenium, tin, boron and the like. the -O -, - S -, - chalcogen atom-containing groups such as Se-; -NH -, - N ( CH 3)
_{2 -, - PH -, -} P (CH 3) 2 - a nitrogen or phosphorus atom-containing groups such _{as; -CH 2 -, - CH 2} -CH 2 -, - C
A hydrocarbon group having 1 to 20 carbon atoms such as (CH ₃ ) ₂ —; a cyclic unsaturated hydrocarbon residue having 6 to 20 carbon atoms such as benzene, naphthalene and anthracene;
A heterocyclic compound residue having 3 to 20 carbon atoms including a heteroatom such as quinoline, thiophene and furan;
A silicon atom-containing group such as H ₂ —, —Si (CH ₃ ) ₂ —,
Tin atom-containing groups such as SnH ₂ — and —Sn (CH ₃ ) ₂ —;
_{-BH -, - B (CH 3} ) -, - and boron atom-containing groups such as BF-, 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 element, and is individually Sc (III), Ti (III), Ti (III).
(IV), Zr (III), Zr (IV), Hf (IV), V (IV), Nb
(V), Ta (V), Co (II), Co (III), Rh (II), R
h (III) and Rh (IV) are shown, but not limited thereto. Among these, Ti (IV), Zr (I
V) and Hf (IV) are preferred.

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. 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. For example, when the metal is Ti (IV), n = 2, when Zr (IV), n = 2, and when Hf (IV), n = 2.

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In the above examples, Me is a methyl group, Et
Represents an ethyl group, iPr represents an i-propyl group, tBu represents a tert-butyl group, and Ph represents a phenyl group. More specifically, the case where Ti is used as the central metal is as follows. Further, compounds in which titanium is replaced with zirconium, hafnium, cobalt or rhodium in these compounds may also be mentioned.

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As the transition metal compound represented by the general formula (I), m is 2 in the general formula (I) represented by the following general formula (Ib), and two R There are compounds in which ¹ is bonded to each other.

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(Wherein, M represents a transition metal atom belonging to Groups 3 to 11 of the periodic table, and R ^{1 to} R ¹⁰ may be the same or different from each other, and represent a hydrogen atom, a halogen atom, a hydrocarbon group, a hetero atom, 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 which are linked to each other 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, Represents a containing group, an aluminum-containing group, a phosphorus-containing group, 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 represented by X Groups are the same or different Even well, and a plurality of groups represented by X may be bonded to each other to form a ring, Y
Represents a divalent linking group containing at least one element selected from the group consisting of oxygen, sulfur, carbon, nitrogen, phosphorus, silicon, selenium, tin, and boron. It is a group consisting of three or more atoms.

In the general formula (Ib), R ⁶ or R ¹⁰
At least one, especially both, 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, Alternatively, it is preferably a tin-containing group.

In the general formula (Ib), M, R ^{1 to} R ¹⁰
As X and X, the same groups as those of M, R ^{1 to} R ⁶ and X described for the compound of the general formula (I) can be used. X is, in particular, a halogen atom, having 1 carbon atom.
Up to 20 hydrocarbon or sulfonate groups are preferred.
When n is 2 or more, the ring formed by linking two or more Xs to each other may be an aromatic ring or an aliphatic ring.

Y is oxygen, sulfur, carbon, nitrogen, phosphorus,
Silicon, selenium, a divalent bonding group containing at least one element selected from the group consisting of tin and boron,
When it is a hydrocarbon group, it is a bonding group consisting of three or more carbon atoms.

These bonding groups Y preferably have 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, these bonding groups may have a substituent.

As the divalent linking group (Y), specifically,
A chalcogen atom such as O-, -S-, -Se-; -NH
-, -N (CH ₃ )-, -PH-, -P (CH ₃ )-and other nitrogen or phosphorus atom-containing groups; -SiH _2- , -Si (C
A silicon atom-containing group such as H ₃ ) _2- ; -SnH _2- , -Sn
(CH _{3) 2} - tin atom-containing groups such as; -BH -, - B
And a boron atom-containing group such as (CH ₃ ) — and —BF—. The hydrocarbon group _{- (CH 2) 4 -,} - (C
_{H 2) 5 -, - (} CH 2) 6 - saturated hydrocarbon group having 3 to 20 carbon atoms such as, cyclohexylidene group, a cyclic saturated hydrocarbon group such as cyclohexylene group, these saturated hydrocarbon groups A part of 1 to 10 hydrocarbon groups, fluorine, chlorine,
A group substituted with a hetero atom such as halogen such as bromine, oxygen, sulfur, nitrogen, phosphorus, silicon, selenium, tin or boron, and a cyclic hydrocarbon having 6 to 20 carbon atoms such as benzene, naphthalene or anthracene. Group, pyridine, quinoline, thiophene, furan and the like, and a residue of a cyclic compound having 3 to 20 carbon atoms including a hetero atom.

The following are specific examples of the transition metal compound represented by the above general formula (Ib), but are not limited thereto.

[0099]

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[0100]

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In the above examples, Me represents a methyl group, Ph represents a phenyl group, and tBu represents a tert-butyl group. In the present invention, a transition metal compound in which titanium metal is replaced with a metal other than titanium, such as zirconium or hafnium, in the compounds described above can also be used.

The method for producing such a transition metal compound (A) is not particularly limited, and can be produced, for example, as follows.

First, the arrangement constituting the transition metal compound (A)
The ligand is a salicylaldehyde compound of the formula R¹-NH
_TwoPrimary amine compounds (R¹In the general formula (I)
R ¹Is synonymous with ), For example, aniline compounds or
Is obtained by reacting with an alkylamine compound.
It is. Specifically, both starting compounds are dissolved in a solvent.
You. Solvents commonly used for such reactions should be used.
Can be used, but especially methanol, ethanol, etc.
Coal solvents or hydrocarbon solvents such as toluene are preferred.
No. Then, the obtained solution is refluxed for about 1 hour from room temperature.
After stirring for ~ 48 hours, the corresponding ligand is in good yield
can get.

When synthesizing the ligand compound,
An acid catalyst such as formic acid, acetic acid, and toluenesulfonic acid may be used. Further, when molecular sieves, magnesium sulfate or sodium sulfate is used as a dehydrating agent, or when dehydration is performed by Dean Stark, it is effective for the progress of the reaction.

Next, by reacting the ligand thus obtained with a compound containing a transition metal M, 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. , -78
The mixture is stirred for about 1 to 48 hours at a temperature from C to room temperature or under reflux. As the solvent, those which are 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 a base used when preparing a phenoxide salt, a lithium salt such as n-butyllithium, a metal salt such as a sodium salt such as sodium hydride, and an organic base such as triethylamine and pyridine are preferable. Not as long.

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.

Further, 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 ^{6 in} the general formula (I) is H, a substituent other than H can be introduced at any stage of the synthesis.

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

Other Transition Metal Compounds Specific examples of the transition metal compounds other than the above transition metal compound (A) include, but are not limited to, the following transition metal compounds. (a-1) Transition metal imide compound represented by the following formula (Ic)

[0110]

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In the formula, M represents a transition metal atom selected from 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 be 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 nitrogen, oxygen, And a hydrocarbon group substituted with a substituent containing at least one element selected from phosphorus, sulfur and silicon.

In the groups represented by R ^{21 to} R ²⁴ , two or more of these groups, preferably adjacent groups, may be connected to each other to form a ring. q shows the integer of 0-4.

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. Represents a group, and 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 (Id) represented by the following formula

[0114]

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In the formula, M represents a transition metal atom selected from Groups 3 to 6 of the periodic table, and is preferably titanium, zirconium or hafnium. R ′ and R ″ may be the same or different from each other, and represent a hydrogen atom, a carbon atom having 1 to 1;
A hydrocarbon group having 50, 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 .

M is an integer of 0 to 2. n is 1 to 5
Is an integer. A represents an atom belonging to Groups 13 to 16 of the periodic table, and specifically, boron, carbon, nitrogen, oxygen, silicon,
Examples include phosphorus, sulfur, germanium, selenium, tin, and the like, and preferably carbon or silicon. 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.

P is an integer from 0 to 4. 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. Is shown. When p is 2 or more, a plurality of groups represented by X may be the same or different from each other. Among them, X is preferably a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a sulfonate group. (a-3) A transition metal diphenoxy compound represented by the following formula (I
-e)

[0119]

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

B is a hydrocarbon group having 1 to 50 carbon atoms,
A halogenated hydrocarbon group having 1 to 50 carbon atoms, R ¹ R ² Z
A group represented by the formula: oxygen or sulfur, wherein R ¹
And R ² is 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 (If)

[0123]

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In the formula, M represents a transition metal atom selected from 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.

A represents 0 or 1. R may be the same or different, and each represents a hydrogen atom, a halogen atom,
A hydrocarbon group, a halogenated hydrocarbon group, a silyl group substituted with a hydrocarbon group, or a hydrocarbon group substituted with a substituent containing at least one element selected from nitrogen, oxygen, phosphorus, sulfur and silicon; Two or more Rs may be connected to each other to form a ring.

B is an integer of 1 to 4, and when b is 2 or more, each [((R) _a ) ₅ -X ₅ ] group may be the same or different, and furthermore, Rs are crosslinked. May be. c
Is a number that satisfies the valence of M.

Y 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. Represents a group.

When c is 2 or more, a plurality of groups represented by Y may be the same or different from each other, and a plurality of groups represented by Y may be bonded to each other to form a ring. in (a-5) formula RB (Pz) ₃ transition metal compound formula represented by MX _n, M is the periodic table 3 to 11 group transition metal compound,
R represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group having 1 to 20 carbon atoms;
z represents a pyrazoyl group or a substituted pyrazoyl group.

N is a number satisfying the valence of M. X 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 n is 2 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) a transition metal compound (Ig) represented by the following formula:

[0130]

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In the formula, Y ₁ and Y ₃ may be the same as or different from each other, and are an element belonging to Group 15 of the periodic table, and Y ₂ is an element belonging to Group 16 of the periodic table. R ^{21 to} R
²⁸ may be the same or different from each other, and represent a hydrogen atom,
A halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group,
It represents a sulfur-containing group or a silicon-containing group, and two or more of these may be linked to each other to form a ring. (a-7) Compound represented by the following formula (Ih) and Periodic Tables Nos. 8 to 1
Compound with Group 0 transition metal atom

[0132]

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In the formula, R ^{31 to} R ³⁴ may be the same or different from each other, and may be a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon having 1 to 20 carbon atoms. And 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 (Ii)

[0134]

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

R ^{41 to} R ⁴⁸ may be the same or different from each other, and may be a hydrogen atom, a halogen atom, a carbon atom having 1 to 2 carbon atoms.
A hydrocarbon group of 0, 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. May be formed.

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 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 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.

(B) Organometallic Compound As the (B) organometallic compound used in the present invention, specifically, the following Periodic Table Groups 1, 2 and 12, 1
A group 3 organometallic compound is used.

[0140] (B-1a) In the formula _{^{R a m Al (OR b)}} n H p X q ( wherein, R ^a and R ^b may be the same or different from each other, the number of carbon atoms from 1 to 15 , Preferably 1 to 4 hydrocarbon groups, X 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. ) An organoaluminum compound represented by the formula:

[0141] (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 metal of Group 1 of the periodic table represented by the formula and aluminum.

(B-1c) Formula R ^a R ^b M ³ (where R ^a and R ^b may be the same or different and each have 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms) A hydrocarbon group, and M ³ is Mg, Zn or Cd.) A dialkyl compound of a metal belonging to Group 2 or Group 12 of the periodic table.

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

More specific examples of the organoaluminum compound belonging to (B-1a) include trimethylaluminum, triethylaluminum, trin-butylaluminum, tripropylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum. Tri-n-alkyl aluminum such as triisopropyl aluminum, triisobutyl aluminum, tri sec-butyl aluminum, tri tert-
Butylaluminum, tri2-methylbutylaluminum, tri3-methylbutylaluminum, tri2-methylpentylaluminum, tri3-methylpentylaluminum, tri4-methylpentylaluminum, tri2-methylhexylaluminum, tri3-methylhexyl Aluminum, tribranched alkyl aluminum such as tri-2-ethylhexyl aluminum; tricycloalkyl aluminum such as tricyclohexyl aluminum and tricyclooctyl aluminum; triaryl aluminum such as triphenyl aluminum and tritolyl aluminum; dialkyl aluminum such as diisobutyl aluminum hydride Hydride; (i-C ₄ H ₉ ) _x
Trialkenyl aluminum such as triisoprenyl aluminum represented by Al _y (C ₅ H ₁₀ ) _z (where x, y and z are positive numbers and z ≧ 2x); isobutylaluminum methoxy Aluminum alkoxides such as dimethyl, isobutylaluminum ethoxide and isobutylaluminum isopropoxide; dialkylaluminum alkoxides such as dimethylaluminum methoxide, diethylaluminum ethoxide and dibutylaluminum butoxide; alkyls such as ethylaluminum sesquiethoxide and butylaluminum sesquibutoxide Aluminum sesquialkoxide; ^Ra
_2.5 Al (OR ^b ) _0.5 partially alkylated alkyl aluminum having an average composition such as _0.5 ; diethyl aluminum phenoxide, diethyl aluminum (2,6-di-t-butyl-4-methylphenoxide), ethyl Aluminum bis (2,6-di-t-butyl-4-methylphenoxide), diisobutylaluminum (2,6-di-t-butyl-4-)
Dialkylaluminum aryloxides such as methylphenoxide) and isobutylaluminum bis (2,6-di-t-butyl-4-methylphenoxide); dimethylaluminum chloride, diethylaluminum chloride, dibutylaluminum chloride, diethylaluminum bromide, diisobutylaluminum chloride Alkyl aluminum sesquihalides such as ethyl aluminum sesquichloride, butyl aluminum sesquichloride and ethyl aluminum sesquibromide; partially such as alkyl aluminum dihalides such as ethyl aluminum dichloride, propyl aluminum dichloride and butyl aluminum dibromide Alkylaluminum halides; diethylaluminum hydride Dialkylaluminum hydrides such as dibutylaluminum hydride; other partially hydrogenated alkylaluminums such as ethylaluminum dihydride, alkylaluminum dihydrides such as propylaluminum dihydride; ethylaluminum ethoxycyclolide, butylaluminum butoxycyclolide, ethylaluminum Partially alkoxylated and halogenated alkyl aluminums such as ethoxy bromide can be mentioned.

Further, a compound similar to (B-1a) can also be used, and examples thereof include an organic aluminum compound in which two or more aluminum compounds are bonded via a nitrogen atom. Specifically, as such a compound,
(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 and LiAl (C ₇ H ₁₅ ) ₄ can be exemplified. In addition, (B) organometallic compounds include methyllithium, ethyllithium, propyllithium, butyllithium, methylmagnesium bromide, methylmagnesium chloride, ethylmagnesium bromide, ethylmagnesium chloride, propylmagnesium bromide, propylmagnesium 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.

Among the organometallic compounds (B), organoaluminum compounds are preferred. The organometallic compound (B) as described above is used alone or in combination of two or more.

(C) Reaction with the transition metal compound (A)
Compound forming an on-pair The compound (C) which forms an ion pair by reacting with the transition metal compound (A) used in the present invention (hereinafter referred to as "ionized ionic compound") is disclosed in JP-A-1-5019.
No. 50, Japanese Unexamined Patent Publication No.
-179005, JP-A-3-179006, JP-A-3-207703, JP-A-3-207
And Lewis acids, ionic compounds, borane compounds and carborane compounds described in US Pat. No. 704, US Pat. No. 5,321,106. Furthermore, heteropoly compounds and isopoly compounds can also be mentioned.

Specifically, examples of the Lewis acid include BR
₃ (R is a phenyl group or a fluorine atom which may have a substituent such as fluorine, a methyl group, and a trifluoromethyl group.), 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 (IV).

[0152]

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In the formula, R ¹⁹ includes H ⁺ , carbonium cation, oxonium cation, ammonium cation, phosphonium cation, cycloheptyltrienyl cation, and ferrocenium cation having a transition metal.

R ^{20 to} R ²³ may be the same or different and are an organic group, 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.

Specific examples of the ammonium cation include trialkylammonium cations such as a trimethylammonium cation, a triethylammonium cation, a tripropylammonium cation, a tributylammonium cation, and a tri (n-butyl) ammonium cation; Nium cation, N,
N, N-dialkylanilinium cations such as N-diethylanilinium cation and N, N-2,4,6-pentamethylanilinium cation; dialkylammonium cations such as di (isopropyl) ammonium cation and dicyclohexylammonium cation No.

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

As R ¹⁹ , 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 can also be mentioned.

Specific examples of the trialkyl-substituted ammonium salt include, for example, triethylammonium tetra (phenyl) boron, tripropylammonium tetra (phenyl) boron, tri (n-butyl) ammonium tetra (phenyl) boron, 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 dialkylammonium 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,
An N, N-diethylanilinium pentaphenylcyclopentadienyl complex, a boron compound represented by the following formula (V) or (VI), and the like can also be mentioned.

[0163]

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

[0165]

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

Specific examples of the carborane compound include, for example, 4-carbanonaborane (14), 1,3-dicarbanonaborane (13), 6,9-dicarbadecaborane (14), dodecahydride-1-phenyl- 1,3-dicarbanonaborane,
Dodecahydride-1-methyl-1,3-dicarbanonaborane, undecahydride-1,3-dimethyl-1,3-dicarbanonaborane, 7,8-dicarboundecaborane (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-carbadeca Borate, tri (n-butyl) ammonium bromo-1-carbadecaborate, tri (n-butyl) ammonium 6-carbadecaborate (14), tri (n-butyl) ammonium 6-carbadecaborate (1
2), tri (n-butyl) ammonium 7-carboundecaborate (13), tri (n-butyl) ammonium 7,8-
Dicarboundecaborate (12), tri (n-butyl)
Ammonium 2,9-dicarboundecaborate (12),
Tri (n-butyl) ammonium dodecahydride-8-
Methyl-7,9-dicarboundecaborate, tri (n-butyl) ammonium undecahydride-8-ethyl-7,9-
Dicarbaune decaborate, tri (n-butyl) ammonium undecahydride-8-butyl-7,9-dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-8-allyl-7,9-dicarbaune Decaborate, tri (n-butyl) ammonium undecahydride-9-trimethylsilyl-7,8-dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-4,6-dibromo-7-carboundecaborate Salts of anions such as tri (n-butyl) ammonium bis (nonahydride-1,3-dicarbanonaborate) cobaltate (III), tri (n-butyl) ammonium bis (undecahydride-7,8 -Dicarboundecaborate) ferrate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarboundecaborate) co Belt salt (III), tri (n- butyl) ammonium bis (undecapeptide 7,8-dicarbaundecaborate deca borate)
Nickelate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-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-dicarboundecaborate) ferrate (III) (N-butyl) ammonium bis (nonahydride-7,8-dimethyl-7,8-dicarboundecaborate) chromate (III), tri (n-butyl) ammonium bis (tribromooctahydride-7,8 -Dicarboundecaborate) cobaltate (II
I), tris [tri (n-butyl) ammonium] bis (undecahydride-7-carboundecaborate) chromate (III), bis [tri (n-butyl) ammonium]
Bis (undecahydride-7-carboundecaborate) manganate (IV), bis [tri (n-butyl) ammonium] bis (undecahydride-7-carboundecaborate) cobaltate (III), Bis [tri (n-butyl) ammonium] bis (undecahydride-7-
Metal carborane anions such as (carboundecaborate) nickelate (IV).

The heteropoly compound includes an atom selected from silicon, phosphorus, titanium, germanium, arsenic, and tin;
It is composed of 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, and salts of these acids, for example, metals of Group 1 or 2 of the Periodic Table, specifically lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium ,barium Salts with and organic salts of triphenyl ethyl salts, can be used but not limited thereto.

The above-mentioned (C) ionized ionic compounds are used alone or in combination of two or more. The catalyst for olefin polymerization used in the present invention may be a carrier (D) as described later, if necessary, together with (A) a transition metal compound, (B) an organometallic compound, and (C) an ionized ionic compound. Can also be used.

(D) Carrier The (D) carrier optionally used in the present invention is an inorganic or organic compound, and is a granular or fine solid.

Of these, the inorganic compound is preferably a porous oxide, inorganic chloride, clay, clay mineral or ion-exchange layered compound. As the porous oxide, specifically, SiO ₂ , Al ₂ O ₃ , MgO, ZrO, TiO ₂ , B
_{Use of 2} O ₃ , CaO, ZnO, BaO, ThO _2, etc., or composites or mixtures containing them, such as natural or synthetic zeolites, SiO ₂ —MgO, SiO ₂ —Al ₂
O ₃ , SiO ₂ -TiO ₂ , SiO ₂ -V ₂ O ₅ , SiO ₂ -C
r 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.

[0172] The above-mentioned inorganic oxide is made of 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 ,
A carbonate, a sulfate, a nitrate, and an oxide component such as Al (NO ₃ ) ₃ , Na ₂ O, K ₂ O, and Li ₂ O may be contained.

The properties of such a porous oxide vary depending on the kind and the production method, but 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, at 10
It is used by firing at 0 to 1000 ° C, preferably 150 to 700 ° C.

The 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 in the present invention is usually composed mainly of a clay mineral. Further, the ion-exchangeable layered compound used in the present invention is a compound having a crystal structure in which planes formed by ionic bonds and the like are stacked in parallel with a weak binding force to each other, and contained ions are exchangeable. . 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 and ionic crystalline compounds having a layered crystal structure such as hexagonal dense packing type, antimony type, CdCl ₂ type, CdI ₂ type, etc. Compounds and the like can be exemplified.

Examples of such clays and clay minerals include kaolin, bentonite, kibushi clay, gairome clay, allophane, hissingelite, pyrophyllite, plum group, montmorillonite group, vermiculite, ryokudeite group, palygorskite, kaolinite, Nacrite, dickite, halloysite, and the like. As the ion-exchangeable layered compound, α-Zr (HAsO ₄ ) ₂ .H
₂ O, α-Zr (HPO ₄ ) ₂ , α-Zr (KPO ₄ ) ₂ .3H ₂
O, α-Ti (HPO ₄ ) ₂ , α-Ti (HAsO ₄ ) ₂ .H ₂
O, α-Sn (HPO ₄ ) ₂ .H ₂ O, γ-Zr (HP
O ₄ ) ₂ , γ-Ti (HPO ₄ ) ₂ , γ-Ti (NH ₄ PO ₄ ) _2.
Crystalline acidic salts of polyvalent metals such as H ₂ O and the like can be mentioned.

Such clays, clay minerals or ion-exchangeable layered compounds preferably have a pore volume of at least 20 mm in radius measured by mercury porosimetry of at least 0.1 cc / g.
Those having 0.3 to 5 cc / g are particularly preferred. Here, the pore volume is measured by a mercury intrusion method using a mercury porosimeter in a range of a pore radius of 20 to 3 × 10 ⁴ Å.

The volume of pores having a radius of 20 ° or more is 0.1 cc /
When a material smaller than g is used as a carrier, a high polymerization activity tends to be hardly obtained. The clay and clay mineral used in the present invention are preferably subjected to a chemical treatment.
Chemical treatment includes surface treatment to remove impurities adhering to the surface, treatment that affects the crystal structure of clay, etc.
Either can be used. Specific examples of the chemical treatment include acid treatment, alkali treatment, salt treatment, and organic substance treatment. The acid treatment increases the surface area by removing impurities on the surface and eluting cations such as Al, Fe, and Mg in the crystal structure. Alkali treatment destroys the crystal structure of the clay, resulting 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 is a layered compound in which the interlayer is expanded by using the ion-exchange property to exchange the exchangeable ion between the layers with another large bulky ion. You may. Such a bulky ion plays a role of a support for supporting the layered structure, and is usually called a pillar. Introducing another substance between layers of the layered compound in this way is called intercalation. Examples of the guest compound to be intercalated include cationic inorganic compounds such as TiCl ₄ and ZrCl ₄ , Ti (OR) ₄ , Zr (OR) ₄ , PO (OR) ₃ ,
Metal alkoxides such as B (OR) ₃ (R is a hydrocarbon group or the like), [Al ₁₃ O ₄ (OH) ₂₄ ] ⁷⁺ , [Zr ₄ (OH) ₁₄ ] ²⁺ ,
And metal hydroxide ions such as [Fe ₃ O (OCOCH ₃ ) ₆ ] ⁺ . These compounds are used alone or in combination of two or more. When intercalating these compounds, Si (OR) ₄ , Al (O
Polymers obtained by hydrolyzing metal alkoxides (R is a hydrocarbon group, etc.) such as R) ₃ and Ge (OR) ₄ , SiO ₂
Colloidal inorganic compounds, etc. can also 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-exchangeable 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 clays or clay minerals, and particularly preferred are montmorillonite, vermiculite, pectolite, 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:
(A) a transition metal compound, (B) an organometallic compound,
(C) An ionizable ionic compound and, if necessary, a carrier (D) and, if necessary, a specific organic compound (E) as described later can also be contained.

(E) Organic Compound Component In the present invention, the (E) organic compound component is used as needed for the purpose of improving polymerization performance and physical properties of a produced polymer. Such organic compounds include, but are not limited to, alcohols, phenolic compounds, carboxylic acids, phosphorus compounds, sulfonates, and the like.

As the alcohols and phenolic compounds, those represented by R ³¹ —OH are usually used.
Here, R ³¹ represents a hydrocarbon group having 1 to 50 carbon atoms or a halogenated hydrocarbon group having 1 to 50 carbon atoms.

As the alcohols, those in which R ³¹ is a halogenated hydrocarbon are preferred. Further, as the phenolic compound, a compound in which the α, α′-position of the hydroxyl group is substituted by a hydrocarbon having 1 to 20 carbon atoms is preferable.

As the carboxylic acid, generally, R³²-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.

As the phosphorus compound, phosphoric acids having a P—O—H bond, P-OR, phosphates having a P ＝ O bond, and phosphine oxide compounds are preferably used.
As the sulfonate, one represented by the following general formula (VII) is used.

[0190]

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.

In the present invention, when polymerizing an olefin in the presence of an olefin polymerization catalyst comprising the transition metal compound (A), the organometallic compound (B) and the ionized ionic compound (C), After the transition metal compound (A) and the organometallic compound (B) are brought into contact with each other in a state where the olefin is not substantially present, the olefin polymerization catalyst is brought into contact with the olefin. Here, in the present invention, the state in which the olefin is not substantially present means a state in which the olefin is not present in the transition metal compound (A) in an equivalent amount or more. FIG. 1 shows an example of a method for preparing an olefin polymerization catalyst used in the present invention.

The contact between the transition metal compound (A) and the organometallic compound (B) is usually performed in a solution state. Specifically, for example, a solution or suspension in which the component (A) is dissolved or suspended in a saturated hydrocarbon or an aromatic hydrocarbon is brought into contact with the component (B). When the component (A) is in a suspended state,
Stirring is performed until a uniform solution is obtained.

The order of contact may be such that the component (B) is added to the solution or suspension containing the component (A), or the solution or suspension containing the component (A) is added to the component (B). . The contact between the component (A) and the component (B) is performed at -78 ° C to 100 ° C,
It is preferably carried out at a temperature of 0 ° C to 80 ° C. The contact time is usually 30 seconds to 20 hours, preferably 1 minute to 10 hours, particularly preferably 1 minute to 5 hours.

When the component (A) and the component (B) are brought into contact with each other, the quantitative ratio of the two components is determined by the molar ratio of the transition metal atom (M) to the component (B) in the component (A) [(B) / M], usually from 0.1 to 100,000, preferably from 1.0 to 1000
0, particularly preferably in the range of 2.0 to 5000.

In the present invention, at least the component (A) and the component (B) among the catalyst components forming the olefin polymerization catalyst are brought into contact with each other in a state where the olefin is not substantially present. Component (C) may be contacted together. Alternatively, one of the components (A) and (B) may be supported on the component (D) and then contacted with the other component.

Component (A), Component (B) and Component (C)
When the component (A) and the component (B) are brought into contact with each other, it is preferable that the contact product of the component (A) and the component (B) is brought into contact with the component (C). Component (C)
Is preferably brought into contact with a contact product of the component (A) and the component (B) in a state of being dissolved or suspended in a saturated hydrocarbon, an aromatic hydrocarbon or a halogenated hydrocarbon.

The contact temperature between the component (C) and the contact product of the component (A) and the component (B) is -78 ° C to 100 ° C, preferably 0 ° C to 80 ° C, and the contact time is usually 10 ° C. The time is from 2 seconds to 5 hours, preferably from 1 minute to 2.5 hours, particularly preferably from 1 minute to 1 hour.

When the component (C) and the contact product of the component (A) and the component (B) are brought into contact with each other, the amount ratio of the component (C) and the contact product is determined as follows. The molar ratio of the component (A) to the transition metal atom (M) [(C) / M] is usually 1 to 1
0, preferably 1-5.

The contact product of the component (A) and the component (B) or the contact product of the component (A), the component (B) and the component (C) which have been brought into contact with each other as described above have an olefin as it is. The contact may be fed to the reactor or the contact may be fed to the reactor with the olefin. In addition, component (A)
The contact product between the component (B) and the contact product between the component (A), the component (B) and the component (C) may be supported on the component (D).

Apart from the component (B) brought into contact with the component (A) as described above, the same or different from the above-mentioned component (B) for the purpose of inactivating the water and impurities of the polymerization system. Component (B) can be added separately to the reactor.

In the polymerization, component (A), component (B),
Component (C) or a contact thereof is added to the reactor in the following manner. (1) A method in which a contact product of the component (A) and the component (B) and the component (C) are added to the reactor in an arbitrary order. (2) Contact product between component (A) and component (B), component (B)
And adding the component (C) to the reactor in any order. In this case, the components (B) may be the same or different. (3) A method in which a contact product of the component (A), the component (B), and the component (C) is added to a reactor. (4) A method in which a contact product of the component (A), the component (B), and the component (C) and the component (B) are added to the reactor in an arbitrary order. In this case, the components (B) may be the same or different. (5) A contact product of the component (A) and the component (B) is used as the component (D)
A method in which the catalyst component and the component (C) supported on a carrier are added to a reactor in any order. (6) A method in which a contact product of the catalyst component in which the component (A) is carried on the component (D) and the component (B) and the component (C) are added to the reactor in an arbitrary order. (7) A method in which a contact product of the catalyst component in which the component (A) is supported on the component (D) and the component (B), the component (B) and the component (C) are added to the reactor in an arbitrary order. In this case, the components (B) may be the same or different. (8) Contact product between component (A) and component (B), component (C)
Is added to the reactor in any order. (9) Contact product between component (A) and component (B), component (C)
Is added to the reactor in any order of the catalyst component carrying the component (D) and the component (B). (10) A method in which a catalyst component in which a contact product of component (A) and component (B) is supported on component (D), component (B) and component (C) are added to the reactor in any order. In this case, the components (B) may be the same or different. (11) A method in which a catalyst component in which a contact product of the component (A), the component (B), and the component (C) is supported on the component (D) is added to a reactor. (12) A method in which a catalyst component in which a contact product of the component (A), the component (B), and the component (C) is supported on the component (D) and the component (C) are added to the reactor in any order. In this case, the components (B) may be the same or different.

In each polymerization method, (E)
In the method (5), (6), (7), (10) to (12), wherein the organic compound component can be added at any time, the catalyst component supported on the carrier is prepolymerized with an olefin. When the olefin is polymerized in the presence of the above-mentioned catalyst, the component (A) is usually used in an amount of 10 ^-12 to 10 ^-2 mol, preferably 10 ^-10 mol, per liter of the reaction volume.
It is used in such an amount that it becomes ^10-3 mol. In the present invention, the olefin can be polymerized with high polymerization activity even when the component (A) is used at a relatively low concentration.

The molar ratio of the component (B) to the transition metal atom (M) in the component (A) [(B) / M] is usually 0.1 to 1
00000, preferably 0.5 to 50,000, particularly preferably 1.0 to 10,000.

Component (C) has a molar ratio [(C) / M] of component (C) to transition metal atom (M) in component (A) of usually 1 to 10, preferably 1 to 5. Used in such amounts.

The component (E) is used in an amount such that the molar ratio [(E) / (B)] is usually 0.01 to 10, preferably 0.1 to 5, with respect to the component (B). . In the present invention, the polymerization can be carried out by any of a liquid phase polymerization method such as a solution polymerization and a 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, cyclohexane, Alicyclic hydrocarbons such as methylcyclopentane; aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as ethylene chloride, chlorobenzene, and dichloromethane, and mixtures thereof; It can also be used as a solvent.

The olefin polymerization temperature 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
Under a condition of 50 kg / cm ² , the polymerization reaction can be carried out by any of a batch system, a semi-continuous system, and a continuous system. Further, the polymerization can be performed in two or more stages having different reaction conditions.

[0210] 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 amount of the component (A) used.

The olefin which can be polymerized by the method of the present invention is a linear or branched α-olefin having 2 to 30, preferably 2 to 20 carbon atoms, for example, ethylene, propylene, 1-butene. , 2-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; having 3 to 3 carbon atoms
0, preferably 3 to 20, cyclic olefins such as cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, 2-methyl
1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene; 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 anhydride, and their sodium, potassium, lithium and zinc salts Metal salts such as salts, magnesium salts and calcium salts; methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, 2-acrylate acrylate Α, β-unsaturated carboxylic esters such as ethylhexyl, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, and isobutyl methacrylate Vinyl acetate, vinyl propionate, vinyl caproate, vinyl caprate, vinyl laurate, vinyl stearate,
Vinyl esters such as vinyl trifluoroacetate; unsaturated glycidyls such as glycidyl acrylate, glycidyl methacrylate, and monoglycidyl itaconate; vinyl chloride; Further, vinylcyclohexane, diene, polyene, or the like can be used.

As the diene or polyene, a cyclic or chain compound having 4 to 30, preferably 4 to 20 carbon atoms and having two or more double bonds is used. 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, 4,8-dimethyl-1,4,8-decatriene; further, aromatic vinyl compounds such as styrene and o-methyl Styrene, m-methylstyrene, p-methylstyrene, o, p-dimethylstyrene, o-ethylstyrene, m-ethylstyrene, p-
Mono- or polyalkylstyrenes such as ethylstyrene; functional-group-containing styrenes such as methoxystyrene, ethoxystyrene, vinylbenzoic acid, methyl vinylbenzoate, vinylbenzyl acetate, hydroxystyrene, o-chlorostyrene, p-chlorostyrene, and divinylbenzene Derivatives; and 3-phenylpropylene, 4-phenylpropylene, α-methylstyrene, and the like. These olefins can be used alone or in combination of two or more.

The olefin polymerization method 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.

[0214]

According to the olefin polymerization method of the present invention, a polymer having a high polymerization activity, a very high molecular weight, and a narrow molecular weight distribution and composition distribution is produced.

[0215]

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

In this example, the intrinsic viscosity ([η]) was measured at 135 ° C. in decalin.

[0219]

Example 1 250 ml of toluene was charged into a glass reactor having an internal volume of 500 ml which had been sufficiently purged with nitrogen, and the liquid phase and gas phase were saturated with 100 liter / hr of ethylene. After that, 0.05m of triisobutylaluminum
mol was added and the mixture was stirred and maintained at 25 ° C.

On the other hand, 5 ml (0.0025 mmol / l) of a toluene solution of compound 1 shown below (0.0005 mmol / l) and 0.05 mmol of triisobutylaluminum were added to a 25 ml glass container, and the mixture was stirred for 5 minutes. 0.005 mmol of lithium tetrakis (pentafluorophenyl) borate was added, and the mixture was further stirred for 5 minutes, and the whole amount was directly added to a polymerization vessel to start polymerization.

5 ° C. at 25 ° C. in an atmosphere of ethylene gas at normal pressure
After conducting the polymerization for 1 minute, the polymerization was stopped by adding a small amount of isobutanol. The obtained polymer solution is
The polymer was precipitated by adding it to 1.5 liters of methanol containing a small amount of hydrochloric acid. The precipitated polymer was washed with methanol and dried at 80 ° C. under reduced pressure for 10 hours. The obtained polyethylene weighed 1.55 g and had a polymerization activity of 74.
40 g / mmol-Zr · hr, intrinsic viscosity [η]
Was 26.8 dl / g.

[0220]

Embedded image

[0221]

Comparative Example 1 250 ml of toluene was charged into a glass reactor having an internal volume of 500 ml which had been sufficiently purged with nitrogen, and the liquid phase and the gas phase were saturated with ethylene 100 liter / hr.
Thereafter, 0.2 g of triisobutylaluminum was added to the reactor.
5 mmol, then 0.001 of compound 1 shown above
mmol and triphenylcarbenium tetrakis (pentafluorophenyl) borate 0.005 mmol were sequentially added to initiate polymerization.

In an atmosphere of ethylene gas at normal pressure, 5 ° C. at 25 ° C.
Allowed to react for minutes. 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. The polymer was dried under reduced pressure at 80 ° C. for 10 hours. The obtained polyethylene was 1.9.
5 g and a polymerization activity of 9360 g / mmol-Zr ·
hr, and the intrinsic viscosity [η] was 0.49 dl / g.

[0223]

Example 2 250 ml of toluene was charged into a glass reactor having an internal volume of 500 ml which was sufficiently purged with nitrogen, and ethylene 50 liter / hr and propylene 150 liter / h
The liquid and gas phases were saturated with r. Thereafter, 0.05 mmol of triisobutylaluminum was added, and the mixture was stirred and maintained at 50 ° C.

On the other hand, 1 ml (0.0005 mmol / l) of a toluene solution of compound 1 shown above (0.0005 mmol / l) and 0.01 mmol of triisobutylaluminum were added to a 25 ml glass container, and stirred for 5 minutes. 0.001 mmol of lithium tetrakis (pentafluorophenyl) borate was added, and the mixture was further stirred for 5 minutes, and the whole amount was directly added to a polymerization vessel to start polymerization.

5 ° C. at 50 ° C. in a normal pressure ethylene gas atmosphere
After conducting the polymerization for 1 minute, the polymerization was stopped by adding a small amount of isobutanol. The obtained polymer solution is
The polymer was precipitated by adding it to 1.5 liters of methanol containing a small amount of hydrochloric acid. The precipitated polymer was washed with methanol and dried at 80 ° C. under reduced pressure for 10 hours. The obtained ethylene-propylene copolymer was 0.937 g, the polymerization activity was 22,500 g / mmol-Zr · hr, and the intrinsic viscosity [η] was 11.2 dl / g.

[0226]

Comparative Example 2 250 ml of toluene was charged into a glass reactor having an inner volume of 500 ml which had been sufficiently purged with nitrogen, and ethylene 50 liter / hr and propylene 150 liter / h
The liquid phase and the gas phase were saturated with the mixed gas of r. afterwards,
Methylaluminoxane is converted to 1.2 in terms of aluminum atom.
5 mmol, 0.005 mmol of compound 1 shown above
In addition, copolymerization was started. After copolymerization at 25 ° C. for 10 minutes, the polymerization was stopped by adding a small amount of isobutanol.

The obtained polymer suspension was added to 1.5 liters of methanol containing a small amount of hydrochloric acid to precipitate a polymer. After removing the solvent by filtration through a glass filter, the resultant was washed with methanol and dried under reduced pressure at 130 ° C. for 10 hours. The obtained ethylene-propylene copolymer is
2.54 g, and the polymerization activity was 3050 g / mmol-
Zr · hr, the propylene content measured by IR is 11 mol%, and the intrinsic viscosity [η] is 0.11 dl.
/ G.

[0228]

Example 3 250 ml of toluene was charged into a 500 ml glass reactor which had been sufficiently purged with nitrogen, and the liquid and gas phases were saturated with 100 liter / hr of ethylene.
0.25 mmol of triisobutylaluminum is added,
Maintained at 25 ° C.

On the other hand, 0.5 ml (0.0005 mmol) of a toluene solution (0.001 mmol / l) of compound 2 shown below and 0.005 mmol of triisobutylaluminum were added to a 25 ml glass container, and the mixture was stirred for 10 minutes and then polymerized. Was added. Subsequently, 0.0005 mmol of triphenylcarbenium tetrakis (pentafluorophenyl) borate was added to the polymerization system to initiate polymerization.

After polymerization was carried out at 25 ° C. for 10 minutes in the above mixed gas atmosphere, the polymerization was stopped by adding a small amount of isobutanol. The obtained polymer solution was added to 1.5 liter of methanol containing a small amount of hydrochloric acid to precipitate a polymer. The precipitated polymer was washed with methanol and dried at 80 ° C. under reduced pressure for 10 hours. The obtained polyethylene was 0.13 g, and the polymerization activity was 1560.
g / mmol-Zr · hr, and the intrinsic viscosity [η] is 3
It was 5.4 dl / g.

[0231]

Embedded image

[0232]

EXAMPLE 4 250 ml of toluene was charged into a glass reactor having an internal volume of 500 ml which had been sufficiently purged with nitrogen, and ethylene 50 liter / hr and propylene 150 liter / h
The liquid phase and the gas phase were saturated with a mixed gas of r, 0.25 mmol of triisobutylaluminum was added, and the mixture was maintained at 25 ° C.

On the other hand, a 25 ml glass container was charged with 5 ml of a toluene solution of compound 2 (0.001 mmol / l).
1 (0.005 mmol) and 0.05 mmol of triisobutylaluminum were added and stirred for 5 minutes, and then 0.006 mmol of triphenylcarbenium tetrakis (pentafluorophenyl) borate was added and stirred for 10 minutes. The catalyst solution thus prepared was added to a polymerization vessel to initiate polymerization.

After polymerization was carried out at 25 ° C. for 10 minutes in the above mixed gas atmosphere, the polymerization was stopped by adding a small amount of isobutanol. The obtained polymer solution was added to 1.5 liter of methanol containing a small amount of hydrochloric acid to precipitate a polymer. The precipitated polymer was washed with methanol and dried under reduced pressure at 130 ° C. for 10 hours. The obtained ethylene / propylene copolymer weighed 1.28 g,
The polymerization activity is 1540 g / mmol-Zr · hr,
The intrinsic viscosity [η] was 12.4 dl / g, and the propylene content in the copolymer was 31.3 mol%.

[0235]

Comparative Example 3 To a glass reactor having an internal volume of 500 ml, which had been sufficiently purged with nitrogen, 250 ml of toluene was charged, and the liquid phase and the gas phase were saturated with 100 l / hr of ethylene.
Thereafter, 0.2 g of triisobutylaluminum was added to the reactor.
5 mmol, and then 5 ml (0.001 mmol / liter) of a toluene solution (0.001 mmol / liter) of compound 2 shown above.
5 mmol), triphenylcarbenium tetrakis (pentafluorophenyl) borate 0.006 mmol
were added sequentially to the reactor to initiate polymerization.

After conducting the polymerization at 25 ° C. for 7 minutes in the above-mentioned ethylene gas atmosphere, the polymerization was stopped by adding a small amount of isobutanol. The obtained polymer solution was added to 1.5 liter of methanol containing a small amount of hydrochloric acid to precipitate a polymer. After washing with methanol, it was dried under reduced pressure at 80 ° C. for 10 hours. The resulting polyethylene is
2.42 g and a polymerization activity of 4150 g / mmol-
Zr · hr, and the intrinsic viscosity [η] is 0.30 dl / g.
Met.

[0237]

Comparative Example 4 250 ml of toluene was charged into a glass reactor having an internal volume of 500 ml which had been sufficiently purged with nitrogen, and ethylene 50 liter / hr and propylene 150 liter / h
The liquid phase and the gas phase were saturated with the mixed gas of r. afterwards,
Methylaluminoxane is converted to 1.2 in terms of aluminum atom.
5 mmol, 0.005 mmol of compound 2 shown above
In addition, copolymerization was started.

After copolymerization at 25 ° C. for 10 minutes, the polymerization was stopped by adding a small amount of isobutanol. The obtained polymer solution is mixed with a small amount of hydrochloric acid for 1.5 times.
Washed with 1 liter of aqueous solution. After the solvent was distilled off under reduced pressure, the residue was dried under reduced pressure at 130 ° C. for 10 hours. The obtained ethylene / propylene copolymer was 8.42 g, the polymerization activity was 10100 g / mmol-Ti · hr, and the IR
Was 29.2 mol%, and the intrinsic viscosity [η] was 0.03 dl / g.

[0239]

EXAMPLE 5 250 ml of toluene was charged into a 500 ml glass reactor which had been sufficiently purged with nitrogen, and the liquid phase and the gas phase were saturated with 100 liter / hr of ethylene to give 0.05 mmol of triisobutylaluminum. In addition, the temperature was maintained at 25 ° C.

On the other hand, 2.5 ml (0.0025 mmol) of a toluene solution (0.001 mmol / l) of the following compound 3 and 0.05 mmol of triisobutylaluminum were added to a 25 ml glass container, and stirred for 5 minutes. Was added. Subsequently, 0.005 mmol of triphenylcarbenium tetrakis (pentafluorophenyl) borate was added to the polymerization system to initiate polymerization.

After polymerization was carried out at 25 ° C. for 5 minutes in an ethylene gas atmosphere, the polymerization was stopped by adding a small amount of isobutanol. The obtained polymer suspension was added to 1.5 liter of methanol containing a small amount of hydrochloric acid to precipitate a polymer. The precipitated polymer was washed with methanol and dried at 80 ° C. under reduced pressure for 10 hours. The resulting polyethylene weighed 0.89 g and had a polymerization activity of 4270.
g / mmol-Zr · hr, and the intrinsic viscosity [η] is 3
0.2 dl / g.

[0242]

Embedded image

[0243]

Comparative Example 5 250 ml of toluene was charged into a glass reactor having an internal volume of 500 ml which had been sufficiently purged with nitrogen, and the liquid phase and gas phase were saturated with 100 liter / hr of ethylene.
Thereafter, 0.2 g of triisobutylaluminum was added to the reactor.
5 mmol, and then 5 ml (0.001 mmol / liter) of a toluene solution of compound 3 shown above (0.001 mmol / liter).
5 mmol), triphenylcarbenium tetrakis (pentafluorophenyl) borate 0.006 mmol
were added sequentially to the reactor to initiate polymerization.

After polymerization was performed in an ethylene gas atmosphere at 25 ° C. for 5 minutes, the polymerization was stopped by adding a small amount of isobutanol. The obtained polymer solution was added to 1.5 liter of methanol containing a small amount of hydrochloric acid to precipitate a polymer. The precipitated polymer was washed with methanol and dried at 80 ° C. under reduced pressure for 10 hours. The obtained polyethylene was 4.64 g, and the polymerization activity was 11,100 g.
/ Mmol-Zr · hr, and the intrinsic viscosity [η] is 0.1.
It was 24 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.

 ──────────────────────────────────────────────────の Continuing on the front page (72) Inventor Terunori Fujita 1-2-1, Waki, Waki-cho, Kuga-gun, Yamaguchi Prefecture F-term in Mitsui Chemicals, Inc. (reference) 4J028 AA01A AC01A AC02A AC08A AC09A AC10A AC18A AC19A AC20A AC22A AC26A AC27A AC28A AC29A AC31A AC32A AC41A AC45A AC49A AC50A BA01B BA02A BB01A BB01B BC13A BC15A BC15B BC16A BC16B BC17A BC17B BC19A BC19B BC24A BC24B BC27A BC27B BC28A BC28B EB02 EB04 EB05 EB07 EB08 EB09 EB10 EB11 EB12 EB13 EB14 EB17 EB18 EB21 EB22 EB24 EB25 EB26 FA01 FA02 FA03 FA04 FA07 GA04 GB01 4J100 AA02P AA03P AA04P AA07P AA09P AA15P AA16P AA17P AA18P AA19P AA21P AC03Q AG04Q AJ02Q AJ08Q AJ09Q AK07Q AK12Q AK31Q AK32Q AL03QAR04 AR03Q08

Claims (1)

[Claims] 1. A compound which reacts with (A) a transition metal compound represented by the following general formula (I), (B) an organometallic compound, and (C) a transition metal compound (A) to form an ion pair. When the olefin is polymerized or copolymerized in the presence of an olefin polymerization catalyst consisting of
And c. In the absence of olefins, and then contacting the olefin polymerization catalyst with an olefin; (Wherein, M represents a transition metal atom selected from Groups 3 to 11 of the periodic table, m represents an integer of ^{1 to 6} , R ^{1 to} R ⁶ may be the same or different, and Atom, halogen atom, hydrocarbon group, heterocyclic compound residue, oxygen-containing group, nitrogen-containing group, boron-containing group, sulfur-containing group, phosphorus-containing group, silicon-containing group, germanium-containing group or tin-containing group, Two or more of these may be connected to each other to form a ring, and when m is 2 or more, two of the groups represented by R ^{1 to} R ⁶ are connected. N is a number satisfying the valence of M; 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, Phosphorus-containing group, halogen-containing group, heterocyclic compound residue, silicon Represents an organic 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; To form a ring.)