JP2002241422A - Catalyst for olefin polymerization and olefin polymerization method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an olefin polymerization catalyst high in polymerization activity and capable of producing an olefin (co)polymer narrow in molecular weight distribution and, when applied for the copolymerization of two or more olefins, capable of producing an olefin copolymer narrow in composition distribution, and to provide an olefin polymerization method capable of producing at a high polymerization activity an olefin (co)polymer narrow in molecular weight distribution. SOLUTION: The olefin polymerization catalyst is characterized in that it has three pyrazolyl groups or their derivatives, and contains a transition metal compound represented by a specified formula. The olefin polymerization method is characterized in that olefin is polymerized or copolymerized in the presence of the above olefin polymerization catalyst.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD 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 for such a Kaminsky catalyst include bis (cyclopentadienyl) zirconium dichloride (see JP-A-58-19309) and ethylene bis (4,5,6,7-tetrahydrochloride). Indenyl) zirconium dichloride (see JP-A-61-130314) and the like are known.

[0003] It is also known that, when a transition metal compound used as a catalyst is different, the olefin polymerization activity and the properties of the obtained polyolefin are greatly different. Recently, olefin polymerization catalysts having a ligand other than a cyclopentadiel group have been proposed, and one of them is a transition metal compound having a pyrazolyl borate ligand. An example in which a transition metal compound having a pyrazolyl borate ligand is used as an olefin polymerization catalyst is disclosed in JP-A-1-95110.
JP, JP-T-7-509016, JP-A-7-7
No. 0224, JP-A-8-127610, JP-A-8-253524 and the like. However, the transition metal compounds used in these prior arts are all compounds in which the oxidation number of the metal has the highest valence, that is, compounds in which the number of d electrons of the transition metal is 0, and the polymerization activity is also high. There was a problem that it was not enough.

[0004] 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 of various properties have been developed. Is desired. Another challenge is to improve productivity. Under such circumstances, the emergence of an olefin polymerization catalyst capable of producing a polyolefin having excellent olefin polymerization activity and excellent properties has been desired.

The inventor of the present invention has conducted intensive studies in view of such circumstances, and has found that a specific transition metal compound containing a transition metal of Group 4 or Group 5 of the trivalent periodic table is used as a main catalyst. The present inventors have found that polymerization of olefins can proceed with extremely high activity, and have completed the present invention.

[0006]

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

[0007]

SUMMARY OF THE INVENTION The olefin polymerization catalyst of the present invention is characterized by containing a transition metal compound represented by the following formula (I). RB Pz ¹ Pz ² Pz ³ MX _m Y _n (I) (wherein, M represents a transition metal of Group 4 or 5 of the trivalent periodic table, and R represents a hydrogen atom, a halogen atom, a carbon atom Hydrogen group, heterocyclic compound residue, oxygen-containing group, sulfur-containing group, nitrogen-containing group, boron-containing group, aluminum-containing group,
A group selected from the group consisting of a phosphorus-containing group, a halogen-containing group, a silicon-containing group, a germanium-containing group, and a tin-containing group, wherein Pz ¹ , Pz ² , and Pz ³ each independently represent a pyrazolyl group or a derivative group thereof. X represents a hydrogen atom, a halogen atom, an oxygen 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 halogen-containing group, a heterocyclic compound residue, silicon Group, a group selected from the group consisting of a germanium-containing group and a tin-containing group, Y represents a neutral ligand having an electron-donating group, and m represents the formal charge of the ligand X. In the case of 1, it is 2; in the case of -2, it is 1;
Represents an integer of 0 to 3. Further, the olefin polymerization catalyst of the present invention comprises (A) a transition metal compound represented by the above formula (I), (B) (B-1) an organometallic compound, and (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.

The olefin polymerization catalyst of the present invention preferably contains a carrier. The olefin polymerization method of the present invention is characterized in that an olefin is polymerized or copolymerized in the presence of the olefin polymerization catalyst of the present invention.

[0009]

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, the present invention will be described specifically. In the present specification, the term polymerization may be used in a sense that encompasses not only homopolymerization but also copolymerization, and the term polymer refers to not only homopolymers but also copolymers. Sometimes used in the inclusive sense.

<Olefin Polymerization Catalyst> The olefin polymerization catalyst of the present invention contains a transition metal compound (A) represented by the following formula (I). RB Pz ¹ Pz ² Pz ³ MX _m Y _n (I) (wherein, M represents a transition metal of Group 4 or 5 of the trivalent periodic table, and R represents a hydrogen atom, a halogen atom, a carbon atom Hydrogen group, heterocyclic compound residue, oxygen-containing group, sulfur-containing group, nitrogen-containing group, boron-containing group, aluminum-containing group,
A group selected from the group consisting of a phosphorus-containing group, a halogen-containing group, a silicon-containing group, a germanium-containing group, and a tin-containing group, wherein Pz ¹ , Pz ² , and Pz ³ each independently represent a pyrazolyl group or a derivative group thereof. X represents a hydrogen atom, a halogen atom, an oxygen 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 halogen-containing group, a heterocyclic compound residue, silicon Group, a group selected from the group consisting of a germanium-containing group and a tin-containing group, Y represents a neutral ligand having an electron-donating group, and m represents the formal charge of the ligand X. In the case of 1, it is 2; in the case of -2, it is 1;
Represents an integer of 0 to 3. In addition, the catalyst for olefin polymerization of the present invention may further comprise (A) an organometallic compound, (B) (B-1) an organometallic compound together with the transition metal compound represented by the formula (I), if necessary. ) 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, and, if necessary, (C) It contains a carrier.

Hereinafter, each component constituting the olefin polymerization catalyst of the present invention will be described. (A) Transition metal compound The transition metal compound (A) constituting the olefin polymerization catalyst of the present invention is a compound represented by the following formula (I). RB Pz ¹ Pz ² Pz ³ MX _m Y _n (I) In the above formula (I), M represents a transition metal of Group 4 or 5 of the periodic table having a trivalent oxidation number, and specifically, Ti (II
I), Zr (III), Hf (III), V (III), Nb (II
I) and Ta (III). In the present invention, among these transition metals M, Zr (III), Ti (III) and V (III) are preferable, and Ti (III) and V (III) are more preferable.

In the above formula (I), R represents a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, It represents a group selected from the group consisting of a phosphorus-containing group, a halogen-containing group, a silicon-containing group, a germanium-containing group, and a tin-containing group. Among them, 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,
1 to 3 carbon atoms such as isobutyl, sec-butyl, tert-butyl, neopentyl, n-pentyl, n-hexyl
0, preferably 1 to 20 linear or branched alkyl groups; linear or branched alkenyl having 2 to 30 carbon atoms, preferably 2 to 20 carbon atoms, such as vinyl, allyl and isopropenyl. 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 cyclic saturated hydrocarbon groups; cyclopentadienyl, indenyl,
A cyclic unsaturated hydrocarbon group having 5 to 30 carbon atoms such as fluorenyl; phenyl, benzyl, naphthyl, mesityl,
Biphenyl, terphenylyl, phenanthryl, anthryl and the like having 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms
And aryl-substituted aryl groups such as tolyl, iso-propylphenyl, t-butylphenyl, dimethylphenyl and di-t-butylphenyl.

In the above hydrocarbon group, a hydrogen atom may be substituted with a halogen, and for example, a halogenated hydrocarbon having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms such as trifluoromethyl, pentafluorophenyl and chlorophenyl. Groups. The hydrocarbon group may have a hydrogen atom substituted by 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,
Oxygen-containing groups such as ether groups, acyl groups, carboxyl groups, carbonate groups, hydroxy groups, peroxy groups, carboxylic anhydride groups; amino groups, imino groups, amide groups, imide groups, hydrazino groups, hydrazono groups, nitro groups, Nitrogen groups, cyano groups, isocyano groups, cyanate ester groups, amidino groups, diazo groups, nitrogen-containing groups such as those in which amino groups are ammonium salts; mercapto groups, thioester groups, dithioester groups, alkylthio groups, arylthio groups A thioacyl group, a thioether group, a thiocyanate group, an isothiocyanate group, a sulfone ester group, a sulfonamide group, a thiocarboxyl group,
A sulfur-containing group such as a dithiocarboxyl group, a sulfo group, a sulfonyl group, a sulfinyl group, a sulfenyl group; 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 tin It may have a contained group.

Among the hydrocarbon groups, among them,
Methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, neopentyl, n-hexyl, etc. having 1 to 30 carbon atoms, preferably 1 to 20 linear or branched An alkyl group having 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms such as phenyl, naphthyl, biphenylyl, terphenylyl, phenanthryl, and anthryl; a halogen atom and 1 to 30 carbon atoms, preferably 1-20
An alkyl or alkoxy group having 6 to 3 carbon atoms
A substituted aryl group in which 1 to 5 substituents such as 0, preferably 6 to 20 aryl groups or aryloxy groups are substituted is preferred.

The heterocyclic compound residue is a cyclic group containing 1 to 5 hetero atoms in the group, and examples of the hetero atom include O, N, S, P and B. Examples of the ring include a 4- to 7-membered monocyclic and polycyclic ring, preferably a 5- to 6-membered monocyclic and polycyclic ring. Specifically, for example, pyrrole, pyridine, pyrimidine, quinoline, residues of nitrogen-containing compounds such as triazine, furan, residues of oxygen-containing compounds such as pyran, residues of sulfur-containing compounds such as thiophene, and the like. The residue has 1 to 30 carbon atoms,
Preferably, the alkyl group has 1 to 20 carbon atoms, and has 1 to 3 carbon atoms.
A group further substituted with 0, preferably 1 to 20 substituents such as an alkoxy group is exemplified.

The oxygen-containing group is a group containing 1 to 5 oxygen atoms in the group, and does not include the above-mentioned heterocyclic compound residue. Further, a group containing a nitrogen atom, a sulfur atom, a phosphorus atom, a halogen atom, or a silicon atom and in which these atoms are directly bonded to an oxygen atom is not included in the oxygen-containing group. Specific examples of the oxygen-containing group include, for example, an alkoxy group, an aryloxy group, an ester group, an ether group, an acyl group, a carboxyl group, a carbonate group, a hydroxy group,
Examples include a peroxy group and a carboxylic anhydride group, and an alkoxy group, an aryloxy group, an acetoxy group, a carbonyl group, and a hydroxy group are preferable. When the oxygen-containing group contains a carbon atom, the number of carbon atoms is desirably in the range of 1 to 30, preferably 1 to 20.

More specifically, for example, the alkoxy group of the oxygen-containing group includes methoxy, ethoxy, n-
Propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, etc., as aryloxy groups,
Phenoxy, 2,6-dimethylphenoxy, 2,4,6-trimethylphenoxy and the like; acyl groups such as formyl, acetyl, benzoyl, p-chlorobenzoyl and p-methoxybensoyl; and ester groups such as acetyl Preferred examples include oxy, benzoyloxy, methoxycarbonyl, phenoxycarbonyl, p-chlorophenoxycarbonyl and the like.

The sulfur-containing group has a sulfur atom in the group of 1 to 1.
It is a group containing 5 heterocyclic compound residues. Specific examples of the sulfur-containing group include, for example, a mercapto group, a thioester group, a dithioester group, an alkylthio group, an arylthio group, a thioacyl group, a thioether group, a thiocyanate ester group, an isothiocyanate ester group, a sulfone ester group, a sulfonamide group, Examples thereof include a thiocarboxyl group, a dithiocarboxyl group, a sulfo group, a sulfonyl group, a sulfinyl group, a sulfenyl group, a sulfonate group, and a sulfinate group. A sulfonate group, a sulfinate group, an alkylthio group, and an arylthio group are preferable. When the sulfur-containing group contains a carbon atom, the number of carbon atoms is desirably in the range of 1 to 30, preferably 1 to 20.

More specifically, among the sulfur-containing groups, for example, alkylthio groups include methylthio, ethylthio, etc., arylthio groups include phenylthio, methylphenylthio, naltylthio, etc., and thioester groups include acetylthio, Benzoylthio, methylthiocarbonyl, phenylthiocarbonyl and the like, as the sulfone ester group, methyl sulfonate, ethyl sulfonate, phenyl sulfonate and the like, and as the sulfonamide group, phenyl sulfonamide, N-methyl sulfonamide, N- Preferable examples include methyl-p-toluenesulfonamide.

Further, as the sulfonate group, methyl sulfonate, trifluoromethane sulfonate,
Phenylsulfonate, benzylsulfonate, p-
Toluenesulfonate, trimethylbenzenesulfonate, triisobutylbenzenesulfonate, p-chlorobenzenesulfonate, pentafluorobenzenesulfonate, etc., and as sulfinate groups, methylsulfinate, phenylsulfinate, benzyl Sulfinate, p-toluenesulfinate, trimethylbenzenesulfinate, pentafluorobenzenesulfinate and the like can be mentioned.

The nitrogen-containing group is a group containing 1 to 5 nitrogen atoms in the group, and does not include the above-mentioned heterocyclic compound residue. Specific examples of the nitrogen-containing group include, for example, 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, and a diazo group. And those in which an amino group is an ammonium salt, and an amino group, an imino group, an amide group, an imide group, a nitro group, and a cyano group are preferable. When the nitrogen-containing group contains a carbon atom, the number of carbon atoms is desirably in the range of 1 to 30, preferably 1 to 20.

More specifically, of the nitrogen-containing groups, for example, amide groups include acetamido, N-methylacetamido, N-methylbenzamide and the like, and amino groups include methylamino, dimethylamino, diethylamino, and diamino. Alkylamino groups such as propylamino, dibutylamino and dicyclohexylamino; phenylamino,
An arylamino group such as diphenylamino, ditolylamino, dinaphthylamino, or methylphenylamino, or an alkylarylamino group, an imide group such as acetimide or benzimide; and an imino group such as methylimino, ethylimino, or propylimino.
Preferred examples include butylimino and phenylimino.

The silicon-containing group is a group containing 1 to 5 silicon atoms in the group, for example, a silyl group, a siloxy group,
Examples thereof include a hydrocarbon-substituted silyl group and a hydrocarbon-substituted siloxy group. Among them, specific examples of the hydrocarbon-substituted silyl group include methylsilyl, dimethylsilyl, trimethylsilyl, ethylsilyl, diethylsilyl, triethylsilyl, diphenylmethylsilyl, triphenylsilyl, dimethylphenylsilyl, dimethyl-t-butylsilyl, dimethyl (pentafluoro Phenyl) 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. When the silicon-containing group contains a carbon atom, the number of carbon atoms is desirably in the range of 1 to 30, preferably 1 to 20.

Specific examples of the germanium-containing group include groups in which silicon in the silicon-containing group is replaced with germanium. Further, specific examples of the tin-containing group include groups in which silicon of the silicon-containing group is substituted with tin. As R in the above formula (I),
A group selected from a hydrogen atom, a halogen atom, a hydrocarbon group, a nitrogen-containing group and an oxygen-containing group is preferable, and a group selected from a hydrogen atom and a hydrocarbon group is more preferable.

In the above formula (I), Pz ¹ , Pz ² , Pz ³
Each independently represents a pyrazolyl group or a derivative group thereof. RB Pz ¹ Pz ² Pz ^{3 in the} above formula (I)
Is a ligand called pyrazolyl borate having a formal charge of -1. The ligand has three pyrazolyl groups or its derivative groups (Pz groups), which may be the same or different. The pyrazolyl borate group specifically has a structure represented by the following general formula (II). In the formula (II), R ^{1 to} R ³ , R ^{1 ′ to} R ^{3 ′} , R ^{1 ″ to} R
^{3 ''} may be the same or different from each other, 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 and Represents a group selected from the group consisting of silicon-containing groups.

[0028]

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In the formula (II), R¹~ R^Three, R^{1 '}~ R^{3 '}And
And R^{1 ''}~ R^{3 ''}, A hydrogen atom, a halogen atom,
Hydrocarbon group, heterocyclic compound residue, oxygen-containing group, nitrogen
As the containing group, sulfur-containing group or silicon-containing group,
Groups similar to those exemplified for R in formula (I) described above;
Can be mentioned. In the formula (II), R¹~
R ^Three, R^{1 '}~ R^{3 '}And R^{1 ''}~ R^{3 ''}In, e
Examples of the iodine-containing group include an alkyl group-substituted boron.
Element, aryl group-substituted boron, boron halide, alkyl
And a group such as a boron-substituted boron halide. Archi
(Et)_TwoB-, (iPr)_Two
B-, (iBu)_TwoB-, (nC_FiveH₁₁)_TwoB-, C ₈H₁₄B
-(9-borabicyclononyl group); aryl-substituted boron
As (C₆H_Five)_TwoB- ,; as boron halide
The BCl_Two-; Alkyl-substituted boron halide
(Et) BCl-, (iBu) BCl-, etc.
No. Here, Et is an ethyl group, iPr is isop
A ropyl group and iBu represent an isobutyl group.

Of these, R ^{1 to} R ³ , R ^{1 ′ to} R ^{3 ′} and R ^{1 ″ to} R ^{3 ″} are preferably a hydrogen atom or a hydrocarbon group. In the above formula (I), X is a hydrogen atom,
Halogen atom, oxygen atom, hydrocarbon group, oxygen containing group, sulfur containing group, nitrogen containing group, boron containing group, aluminum containing group, halogen containing group, heterocyclic compound residue, silicon containing group, germanium containing group and tin It shows a group selected from the group consisting of contained groups. X has a formal value of -1.
Or -2 anionic group. In the formula (I), when the formal charge of the ligand X is -1, m indicating the number of X is 2, and when the formal charge of X is -2, m is 1.

The halogen atom used as X in the formula (I) includes fluorine, chlorine, bromine and iodine. As the hydrocarbon group, specifically, methyl, ethyl, propyl, butyl, hexyl, octyl, nonyl,
Alkyl groups such as 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, anthryl and phenanthryl And an aryl group. These hydrocarbon groups also include halogenated hydrocarbons, specifically, groups in which at least one hydrogen of a hydrocarbon group having 1 to 30 carbon atoms has been substituted with halogen. Among them, those having 1 to 20 carbon atoms are preferable.

Specific examples of the oxygen-containing group include an oxy group; a peroxy group; a hydroxy group; a hydroperoxy group; an alkoxy group such as methoxy, ethoxy, propoxy and butoxy; and a phenoxy, methylphenoxy, dimethylphenoxy and naphthoxy group. Aryloxy groups; arylalkoxy groups such as phenylmethoxy and phenylethoxy; acetoxy groups; carbonyl groups; acetylacetonato groups (acac); oxo groups and the like.

Examples of the sulfur-containing group include methyl sulfonate, trifluoromethane sulfonate, phenyl sulfonate, benzyl sulfonate, p-toluene sulfonate, trimethylbenzene sulfonate, triisobutyl Sulfonate groups such as benzenesulfonate, p-chlorobenzenesulfonate and pentafluorobenzenesulfonate; methylsulfinate, phenylsulfinate, benzylsulfinate, p-toluenesulfinate, trimethylbenzenesulfinate Sulfonate groups such as catenate and pentafluorobenzene sulfinate; alkylthio groups; arylthio groups; sulfate groups; sulfide groups; polysulfide groups;

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

As the boron-containing group, specifically, 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 aluminum-containing group include AlR ₄ (R represents hydrogen, an alkyl group, an aryl group which may have a substituent, a halogen atom, or the like). The halogen-containing group, specifically, fluorine-containing groups such as PF _6, BF _4, chlorine-containing groups, such as ClO _4, SbCl _6, and iodine-containing groups, such as IO _4.

Specific examples of the heterocyclic compound residues include residues such as nitrogen-containing compounds such as pyrrole, pyridine, pyrimidine, quinoline, and triazine; oxygen-containing compounds such as furan and pyran; and sulfur-containing compounds such as thiophene. Group,
And the heterocyclic compound residue has 1 carbon atom
To 30 and preferably 1 to 20 groups further substituted with a substituent such as an alkyl group or an alkoxy group.

Specific examples of the silicon-containing group include phenylsilyl, diphenylsilyl, trimethylsilyl, triethylsilyl, tripropylsilyl, tricyclohexylsilyl, triphenylsilyl, methyldiphenylsilyl, tritolylsilyl, and trinaphthylsilyl. Hydrocarbon-substituted silyl groups such as trimethylsilyl ether; silicon-substituted alkyl groups such as trimethylsilylmethyl; and silicon-substituted aryl groups such as trimethylsilylphenyl.

Specific examples of the germanium-containing group include groups in which silicon of the above-mentioned silicon-containing group is substituted with germanium. As the tin-containing group, specifically,
And a group in which silicon of the silicon-containing group is substituted with tin. In such X, when m is 2, that is, when the formal charge of the ligand X is -1, two atoms or groups represented by X may be the same or different from each other; It may combine with each other to form a ring.

In the formula (I), Y represents a neutral ligand having an electron donating group, and n representing the number of Y is 0.
And represents an integer of 1 to 3, preferably 1 or 2.
The electron donating group is a group having an unpaired electron that can be donated to a metal, and Y may be any neutral ligand having an electron donating property. Specific examples of the neutral ligand Y include linear or cyclic saturated or unsaturated ethers such as diethyl ether, dimethyl ether, diisopropyl ether, tetrahydrofuran, furan, dimethylfuran, anisole, diphenyl ether, and methyl-t-butyl ether. Linear or cyclic saturated or unsaturated aldehydes such as acetaldehyde, propionaldehyde, n-butyraldehyde, benzaldehyde, p-nitrobenzaldehyde, p-tolualdehyde, phenylacetaldehyde, for example, acetone, methyl ethyl ketone, methyl-n- Linear or cyclic saturated or unsaturated ketones such as propyl ketone, acetophenone, benzophenone, n-butyrophenone, and benzyl methyl ketone, for example, formamide, acetoacetate De, benzamide, n- valeramide, stearylamide, N, N-dimethylformamide, N, N- dimethylacetamide, N, N-diethyl propionamide, N, N-dimethyl
linear or cyclic saturated or unsaturated amides such as -n-butylamide, for example, linear or cyclic saturated or unsaturated acid anhydrides such as acetic anhydride, succinic anhydride, maleic anhydride, etc., such as succinimide, phthalimide, etc. Linear or cyclic saturated or unsaturated imide compounds such as methyl acetate, ethyl acetate, benzyl acetate, phenyl acetate, ethyl formate, ethyl propionate, ethyl stearate,
Linear or cyclic saturated or unsaturated esters such as ethyl benzoate, for example, linear or cyclic saturated or unsaturated amines such as trimethylamine, triethylamine, triphenylamine, dimethylamine, aniline, pyrrolidine, piperidine, and morpholine; For example, pyridine,
nitrogen-containing heterocyclic compounds such as α-picoline, β-picoline, quinoline, isoquinoline, 2-methylpyridine, pyrrole, oxazole, imidazole, indole,
For example, sulfur-containing heterocyclic compounds such as thiophene and thiazole, for example, phosphines such as trimethylphosphine, triethylphosphine, tri-n-butylphosphine, and triphenylphosphine; for example, saturated or unsaturated nitriles such as acetonitrile and benzonitrile; Is exemplified. Further, a compound in which a part of these compounds is substituted with a substituent such as an alkyl group, a halogen group, a nitro group, a carbonyl group, and an amino group may be used. As Y in the above formula (I), ethers, aldehydes and ketones are preferable among these neutral coordination Ys.

The transition metal compound (A) represented by the above formula (I) may be produced by any method, and the production method is not particularly limited.
It can be produced by the method described in Chem. Soc. Jpn., 73, 1735 (2000) or a method similar thereto. An example of a specific structure of such a transition metal compound (A) represented by the above formula (I) is shown below in the case where the central metal M is Ti (III). In addition, Ti of the central metal of these exemplified compounds is represented by Zr, Hf, V, Nb, Ta.
Compounds replaced by can also be exemplified. In this specification, a methyl group is Me, an ethyl group is Et, an isopropyl group is iPr, a mesityl group is Mes, and a phenyl group is Ph.
May be abbreviated.

[0041]

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[0042]

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Component (B) The catalyst for olefin polymerization of the present invention may optionally contain
At least one 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. Component (B), which is a compound of the formula (I), is preferably contained.

Hereinafter, each component will be described. (B-1) Organometallic Compound Specific examples of the organometallic compound (B-1) include organometallic compounds of Groups 1, 2 and 12 and 13 of the periodic table as described below. (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 1 to 15 carbon atoms, preferably 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 <
The number is 3, and m + n + p + q = 3. The organoaluminum compound represented by).

[0045] (B-1b) Formula M ² AlR ^a ₄ (wherein, M ² represents a Li, Na or K, R ^a is from 1 to 15 carbon atoms, preferably 1-4 hydrocarbon group A complex alkylated product of a Group 1 metal and aluminum represented by the following formula: (B-1c) Formula R ^a R ^b M ³ (where R ^a and R ^b may be the same or different from each other, and have 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms. Wherein 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 may be the same or different, from 1 to 15 carbon atoms, preferably 1-4 hydrocarbon group indicates, m is preferably a number of 1.5 ≦ m ≦ 3. the organic aluminum compound represented by), the general formula R ^a _m AlX _3-m (wherein, R ^a is from 1 to 15 carbon atoms , Preferably 1-4
X is a halogen atom, and m is preferably 0 <m <3. An organoaluminum compound represented by), the general formula R ^a _m AlH _3-m (wherein, R ^a is from 1 to 15 carbon atoms, preferably 1 to 4
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).

As the organoaluminum compound belonging to (B-1a), more specifically, trimethylaluminum, triethylaluminum, trin-butylaluminum, tripropylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum,
Tri-n-alkylaluminums such as tridecylaluminum; triisopropylaluminum, triisobutylaluminum, tri-sec-butylaluminum, tri-te
rt-butyl aluminum, tri-2-methylbutyl aluminum, tri-3-methylbutyl aluminum, tri-2-methylpentyl aluminum, tri-3-methylpentyl aluminum, tri-4-methylpentyl aluminum, tri-
Tri-branched alkyl aluminum such as 2-methylhexyl aluminum, tri-3-methylhexyl aluminum and tri-2-ethylhexyl aluminum; tricycloalkyl aluminum such as tricyclohexyl aluminum and tricyclooctyl aluminum; triphenyl aluminum and tolyl aluminum triaryl aluminum such as diethyl aluminum hydride, dialkylaluminum hydride such as diisobutylaluminum _{hydride; (i-C 4 H 9} ) x Al
_y (C ₅ H ₁₀ ) _z (where x, y, and z are positive numbers, and z ≧
2x. Trialkenyl aluminum such as triisoprenyl aluminum; alkyl aluminum alkoxides such as isobutyl aluminum methoxide, isobutyl aluminum ethoxide and isobutyl aluminum isopropoxide; dimethyl aluminum methoxide, diethyl aluminum ethoxide,
Alkyl sesquichloride alkoxides such as ethyl aluminum sesqui ethoxide, butyl aluminum sesqui butoxide; alkylaluminum alkoxides such as dibutyl aluminum butoxide R ^a _2.5 Al
(OR ^b ) a partially alkoxylated alkylaluminum having an average composition represented by _0.5 or the like; diethylaluminum phenoxide, diethylaluminum (2,6-
Di-t-butyl-4-methylphenoxide), ethylaluminum bis (2,6-di-t-butyl-4-methylphenoxide),
Diisobutylaluminum (2,6-di-t-butyl-4-methylphenoxide), isobutylaluminum bis (2,6-
Dialkylaluminum aryloxides such as di-t-butyl-4-methylphenoxide); dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, dibutylaluminum chloride, diethylaluminum bromide and diisobutylaluminum chloride; ethylaluminum sesquichloride, butyl Alkyl aluminum sesquihalides such as aluminum sesquichloride and ethyl aluminum sesquibromide; partially halogenated alkyl aluminum such as alkyl aluminum dihalides such as ethyl aluminum dichloride, propyl aluminum dichloride and butyl aluminum dibromide; diethyl aluminum hydride and dibutyl Dialkyl aluminum such as aluminum hydride Other partially hydrogenated alkylaluminums such as alkylaluminum dihydrides such as ethylaluminum dihydride and propylaluminum dihydride; partially alkoxy such as ethylaluminum ethoxycyclolide, butylaluminum butoxycyclolide and ethylaluminum ethoxybromide And halogenated alkyl aluminum.

Also, a compound similar to (B-1a) may be used.
For example, two or more aluminum
Organoaluminum compounds to which compound
You. As such a compound, specifically, (C_TwoH_Five)_Two
AlN (C_TwoH_Five) Al (C_TwoH_Five)_TwoAnd the like. Said
Compounds belonging to (B-1b) include LiAl (C_TwoH_Five)_Four,
LiAl (C₇H₁₅) _FourAnd the like.

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

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

(B-2) Organoaluminum Oxy Compound The organoaluminum oxy compound (B-2) may be a conventionally known aluminoxane.
It may be a benzene-insoluble organic aluminum oxy compound as exemplified in JP-A-7. A conventionally known aluminoxane can be produced, for example, by the following method, and is usually obtained as a solution of a hydrocarbon solvent. (1) Compounds containing adsorbed water or salts containing water of crystallization, for example, magnesium chloride hydrate, copper sulfate hydrate,
An organic aluminum compound such as trialkylaluminum is added to a hydrocarbon medium suspension such as aluminum sulfate hydrate, nickel sulfate hydrate or cerous chloride hydrate, and adsorbed water or water of crystallization is added to the organic aluminum. A method of reacting with a compound. (2) A method in which water, ice or steam is allowed to directly act on an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether or tetrahydrofuran. (3) A method of reacting an organoaluminum compound such as trialkylaluminum with an organotin oxide such as dimethyltin oxide or dibutyltin oxide in a medium such as decane, benzene or toluene.

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

Solvents used for the preparation of aluminoxanes 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. An alicyclic hydrocarbon such as cyclopentane, cyclohexane, cyclooctane, methylcyclopentane, a petroleum fraction such as gasoline, kerosene or light oil, or a halide of the above aromatic hydrocarbon, aliphatic hydrocarbon or alicyclic hydrocarbon; (For example, chlorinated products, brominated products, etc.). 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 organic aluminum oxy compound, the Al component soluble in benzene at 60 ° C. is usually 10% or less, preferably 5% or less in terms of Al atom.
Particularly preferably, the content is 2% or less, that is, those which are insoluble or hardly soluble in benzene. Examples of the organic aluminum oxy compound include an organic aluminum oxy compound containing boron represented by the following general formula (i).

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In the formula, R ²⁰ represents a hydrocarbon group having 1 to 10 carbon atoms. R ²¹ represents a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 10 carbon atoms, which may be the same or different. The organoaluminum oxy compound containing boron represented by the general formula (i) includes an alkylboronic acid represented by the following general formula (ii) and R ²⁰ -B- (OH) ₂ ... (Ii) (In the formula, R ²⁰ represents the same group as described above.) An organoaluminum compound and an inert aluminum gas are mixed in an inert solvent under an inert gas atmosphere.
It can be produced by reacting 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-boronic acid. Hexylboronic acid, cyclohexylboronic acid, phenylboronic acid, 3,5-difluorophenylboronic acid, pentafluorophenylboronic acid, 3,5-bis (trifluoromethyl) phenylboronic acid, and the like. Among these, methylboronic acid, n-butylboronic acid, isobutylboronic acid, 3,5-difluorophenylboronic acid, and pentafluorophenylboronic acid are preferred. These are used alone or in combination of two or more.

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

The above (B-2) organoaluminum oxy compounds are used alone or in combination of two or more. (B-3) Reaction with transition metal compound (A) to form an ion pair
The compound (B-3) that reacts with the transition metal compound (A) to form an ion pair is a compound that can form an ion pair by contacting at least the transition metal compound (A).

Such compounds are described in JP-A No. 1-5
01950, JP-A-1-50203, JP-A-3-179005, JP-A-3-179006
JP, JP-A-3-207703, JP-A-3-2703
No. 07704, U.S. Pat. No. 5,321,106, and the like, Lewis acids, ionic compounds, borane compounds, carborane compounds, and the like. further,
Heteropoly compounds and isopoly compounds can also be mentioned.

Specifically, as the Lewis acid, BR is used.
₃ (R is a phenyl group which may have a substituent such as fluorine, a methyl group, and 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 (iii).

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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 may be the same or different, and represent 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. 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. The R ^22, is preferably such as carbonium cation, ammonium cation, particularly triphenyl carbonium cation, N, N- dimethylanilinium cation, N, is N- diethylanilinium cation.

As the ionic compound, a trialkyl-substituted ammonium salt, an N, N-dialkylanilinium salt,
Dialkylammonium salts, triarylphosphonium salts and the like are also included. Specific examples of the trialkyl-substituted ammonium salt include, for example, triethylammonium tetra (phenyl) boron, tripropylammonium tetra (phenyl) boron, tri (n-butyl) ammonium tetra (phenyl) boron, trimethylammonium tetra (p-tolyl) Boron, trimethylammonium tetra (o-tolyl) boron, tri (n-butyl) ammonium tetra (pentafluorophenyl) boron, tripropylammonium tetra (o, p-dimethylphenyl) boron, tri (n-butyl) ammonium tetra ( m, m-dimethylphenyl) boron, tri (n-butyl) ammoniumtetra (p-trifluoromethylphenyl) boron, tri (n-butyl) ammoniumtetra (3,5-ditrifluoromethylphenyl) boron, tri (n -Butyl) ammonium Such as tetra (o- tolyl) boron and the like.

Specific examples of the N, N-dialkylanilinium salt include N, N-dimethylanilinium tetra (phenyl) boron, N, N-diethylanilinium tetra (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 (iv) or (v), and the like are also included.

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

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

Specific examples of the carborane compound include, for example, 4-carbanonaborane, 1,3-dicarbanonaborane, 6,9-
Dicarbadecaborane, dodecahydride-1-phenyl-
1,3-dicarbanona borane, dodeca hydride-1-methyl-1,3-dicarbanona borane, undeca hydride-1,
3-dimethyl-1,3-dicarbanonaborane, 7,8-dicarboundecaborane, 2,7-dicarboundecaborane, 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) ammonium 6-carbadecaborate , Tri (n-butyl) ammonium 6-carbadecaborate, tri (n-butyl) ammonium 7-carboundecaborate, tri (n-butyl) ammonium 7,8-dicarbaun Decaborate, tri (n-butyl) ammonium 2,9-dicarboundecaborate, tri (n-butyl) ammonium dodecahydride-8-methyl-7,9-dicarboundecaborate, tri (n-butyl) ammoniumundeca Hydride-8-ethyl-7,9-dicarboundecaborate, tri (n-butyl) ammonium undecahydride -8-butyl-7,9-dicarboundecaborate, tri (n-butyl) ammonium undecahydride- 8-allyl-7,9
-Dicarboundecaborate, tri (n-butyl) ammonium undecahydride-9-trimethylsilyl-7,8-
Salts of anions such as dicarboundecaborate and tri (n-butyl) ammonium undecahydride-4,6-dibromo-7-carboundecaborate; 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) cobaltate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarboundecaborate) nickelate (III), (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 (II
I), 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-
Carbaundecaborate) chromate (III), bis [tri (n-butyl) ammonium] bis (undecahydride-7-carboundecaborate) manganate (I
V), bis [tri (n-butyl) ammonium] bis (undecahydride-7-carboundecaborate) cobaltate (III), bis [tri (n-butyl) ammonium] bis (undecahydride-7) -Carbaundecaborate) nickel carboxane (IV) salts and the like.

The heteropoly compound is composed of atoms consisting of silicon, phosphorus, titanium, germanium, arsenic or tin, and one or more atoms selected from vanadium, niobium, molybdenum and tungsten. Specifically, phosphorus vanadic acid, germanovanadate, arsenic vanadate, phosphorus niobate, germanoniobate, siliconomolybdate, phosphomolybdate, titanium molybdate, germanomolybdate, arsenic molybdate, tin molybdate, phosphorus molybdate, phosphorus Tungstic acid, germanotungstic acid, tin tungstic acid, phosphomolybdovanadic acid, phosphorus tungstovanadic acid, germanotangostovanadate acid, phosphomolybdatovantovanadate acid, germanomolybdatovantovanadate acid, phosphomolybdine Tungstic acid, phosphomolybdniobic acid, salts of these acids, for example metals of Group 1 or 2 of the Periodic Table, specifically lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, With barium etc. And organic salts such as triphenylethyl salt, and isopoly compounds, and the like.

The heteropoly compound and isopoly compound are not limited to one of the above compounds, and two or more can be used. As described above, the compound (B-3) which reacts with the transition metal compound (A) to form an ion pair is 1
These can be used alone or in combination of two or more. (C) Carrier The olefin polymerization catalyst of the present invention may optionally contain a carrier (C).

That is, in the present invention, the above-mentioned transition metal compound (A), the above-mentioned component (B) used as needed, and other components described later as needed are supported on a carrier (C) and used. be able to. The carrier (C) that can be used in the present invention is an inorganic or organic compound,
It is a granular or particulate solid.

Of these, the inorganic compound carrier 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 -Cr
₂ O ₃ , SiO ₂ —TiO ₂ —MgO or the like can be used. Of these, SiO ₂ and / or Al ₂ O ₃
The main component is preferably.

The above-mentioned inorganic oxide is composed 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 , carbonates such as Al (NO ₃ ) ₃ , Na ₂ O, K ₂ O, and Li ₂ O, sulfates, nitrates, and oxide components may be contained. 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.
200 μm and a specific surface area of 50 to 1000 m ² /
g, preferably in the range of 100 to 700 m ² / g,
It is desirable that the pore volume is in the range of 0.3 to 3.0 cm ³ / g. Such a carrier may be 100-
It is used after firing at 1000C, preferably 150-700C.

As inorganic chlorides, 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 is usually composed mainly of a clay mineral. The ion-exchangeable layered compound used as a carrier is a compound having a crystal structure in which planes formed by ionic bonds and the like are stacked in parallel with a weak bonding force, and the 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. In addition, as clay, clay mineral or ion-exchangeable layered compound, clay, clay mineral,
Hexagonal fine packing type, antimony type, CdCl ₂ type,
Examples thereof include ionic crystalline compounds having a layered crystal structure such as CdI ₂ type.

Examples of such clays and clay minerals include kaolin, bentonite, kibushi clay, gairome clay, allophane, hysingelite, pyrophyllite, pumice 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 · 3
H 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 )
Such polyvalent metal crystalline acid salts of such ₂ · H ₂ O and the like.

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

It is also preferable that the clay and the clay mineral are subjected to 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. The acid treatment removes impurities on the surface and increases the surface area by 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 salt treatment and organic matter treatment,
Form ion complexes, molecular complexes, organic derivatives, etc.
The surface area and interlayer distance can be changed.

The ion-exchange layered compound has an ion-exchange property.
To exchange the exchangeable ions between the layers with another large bulky ion.
Layered by exchanging with
It may be a compound. Such bulky ions are layered
It plays a pillar-like role in supporting the structure, usually a pillar
Called. In addition, another layer is formed between the layers of the layered compound.
Introducing a substance is called intercalation. I
The guest compound to be intercalated is TiC
l_Four, ZrCl_FourCationic inorganic compounds such as Ti (O
R)_Four, Zr (OR)_Four, PO (OR)_Three, B (OR)_ThreeWhat
Which metal alkoxide (R is a hydrocarbon group, etc.), [Al
₁₃O_Four(OH)_{twenty four}]⁷⁺, [Zr_Four(OH) ₁₄]²⁺, [Fe
_ThreeO (OCOCH_Three)₆]⁺Such as metal hydroxide ions
Is mentioned. These compounds may be used alone or in combination of two or more.
Used in combination.

When intercalating these compounds, Si (OR) ₄ , Al (OR) ₃ , Ge
A polymer obtained by hydrolyzing a metal alkoxide (R is a hydrocarbon group or the like) such as (OR) _4, a colloidal inorganic compound such as SiO _2, or the like can also be present. 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 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, hectorite, teniolite and synthetic mica.

The organic compound carrier has a particle size of 10 to 3
Granular or particulate solids in the range of 00 μm can be mentioned. Specifically, (co) polymers mainly composed of 2 to 14α-olefins having 2 to 14 carbon atoms such as ethylene, propylene, 1-butene and 4-methyl-1-pentene, or vinylcyclohexane and styrene are mainly used. Examples thereof include (co) polymers produced as components and modified products thereof.

Other Components The catalyst for olefin polymerization of the present invention comprises, in addition to the transition metal compound (A) and, if necessary, the component (B) and the carrier (C), if necessary, a specific organic compound. (D) A component such as a transition metal compound (E) other than the above-described transition metal compound (A) may be contained.

(D) Organic Compound The olefin polymerization catalyst of the present invention may contain a specific organic compound (D), if necessary. The organic compound component (D) is used, if necessary, for the purpose of improving the polymerization performance and the physical properties of the produced polymer. Such organic compounds include alcohols, phenolic compounds,
Examples include carboxylic acids, carboxylic esters, phosphorus compounds, sulfonates, halogenated hydrocarbons, and the like.

As the alcohols and phenolic compounds, those represented by the general formula R ³¹ -OH are usually used (where R ³¹ is a hydrocarbon group having 1 to 50 carbon atoms or a carbon atom having 1 carbon atom). To 50), and the alcohols are preferably those wherein R31 is a halogenated hydrocarbon. Further, as the phenolic compound, a compound in which the α, α′-position of the hydroxyl group is substituted with a hydrocarbon having 1 to 20 carbon atoms is preferable.

The carboxylic acid generally has the general formula R ^32-
The one represented by COOH is used. R ³² represents a hydrocarbon group having 1 to 50 carbon atoms or a halogenated hydrocarbon group having 1 to 50 carbon atoms, particularly preferably a halogenated hydrocarbon group having 1 to 50 carbon atoms. The carboxylic acid ester alkyl or aryl esters of the carboxylic acid represented by the general formula R ³² -COOH is used, having among them for example halogenated hydrocarbon groups such as perchlorethylene crotonic acid n- butyl or ethyl trichloroacetate Esters of carboxylic acids are desirable for enhancing polymerization activity.

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, those represented by the following general formula are preferably used.

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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
It is. Examples of the halogenated hydrocarbon include, for example, chloroform and carbon tetrachloride. (E) Transition metal compound other than transition metal compound (A) The transition metal compound (E) other than the above-mentioned transition metal compound (A) which may be contained in the olefin polymerization catalyst of the present invention is not particularly limited. Although not specific,
For example, the following transition metal compounds can be mentioned.

(A-1) a transition metal imide compound represented by the following general formula:

[0097]

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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 ^{31 to} R ³⁴ 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 ^{31 to} R ³⁴ , 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, When q is 2 or more, a plurality of groups represented by X may be the same or different.

(A-2) a transition metal amide compound represented by the following general formula;

[0101]

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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, and each represents a hydrogen atom, a hydrocarbon group having 1 to 50 carbon atoms, a halogenated hydrocarbon group having 1 to 50 carbon atoms, a hydrocarbon-substituted silyl group, or And 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 selected from Groups 13 to 16 of the periodic table, and specific examples include boron, carbon, nitrogen, oxygen, silicon, phosphorus, sulfur, germanium, selenium, and tin. Preferably, there is. When n is 2 or more, a 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 of 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. Represents a group, and when p is 2 or more,
A plurality of groups represented by X may be the same or different. Of these, X represents a halogen atom and 1 carbon atom.
It is preferably from 20 to 20 hydrocarbon groups or sulfonate groups.

(A-3) A transition metal diphenoxy compound represented by the following general formula;

[0107]

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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 1 to 50 carbon atoms having a substituent containing oxygen, sulfur or silicon, or halogenation having 1 to 50 carbon atoms It is a hydrocarbon group, and A 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.

P 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) At least one of the following general formulas
Transition metal compound containing a ligand having a cyclopentadienyl skeleton containing two heteroatoms;

[0112]

Embedded image

In the formula, M represents a transition metal atom selected from Groups 3 to 11 of the periodic table. X represents an atom selected from Groups 13, 14 and 15 of the periodic table, and at least one of Xs is an element other than carbon. a is 0 or 1. R may be the same or different from each other, and represents a hydrogen atom, a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a hydrocarbon-substituted silyl group, or selected from nitrogen, oxygen, phosphorus, sulfur and silicon. A hydrocarbon group having a substituent containing at least one element,
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 further, Rs are crosslinked. It may be. c is M
Is a number that satisfies the valence of Y is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms,
20 halogenated hydrocarbon groups, oxygen-containing groups, sulfur-containing groups, silicon-containing groups or nitrogen-containing groups. 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.

[0115] (a-5) formula RB (Pz) ₃ transition metal compound represented by MX _n; wherein, M represents a transition metal selected from periodic table 3 to 11 group. R is a hydrogen atom, having 1 to 20 carbon atoms
Or a halogenated hydrocarbon group having 1 to 20 carbon atoms. Pz represents a pyrazolyl group or a derivative group thereof.

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) a transition metal compound represented by the following general formula;

[0118]

Embedded image

In the formula, M represents a transition metal selected from Groups 3 to 11 of the periodic table, preferably Ni. Y ¹ and Y ³ are
They may be the same or different from each other.
Y ² is an element selected from Group 16 of the periodic table. R ^{41 to} R ⁴⁸ may be the same or different from each other, and include 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) a compound of the following general formula and a transition metal atom belonging to Groups 8 to 10 of the periodic table;

[0121]

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In the formula, R ^{51 to} R ⁵⁴ 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 general formula;

[0123]

Embedded image

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

R ^{61 to} R ⁶⁸ may be the same or different from each other, and include a hydrogen atom, a halogen atom, and 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. , Q
Is two or more, the groups represented by X may be the same 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 selected from Group 14, 15, or 16 of the periodic table. (a-9) A transition metal compound containing a ligand having a cyclopentadienyl skeleton other than the above (a-4) (a-10) A compound containing magnesium, titanium and halogen as essential components.

The olefin polymerization catalyst of the present invention is prepared from each of the above-mentioned components, and the preparation method is not particularly limited, and may be prepared by any method. Such an olefin polymerization catalyst of the present invention exhibits high polymerization activity, and when the catalyst is used for olefin polymerization, an olefin polymer having a narrow molecular weight distribution can be produced. Further, the olefin polymerization catalyst of the present invention
When used for copolymerization of two or more olefins, an olefin copolymer having a narrow composition distribution can be produced.

<Olefin Polymerization Method> The olefin polymerization method of the present invention involves (co) polymerizing an olefin in the presence of the above-mentioned olefin polymerization catalyst of the present invention. In the present invention, any of a nonpolar olefin and a polar olefin can be used as the olefin which is a (co) polymerization raw material.

The non-polar olefin is an unsaturated hydrocarbon consisting of only a carbon atom and a hydrogen atom. Specific examples of the non-polar olefin which can be used in the present invention include ethylene, propylene, -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-
2-20 carbon atoms such as octadecene and 1-eicosene
Α-olefins; cyclopentene, cycloheptene,
C3-C20 cyclic olefins such as norbornene, 5-methyl-2-norbornene, and tetracyclododecene; 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, vinylnorbornene, dicyclopentadiene; 7-methyl-1,6-octadiene, 4-ethylidene-8-methyl-1,7-nonadiene, 5,9- Cyclic or linear diene or polyene having 4 to 30, preferably 4 to 20 carbon atoms and having two or more double bonds such as dimethyl-1,4,8-decatriene; styrene, o-methylstyrene, m -Methylstyrene, p-methylstyrene, o, p-dimethylstyrene, o-
Aromatic vinyl compounds such as ethylstyrene, m-ethylstyrene and p-ethylstyrene; and vinylcyclohexane.

The polar olefin is an unsaturated hydrocarbon having a polar group. Specific examples of the polar olefin usable in the present invention include acrylic acid, methacrylic acid, fumaric acid, itaconic acid, and the like. Unsaturated carboxylic acids such as bicyclo [2.2.1] -5-heptene-2,3-dicarboxylic acid and their unsaturated carboxylic acids such as sodium, potassium, lithium, zinc, magnesium, and calcium salts Metal salts; unsaturated carboxylic anhydrides such as maleic anhydride, itaconic anhydride, bicyclo [2.2.1] -5-heptene-2,3-dicarboxylic anhydride; methyl acrylate, ethyl acrylate, and acrylic acid n -Propyl, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, 2-ethylhexyl acrylate, methacrylic acid Vinyl acetate; chill, ethyl methacrylate, n- Buropiru, isopropyl methacrylate, n- butyl, unsaturated carboxylic acid esters such as isobutyl methacrylate
Vinyl esters such as vinyl propionate, vinyl caproate, vinyl caprate, vinyl laurate, vinyl stearate and vinyl trifluoroacetate; unsaturated glycidyl esters such as glycidyl acrylate, glycidyl methacrylate and monoglycidyl itaconate;
Halogenated olefins such as vinyl chloride, vinyl fluoride and allyl fluoride; unsaturated cyano compounds such as acrylonitrile and 2-cyano-bicyclo [2.2.1] -5-heptene; unsaturated ether compounds such as methyl vinyl ether and ethyl vinyl ether An unsaturated amide such as acrylamide, methacrylamide, N, N-dimethylacrylamide; methoxystyrene, ethoxystyrene, vinylbenzoic acid,
Functional group-containing styrene derivatives such as methyl vinyl benzoate, vinyl benzyl acetate, hydroxystyrene, o-chlorostyrene, p-chlorostyrene, and divinylbenzene; and N-vinylpyrrolidone.

In the olefin polymerization method of the present invention, the olefin can be (co) polymerized in the presence of the above-mentioned olefin polymerization catalyst of the present invention, whereby the olefin can be polymerized with high polymerization activity and the molecular weight distribution can be increased. Can be produced. In the present invention, when copolymerization is performed, an olefin copolymer having a narrow composition distribution can be produced.

In the present invention, the polymerization or copolymerization of an α-olefin can be carried out with high activity, and an α-olefin (co) polymer having a narrow molecular weight distribution can be produced. In the olefin polymerization method of the present invention, the above-mentioned non-polar olefin and polar olefin can be polymerized or copolymerized, and α-olefin and conjugated diene can be copolymerized.

The α-olefin used here has the same number of carbon atoms as described above in 2 to 30, preferably 2 to 30.
To 20 linear or branched α-olefins. Among them, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene and 1-octene are preferred, and ethylene and propylene are particularly preferred.
These α-olefins can be used alone or in combination of two or more.

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

In the present invention, an α-olefin and a polar monomer can be copolymerized. Examples of the polar monomer to be used include the same ones as described above. In the present invention, an α-olefin and a non-conjugated diene or polyene can be further copolymerized. Non-conjugated dienes or polyenes used include 1,4-pentadiene, 1,5-hexadiene, 1,4-hexadiene,
1,4-octadiene, 1,5-octadiene, 1,6-octadiene, 1,7-octadiene, ethylidene norbornene, vinylnorbornene, dicyclopentadiene, 7-methyl-
Examples thereof include 1,6-octadiene, 4-ethylidene-8-methyl-1,7-nonadiene, and 5,9-dimethyl-1,4,8-decatriene.

In the present invention, the method of preparing the catalyst used for the polymerization or the method of addition at the time of the polymerization are not particularly limited. And the above-mentioned transition metal compound (A) (hereinafter also referred to as component (A)) and component (B) as a catalyst.
When using a catalyst consisting of the following, the following method is exemplified. (1) A method in which the component (A) and the component (B) are added to a polymerization vessel in an arbitrary 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 catalyst component in which the component (A) and the component (B) are brought into contact in advance,
And adding component (B) to the polymerization reactor in any order. In this case, the components (B) may be the same or different.

Further, for example, when a catalyst comprising the above-mentioned transition metal compound (A), component (B) and carrier (C) is used as a catalyst, the following method is exemplified. (4) A method in which the catalyst component in which the component (A) is supported on the carrier (C) and the component (B) are added to the polymerization reactor in any order. (5) A method in which a catalyst in which the component (A) and the component (B) are supported on a carrier (C) is added to a polymerization reactor. (6) A method in which the catalyst component in which the component (A) and the component (B) are supported on the carrier (C) and the component (B) are added to the polymerization reactor in an arbitrary order. In this case, the components (B) may be the same or different. (7) A method in which the catalyst component in which the component (B) is supported on the carrier (C) and the component (A) are added to the polymerization reactor in any order. (8) A method in which the catalyst component in which the component (B) is supported on the carrier (C), the component (A), and the component (B) are added to the polymerization reactor in any 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) Component in which component (A) is supported on carrier (C), component (B)
In which the component (B) is supported on the carrier (C) and the component (B) are added to the polymerization vessel in any order. In this case, the components (B) may be the same or different.

Further, for example, a catalyst comprising the above-mentioned transition metal compound (A), component (B), carrier (C) and organic compound component (D) (hereinafter also referred to as component (D)) is used as the catalyst. In such a case, the following method is exemplified. (11) A method in which the component (A), the component (B), and the component (D) are added to the polymerization vessel in any order. (12) A method in which the component (B) and the component (D) are brought into contact in advance, and the component (A) is added to the polymerization reactor in any order. (13) A method in which the component (B) and the component (D) supported on the carrier (C) and the component (A) are added to the polymerization vessel in any order. (14) 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. (15) 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) and the component (D) are brought into contact in advance are added to the polymerization reactor in an arbitrary order. (16) A method in which a catalyst in which the components (A), (B) and (D) are supported on a carrier (C) is added to a polymerization reactor. (17) A method in which the catalyst component in which the component (A), the component (B), and the component (D) are supported on the carrier (C), and the component (B) are added to the polymerization reactor in any order. In this case, the components (B) may be the same or different.

Further, for example, when a catalyst comprising the above-mentioned transition metal compound (A), component (B) and organic compound component (D) (hereinafter also referred to as component (D)) is used, Are exemplified. (18) 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. (19) 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 an arbitrary order. (20) 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. (21) A method in which the component (A), the component (B), and the component (D) are brought into contact in advance in an arbitrary order, and a catalyst component is added to the polymerization reactor. (22) A method in which the component (A), the component (B) and the component (D) are brought into contact with each other in advance, and the component (B) is added to the polymerization reactor in any order. In this case, the components (B) may be the same or different.

Among them, the solid catalyst or the solid catalyst component in which the component (A) and, if necessary, the component (B) and / or the component (D) are supported on the above-mentioned carrier (C), is obtained by preliminarily preparing an olefin. It may be polymerized. 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.

In the liquid phase polymerization method, an inert hydrocarbon medium can be used as a solvent. As the inert hydrocarbon medium used in the liquid phase polymerization method, specifically, aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane and kerosene; cyclopentane and cyclohexane Examples thereof include alicyclic hydrocarbons such as xane and methylcyclopentane; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as ethylene chloride, chlorobenzene and dichloromethane, and mixtures thereof. Also,
The non-polar or polar olefin itself, which is a raw material for (co) polymerization, can be used as the solvent.

In carrying out the (co) polymerization of an olefin using the above-mentioned catalyst, the component (A) contains a reaction volume of 1
Liter, usually 10 ^-12 to 10 ^-2 mol, used in an amount such preferably 10 ^-10 to 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.

When the above-mentioned component (B-1) is used as the catalyst component, the molar ratio of the component (B-1) to the transition metal atom (M) in the component (A) [(B-1 ) / M] is usually 0.01 to
It is used in an amount such that it is 100,000, preferably 0.05 to 50,000. When the above-mentioned component (B-2) is used as the catalyst component, the component (B-2) is replaced with the component (B-
The molar ratio [(B-2) / M] between the aluminum atom in 2) and the transition metal atom (M) in the component (A) is usually 10 to 50.
It is used in an amount such that it becomes 0000, preferably 20 to 100,000.

Further, as the catalyst component, the above-mentioned component (B
When -3) is used, the component (B-3) is a component (B-3) and the molar ratio of 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. When the component (D) and the component (B) are used in combination, when the component (B) is the component (B-1), the molar ratio [(D) / (B-1)] is usually 0.1. 01 to 10, preferably 0.1 to 5 and the component (B) is the component (B-
In the case of (2), the molar ratio of the component (D) to the aluminum atom in the component (B-2) [(D) / (B-2)] is usually 0.001.
To 2, preferably 0.005 to 1, and when component (B) is component (B-3), the molar ratio [(D) / (B-3)] is usually It is used in such an amount as to be 0.01 to 10, preferably 0.1 to 5.

The amount of the olefin used for the polymerization is not particularly limited, and is appropriately selected depending on the kind of the olefin used, the copolymerization ratio of the copolymer to be obtained, and the like. Further, the polymerization temperature using such a polymerization catalyst is usually -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 polar olefin copolymer can be adjusted by allowing hydrogen to be present in the polymerization system or by changing the polymerization temperature. further,
It can also be adjusted by the difference of the component (B) used.

[0147]

According to the present invention, it has a high polymerization activity,
An olefin (co) polymer having a narrow molecular weight distribution can be produced, and when used for copolymerization of two or more olefins,
An olefin polymerization catalyst capable of producing an olefin copolymer having a narrow composition distribution can be provided.

Further, according to the olefin polymerization method of the present invention, an olefin (co) polymer having a high polymerization activity and a narrow molecular weight distribution can be produced.

[0149]

EXAMPLES Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to these examples. In the present example, measurement and evaluation of various properties were performed by the following methods. IR (nujol / CsI): measured by the nujol method. UV / vis: measured as a tetrahydrofuran (THF) solution. ESR: Measured as a toluene solution. -Intrinsic viscosity [η] of polymer; measured at 135 ° C in decalin.

In this example, hydrotrispirazolyl borate is Tp, hydrotris (3,5-dimethyl) pyrazolyl borate is Tp ^* , and tetrahydrofuran is THp.
F and normal butyl group are abbreviated as Bu, respectively.

[0151]

[Synthesis Example 1] (Synthesis of Tp ^* SnClBu ₂ ) A rotator was placed in a Schlenk-type reaction vessel, and argon was replaced with an argon line. To this, Tp ^* K (3.0 g, 8.
9 mmol) and dichloromethane (30 ml) were added and stirred. This colorless suspension Bu ₂ SnCl ₂ (2.7g,
8.9 mmol) and stirred at 25 ° C. for 4 hours. After removing the by-products precipitated in the reaction solution by centrifugation,
The supernatant solution was concentrated, hexane was slowly added, and the mixture was left in a freezer for 1 day. Thereby, Tp ^* SnClBu ₂ was obtained as colorless crystals in a yield of 47% (2.4 g, 4.1 mmol).

The IR of the obtained crystal was as follows. IR (nujol / CsI, cm ^-1 ): 2554ν
(BH), 258v (Sn-Cl)

[0153]

[Synthesis Example 2] (Synthesis of Tp ^* TiCl ₂ (THF)) A rotator was placed in a Schlenk-type reaction vessel, and argon was replaced with an argon line. In addition, TiCl ₃ (THF) ₃
(1.2 g, 3.1 mmol) and THF (25 ml) were added and stirred to form a blue-violet suspension. The Tp ^* SnClBu ₂ obtained in Synthesis Example 1 (1.8 g, 3.
1 mmol) and stirred at 25 ° C. for 18 hours. The resulting dark blue solution is concentrated, and the by-product Bu ₂ SnC
To remove the l _2, while stirred hexane (40 m
When l) was added, a blue powder precipitated. To remove the supernatant, washed twice residue with hexane (20ml), Tp ^* Ti
1.5 g (3.1 m) of Cl ₂ (THF) as a blue solid
mol). After dissolving the obtained solid in THF (35 ml), hexane (43 ml) was slowly added thereto.
When left in a freezer at −20 for 2 days, Tp ^* TiCl
₂ (THF) complex as blue crystals in a yield of 69% (1.0%).
g, 2.1 mmol).

Melting point (mp), IR, UV of the obtained crystal
/ Vis and ESR were as follows: mp: 150 ° C. (dec.) IR (nujol / CsI, cm ⁻¹ ): 2547 ν (B
-H), 1010v (C-O-C), 865v (C-O
-C), 316v (Ti-Cl), 339v (Ti-C
l) UV / vis (THF): λ _max (ε) 574.5 nm
(17) ESR (toluene, 25 ° C.): g = 1.913

[0155]

Synthesis Example 3 (Synthesis of Tp ^* VCl ₂ (THF)) A rotor was placed in a Schlenk-type reaction vessel, and argon was replaced with an argon line. In addition, VCl ₃ (THF)
₃ (1.1 g, 3.0 mmol) and THF (30 m
l) was added and stirred to give a red solution. To this solution was added the Tp ^* SnClBu ₂ (1.7 g, 3.
0 mmol) and stirred at 60 ° C. for 14 hours. The resulting dark green solution is concentrated, and the by-product Bu ₂ SnC
To remove the l _2, while stirred hexane (40 m
l) and further washed with hexane (30 ml) to give Tp ^* VCl ₂ (THF) as a green solid (1.4 g, 2.
8 mmol) were obtained. Further, after it dissolved in THF (35 ml), where slowly added hexane (40 ml), and left for 2 days in a -20 ° C. freezer, Tp ^* V
The Cl ₂ (THF) complex was converted to green crystals in a yield of 63%.
(0.91 g, 1.9 mmol).

The IR, UV / vis and ESR of the obtained crystals were as follows. IR (nujol / CsI, cm ^-1 ): 2450 ν (B
-H), 1010v (C-OC), 316v (Ti-
Cl) UV / vis (THF): λ _max (ε) 636.0 nm
(25) ESR (toluene, 25 ° C.): g = 1.990

[0157]

[Synthesis Example 4] (Synthesis of TpSnClBu ₂ ) A rotator was placed in a Schlenk-type reaction vessel, and argon was replaced with an argon line. To this, TpNa (3.3 g, 14 m
mol) and dichloromethane (40 ml) were added and stirred. Bu ₂ SnCl ₂ (4.2 g,
14 mmol) and stirred at 25 ° C. for 18 hours. After the by-product precipitated in the reaction solution of sodium chloride was removed by centrifugation, concentrating the colorless supernatant solution, where the slowly added a saturated solution of hexane, allowed to stand for 1 day in a freezer, TpSnClBu ₂ is, It was obtained as colorless crystals in a yield of 67% (4.5 g, 9.3 mmol).

Melting point (mp), IR, ¹ H of the obtained crystal
The NMR and ¹³ C NMR measurements were as follows. mp: 126-130 ° C IR (nujol / CsI, cm ^-1 ): 2484ν (B
-H), 265ν (Sn-Cl) ¹ H NMR (CD ₂ Cl ₂ , -50 ° C): δ 0.89 (t, J =
7.2 Hz, 6H), 1.27-1.80 (m, 12H), 4.50 (br s, 1H), 6.21 (t,
J = 2.1 Hz, 2H), 6.31 (t, 1H), 7.57 (d, J = 2.1 Hz,
2H), 7.64 (d, 1H), 7.75 (d, J = 2.1 Hz, 1H), 7.87
(d, J = 1.5 Hz, 2H) ¹³ C NMR (CD ₂ Cl ₂ , -10 ° C.): δ 13.8,
26.9, 28.8, 32.3, 104.6, 105.
1, 105.4, 134.1, 135.3, 138.
7,139.5

[0159]

Synthesis Example 5 (Synthesis of TpTiCl ₂ (THF)) A rotor was placed in a Schlenk-type reaction vessel, and argon was replaced with an argon line. In addition, TiCl ₃ (THF) ₃
(0.89 g, 2.4 mmol) and THF (2
0 ml) and stirred to form a blue-violet suspension. The TpSnClBu obtained in Synthesis Example 4 was added to this suspension.
₂ (1.2 g, 2.4 mmol) was added and the mixture was stirred at 25 ° C. for 22 hours. To remove the by-product Bu ₂ SnCl ₂ , hexane (30 ml) was added to the resulting dark blue suspension while stirring, and then hexane (20 ml) was added.
After repeated washing, a TpTiCl ₂ (THF) complex was obtained as a blue solid in a yield of 91% (0.09 g, 2.2 mmol).

The melting point (mp), IR and UV / vis of the obtained solid were as follows. mp: 147 ° C. (dec.) IR (nujol / CsI, cm ⁻¹ ): 2510 ν (B
-H), 1011v (C-O-C), 862v (C-O
-C), 378ν (Ti-Cl), 350ν (Ti-C
l), 333ν (Ti-Cl), 307ν (Ti-C
l), 280ν (Ti-Cl) UV / vis (CH ₂ Cl ₂ ): λ _max (ε) 563.0
nm (64)

[0161]

Example 1 250 ml of toluene was charged into a 500 ml-volume glass autoclave sufficiently purged with nitrogen.
The liquid and gas phases were saturated with ethylene at 100 l / hr of ethylene. Then, methylaluminoxane (M
AO) was 1.25 mmol in terms of aluminum atoms, and subsequently Tp ^* TiCl ₂ (THF) obtained in Synthesis Example 2.
Was added to initiate polymerization. After reacting at 25 ° C. for 30 minutes under an atmosphere of ethylene gas at normal pressure, the polymerization was stopped by adding a small amount of isobutanol. After completion of the polymerization, the reaction product was poured into a large amount of methanol to precipitate the entire amount of the polymer, and hydrochloric acid was added, followed by filtration through a glass filter. After drying the polymer under reduced pressure at 80 ° C. for 10 hours, 0.169 g of polyethylene was obtained. Polymerization activity of 67.6 kg / mol · h per 1 mol of titanium
r, the intrinsic viscosity [η] of the obtained polyethylene is 13.5
dl / g.

[0162]

Embodiment 2 In Embodiment 1, Tp ^* TiCl ₂ (TH
Fp) instead of Tp ^* VCl ₂ (TH
Polymerization and post-treatment were carried out in the same manner as in Example 1 except that 0.005 mmol of F) was used to obtain 0.596 g of polyethylene. The polymerization activity per 1 mol of vanadium was 238 kg / mol · hr, and the intrinsic viscosity [η] of the obtained polyethylene was 3.03 dl / g.

[0163]

Embodiment 3 In Embodiment 1, Tp ^* TiCl ₂ (TH
F) instead of TpTiCl ₂ (T
Polymerization and post-treatment were carried out in the same manner as in Example 1 except that 0.005 mmol of HF) was used to obtain 0.282 g of polyethylene. The polymerization activity per 1 mol of titanium was 113 kg / mol · hr, and the intrinsic viscosity [η] of the obtained polyethylene was 18.0 dl / g.

[0164]

Example 4 Polymerization and post-treatment were carried out in the same manner as in Example 3 except that the polymerization temperature was changed to 50 ° C., and 0.180 g of polyethylene was obtained. Titanium 1m
The polymerization activity per ol was 72.0 kg / mol · hr, and the intrinsic viscosity [η] of the obtained polyethylene was 18.5 dl /
g.

[0165]

Example 5 250 ml of toluene was charged into a 500 ml-volume glass autoclave sufficiently purged with nitrogen.
The liquid and gas phases were saturated with 100 l / hr of ethylene. Then, triisobutylaluminum was added for 0.2
5 mmol, followed by TpTiCl synthesized in Synthesis Example 5.
₂ 0.005 mmol of (THF) and 0.006 mmol of triphenylcarbenium tetrakis (pentafluorophenyl) borate were added to initiate polymerization. Thereafter, polymerization and post-treatment were carried out in the same manner as in Example 1 to obtain 0.119 g of polyethylene. The polymerization activity per 1 mol of titanium was 47.6 kg / mol · hr, and the intrinsic viscosity [η] of the obtained polyethylene was 4.94 dl / g.

 ────────────────────────────────────────────────── ─── Continuing from the front page (72) Inventor Yoshinao Inoue 580-32 Nagaura, Sodegaura-shi, Chiba F-term in Mitsui Chemicals, Inc. BB00A BB00B BB01B BC01B BC03B BC05B BC08B BC09B BC11B BC15B BC16B BC24B BC25B CA24C CA25C CA26C CA27C CA28C CA29C CA30C CB09C CB70B CB94B CB95B CB96B EB01 EB02 EB04 EB05 EB07 EB08 EB09 EB10 EB12 EB13 EB14 EB17 EB18 EB21 4J128 AA01 AB00 AB01 AC01 AC13 AC18 AC20 AC30 AC31 AC37 AC39 AD00 AE00 BA00A BA00B BA01B BB00A BB00B BB01B BC01B BC03B BC05B BC08B BC09B BC11B BC15B BC16B BC24B BC25B CA24C CA25C CA26C CA27C CA28C CA29C CA30C CB09C CB70B CB94 EB EB EB EB EB EB EB EB EB EB EB EB EB EB EB EB EB 95

Claims (4)

[Claims] 1. An olefin polymerization catalyst comprising a transition metal compound represented by the following formula (I): RB Pz ¹ Pz ² Pz ³ MX _m Y _n ... (I) Represents a transition metal of Group 4 or Group 5 of the trivalent periodic table, and R represents a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a sulfur-containing group, or a nitrogen-containing group. , Boron-containing groups, aluminum-containing groups, phosphorus-containing groups,
A group selected from the group consisting of a halogen-containing group, a silicon-containing group, a germanium-containing group, and a tin-containing group; Pz ¹ , Pz ² , and Pz ³ each independently represent a pyrazolyl group or a derivative group thereof; , Hydrogen atom, halogen atom, oxygen atom, hydrocarbon group, oxygen containing group, sulfur containing group, nitrogen containing group, boron containing group, aluminum containing group, halogen containing group, heterocyclic compound residue, silicon containing group, germanium Y represents a neutral ligand having an electron-donating group; and m represents a case where the formal charge of the ligand X is -1. 2 and-
In the case of 2, it is 1, and n represents an integer of 0 to 3. ). (A) a transition metal compound represented by the following formula (I): RB Pz ¹ Pz ² Pz ³ MX _m Y _n (I) wherein M is a trivalent periodic table And R represents a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a boron-containing group, or an aluminum-containing group. , A phosphorus-containing group,
A group selected from the group consisting of a halogen-containing group, a silicon-containing group, a germanium-containing group, and a tin-containing group; Pz ¹ , Pz ² , and Pz ³ each independently represent a pyrazolyl group or a derivative group thereof; , Hydrogen atom, halogen atom, oxygen atom, hydrocarbon group, oxygen containing group, sulfur containing group, nitrogen containing group, boron containing group, aluminum containing group, halogen containing group, heterocyclic compound residue, silicon containing group, germanium Y represents a neutral ligand having an electron-donating group; and m represents a case where the formal charge of the ligand X is -1. 2 and-
In the case of 2, it is 1, and n represents an integer of 0 to 3. (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. Olefin polymerization catalyst comprising at least one compound selected from the group consisting of: 3. The olefin polymerization catalyst according to claim 1, further comprising a carrier. 4. A method for polymerizing olefins, comprising polymerizing or copolymerizing olefins in the presence of the catalyst for olefin polymerization according to claim 1.