JP2000169513A - Olefin polymerization catalyst and process - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a catalyst having excellent olefin polymerization activity by using a transition metal compound and a compound selected from among an organometallic compound, an organoaluminumoxy compound, and a compound which reacts with the transition metal compound to form an ionic pair. SOLUTION: A group 3-11 transition metal compound having a ligand of the formula is used. In the formula, A is O, S, Se, or N having a bonding group- R5; A' is O, S, Se or N having a bonding group-R5; R1 to R8 and R1' to R5' are each H, a halogen, a hydrocarbon group, a heterocyclic compound residue, an O-containing group, a Ge-containing group or an Sn-containing group, provided that at least two of them may be combined with each other to form a ring. The transition metal compound used is desirably one obtained by reacting a compound of the formula with a metal compound of the formula: MXk, (wherein M is a group 3-11 transition metal; and X is a group as defined in R1 to R8 and R1' to R5' or an aluminum-containing group).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to an olefin polymerization catalyst comprising a transition metal compound and a method for polymerizing olefins using the olefin polymerization catalyst.

[0002]

TECHNICAL BACKGROUND OF THE INVENTION Olefin polymerization catalysts include:
So-called Kaminsky catalysts are well known. This catalyst is characterized by a very high polymerization activity and a polymer having a narrow molecular weight distribution. Examples of the transition metal compound used in such a Kaminsky catalyst include bis (cyclopentadienyl) zirconium dichloride (see JP-A-58-19309) and ethylenebis (4,5,6,7-tetrahydrochloride). Indenyl) zirconium dichloride (see JP-A-61-130314) and the like are known. It is also known that when the transition metal compound used for the polymerization is different, the olefin polymerization activity and the properties of the obtained polyolefin are greatly different. More recently, a transition metal compound having a ligand having a diimine structure has been used as a new catalyst for olefin polymerization (International Patent Publication No. 962301).
No. 0) has been proposed.

[0003] Polyolefins are generally used in various fields, such as for various molded articles, because of their excellent mechanical properties. However, in recent years, the demand for physical properties of polyolefins has been diversified, and polyolefins having various properties have been developed. Is desired. Another challenge is to improve productivity.

Under these circumstances, there is a demand for an olefin polymerization catalyst which is capable of producing a polyolefin having excellent olefin polymerization activity and excellent properties.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide an olefin polymerization catalyst comprising a transition metal compound and having excellent olefin polymerization activity, and an olefin polymerization method using the catalyst.

[0006]

The olefin polymerization catalyst according to the present invention comprises (A) a transition metal compound having a ligand represented by the following formula (I) and belonging to groups 3 to 11 of the periodic table. ,
(B) selected from the group consisting of (B-1) an organometallic compound, (B-2) an organoaluminum oxy compound, and (B-3) a compound which reacts with the transition metal compound (A) to form an ion pair. It is characterized by comprising at least one compound.

Embedded image (Wherein, A represents an oxygen atom, a sulfur atom, a selenium atom, or a nitrogen atom having a bonding group —R ⁵ , and A ′ represents an oxygen atom, a sulfur atom, a selenium atom which may be the same as or different from A. Or a nitrogen atom having a bonding group —R ⁵ ′, wherein R ^{1 to} R ⁸ and R ¹ ′ to R ⁵ ′ are a hydrogen atom, a halogen atom, a hydrocarbon group, and a heterocyclic ring which may be the same or different from each other. Represents a formula 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, of which two or more are linked to each other To form a ring.)

In the catalyst for olefin polymerization according to the present invention,
It is preferable that the transition metal compound (A) is obtained by reacting the compound represented by the formula (I) with a metal compound represented by the following formula (II). MXk (II) (wherein, M represents a transition metal atom of Groups 3 to 11 of the periodic table, k is a number satisfying the valence of M, and X is a hydrogen atom, a halogen atom, a carbon atom Hydrogen group, oxygen-containing group, sulfur-containing group, nitrogen-containing group, boron-containing group, aluminum-containing group, phosphorus-containing group, halogen-containing group, heterocyclic compound residue, silicon-containing group, germanium-containing group, or tin-containing group And when k is 2 or more, a plurality of groups represented by X may be the same or different from each other, and a plurality of groups represented by X may be bonded to each other to form a ring.)

In the olefin polymerization catalyst according to the present invention, the transition metal compound (A) is preferably one represented by the following formula (Ia).

Embedded image (Wherein, A represents an oxygen atom, a sulfur atom, a selenium atom, or a nitrogen atom having a bonding group —R ⁵ , and A ′ represents an oxygen atom, a sulfur atom, a selenium atom which may be the same as or different from A. or 'represents nitrogen atom ^{having, R 1 ~R 8, R 1} ' bonding group -R ⁵ to R ⁵ 'are, R ¹ ~ of the formula (I)
R ^{8 has} the same meaning as R ¹ ′ to R ⁵ ′, M represents a transition metal atom of Groups 3 to 11 of the periodic table, n is a number satisfying the valence of M, and X is In the above formula (II), X has the same meaning as X, and when n is 2 or more, a plurality of groups represented by X may be the same or different from each other, and a plurality of groups represented by X are bonded to each other To form a ring. )

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

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

[0011]

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

The olefin polymerization catalyst according to the present invention comprises:
(A) the above transition metal compound, (B) (B-1) an organometallic compound, (B-2) an organoaluminum oxy compound, and
(B-3) at least one compound selected from the group consisting of compounds that form an ion pair by reacting with the transition metal compound (A). First, together with the transition metal compound (A) of the present invention, each catalyst component forming an olefin polymerization catalyst comprising the same will be described.

(A) Transition Metal Compound The transition metal compound used in the present invention has a ligand represented by the following formula (I).

Embedded image

In the formula (I), A represents an oxygen atom, a sulfur atom, a selenium atom, or a nitrogen atom having a bonding group —R ⁵ , and A ′ is an oxygen atom which may be the same as or different from A; sulfur atom, a selenium atom or a nitrogen atom having a bonding group -R ⁵ ',. R ^{1 to} R ⁸ and R ¹ ′ to R ⁵ ′ 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, even if two or more of these are connected to each other to form a ring Good.

Specifically, R ^{1 to} R ⁸ and R ¹ ′ to R ⁵ ′ represent a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, a hydrocarbon-substituted silyl group, or a hydrocarbon-substituted siloxy group. ,
Alkoxy group, alkylthio group, aryloxy group, arylthio group, acyl group, ester group, thioester group,
It is preferably an amide group, an imide group, an amino group, an imino group, a sulfone ester group, a sulfonamide group, a cyano group, a nitro group, a carboxyl group, a sulfo group, a mercapto group or a hydroxy group.

Here, the halogen atom includes 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, n-hexyl and the like.
30, preferably 1 to 20 linear or branched alkyl groups; vinyl, allyl, isopropenyl, etc., having 2 to 30 carbon atoms, preferably 2 to 20 linear or branched alkyl groups. An alkenyl group; a linear or branched alkynyl group having 2 to 30, preferably 2 to 20 carbon atoms such as ethynyl and propargyl; and a carbon atom having 3 to 30 carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and adamantyl. , Preferably 3 to 20
A cyclic unsaturated hydrocarbon group having 5 to 30 carbon atoms such as cyclopentadienyl, indenyl, and fluorenyl; and a carbon atom having 5 to 30 carbon atoms such as phenyl, benzyl, naphthyl, biphenyl, terphenyl, phenanthryl and anthracenyl. 6 to 30, preferably 6 to 20 aryl groups; and alkyl-substituted aryl groups such as tolyl, iso-propylphenyl, t-butylphenyl, dimethylphenyl and di-t-butylphenyl.

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

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

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

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

The oxygen-containing group, nitrogen-containing group, boron-containing group, sulfur-containing group and phosphorus-containing group represented by R ^{1 to} R ⁸ and R ¹ ′ to R ⁵ ′ are included in the above hydrocarbon groups. And the same substituents as those exemplified above.

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

Next, R ^{1 to} R ⁸ and R ¹ ′ to R ⁵ ′ described above.
The example 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, 2,6-dimethylphenoxy, 2,4,6-trimethylphenoxy and the like, as an acyl group, a formyl group,
Acetyl group, benzoyl group, p-chlorobenzoyl group,
A p-methoxybenzoyl group or the like, as an ester group,
Acetyloxy, benzoyloxy, methoxycarbonyl, phenoxycarbonyl, p-chlorophenoxycarbonyl and the like are preferably exemplified.

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.

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

R ^{1 to} R ⁸ and R ¹ ′ to R ⁵ ′ are two or more of these groups, preferably adjacent groups are linked to each other to form an aliphatic ring, an aromatic ring or a nitrogen atom. It may form a hydrocarbon ring containing atoms, and these rings may further have a substituent.

The transition metal compound according to the present invention is preferably obtained by reacting the compound represented by the formula (I) with a metal compound represented by the following formula (II). MXk (II)

In the formula (II), M represents a transition metal atom of Groups 3 to 11 of the periodic table (Group 3 includes lanthanoids), preferably Group 3 to 10 (Group 3 includes lanthanoids). ), More preferably a group 8-10 metal atom. Specifically, scandium, yttrium, lanthanoid, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, rhenium, iron, ruthenium, cobalt, rhodium, nickel, palladium, etc., preferably Scandium, lanthanoid, titanium, zirconium, hafnium, vanadium, niobium,
Tantalum, iron, cobalt, nickel, ruthenium, rhodium, palladium, etc., more preferably titanium, zirconium, hafnium, vanadium, niobium,
Tantalum, iron, cobalt, nickel, ruthenium, rhodium, palladium and the like, and particularly preferably iron, cobalt, nickel, ruthenium, rhodium and palladium.

X represents a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, a halogen-containing group, or a heterocyclic compound residue. , A silicon-containing group, a germanium-containing group, or a tin-containing group. k is a number that satisfies the valence of M, and is specifically 0 to 5, preferably 1 to
4, more preferably an integer of 1 to 3.

Here, the halogen atom includes fluorine,
Chlorine, bromine and iodine. Examples of the hydrocarbon group include the same groups as those exemplified for R ^{1 to} R ⁸ and R ¹ ′ to R ⁵ ′ in the formula (I). 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, biphenyl, naphthyl, methylnaphthyl,
Examples include, but are not limited to, aryl groups such as anthryl and phenanthryl. Also,
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 by halogen. Among them, those having 1 to 20 carbon atoms are preferable.

Examples of the heterocyclic compound residue include the same as those exemplified for R ^{1 to} R ⁸ and R ¹ ′ to R ⁵ ′ in the formula (I).

As the oxygen-containing group, R ^{1 of the} above formula (I)
To R ⁸ and R ¹ ′ to R ⁵ ′, and specific examples thereof include a hydroxy group; an alkoxy group such as methoxy, ethoxy, propoxy and butoxy; and phenoxy, methylphenoxy and dimethylphenoxy. Aryloxy groups such as phenyl, naphthoxy and the like; 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 R of the above formula (I)
^{1 to} R ⁸ and the same as those exemplified for R ¹ ′ to R ⁵ ′, specifically, methyl sulfonate, trifluoromethane sulfonate, phenyl sulfonate, benzyl sulfonate, sulfonate groups such as p-toluenesulfonate, trimethylbenzenesulfonate, triisobutylbenzenesulfonate, p-chlorobenzenesulfonate and pentafluorobenzenesulfonate; methylsulfinate, phenylsulfinate, benzyl Examples include, but are not limited to, sulfinate groups such as sulfinate, p-toluenesulfinate, trimethylbenzenesulfinate, and pentafluorobenzenesulfinate; alkylthio groups; arylthio groups.

Specific examples of the nitrogen-containing group include the same groups as those exemplified for R ^{1 to} R ⁸ and R ¹ ′ to R ⁵ ′ in the above formula (I). Alkylamino groups such as methylamino, dimethylamino, diethylamino, dipropylamino, dibutylamino, dicyclohexylamino; phenylamino, diphenylamino,
Examples include, but are not limited to, arylamino groups such as ditolylamino, dinaphthylamino, and methylphenylamino, or alkylarylamino groups.

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 same as those exemplified for R ^{1 to} R ⁸ and R ¹ ′ to R ⁵ ′ in the above formula (I), and specifically, phenylsilyl Hydrocarbon-substituted silyl groups such as diphenylsilyl, trimethylsilyl, triethylsilyl, tripropylsilyl, tricyclohexylsilyl, triphenylsilyl, methyldiphenylsilyl, tritolylsilyl, and trinaphthylsilyl; hydrocarbon-substituted silyl ether groups such as trimethylsilyl ether A silicon-substituted alkyl group such as trimethylsilylmethyl; a silicon-substituted aryl group such as trimethylsilylphenyl.

Specific examples of the germanium-containing group include the same as those exemplified for R ^{1 to} R ⁸ and R ¹ ′ to R ⁵ ′ in the above formula (I). Examples include a group in which silicon in the contained group is substituted with germanium.

Examples of the tin-containing group include R ^{1 of the} above formula (I)
To R ⁸ and R ¹ ′ to R ⁵ ′, and more specifically, a group obtained by substituting silicon in the silicon-containing group with tin.

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

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

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

The method of reacting the compound represented by the formula (I) with the metal compound represented by the formula (II) is not particularly limited, but may be, for example, as described below in a solvent. And direct reaction.

The transition metal compound according to the present invention is preferably a compound represented by the following formula (Ia).

Embedded image (In the above formula, N... M indicates a coordinate bond.)

In the formula (Ia), A represents an oxygen atom, a sulfur atom, a selenium atom, or a nitrogen atom having a bonding group —R ⁵ , and A ′ represents an oxygen atom which may be the same as or different from A; sulfur atom, a selenium atom or a nitrogen atom having a bonding group -R ⁵ ',. ^{R 1 ~R 8, R 1 '} ~R 5' has the same meaning as ^{R 1 ~R 8, R 1 '} ~R 5' of the formula (I).

M represents a transition metal atom belonging to Groups 3 to 11 of the periodic table. n is a number that satisfies the valence of M, and is specifically an integer of 0 to 5, preferably 1 to 4, and more preferably 1 to 3. When n is 2 or more, a plurality of groups represented by X may be the same or different, and a plurality of groups represented by X may be bonded to each other to form a ring.

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

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

N is determined by the valence of the metal M. For example, n = 2 for a divalent metal, n = 3 for a trivalent metal, n = 4 for a tetravalent metal, and n = 5 for a pentavalent metal. Specifically, when the metal M is Ti (IV), n = 4, and when the metal M is Zr (IV), n = 4.
4, n = 4 for Hf (IV), n = 2 for Co (II), Fe (I
In I), n = 2, in Rh (II), n = 2, and in Ni (II), n = 2.
2. In Pd (II), n = 2. In the examples of the compounds, Me represents 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.

[0049]

Embedded image

The transition metal compounds (A) as described above are used alone or in combination of two or more. In addition, the catalyst for olefin polymerization of the present invention, the transition metal compound
(A) together with other transition metal compounds such as nitrogen, oxygen,
Known transition metal compounds comprising a ligand containing a hetero atom such as sulfur, boron or phosphorus can also be used in combination. Hereinafter, other transition metal compounds that can be used in combination will be described.

Other transition metal compounds As transition metal compounds other than the above transition metal compound (A),
Specifically, the following transition metal compounds can be used. However, it is not limited to these.

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

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

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

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

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

Embedded image In the above formula, M represents a transition metal atom of 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 include a hydrogen atom, a hydrocarbon group having 1 to 50 carbon atoms, a halogenated hydrocarbon group having 1 to 50 carbon atoms, a hydrocarbon-substituted silyl group, Or a substituent having at least one element selected from nitrogen, oxygen, phosphorus, sulfur, and silicon.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

[0071] R ⁴¹ to R ^{4 8} are each optionally hydrogen atoms be the same or different, a halogen atom, carbon atom 20
Hydrocarbon group, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group, a sulfur-containing group, a silicon-containing group or a nitrogen-containing group, two or more of which are connected to each other to form a ring. It may be formed.

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

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

Next, each compound of the component (B) will be described. (B-1) Organometallic Compound As the (B-1) organometallic compound used in the present invention, specifically, the following Periodic Table Groups 1, 2 and 12,
Group 13 organometallic compounds are used.

[0076] (B-1a) In the formula _{^{R a m Al (OR b)}} n H p X q ( wherein, R ^a and R ^b, a good number of carbon atoms may be the same or different 1 to 15, It preferably represents 1 to 4 hydrocarbon groups, X represents a halogen atom, and m represents 0 <m ≦
3, n is 0 ≦ n <3, p is 0 ≦ p <3, q is 0 ≦ q <3
And m + n + p + q = 3. The organoaluminum compound represented by).

[0077] (B-1b) In the general formula M ² AlR ^a ₄ (wherein, M ² represents a Li, Na or K, R ^a is the number of carbon atoms 1 to 15, preferably 1 to 4 hydrocarbon groups A complex alkylated product of a Group 1 metal and aluminum represented by the formula: (B-1c) a general formula R ^a R ^b M ³ (where R ^a and R ^b each represent a hydrocarbon group having 1 to 15, preferably 1 to 4 carbon atoms which may be the same or different from each other) And M ³ is Mg, Zn or Cd.)
A dialkyl compound of a Group 2 or Group 12 metal represented by the formula:

As the organoaluminum compound belonging to the above (B-1a), the following compounds can be exemplified. In the general formula _{^{R a m Al (OR b)}} 3-m ( wherein, R ^a and R ^b, a good number of carbon atoms may be the same or different 1 to 15, preferably 1 to 4 hydrocarbon groups indicates, m is preferably a number of 1.5 ≦ m ≦ 3.) an organoaluminum compound represented by the general formula R ^a _m AlX _3-m (wherein, R ^a is 1 to carbon atoms 15, preferably 1
4 represents a hydrocarbon group, X represents a halogen atom, and m is preferably 0 <m <3. An organoaluminum compound represented by

[0079] formula R ^a _m AlH _3-m (wherein, R ^a is the number of carbon atoms 1 to 15, preferably 1 to
4 represents a hydrocarbon group, and m is preferably 2 ≦ m <3. An organoaluminum compound represented by), the general formula _{^{R a m Al (OR b)}} n X q ( wherein, R ^a and R ^b, a good number of carbon atoms may be the same or different 1 to 15, preferably Represents a hydrocarbon group of 1 to 4, X represents a halogen atom, and m represents 0 <m ≦
3, n is a number satisfying 0 ≦ n <3, q is a number satisfying 0 ≦ q <3, and m + n + q = 3. The organoaluminum compound represented by).

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

Tricycloalkyl aluminum such as tricyclohexyl aluminum and tricyclooctyl aluminum; triaryl aluminum such as triphenyl aluminum and tritolyl aluminum; dialkyl aluminum hydride such as diisobutyl aluminum hydride and diisobutyl aluminum hydride; (i-C ₄ H ₉ ) _x Al _y (C ₅ H ₁₀ ) _z (where x, y,
z is a positive number and z ≧ 2x. ) And other trialkenyl aluminums such as triisoprenyl aluminum;

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

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

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

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. As such a compound, specifically, (C ₂ H
₅ ) ₂ AlN (C ₂ H ₅ ) Al (C ₂ H ₅ ) ₂ .

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

In addition, (B-1) organometallic compounds include methyllithium, ethyllithium, propyllithium, butyllithium, methylmagnesium bromide, methylmagnesium chloride, ethylmagnesium bromide, ethylmagnesium chloride, and propylmagnesium bromide. , Propyl magnesium chloride, butyl magnesium bromide, butyl magnesium chloride, dimethyl magnesium, diethyl magnesium, dibutyl magnesium, butyl ethyl magnesium and the like can also be used.

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

(B-2) Organoaluminum oxy compound The (B-2) organoaluminum oxy compound used in the present invention may be a conventionally known aluminoxane, and is exemplified in JP-A-2-78687. May be a benzene-insoluble organic aluminum oxy compound.

The conventionally known aluminoxane can be produced, for example, by the following method, and is usually obtained as a solution of a hydrocarbon solvent. (1) Compounds containing water of adsorption or salts containing water of crystallization such as hydrated magnesium chloride, hydrated copper sulfate, hydrated aluminum sulfate, hydrated nickel sulfate, hydrated cerium chloride A method of adding an organoaluminum compound such as a trialkylaluminum to a suspension of a hydrocarbon medium of the above, and reacting the water of adsorption or water of crystallization with the organoaluminum compound.

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

The aluminoxane may contain a small amount of an organic metal component. The solvent or unreacted organoaluminum compound may be removed from the recovered solution of the aluminoxane by distillation, and then redissolved in a solvent or suspended in a poor solvent for the aluminoxane.

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

Solvents used for the preparation of aluminoxane include aromatic hydrocarbons such as benzene, toluene, xylene, cumene and cymene, and aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane and octadecane. , Cyclopentane, cyclohexane, cyclooctane, methylcyclopentane and other alicyclic hydrocarbons, petroleum fractions such as gasoline, kerosene and gas oil, or halides of the above aromatic hydrocarbons, aliphatic hydrocarbons and alicyclic hydrocarbons Among them, hydrocarbon solvents such as chlorinated products and brominated products are exemplified. Further, ethers such as ethyl ether and tetrahydrofuran can also be used. Among these solvents, aromatic hydrocarbons and aliphatic hydrocarbons are particularly preferred.

In the benzene-insoluble organoaluminum oxy compound used in the present invention, the Al component soluble in benzene at 60 ° C. is usually 10% or less, preferably 5% or less, particularly preferably 2% or less in terms of Al atom. Certain, ie, those that are insoluble or poorly soluble in benzene, are preferred.

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

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

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

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

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

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

(B-3) Reaction with transition metal compound (A)
Compound that forms an ion pair The compound (B-3) that reacts with the transition metal compound (A) to be used in the present invention to form an ion pair (hereinafter referred to as “ionized ionic compound”) is the aforementioned transition metal compound ( It is a compound that reacts with A) to form an ion pair. Therefore, compounds that form an ion pair by contacting at least the transition metal compound (A) are included in this compound. Examples of such a compound include JP-A-1-501950 and JP-A-1-501950.
JP-5020236, JP-A-3-179005, JP-A-3-179006, JP-A-3-207
703, JP-A-3-207704, USP
And Lewis acids, ionic compounds, borane compounds and carborane compounds described in US Pat. No. 5,321,106. Furthermore, a heteropoly compound and an isopoly compound can also be mentioned.

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

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

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

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

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

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

The ionic compounds include trialkyl-substituted ammonium salts, N, N-dialkylanilinium salts,
Dialkylammonium salts, triarylphosphonium salts and the like are also included.

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

Specific examples of the N, N-dialkylanilinium salt include, for example, N, N-dimethylaniliniumtetra (phenyl) boron, N, N-diethylaniliniumtetra (phenyl) boron, N, N-2, 4,6-pentamethylanilinium tetra (phenyl) boron and the like. Specific examples of the dialkyl ammonium salt include di (1-propyl) ammonium tetra (pentafluorophenyl) boron and dicyclohexylammonium tetra (phenyl) boron.

Further, as an ionic compound, triphenylcarbenium tetrakis (pentafluorophenyl)
Borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, ferrocenium tetra (pentafluorophenyl) borate, triphenylcarbenium pentaphenylcyclopentadienyl complex,
N, N-diethylanilinium pentaphenylcyclopentadienyl complex, and a boron compound represented by the following formula (VII) or (VIII) are also included.

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

Embedded image

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

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

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

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

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

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

The catalyst for olefin polymerization according to the present invention comprises the above-mentioned transition metal compound (A), (B-1) an organometallic compound,
(B-2) an organic aluminum oxy compound, and (B-3) at least one compound (B) selected from ionized ionic compounds, and a carrier (C) as described below, if necessary.
Can also be used.

(C) Carrier The (C) carrier used in the present invention is an inorganic or organic compound, and is a granular or particulate solid.
Among them, the inorganic compound is preferably a porous oxide, an inorganic chloride, a clay, a clay mineral or an ion-exchange layered compound.

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

The above-mentioned inorganic oxide is 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.

Although the properties of such a porous oxide vary depending on the kind and the production method, the carrier preferably used in the present invention has a particle size of 10 to 300 μm, preferably 20 to 300 μm.
And a specific surface area of 50 to 1000 m ^2.
/ G, preferably in the range of 100 to 700 m ² / g, and the pore volume is desirably in the range of 0.3 to 3.0 cm ³ / g. Such a carrier may be used, if necessary, 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 as a carrier in the present invention usually comprises a clay mineral as a main component. Further, the ion-exchangeable layered compound used as a carrier in the present invention is a compound having a crystal structure in which surfaces formed by ionic bonds and the like are stacked in parallel with weak bonding force to each other, and the contained ions are exchangeable. It is. Most clay minerals are ion-exchangeable layered compounds. In addition, as these clays, clay minerals and ion-exchangeable layered compounds, not only natural ones but also artificially synthesized ones can be used. As the clay, clay mineral or ion-exchangeable layered compound, clay, clay mineral, ionic crystalline compound having a layered crystal structure such as hexagonal dense packing type, antimony type, CdCl ₂ type, CdI ₂ type, and the like. Examples can be given.

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

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

[0127] The ion-exchangeable layered compound used in the present invention is a layered compound in which the interlayer is enlarged by utilizing the ion-exchange property and exchanging 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, etc.), [Al ₁₃ O ₄ (OH) ₂₄ ] ⁷⁺ , [Zr ₄ (O
H) 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 (OR) ₃ ,
A polymer obtained by hydrolyzing a metal alkoxide (R is a hydrocarbon group or the like) such as Ge (OR) _4, a colloidal inorganic compound such as SiO _2, or the like can be coexisted.
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 clay or clay minerals, and particularly preferred are montmorillonite, vermiculite, hectorite, teniolite and synthetic mica.

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

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

(D) Organic Compound Component In the present invention, the (D) organic compound component is used, if necessary, 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.

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

As the carboxylic acid, R is usually³²-COO
The one represented by H is used. R ³²Represents 1 to 1 carbon atoms
50 hydrocarbon groups or halogens having 1 to 50 carbon atoms
A halogenated hydrocarbon group, particularly a halogenated group having 1 to 50 carbon atoms.
Hydrogenated hydrocarbon groups are preferred. Phosphorus compounds include P-
Phosphorus having O—H bond, P-OR, P = O bond
Phosphates and phosphine oxide compounds are preferred.
Used properly.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

The polymerization temperature of the olefin using such an olefin polymerization catalyst is usually from -50 to 200.
° C, preferably in the range of 0 to 170 ° C. The polymerization pressure is usually from normal pressure to 100 kg / cm ² , preferably from normal pressure to 50 kg / cm ² , and the polymerization reaction can be performed in any of a batch system, a semi-continuous system, and a continuous system. it can. Further, the polymerization can be performed in two or more stages having different reaction conditions.

The molecular weight of the obtained olefin polymer can be adjusted by adding hydrogen to the polymerization system or changing the polymerization temperature. Furthermore, it can be adjusted by the difference of the component (B) used.

The olefin that can be polymerized with such an olefin polymerization catalyst has 2 carbon atoms.
Α-20 olefins such as ethylene, propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene,
1-octene, 1-decene, 1-dodecene, 1-tetradecene,
1-hexadecene, 1-octadecene, 1-eicosene; a cyclic olefin having 3 to 20 carbon atoms, for example, cyclopentene, cycloheptene, norbornene, 5-methyl-2-
Norbornene, tetracyclododecene, 2-methyl 1,4,5,
8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene;

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

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

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

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

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

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

In the present invention, an α-olefin and a non-conjugated diene or polyene can be further copolymerized.
The non-conjugated diene or polyene used is 1,
4-pentadiene, 1,5-hexadiene, 1,4-hexadiene, 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 and the like can be mentioned.

Next, a method for producing a transition metal compound will be described. Method for Producing Transition Metal Compound The transition metal compound according to the present invention can be produced, for example, as follows, without any particular limitation.

First, a ligand represented by the above formula (I) is synthesized. Next, by reacting the obtained ligand with the transition metal M-containing compound represented by the formula (II), a corresponding transition metal compound can be synthesized. Specifically, after chlorinating pyridine-2,6-dicarboxylic acid, a β-amino alcohol of the following formula is reacted.

Embedded image (Wherein, R ^{a to} R ^d are hydrogen, an alkyl group having 1 to 12 carbon atoms, an aryl group, or an aralkyl group, or an ester group, a carbamoyl group, an amide group, a hydroxyl group, an imidazole group or An alkyl group, an aryl group or an aralkyl group containing an indole group.) Next, the product is chlorinated to open the amide alcohol skeleton, and then neutralized to obtain the compound represented by the formula (I).
Is synthesized. Dissolve the synthesized ligand in a solvent,
The transition metal compound of the present invention can be easily obtained by mixing and stirring the compound of the formula (II), for example, a transition metal halide at a low temperature. As the solvent, those which are commonly used for such a reaction can be used.
A polar solvent such as tetrahydrofuran (THF) and a hydrocarbon solvent such as toluene are preferably used.

Furthermore, the metal M in the synthesized transition metal compound can be exchanged for another transition metal by a conventional method. Further, for example, when any of R ^{1 to} R ⁸ and R ¹ ′ to R ⁵ ′ is a hydrogen atom, a substituent other than a hydrogen atom can be introduced at any stage of the synthesis.

[0162]

According to the present invention, an olefin polymerization catalyst having high polymerization activity is provided. Further, according to the olefin polymerization method of the present invention, an olefin (co) polymer can be produced with high polymerization activity.

[0163]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited to these Examples. The structures of the compounds obtained in the synthesis examples were analyzed by FD-mass spectrometry (JEOL SX-102A type), metal content analysis (dry ashing and dissolution in diluted nitric acid, and then by ICP method, equipment: SHIMAZU ICPS-8000 type). ).

Example 1 44 mg of cobalt dichloride (0.
339 mmol) was dissolved in 10 ml of tetrahydrofuran, and 2,6-bis (4 ′-(S) -isopropyl-2′-) represented by the following formula (L-1) was dissolved.
102 mg (0.338 mmol) of oxazolyl) pyridine was added, and the mixture was stirred at room temperature for 1 hour. After concentrating the reaction solution and extracting with tetrahydrofuran, the solvent was distilled off under reduced pressure.
Dichloro (2,6-bis (4 ′-(S) -isopropyl-2′-oxazolyl) pyridine) cobalt represented by the following formula (A-1) was obtained as a green-white solid (yield 88 mg, 60 %). FD-mass spectrometry: (M ⁺ ) 430: Co 13.4% (13.7%) ・ ・ ・ Calculated values in ()

[0165]

Embedded image

Embedded image

Example 2 46.5 mg of iron dichloride (0.36
7 mmol) was dissolved in 10 ml of tetrahydrofuran, 107 mg (0.354 mmol) of the compound of the formula (L-1) was added, and the mixture was stirred at room temperature for 1 hour. After the reaction solution was concentrated and extracted with tetrahydrofuran, the solvent was distilled off under reduced pressure, and dichloro (2,6-bis (4 ′-(S) -isopropyl) represented by the following formula (A-2) was obtained.
-2'-Oxazolyl) pyridine) iron was obtained as a blue-violet solid (yield 131 mg, 86%). FD-mass spectrometry: (M ⁺ ) 427: Fe 12.8% (13.0%) ・ ・ ・ Calculated values in ()

Embedded image

(Polymerization Example) In a 200 ml-volume glass flask sufficiently purged with argon, 0.05 mmol of the compound of the formula (A-2), 5 mmol of methylaluminoxane in terms of aluminum atom, and 50 m of toluene.
and ethylene was introduced into the flask from a balloon. After reacting at 25 ° C. for 24 hours in an ethylene gas atmosphere at normal pressure, the polymerization was stopped by adding a small amount of isobutanol. After completion of the polymerization, the reaction product was poured into methanol to precipitate the entire amount of the polymer, and hydrochloric acid was added, followed by filtration through a glass filter. After drying the polymer under reduced pressure at 80 ° C. for 10 hours, 25.7 mg of polyethylene (PE) was obtained. The polymerization activity per 1 mmol of Fe atom / hour is 0.1.
021 g.

[Brief description of the drawings]

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

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Nariwa Matsui 6-1-2, Waki, Waki-machi, Kuga-gun, Yamaguchi Prefecture Inside Mitsui Chemicals, Inc. (72) Inventor Terunori Fujita Waki-machi, Kuga-gun, Yamaguchi Prefecture 6-1-2 1-2 Mitsui Chemicals Co., Ltd. F-term (reference) 4J028 AA01A AB00A AB01A AC01A AC08A AC09A AC18A AC19A AC26A AC27A AC31A AC37A AC38A AC41A AC42A AC44A AC45A AC46A AC47A AC48A BA00A BA01B BA02BBAB BCB BCB BCB BCB BCB BCB BC BC25B BC27B BC28B BC29B EB01 EB02 EB03 EB04 EB05 EB06 EB07 EB08 EB09 EB12 EB13 EB14 EB17 EB18 EB21 EB24 EB25 EC01 GA06 GB01 4J100 AA02P AA02Q AA03P AA03Q AA04P AA04Q AA07P AA07Q AA09P AA15P AA16P AA16Q AA17P AA17Q AA19P AA19Q AB02P AB04P AB07P AG02P AG04P AJ02P AJ08P AJ09P AK08P AK13P AK31P AK32P AL03P AL04P AL10P AR04P AR05P AR11P AR22Q AS02P AS02Q AS03P A S03Q AS11P AS11Q AS13Q AU21P AU21Q BA03P BA04P BC27P BC27Q CA01 CA04 FA09 FA10

Claims (5)

[Claims] (A) a transition metal compound having a ligand represented by the following formula (I), which belongs to Groups 3 to 11 of the periodic table: (B) (B-1) an organometallic compound, B-2) an organic aluminum oxy compound, and (B-3) at least one compound selected from the group consisting of a compound which reacts with the transition metal compound (A) to form an ion pair. Olefin polymerization catalyst; (Wherein, A represents an oxygen atom, a sulfur atom, a selenium atom, or a nitrogen atom having a bonding group —R ⁵ , and A ′ represents an oxygen atom, a sulfur atom, a selenium atom which may be the same as or different from A. Or a nitrogen atom having a bonding group —R ⁵ ′, wherein R ^{1 to} R ⁸ and R ¹ ′ to R ⁵ ′ are a hydrogen atom, a halogen atom, a hydrocarbon group, and a heterocyclic ring which may be the same or different from each other. Represents a formula 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, of which two or more are linked to each other To form a ring.) 2. The method according to claim 1, wherein the transition metal compound (A) is obtained by reacting the compound represented by the formula (I) with a metal compound represented by the following formula (II). MXk (II) (wherein M represents a transition metal atom belonging to Group 3 to 11 of the periodic table, and k represents a number that satisfies the valency 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, a phosphorus-containing group, a halogen-containing group, a heterocyclic compound residue Represents a silicon-containing group, a germanium-containing group, or a tin-containing group, and when k is 2 or more, a plurality of groups represented by X may be the same or different from each other, and a plurality of groups represented by X It may combine with each other to form a ring.) 3. The transition metal compound (A) is represented by the following formula (I-
2. The catalyst for olefin polymerization according to claim 1, which is a transition metal compound represented by a). (Wherein, A represents an oxygen atom, a sulfur atom, a selenium atom, or a nitrogen atom having a bonding group —R ⁵ , and A ′ represents an oxygen atom, a sulfur atom, a selenium atom which may be the same as or different from A. or 'represents nitrogen atom ^{having, R 1 ~R 8, R 1} ' bonding group -R ⁵ to R ⁵ 'are, R ¹ ~ of the formula (I)
R ^{8 has} the same meaning as R ¹ ′ to R ⁵ ′, M represents a transition metal atom of Groups 3 to 11 of the periodic table, n is a number satisfying the valence of M, and X is In the above formula (II), X has the same meaning as X, and when n is 2 or more, a plurality of groups represented by X may be the same or different from each other, and a plurality of groups represented by X are bonded to each other To form a ring. ) 4. A reaction between the transition metal compound (A) and (B-1): an organometallic compound, (B-2): an organoaluminum oxy compound, and (B-3): a transition metal compound (A). The catalyst for olefin polymerization according to any one of claims 1 to 3, comprising at least one compound (B) selected from the group consisting of compounds that form an ion pair, and a carrier (C). 5. A method for polymerizing an olefin, comprising polymerizing or copolymerizing an olefin in the presence of the catalyst for olefin polymerization according to claim 1. Description: