JP2000230010A - Olefin polymerization catalyst and olefin polymerization method using same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce an olefin polymer having a high mol.wt. and a wide mol.wt. distribution by using a catalyst comprising a transition metal compound and at least one compound selected from among organometallic compounds, organoaluminumoxy compounds, and compounds capable of reacting with a transition metal compound to form an ion pair. SOLUTION: The transition metal compound, one of the two ingredients constituting the catalyst, is represented by the formula, wherein M is a transition metal atom of the group 4 or 5; m is 1 or 2; R1 is an optionally substituted aromatic hydrocarbon group; R2 to R5 are each independently H, halogen, a hydrocarbon group or the like; R6 is a hydrocarbon group or a hydrocarbon- substituted silyl group; n is a number satisfying the valency of M; and X is H, halogen, a hydrocarbon group or the like. An organoaluminumoxy compound is preferable as the other ingredient of the catalyst.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel olefin polymerization catalyst and a method for olefin polymerization using the olefin polymerization catalyst, and more particularly to an olefin polymerization catalyst capable of producing a polyolefin having a high molecular weight and a wide molecular weight distribution. The present invention relates to a catalyst and a method for polymerizing an olefin.

[0002]

BACKGROUND OF THE INVENTION Generally, polyolefins are used in various fields, such as for various molded articles, because of their excellent mechanical properties and the like, and in recent years, demands for physical properties of polyolefins have been diversified. For this reason, polyolefins of various properties are desired, but particularly in the field of molded articles, polyolefins having a wide molecular weight distribution and excellent moldability are desired. Conventionally, as a catalyst for producing an olefin polymer, a titanium-based catalyst comprising a titanium compound and an organoaluminum compound and a vanadium-based catalyst comprising a vanadium compound and an organoaluminum compound are known. Further, as a catalyst capable of producing an olefin polymer with high polymerization activity, a Ziegler-type catalyst comprising a metallocene compound such as zirconocene and an organic aluminum oxy compound (aluminoxane) is known.

Recently, a transition metal compound having a ligand having a diimine structure (see International Publication No. WO9623010) has been proposed as a new catalyst for olefin polymerization. Furthermore, as a new olefin polymerization catalyst, the present applicant has proposed a transition metal compound having a salicylaldoimine ligand as Japanese Patent Application No. 10-132706. Although this complex shows high olefin polymerization activity, the narrow molecular weight distribution and relatively low molecular weight of the produced polymer leave room for improvement in these respects.

[0004]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above-mentioned prior art, and provides an olefin polymerization catalyst capable of producing a polymer having a high polymerization activity and a high molecular weight and a wide molecular weight distribution. It is intended to provide. Another object of the present invention is to provide a method for polymerizing an olefin using a catalyst having such good properties.

The olefin polymerization catalyst of the present invention comprises (A) a transition metal compound represented by the following general formula (I), (B) an organometallic compound (B-1), and (B-2) And (B-3) at least one compound selected from compounds which react with the transition metal compound (A) to form an ion pair.

[Formula 2] In the formula, M represents a transition metal atom belonging to Groups 4 to 5 of the periodic table;
Represents an integer of 1 to 2, R ¹ is one or more aromatic optionally substituted hydrocarbon group, R ² ~
R ⁵ may be the same or different, and each represents a hydrogen atom,
A group selected from a halogen atom, a hydrocarbon group, a hydrocarbon-substituted silyl group, a hydrocarbon-substituted siloxy group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, a halogen-containing group, and a heterocyclic compound residue. And at least one selected from the group consisting of the substituents R ¹ and R ^{2 to} R ⁵ has a halogen atom, an oxygen-containing group, a sulfur-containing group,
A group selected from a nitrogen-containing group, a phosphorus-containing group, a halogen-containing group, and a heterocyclic compound residue, or a hydrocarbon group or a hydrocarbon-substituted silyl group containing the group;
⁶ represents a hydrocarbon group or a hydrocarbon-substituted silyl group, two or more of R ^{1 to} R ⁶ may be connected to each other to form a ring, and n satisfies the valence of M Number,
X represents a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, a halogen-containing group, a heterocyclic compound residue, or a silicon-containing residue. A group, a germanium-containing group, or a tin-containing group, and when n is 2 or more, a plurality of groups represented by X may be the same or different from each other, and a plurality of groups represented by X bind to each other To form a ring. )

In the general formula (I), at least one selected from the group consisting of a substituent of R ¹ and R ^{2 to} R ⁵ is a heterocyclic compound residue, an alkylthio group, an aryloxy group. , An arylthio group, an amino group, an imino group, a cyano group, or a nitro group, or a hydrocarbon group containing such a group.

In the above general formula (I), at least one or more selected from the group consisting of R ¹ and R ^{2 to} R ⁵ is an alkoxy group and at least one of the remaining substituents is an alkoxy group. At least one is a group selected from a heterocyclic compound residue, an alkoxy group, an alkylthio group, an aryloxy group, an arylthio group, an amino group, an imino group, a cyano group, or a nitro group, or a hydrocarbon containing such a group Also preferred is a group.

In the present invention, (B-2)
It is preferable to use an organic aluminum oxy compound.

In the olefin polymerization method of the present invention, an olefin is polymerized in the presence of the olefin polymerization catalyst, the intrinsic viscosity [η] is 2.0 dl / g or more, and the Mw / Mn determined by GPC.
Is characterized by producing a polyolefin having a value of 5.0 or more.

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

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

The olefin polymerization catalyst used in the present invention comprises (A) a transition metal compound represented by the following general formula (I), (B) (B-1) an organometallic compound, and (B-2) an organic metal compound. Aluminum oxy compound and (B-3) transition metal compound (A)
Alternatively, it is formed from at least one compound selected from compounds which form an ion pair by reacting with the transition metal compound (B).

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

[0012]

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(Note that N ... M generally indicates coordination, but in the present invention, it may or may not be coordinated.) In the general formula (I), M represents a transition metal atom of Groups 4 to 5 of the periodic table, preferably a Group 4 metal atom, specifically, titanium, zirconium, or hafnium, and more preferably zirconium.

M represents an integer of 1 to 2, preferably 2
It is. R ¹ is an aromatic hydrocarbon group which may have a substituent, and R ^{2 to} R ⁵ may be the same or different from each other, and include a hydrogen atom, a halogen atom, a hydrocarbon group, and a hydrocarbon-substituted silyl group. , A hydrocarbon-substituted siloxy group, an oxygen-containing group,
A substituent selected from a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, a halogen-containing group, and a heterocyclic compound residue;
At least one selected from the group consisting of a substituent of R ¹ and R ^{2 to} R ⁵ is a halogen atom, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, a halogen-containing group, a heterocyclic group. or a group selected from compound residue, a hydrocarbon group or a hydrocarbon-substituted silyl group containing these groups, R ⁶ is a hydrocarbon group or a hydrocarbon-substituted silyl group,, R ¹ to R Two or more of ⁶ may be linked to each other to form a ring, n is a number that satisfies the valence of M, and X is a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group. , A sulfur-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, a halogen-containing group, a heterocyclic compound residue, a silicon-containing group, a germanium-containing group, or a tin-containing group; In the above case, it is indicated by X A plurality of groups may be the same or different from each other, and a plurality of groups represented by X may be bonded to each other to form a ring that. )

R ¹ is an aromatic hydrocarbon group which may have a substituent. Specifically, R ¹ has 6 to 30 carbon atoms such as phenyl, benzyl, naphthyl, biphenyl, terphenyl, phenanthryl and anthracenyl. And preferably 6 to 20 aromatic hydrocarbon groups.

The substituent of R ¹ is not particularly limited,
Selected from a hydrogen atom, a halogen atom, a hydrocarbon group, a hydrocarbon-substituted silyl group, a hydrocarbon-substituted siloxy group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, a halogen-containing group, and a heterocyclic compound residue. Or a hydrocarbon group or a hydrocarbon-substituted silyl group containing those groups.

Specific examples of the substituent which R ¹ may have include methoxymethyl, ethoxymethyl, butoxymethyl, phenoxymethyl, methoxyethyl, ethoxyethyl, butoxyethyl, phenoxyethyl and the like. Ethyl group methoxyphenyl group, ethoxyphenyl group, butoxyphenyl group, phenoxyphenyl group, dimethylaminomethyl group, dimethylaminoethyl group, dimethylaminophenyl group, nitromethyl group, nitroethyl group, nitrophenyl group, cyanomethyl group, cyanoethyl group, cyano Phenyl group, dimethyl (methoxy) silyl group,
A dimethyl (ethoxy) silyl group; a dimethyl (phenoxy) silyl group;

R ^{2 to} R ⁵ may be the same or different, and each represents a hydrogen atom, a halogen atom, a hydrocarbon group, a hydrocarbon-substituted silyl group, a hydrocarbon-substituted siloxy group, an oxygen-containing group,
A group selected from a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, a halogen-containing group, and a heterocyclic compound residue, or a hydrocarbon group or a hydrocarbon-substituted silyl group containing such a group.

At least one selected from the group consisting of a substituent of R ¹ and R ^{2 to} R ⁵ is a halogen atom, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, a halogen-containing group. Or a group selected from heterocyclic compound residues, or a hydrocarbon group or a hydrocarbon-substituted silyl group containing such a group.

Preferred examples of the oxygen-containing group, sulfur-containing group, nitrogen-containing group, phosphorus-containing group and halogen-containing group include hydrocarbon-substituted siloxy, alkoxy, alkylthio, aryloxy, arylthio, acylthio, acyl, and the like. Ester group, thioester group, amide group, imide group, amino group, imino group, sulfone ester group, sulfonamide group, cyano group, nitro group, carboxyl group, sulfo group,
Examples include a mercapto group or a hydroxy group.

Next, with respect to the examples of the substituents described above,
This will be described more specifically.

Examples of the halogen atom include fluorine, chlorine, bromine and iodine.

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

In the above hydrocarbon group, a hydrogen atom may be substituted with a halogen. For example, a halogenated hydrocarbon having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms such as trifluoromethyl, pentafluorophenyl and chlorophenyl. And a hydrogen group.

The hydrocarbon group may be substituted with another hydrocarbon group, for example, an aryl-substituted alkyl group such as benzyl and cumyl.

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

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

Specific examples of the hydrocarbon-substituted silyl group and hydrocarbon-substituted siloxy group include methylsilyl, dimethylsilyl, trimethylsilyl, ethylsilyl, diethylsilyl, triethylsilyl, diphenylmethylsilyl, triphenylsilyl, dimethylphenylsilyl, dimethyl
-t-butylsilyl, dimethyl (pentafluorophenyl) silyl and the like. Among them, methylsilyl, dimethylsilyl, trimethylsilyl, ethylsilyl, diethylsilyl, triethylsilyl, dimethylphenylsilyl, triphenylsilyl and the like are preferable. Particularly, trimethylsilyl, triethylsilyl, triphenylsilyl and dimethylphenylsilyl are preferred. Specific examples of the hydrocarbon-substituted siloxy group include trimethylsiloxy.

Examples of the oxygen-containing group include an alkoxy group, an aryloxy group, an acyl group and an ester group. For example, specific examples of the alkoxy group include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy and the like. Specific examples of the aryloxy group include phenoxy, 2,6-dimethylphenoxy, and 2,4,6-trimethylphenoxy.

Specific examples of the acyl group include a formyl group, an acetyl group, a benzoyl group, a p-chlorobenzoyl group, and a p-methoxybenzoyl group. Specific examples of the ester group include acetyloxy, benzoyloxy, methoxycarbonyl, phenoxycarbonyl, p-chlorophenoxycarbonyl and the like.

Examples of the sulfur-containing group include an alkylthio group, an arylthio group, a thioester group, a sulfone ester group, and a sulfonamide group. Specific examples of the alkylthio group include methylthio, ethylthio, and the like. Specific examples of the arylthio group include phenylthio, methylphenylthio, and naphthylthio.

Specific examples of the thioester group include acetylthio, benzoylthio, methylthiocarbonyl, phenylthiocarbonyl and the like. Specifically as the sulfone ester group, methyl sulfonate,
Examples include ethyl sulfonate and phenyl sulfonate.

Specific examples of the sulfonamide group include phenylsulfonamide, N-methylsulfonamide, N-methyl-p-toluenesulfonamide and the like.

Examples of the nitrogen-containing group include an amide group, an imide group, an amino group, an imino group, a cyano group and a nitro group. Specific examples of the amide group include acetamido, N-methylacetamido, N-methylbenzamide, and the like.

Specific examples of the imide group include acetimide and benzimide. Specific examples of the amino group include dimethylamino, ethylmethylamino, diphenylamino and the like.

Specific examples of the imino group include methylimino, ethylimino, propylimino, butylimino, phenylimino and the like.

At least one selected from the group consisting of a substituent of R ¹ and R ^{2 to} R ⁵ is a heterocyclic compound residue, an alkylthio group, an aryloxy group, an arylthio group, an amino group, an imino group, It is preferably a group selected from a cyano group or a nitro group, or a hydrocarbon group containing such a group. Particularly preferably, at least one or more selected from the group consisting of the substituent of R ¹ and R ^{2 to} R ⁵ is a substituent selected from an aryloxy group, an amino group or a nitro group.

In addition, at least one selected from the group consisting of a substituent of R ¹ and R ^{2 to} R ⁵ is an alkoxy group, and at least one of the remaining substituents is a heterocyclic compound residue, an alkoxy group, A group selected from an alkylthio group, an aryloxy group, an arylthio group, an amino group, an imino group, a cyano group, and a nitro group, or a hydrocarbon group containing these groups is also preferable.

R ⁶ is a hydrocarbon group or a hydrocarbon-substituted silyl group. Preferred hydrocarbon groups as R ⁶ include those having 1 to 30 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, neopentyl, and n-hexyl. Is a linear or branched alkyl group having 1 to 20; 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; phenyl,
Aryl groups having 6 to 30, preferably 6 to 20 carbon atoms, such as benzyl, naphthyl, biphenylyl and triphenylyl; and those groups having 1 to 30 carbon atoms;
Preferably, it has 1 to 20 alkyl groups or 6 carbon atoms.
Preferred examples include groups further substituted with a substituent such as an aryl group of from 30 to 30, preferably 6 to 20.

Preferred hydrocarbon-substituted silyl groups for R ⁶ include methylsilyl, dimethylsilyl, trimethylsilyl, ethylsilyl, diethylsilyl, triethylsilyl, diphenylmethylsilyl, triphenylsilyl,
Dimethylphenylsilyl, dimethyl-t-butylsilyl,
Dimethyl (pentafluorophenyl) silyl and the like. Particularly preferred are trimethylsilyl, triethylphenyl, diphenylmethylsilyl, isophenylsilyl, dimethylphenylsilyl, dimethyl-t-butylsilyl, dimethyl (pentafluorophenyl) silyl and the like.

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

R ^{1 to} R ⁶ represent two or more of these groups, preferably adjacent groups, which are connected to each other to form an aliphatic ring, an aromatic ring, or a hydrocarbon ring containing a hetero atom such as a nitrogen atom. And these rings may further have a substituent.

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

N is a number that satisfies the valency of M, and is specifically an integer of 2 to 4, preferably 2. X is
Hydrogen atom, halogen atom, hydrocarbon group, oxygen-containing group, sulfur-containing group, nitrogen-containing group, boron-containing group, aluminum-containing group, phosphorus-containing group, halogen-containing group, heterocyclic compound residue, silicon-containing group, germanium Shows a containing group or a tin-containing group. When n is 2 or more, a plurality of groups represented by X may be the same as or different from each other, and a plurality of groups represented by X may be bonded to each other to form a ring. Is also good.

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

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

Specific examples of the oxygen-containing group include a hydroxy group; an alkoxy group such as methoxy, ethoxy, propoxy and butoxy; an aryloxy group such as phenoxy, methylphenoxy, dimethylphenoxy and naphthoxy;
Arylalkoxy groups such as phenylmethoxy and phenylethoxy; acetoxy groups; carbonyl groups, and the like, but are not limited thereto.

Specific 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 And sulfonate groups such as pentafluorobenzenesulfinate; alkylthio group; arylthio group and the like, but are not limited thereto.

Specific examples of the nitrogen-containing group include an amino group; an alkylamino group such as methylamino, dimethylamino, diethylamino, dipropylamino, dibutylamino and dicyclohexylamino; phenylamino, diphenylamino, ditolylamino An arylamino group such as dinaphthylamino, methylphenylamino or an alkylarylamino group.
It is not limited to these.

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

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

Specific examples of the germanium-containing group include groups in which silicon in the silicon-containing group is replaced with germanium.

Specific examples of the tin-containing group include a group in which silicon of the silicon-containing group is substituted with tin.

Specific examples of the halogen-containing group include P
F₆, BF_FourFluorine-containing groups such as ClO _Four, SbCl₆What
Which chlorine-containing groups, IO_FourAnd iodine-containing groups such as
However, the present invention is not limited to these.

As the aluminum-containing group, specifically, A
lR ₄ (R represents hydrogen, an alkyl group, an aryl group which may have a substituent, a halogen atom, etc.),
It is not limited to these. Hereinafter, specific examples of the transition metal compound represented by the general formula (I) are shown, but the invention is not limited thereto.

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Embedded image In the above examples, Me represents a methyl group, Et represents an ethyl group, Pr represents a propyl group, Bu represents a butyl group, and Ph represents a phenyl group. In the present invention, a transition metal compound in which zirconium metal is replaced with a metal other than zirconium, such as titanium or hafnium, in the compounds as described above can also be used.

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

First, the ligand constituting the transition metal compound (I) is a salicylaldehyde compound represented by the formula R ¹ -NH
₂ primary amine compounds (R ¹ is as defined above), for example, by reacting with an aniline compound or an alkylamine compound. Specifically, both starting compounds are dissolved in a solvent. As the solvent, those commonly used in such reactions can be used, and among them, alcohol solvents such as methanol and ethanol, and hydrocarbon solvents such as toluene are preferable. Then, the obtained solution is stirred under a reflux condition from room temperature for about 1 to 48 hours to obtain a corresponding ligand in a good yield.

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

Next, by reacting the ligand thus obtained with a compound containing a transition metal M, a corresponding transition metal compound can be synthesized. Specifically, the synthesized ligand is dissolved in a solvent, and if necessary, contacted with a base to prepare a phenoxide salt, and then mixed with a metal compound such as a metal halide or a metal alkylate at a low temperature. , -78
The mixture is stirred for about 1 to 48 hours at a temperature from C to room temperature or under reflux. As the solvent, those which are commonly used in such reactions can be used, and among them, polar solvents such as ether and tetrahydrofuran (THF), and hydrocarbon solvents such as toluene are preferably used. Further, as a base used when preparing a phenoxide salt, a lithium salt such as n-butyllithium, a metal salt such as a sodium salt such as sodium hydride, and an organic base such as triethylamine and pyridine are preferable. Not as long.

Depending on the properties of the compound, the corresponding transition metal compound can also be synthesized by directly reacting the ligand with the metal compound without going through the preparation of a phenoxide salt.

Further, the metal M in the synthesized transition metal compound can be exchanged for another transition metal by a conventional method. Further, for example, when any of R ^{2 to} R ⁶ is H, a substituent other than H can be introduced at any stage of the synthesis.

Further, the reaction solution of the ligand and the metal compound can be used as it is for the polymerization without isolating the transition metal compound.

The above (A) transition metal compound (I)
Are used alone or in combination of two or more.

[(B-1) Organometallic compound] As the (B-1) organometallic compound used in the present invention, specific examples of the first, second and twelfth and thirteenth groups of the periodic table are as follows. Organometallic compounds are used.

[0065] (B-1a) In the formula _{^{R a m Al (OR b)}} n H p X q ( wherein, R ^a and R ^b may be the same or different from each other, the number of carbon atoms from 1 to 15 , Preferably 1 to 4 hydrocarbon groups, X represents a halogen atom, and m represents 0 <
m ≦ 3, n is 0 ≦ n <3, p is 0 ≦ p <3, q is 0 ≦ q
<3 and m + n + p + q = 3. The organoaluminum compound represented by).

[0066] (B-1b) In the general formula M ² AlR ^a ₄ (wherein, M ² represents a Li, Na or K, R ^a is the number of carbon atoms 1 to 15, preferably 1 to 4 hydrocarbon groups A complex alkylated product of a metal belonging to Group 1 of the periodic table and aluminum.

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

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

[0069] formula R ^a _m AlH _3-m (wherein, R ^a is the number of carbon atoms 1 to 15, preferably 1 to
4 represents a hydrocarbon group, and m is preferably 2 ≦ m <3. An organoaluminum compound represented by), the general formula _{^{R a m Al (OR b)}} n X q ( wherein, R ^a and R ^b may be the same or different from each other, the number of carbon atoms 1 to 15, It preferably represents 1 to 4 hydrocarbon groups, X represents a halogen atom, and m represents 0 <m
≦ 3, n is a number of 0 ≦ n <3, q is a number of 0 ≦ q <3, and m + n + q = 3. The organoaluminum compound represented by).

More specifically, the organoaluminum compounds belonging to (B-1a) include trimethylaluminum, triethylaluminum, tri-n-butylaluminum, tripropylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum. Tri-n-alkyl aluminum such as triisopropyl aluminum, triisobutyl aluminum, tri sec-butyl aluminum, tri tert-
Butylaluminum, tri2-methylbutylaluminum, tri3-methylbutylaluminum, tri2-methylpentylaluminum, tri3-methylpentylaluminum, tri4-methylpentylaluminum, tri2-methylhexylaluminum, tri3-methylhexyl Aluminum, tribranched alkyl aluminum such as tri-2-ethylhexyl aluminum;

Tricycloalkyl aluminum such as tricyclohexyl aluminum and tricyclooctyl aluminum; triaryl aluminum such as triphenyl aluminum and tritolyl aluminum; dialkyl aluminum hydride such as diisobutyl aluminum 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), and a trialkenyl aluminum such as triisoprenyl aluminum;

Alkyl aluminum alkoxides such as isobutylaluminum methoxide, isobutylaluminum ethoxide and isobutylaluminum isopropoxide; dialkylaluminum alkoxides such as dimethylaluminum methoxide, diethylaluminum ethoxide and dibutylaluminum butoxide; ethylaluminum sesquiethoxide and butyl Alkyl aluminum sesqui alkoxides such as aluminum sesquibutoxide; partially alkoxylated alkyl aluminum having an average composition represented by ^Ra _2.5 Al (OR ^b ) _{0.5 and the} like; diethyl aluminum phenoxide, diethyl aluminum (2,6-dialkyl -t-butyl-4-methylphenoxide), ethyl aluminum bis (2,6-di-t-butyl-4-methylphenoxide), Seo-butylaluminum (2,6
Dialkylaluminum aryloxides such as di-t-butyl-4-methylphenoxide) and isobutylaluminum bis (2,6-di-t-butyl-4-methylphenoxide);

Dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, dibutylaluminum chloride, diethylaluminum bromide and diisobutylaluminum chloride; alkylaluminum sesquichlorides such as ethylaluminum sesquichloride, butylaluminum sesquichloride and ethylaluminum sesquibromide; ethyl Partially aluminum halides such as alkylaluminum dihalides such as aluminum dichloride, propylaluminum dichloride, butylaluminum dibromide; dialkylaluminum hydrides such as diethylaluminum hydride, dibutylaluminum hydride; ethylaluminum dihydride;
Other partially hydrogenated alkyl aluminums such as alkylaluminum dihydrides such as propylaluminum dihydride; partially alkoxylated and halogenated alkyls such as ethylaluminum ethoxycyclolide, butylaluminum butoxycyclolide, ethylaluminum ethoxybromide Aluminum and the like can be given.

Compounds similar to (B-1a) can also be used, and examples thereof include organoaluminum compounds in which two or more aluminum compounds are bonded via a nitrogen atom. Specifically, as such a compound,
(C ₂ H ₅ ) ₂ AlN (C ₂ H ₅ ) Al (C ₂ H ₅ ) ₂ .

The compound belonging to the above (B-1b) includes Li
Al (C ₂ H ₅ ) ₄ and LiAl (C ₇ H ₁₅ ) ₄ can be exemplified. In addition, (B-1) as the organometallic compound, methyl lithium, ethyl lithium, propyl lithium, butyl lithium, methyl magnesium bromide, methyl magnesium chloride, ethyl magnesium bromide, ethyl magnesium chloride, propyl magnesium bromide, propyl magnesium Chloride, butylmagnesium bromide, butylmagnesium chloride, dimethylmagnesium, diethylmagnesium, dibutylmagnesium, butylethylmagnesium 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 alkyllithium, or a combination of aluminum halide and alkylmagnesium can also be used.

(B-1) Among the organometallic compounds, an organoaluminum compound is preferred. The above-mentioned (B-1) organometallic compounds are used alone or in combination of two or more.

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

The conventionally known aluminoxane can be produced, for example, by the following method, and is usually obtained as a solution of a hydrocarbon solvent. (1) Compounds containing water of adsorption or salts containing water of crystallization such as hydrated magnesium chloride, hydrated copper sulfate, hydrated aluminum sulfate, hydrated nickel sulfate, hydrated cerium chloride A method of adding an organoaluminum compound such as a trialkylaluminum to a suspension of a hydrocarbon medium of the above, and reacting the water of adsorption or water of crystallization with the organoaluminum compound. (2) A method in which water, ice or steam is allowed to directly act on an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether or tetrahydrofuran. (3) A method of reacting an organoaluminum compound such as trialkylaluminum with an organotin oxide such as dimethyltin oxide or dibutyltin oxide in a medium such as decane, benzene or toluene.

The aluminoxane may contain a small amount of 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 for preparing the aluminoxane include the compounds (B-1a)
And the same organoaluminum compounds as those exemplified as the organoaluminum compounds belonging to the above.

Of these, trialkylaluminum and tricycloalkylaluminum are preferred, and trimethylaluminum is particularly preferred. The above-mentioned organoaluminum compounds are used alone or in combination of two or more.

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

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

As the organic aluminum oxy compound used in the present invention, an organic aluminum oxy compound containing boron represented by the following general formula (II) can also be mentioned.

[0086]

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In the formula, R ⁷ represents a hydrocarbon group having 1 to 10 carbon atoms. R ⁸ may be the same or different, and each has a hydrogen atom, a halogen atom, and 1 to 10 carbon atoms.
Represents a hydrocarbon group.

The boron-containing organoaluminum oxy compound represented by the general formula (II) is represented by the following general formula (I)
An alkylboronic acid represented by II) and R ⁷ -B- (OH) ₂ ... (III) (wherein R ⁷ represents the same group as described above). It can be produced by reacting in an inert solvent at a temperature of -80C to room temperature for 1 minute to 24 hours.

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

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

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

[(B-3) Compound which forms an ion pair by reacting with transition metal compound (I)] (A) used in the present invention
Examples of the compound (B-3) which reacts with the transition metal compound (I) to form an ion pair (hereinafter referred to as "ionized ionic compound") include JP-A-1-501950 and JP-A-1-502036. JP, JP-A-3-179005, JP-A-3-179006, JP-A-3-20
JP 7703, JP-A-3-207704, US
Examples thereof include Lewis acids, ionic compounds, borane compounds and carborane compounds described in P-5321106. Furthermore, heteropoly compounds and isopoly compounds can also be mentioned.

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

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

[0095]

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In the formula, R ⁹ includes H ⁺ , a carbonium cation, an oxonium cation, an ammonium cation, a phosphonium cation, a cycloheptyltrienyl cation, and a ferrocenium cation having a transition metal.

R ^{10 to} R ¹³ may be the same or different and are an organic group, preferably an aryl group or a substituted aryl group. Specific examples of the carbonium cation include trisubstituted carbonium cations such as triphenylcarbonium cation, tri (methylphenyl) carbonium cation, and tri (dimethylphenyl) carbonium cation.

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

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

As R ⁹ , a carbonium cation, an ammonium cation and the like are preferable, and a triphenylcarbonium cation, an N, N-dimethylanilinium cation and an N, N-diethylanilinium cation are particularly preferable.

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

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

Specific examples of the N, N-dialkylanilinium salt include N, N-dimethylaniliniumtetra (phenyl) boron, N, N-diethylaniliniumtetra (phenyl) boron, N, N-2, 4,6-pentamethylanilinium tetra (phenyl) boron and the like.

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

Further, as an ionic compound, triphenylcarbenium tetrakis (pentafluorophenyl)
Borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, ferrocenium tetra (pentafluorophenyl) borate, triphenylcarbenium pentaphenylcyclopentadienyl complex,
N, N-diethylanilinium pentaphenylcyclopentadienyl complex, a boron compound represented by the following formula (V) or (VI), and the like can also be mentioned.

[0106]

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

[0108]

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

Specific examples of the carborane compound include, for example, 4-carbanonaborane (14), 1,3-dicarbanonaborane (13), 6,9-dicarbadecaborane (14), dodecahydride-1-phenyl- 1,3-dicarbanonaborane,
Dodecahydride-1-methyl-1,3-dicarbanonaborane, undecahydride-1,3-dimethyl-1,3-dicarbanonaborane, 7,8-dicarboundecaborane (13), 2,
7-dicarboundecaborane (13), undecahydride-7,8-dimethyl-7,8-dicarboundecaborane, dodecahydride-11-methyl-2,7-dicarboundecaborane, tri (n-butyl ) Ammonium 1-carbadecaborate, tri (n-butyl) ammonium 1-carboundecaborate, tri (n-butyl) ammonium 1-carbadodecaborate, tri (n-butyl) ammonium 1-trimethylsilyl-1-carbadeca Borate, tri (n-butyl) ammonium bromo-1-carbadecaborate, tri (n-butyl) ammonium 6-carbadecaborate (14), tri (n-butyl) ammonium 6-carbadecaborate (1
2), tri (n-butyl) ammonium 7-carboundecaborate (13), tri (n-butyl) ammonium 7,8-
Dicarboundecaborate (12), tri (n-butyl)
Ammonium 2,9-dicarboundecaborate (12),
Tri (n-butyl) ammonium dodecahydride-8-
Methyl-7,9-dicarboundecaborate, tri (n-butyl) ammonium undecahydride-8-ethyl-7,9-
Dicarbaune decaborate, tri (n-butyl) ammonium undecahydride-8-butyl-7,9-dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-8-allyl-7,9-dicarbaune Decaborate, tri (n-butyl) ammonium undecahydride-9-trimethylsilyl-7,8-dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-4,6-dibromo-7-carboundecaborate Salts of anions such as;

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

The heteropoly compound includes an atom selected from silicon, phosphorus, titanium, germanium, arsenic, and tin;
It is composed of one or more atoms selected from vanadium, niobium, molybdenum and tungsten.
Specifically, phosphorus vanadic acid, germanovanadate, arsenic vanadate, phosphorus niobate, germanoniobate, siliconomolybdate, phosphomolybdate, titanium molybdate, germanomolybdate, arsenic molybdate, tin molybdate, phosphorus molybdate, phosphorus Tungstic acid, germanotungstic acid, tin tungstic acid, phosphomolybdovanadic acid, phosphorus tungstovanadic acid, germanotangostovanadate acid, phosphomolybdatovantovanadate acid, germanomolybdatovantovanadate acid, phosphomolybdine Tungstic acid, phosphomolybdniobic acid, and salts of these acids, for example, metals of Group 1 or 2 of the Periodic Table, specifically lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium ,barium Salts with organic salts of triphenyl ethyl salts, and the like can be used but not limited thereto.

The above (B-3) ionized ionic compounds are used alone or in combination of two or more. When the transition metal compound according to the present invention is used as a catalyst, particularly when used in combination with an organoaluminum oxy compound (B-2) such as methylaluminoxane as a co-catalyst component, it exhibits a particularly high polymerization activity for olefin compounds, and The resulting polyolefin has a high molecular weight and a broad molecular weight distribution.

The olefin polymerization catalyst according to the present invention comprises:
(A) the transition metal compound represented by the above (I), and (B)
(B-1) Organometallic compound (B-2) Organoaluminum oxy compound, and (B-3)
(A) It may be formed from at least one compound selected from compounds which form an ion pair by reacting with the transition metal compound (I). In this case, these compounds are used in the polymerization system.

[0115]

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A compound such as is formed. (R in the formula
^{1 to} R ⁶ , M, m, n and X are the same as in (I), and Y represents a so-called weakly coordinating anion. In this formula, the bond between the metal M and Y may be a covalent bond or an ionic bond. R ^{1 to} R ⁶ in the formula, M,
Specific examples of m, n, and X are the same as those in (I), and examples of Y include Chemical Review, vol. 88, p. 1405 (1988), and Chemical Review, vol. 93, p. 927 (1993). WO 98/306126. include weakly coordinating anions according to pages, specifically AlR ₄ in ^- (R may be a kind in two or more, an oxygen atom, a nitrogen atom, phosphorus atom, hydrogen atom, contain halogen atoms or their A substituent and an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or an alicyclic hydrocarbon group which may have a substituent containing an oxygen atom, a nitrogen atom, a phosphorus atom, a hydrogen atom, or a halogen atom) BR ₄ ^- (R may be two or more in one, an oxygen atom, a nitrogen atom, phosphorus atom, a hydrogen atom, a halogen atom or a substituent, and an aliphatic hydrocarbon group containing them, aromatic hydrocarbon group, alicyclic Oxygen atom, nitrogen atom, phosphorus atom, hydrogen atom in a cyclic hydrocarbon group May have a substituent containing a halogen atom) or PF ₆ ^-, SbF ₅ ^-, trifluoromethanesulfonate, p- toluenesulfonate, and the like.

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

[(C) Carrier] The (C) carrier optionally used in the present invention is an inorganic or organic compound,
It is a granular or particulate solid.

Of these, the inorganic compound is preferably a porous oxide, inorganic chloride, clay, clay mineral or ion-exchange layered compound. As the porous oxide, specifically, SiO ₂ , Al ₂ O ₃ , MgO, ZrO, TiO ₂ , B
_{Use of 2} O ₃ , CaO, ZnO, BaO, ThO _2, etc., or composites or mixtures containing them, such as natural or synthetic zeolites, SiO ₂ —MgO, SiO ₂ —Al ₂
O ₃ , SiO ₂ -TiO ₂ , SiO ₂ -V ₂ O ₅ , SiO ₂ -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 made of a small amount of Na ₂ C
O ₃ , K ₂ CO ₃ , CaCO ₃ , MgCO ₃ , Na ₂ SO ₄ ,
Al ₂ (SO ₄ ) ₃ , BaSO ₄ , KNO ₃ , Mg (NO ₃ ) ₂ ,
A carbonate, a sulfate, a nitrate, and an oxide component such as Al (NO ₃ ) ₃ , Na ₂ O, K ₂ O, and Li ₂ O may be contained.

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

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

The clay used in the present invention is usually composed mainly of a clay mineral. Further, the ion-exchangeable layered compound used in the present invention is a compound having a crystal structure in which planes formed by ionic bonds and the like are stacked in parallel with a weak binding force to each other, and contained ions are exchangeable. . Most clay minerals are ion-exchangeable layered compounds. In addition, as these clays, clay minerals and ion-exchangeable layered compounds, not only natural ones but also artificially synthesized ones can be used.

Further, as the clay, clay mineral or ion-exchangeable layered compound, clay, clay mineral and ionic crystalline compounds having a layered crystal structure such as hexagonal dense packing type, antimony type, CdCl ₂ type, CdI ₂ type, etc. Compounds and the like can be exemplified.

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

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

The volume of pores having a radius of 20 ° or more is 0.1 cc /
When a material smaller than g is used as a carrier, a high polymerization activity tends to be hardly obtained. The clay and clay mineral used in the present invention are preferably subjected to a chemical treatment.
Chemical treatment includes surface treatment to remove impurities adhering to the surface, treatment that affects the crystal structure of clay, etc.
Either can be used. Specific examples of the chemical treatment include an acid treatment, an alkali treatment, a salt treatment, and an 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 the salt treatment and the organic substance treatment, an ion complex, a molecular complex, an organic derivative, and the like are formed, and the surface area and the interlayer distance can be changed.

The ion-exchangeable layered compound used in the present invention is a layered compound in which the interlayer is expanded by using the ion-exchange property to exchange the exchangeable ion between the layers with another large bulky ion. You may. Such a bulky ion plays a role of a support for supporting the layered structure, and is usually called a pillar. Introducing another substance between layers of the layered compound in this way is called intercalation. Examples of the guest compound to be intercalated include cationic inorganic compounds such as TiCl ₄ and ZrCl ₄ , Ti (OR) ₄ , Zr (OR) ₄ , PO (OR) ₃ ,
Metal alkoxides such as B (OR) ₃ (R is a hydrocarbon group or the like), [Al ₁₃ O ₄ (OH) ₂₄ ] ⁷⁺ , [Zr ₄ (OH) ₁₄ ] ²⁺ ,
And metal hydroxide ions such as [Fe ₃ O (OCOCH ₃ ) ₆ ] ⁺ . These compounds are used alone or in combination of two or more. When intercalating these compounds, Si (OR) ₄ , Al (O
Polymers obtained by hydrolyzing metal alkoxides (R is a hydrocarbon group, etc.) such as R) ₃ and Ge (OR) ₄ , SiO ₂
Colloidal inorganic compounds, etc. can also be allowed to coexist. Examples of the pillars include oxides formed by intercalating the metal hydroxide ions between layers and then heating and dehydrating the layers.

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

Among these, preferred are clays or clay minerals, and particularly preferred are montmorillonite, vermiculite, pectrite, teniolite and synthetic mica.

The organic compound has a particle size of 10 to 300.
Granular or particulate solids in the range of μm can be mentioned. Specifically, ethylene, propylene,
-2 carbon atoms such as butene and 4-methyl-1-pentene
(Co) polymers formed mainly with α-olefins of No. to 14 or vinylcyclohexane, (co) polymers formed mainly with styrene, and modified products thereof.

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

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

As the alcohols and phenolic compounds, those represented by R ¹⁴ —OH are usually used.
Here, R ¹⁴ represents a hydrocarbon group having 1 to 50 carbon atoms or a halogenated hydrocarbon group having 1 to 50 carbon atoms.

As the alcohols, those in which R ¹⁴ is a halogenated hydrocarbon are preferred. Further, as the phenolic compound, a compound in which the α, α′-position of the hydroxyl group is substituted with a hydrocarbon having 1 to 20 carbon atoms is preferable.

As the carboxylic acid, R is usually¹⁵-COO
The one represented by H is used. R ¹⁵Represents 1 to 1 carbon atoms
50 hydrocarbon groups or halogens having 1 to 50 carbon atoms
A halo group having 1 to 50 carbon atoms.
Genated hydrocarbon groups are preferred.

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

[0138]

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In the formula, M is an element belonging to Groups 1 to 14 of the periodic table. R ¹⁶ is hydrogen, a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group having 1 to 20 carbon atoms.

X is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon group having 1 to 20 carbon atoms. m is an integer of 1 to 7, and n
Is 1 ≦ n ≦ 7.

FIG. 1 shows an example of a process for preparing the catalyst for olefin polymerization according to the present invention. At the time of polymerization, the method of use and the order of addition of each component are arbitrarily selected, and the following methods are exemplified. (1) 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 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. (3) 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. (4) A method in which a catalyst component in which the component (A) and the component (B) are supported on a carrier (C) is added to a polymerization reactor.

In each of the above methods (1) to (4), at least two or more of the catalyst components may be brought into contact with each other in advance. In each of the above methods (3) and (4) in which the component (B) is supported, the component (B) which is not supported is optionally provided.
May be added in any order. In this case, component (B)
May be the same or different.

A solid catalyst component in which the component (A) and the component (B) are supported on the component (C), and a solid catalyst component in which the component (A) and the component (B) are supported on the component (C) In the above, the olefin may be pre-polymerized, and the catalyst component may be further supported on the pre-polymerized solid catalyst component.

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

In the present invention, the polymerization can be carried out by any of liquid phase polymerization such as solution polymerization and suspension polymerization or gas phase polymerization. Specific examples of the inert hydrocarbon medium used in the liquid phase polymerization method include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; cyclopentane, cyclohexane, methylcyclopentane Alicyclic hydrocarbons such as benzene, toluene, xylene, etc .; halogenated hydrocarbons such as ethylene chloride, chlorobenzene, dichloromethane and the like, and mixtures thereof, and the olefin itself is used as a solvent. You can also.

In conducting olefin polymerization using the olefin polymerization catalyst as described above, the component (A)
Usually 10 ^-12 to 10 ^-2 mol per liter of reaction volume,
Preferably, it is used in such an amount that it becomes 10 ^-10 to 10 ^-3 mol.

Component (B-1) is composed of component (B-1) and component (A)
Molar ratio with all transition metal atoms (M) in the solution [(B-1) / M]
But usually 0.01 to 100000, preferably 0.05
It is used in such an amount that it becomes ５０50,000. Ingredient (B-2)
Has a molar ratio [(B-2) / M] of the aluminum atom in the component (B-2) to the transition metal atom (M) in the component (A) of usually 10 to 500,000, preferably 20 to 50 100000
It is used in such an amount that Component (B-3) is replaced by component (B-
The molar ratio of the component (3) to the component (the transition metal atom (M) in A [(B-3) / M]) is usually 1 to 10, preferably 1 to 5.

Component (D) is obtained by converting component (B) to component (B-1)
, The molar ratio [(D) / (B-1)] is usually 0.0
When the component (B) is the component (B-2) in such an amount as to be 1 to 10, preferably 0.1 to 5, the molar ratio [(D) /
(B-2)] is usually 0.001-2, preferably 0.00
When the component (B) is the component (B-3) in such an amount as to be 5 to 1, the molar ratio [(D) / (B-3)] is usually 0.01.
-10, preferably 0.1-5.

The polymerization temperature of olefin using such an olefin polymerization catalyst is usually -50 to +200.
° C, preferably 0-170 ° C, particularly preferably 40-1 ° C.
It is in the range of 70 ° C. The polymerization pressure is usually from normal pressure to 100 k.
g / cm ^2, preferably under conditions of normal pressure to 50 kg / cm ^2, particularly preferably under conditions of 5 to 50 kg / cm ^2. Further, the polymerization reaction can be carried out in any of a batch system, a semi-continuous system, and a continuous system. Further, the polymerization can be performed in two or more stages having different reaction conditions.

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

The compound selected from B is preferably an organoaluminum oxy compound. As a characteristic of these polymerization methods, the intrinsic viscosity [η] is 2.0 dl / g or more, preferably 3.0 dl / g or more. There is usually 40.0dl / g or less,
It is a high molecular weight substance, and the value of Mw / Mn determined by GPC is 5.0 or more, preferably 20.0 or more and usually 100.0 or more.
It is possible to produce the following polyolefin having a wide molecular weight distribution.

Examples of the olefin that can be polymerized with such an olefin polymerization catalyst include linear or branched α-olefins having 2 to 30, preferably 2 to 20 carbon atoms, such as ethylene, propylene, and the like. 1-butene, 2-butene, 1-pentene, 3-methyl-1-butene, 1-
Hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene;
Cyclic olefins having 3 to 30, preferably 3 to 20 carbon atoms, such as cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, 2-methyl 1,4,5,8-dimethano- 1,2,3,4,4a, 5,8,
8a-octahydronaphthalene;

Polar monomers such as acrylic acid, methacrylic acid, fumaric acid, maleic anhydride, itaconic acid,
Α, β-unsaturated carboxylic acids such as itaconic anhydride, bicyclo (2,2,1) -5-heptene-2,3-dicarboxylic anhydride, and their sodium, potassium and lithium salts;
Metal salts such as zinc, magnesium and calcium salts;
Methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate,
Α, β-unsaturated carboxylic esters such as 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate; vinyl acetate, propionic acid Vinyl esters such as vinyl, vinyl caproate, vinyl caprate, vinyl laurate, vinyl stearate, and vinyl trifluoroacetate; unsaturated glycidyls such as glycidyl acrylate, glycidyl methacrylate, and monoglycidyl itaconate; Vinyl, vinyl chloride, vinyl bromide,
Examples thereof include halogenated olefins such as vinyl iodide.

As the olefin, vinylcyclohexane, diene, polyene or the like can be used. The diene or polyene has 4 to 4 carbon atoms.
A cyclic or chain compound having 30, preferably 4 to 20, and having two or more double bonds is used. Specifically, butadiene, isoprene, 4-methyl-1,3-pentadiene, 1,3-pentadiene, 1,4-pentadiene, 1,5-hexadiene, 1,4-hexadiene, 1,3-hexadiene, 1 , 3-
Octadiene, 1,4-octadiene, 1,5-octadiene,
1,6-octadiene, 1,7-octadiene, ethylidene norbornene, vinylnorbornene, dicyclopentadiene; 7-methyl-1,6-octadiene, 4-ethylidene-8-methyl-1,7-nonadiene, 5,9- Dimethyl-1,4,8-decatriene;

Further, as the olefin, an aromatic vinyl compound such as styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o, p-dimethylstyrene,
mono- or polyalkylstyrenes such as o-ethylstyrene, m-ethylstyrene and p-ethylstyrene; methoxystyrene, ethoxystyrene, vinylbenzoic acid, methylvinylbenzoate, vinylbenzylacetate, hydroxystyrene, o-chlorostyrene, p Functional group-containing styrene derivatives such as -chlorostyrene and divinylbenzene; and 3-phenylpropylene, 4-phenylpropylene, α-
Methyl styrene and the like can be mentioned. These olefins can be used alone or in combination of two or more.

[0156]

The catalyst for olefin polymerization according to the present invention comprises:
A polyolefin having a high molecular weight and a wide molecular weight distribution can be produced with high polymerization activity. The olefin polymerization method according to the present invention can produce a polyolefin having a high molecular weight and a wide molecular weight distribution with high polymerization activity.

[0157]

EXAMPLES Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to these examples. In this example, the intrinsic viscosity [η]
Was measured in 135 ° C decalin. Molecular weight distribution (Mw
/ Mn) is 140 using o-dichlorobenzene as a solvent.
It measured and measured by gel permeation chromatography (GPC) in ° C. The structure of the compound obtained in the synthesis example was 270 MHz ¹ H NMR (JEOL GSH-2
70), using FD-mass spectrometry (JEOL SX-102A).

(1) Synthesis of ligand [(1-1) Synthesis of ligand L-1]

[Synthesis Example] 7.51 g (50 mmol) of 2-tert-butylphenol and 54 ml of tetrahydrofuran are charged into a 500 ml reactor sufficiently dried and purged with argon, and 18.53 ml of ethylmagnesium bromide (ether solution, 3.0N, 55.6 g) is added at 0 ° C. mmo
l) was added dropwise over 15 minutes, and then the temperature was slowly raised to room temperature, followed by stirring at room temperature for 1 hour. Add 180 ml of toluene and add 10
The mixture was heated by heating to 0 ° C., and about 40 ml of a mixed solution of ether / THF was distilled off to obtain a cloudy slurry. After cooling to room temperature, 3.95 g (125 mmol) of paraformaldehyde and 10.45 ml (75 mmol) of triethylamine were added, and the mixture was stirred at 88 ° C for 1 hour. After allowing to cool to room temperature, the mixture was quenched with 10% hydrochloric acid, and the organic layer was concentrated and purified by a silica gel column to give 6.22 g of 3-t-butylsalicylaldehyde (yield 7
0%). _{^{1 H-NMR (CDCl 3)}} : 1.42 (s, 9H) 6.94 (t, 1H) 7.25-7.54 (m, 2
H) 9.86 (s, 1H) 11.79 (s, 1H)

A 100-ml reactor purged with nitrogen was charged with 40 ml of ethanol, 0.93 g (7.62 mmol) of 4-methoxyaniline and 1.35 g (7.58 mmol) of 3-t-butylsalicylaldehyde, and the mixture was stirred at room temperature for 24 hours. Continued. The reaction solution was concentrated under reduced pressure to remove the solvent.
Stirring was continued for 12 hours. The reaction solution was concentrated under reduced pressure, and 2.05 g (7.23 mmol, yield 95%) of an orange oil compound represented by L-1 was obtained.
%). ¹ H-NMR (CDCl ₃ ): 1.47 (s, 9H) 6.88 (dd, 1H) 7.24-7.31 (m,
4H) 7.38-7.46 (m, 3H) 8.64 (s, 1H) 13.95 (s, 1H) IR (neat): 1575, 1590, 1610 cm ^-1 FD-Mass spectrometry: 253

[0160]

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In the same manner, ligands L-2 to L-7 were synthesized from the corresponding phenol compounds and aniline compounds. [Synthesis result of (1-2) ligand (L-2)] ¹ H-NMR (CDCl ₃ ): 1.40 (s, 9H) 3.70 (s, 3H) 6.60-7.50 (m, 7
H) 8.5 (s, 1H) 13.60 (s, 1H)

[Synthesis result of (1-3) ligand (L-3)] ¹ H-NMR (CDCl ₃ ): 1.47 (s, 9H) 6.90-6.95 (m, 1H) 7.26-7.48
(m, 4H) 8.28-8.34 (m, 2H) 8.65 (s, 1H) 13.27 (s, 1H)

[Synthesis result of (1-4) ligand (L-4)] ¹ H-NMR (CDCl ₃ ): 1.52 (s, 9H) 3.04 (s, 6H) 6.70-6.90 (m, 3
H) 7.20-7.40 (m, 4H) 8.65 (s, 1H) 14.35 (s, 1H)

[Synthesis result of (1-5) ligand (L-5)] ¹ H-NMR (CDCl ₃ ): 1.45 (s, 9H) 3.82 (s, 3H) 3.87 (s, 3H) 6.7
2 (s, 1H) 6.95-6.99 (d, 2H) 7.03 (s, 1H) 7.28-7.32 (d, 2H)
8.59 (s, 1H) 13.67 (s, 1H)

[Synthesis result of (1-6) ligand (L-6)] ¹ H-NMR (CDCl ₃ ): 1.80 (s, 6H) 2.00-2.19 (m, 3H) 2.20 (s, 6)
H) 2.31 (s, 3H) 3.84 (s, 3H) 6.92-7.28 (m, 6H) 8.56 (s, 1
H) 13.83 (s, 1H)

[Synthesis result of (1-7) ligand (L-7)] ¹ H-NMR (CDCl ₃ ): 1.70 (s, 6H) 1.73 (s, 6H) 3.80 (s, 3H) 6.8
4-6.89 (m, 2H) 7.12-7.41 (m, 14H) 8.49 (s, 1H) 13.39 (s, 1
H)

[0167]

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(2) Synthesis of transition metal compound

[Synthesis Example 1] In a 100 ml reactor which was sufficiently dried and purged with argon, 0.577 g (2.04 mmol) of compound L-1 and 25 ml of THF were charged, cooled to -78 ° C and stirred. N-butyl lithium
1.40 ml (n-hexane solution, 1.54 M, 2.14 mmol) was added dropwise over 10 minutes, and then the temperature was slowly raised to room temperature.
Stirring was continued for 2 hours to prepare a lithium salt solution. This solution was cooled to −40 ° C. and the ZrCl ₄ (THF) ₂ complex 0.385 g (1.02 mm
ol) in 20 ml of THF. After completion of the dropwise addition, stirring was continued while slowly raising the temperature to room temperature. 15 at room temperature
After stirring for an hour, the reaction solution was evaporated. The obtained solid was dissolved in 40 ml of dichloromethane, and after removing insolubles in the solution, the solution was concentrated under reduced pressure. By recrystallizing the obtained solid with dichloromethane, 0.285 g of a compound of a bright yellow crystal represented by the following formula (1) (0.39 mmol, yield 38)
%)Obtained. ¹ H-NMR (CDCl ₃ ): 1.40 (s, 18H) 3.75 (s, 6H) 6.40-7.70
(m, 14H) 8.10 (s, 2H) FD-Mass Spectrometry: 726 (M +) Elemental Analysis: Zr; 12.3% (12.6)
Figures in parentheses are calculated values

[0169]

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[0170]

[Synthesis Example 2] In a 100 ml reactor which was sufficiently dried and purged with argon, 0.64 g (2.26 mmol) of compound L-2 and 20 ml of diethyl ether were charged, cooled to -78 ° C and stirred. 1.40 ml of n-butyllithium (n-hexane solution, 1.61M, 2.26mmo)
l) was added dropwise over 5 minutes, then the temperature was slowly raised to room temperature, and stirring was continued at room temperature for 4 hours to prepare a lithium salt solution. This solution was cooled to −78 ° C. with ZrCl ₄ (THF) ₂ complex 0.42
g (1.10 mmol) was slowly added dropwise to a solution of THF (20 ml). After completion of the dropwise addition, stirring was continued while slowly raising the temperature to room temperature. After further stirring at room temperature for 15 hours, the reaction solution was evaporated. The obtained solid was dissolved in 50 ml of methylene chloride, and insolubles were removed with a glass filter. The filtrate is concentrated under reduced pressure,
The precipitated solid was reprecipitated with methylene chloride and hexane, and dried under reduced pressure to obtain 0.25 g (0.34 mmol, 31% yield) of a yellow-green powder compound represented by the following formula (2). ¹ H-NMR (CDCl ₃ ): 1.20-1.60 (m, 18H) 3.66-3.86 (m, 6H)
6.50-7.50 (m, 14H) 8.05-8.20 (m, 2H) FD-Mass spectrometry: 726 (M +) Elemental analysis: Zr; 12.4% (12.6)
Figures in parentheses are calculated values

[0171]

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[0172]

[Synthesis Example 3] To a 50 ml reactor which was sufficiently dried and purged with argon, 0.57 g (1.50 mmol) of ZrCl ₄ (THF) ₂ complex in 20 ml of THF was charged, cooled to 0 ° C and stirred. Compound L-3 0.90
g (3.00 mmol) of THF (20 ml) was added dropwise over 5 minutes. After completion of the dropwise addition, the temperature was raised to room temperature, and the mixture was stirred at room temperature for 1.5 hours. The obtained solid was dissolved in 10 ml of ether and 10 ml of methylene chloride, and insolubles were removed with a glass filter. The filtrate was concentrated under reduced pressure.
After dissolving with 10 ml, insoluble matter in the solution is removed by a glass filter, and then dried under reduced pressure to obtain the following formula (3).
0.43 g (0.57 mmol, yield 38) of a yellow powdered compound represented by
%)Obtained. ¹ H-NMR (CDCl ₃ ): 1.44 (s, 9H) 1.49 (s, 9H) 6.62-7.50 (m,
10H) 8.07-8.35 (m, 4H) 8.67 (s, 2H) FD-Mass Spec: 755

[0173]

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[0174]

Synthesis Example 4 1.09 g (3.68 mmol) of compound L-4 and 22 ml of diethyl ether were charged into a 100 ml reactor which had been thoroughly dried and purged with argon, cooled to 0 ° C. and stirred. 2.51 ml of n-butyllithium (n-hexane solution, 1.54M, 3.68mmo)
l) was added dropwise over 5 minutes, and then the temperature was slowly raised to room temperature, and stirring was continued at room temperature for 3 hours to prepare a lithium salt solution. This solution was cooled to -78 ° C and zirconium tetrachloride
_A solution of 0.43 g (3.68 mmol) in 20 ml of ether was slowly added dropwise. After dropping, slowly raise the temperature to room temperature.
After stirring for an hour, the reaction solution was filtered. The obtained solid was washed with 2 ml of dichloromethane, 10 ml of hexane and 5 ml of ether, and dried under reduced pressure to obtain 0.35 g (0.46 mmol, 25% yield) of a yellow-green powder compound represented by the following formula (4). . ¹ H-NMR (CDCl ₃ ): 1.42 (s, 18H) 2.76 (s, 6H) 2.98 (s, 6H)
6.30-7.45 (m, 14H) 8.00 (s, 2H) FD-Mass Spec: 752

[0175]

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[0176]

[Synthesis Example 5] In a 100 ml reactor which was sufficiently dried and purged with argon, 0.69 g (2.21 mmol) of compound L-5 and 30 ml of diethyl ether were charged, cooled to -78 ° C and stirred. 1.55 ml of n-butyllithium (n-hexane solution, 1.54M, 2.27mm
ol) was added dropwise over 5 minutes, then the temperature was slowly raised to room temperature, and stirring was continued at room temperature for 4 hours to prepare a lithium salt solution. This solution was cooled to −78 ° C. to obtain a ZrCl ₄ (THF) ₂ complex _.
A solution of 42 g (1.10 mmol) in 30 ml of THF was slowly added dropwise. After completion of the dropwise addition, stirring was continued while slowly raising the temperature to room temperature. After further stirring at room temperature for 16 hours, the reaction solution was evaporated. After the obtained solid was washed with 30 ml of hexane, 25 ml of ether and 20 ml of hexane were added. After filtering this solution, the filtrate was concentrated to 20 ml. The precipitated solid is washed with hexane
It was filtered while washing with 10 ml and ether 3 ml. The obtained solid was dried under reduced pressure to obtain 0.19 g (0.24 mmol, 22% yield) of a compound of a yellow-green powder represented by the following formula (5).
Obtained. ¹ H-NMR (CDCl ₃ ): 1.35 (s, 18H) 3.60-3.90 (s, 12H) 6.40-
7.30 (m, 12H) 8.05 (s, 2H) FD-Mass spectrometry: 786

[0177]

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[0178]

Synthesis Example 6 0.82 g (2.18 mmol) of compound L-6 and diethyl ether were placed in a 30 ml reactor which was sufficiently dried and purged with argon.
20 ml was charged, cooled to -78 ° C and stirred. 1.55 ml of n-butyllithium (n-hexane solution, 1.54M, 2.27mmo
l) was added dropwise over 10 minutes, then the temperature was slowly raised to room temperature, and stirring was continued at room temperature for 5 hours to prepare a lithium salt solution. This solution was cooled to −78 ° C. to obtain a ZrCl ₄ (THF) ₂ complex _.
A solution of 41 g (1.09 mmol) in 20 ml of THF was slowly added dropwise. After completion of the dropwise addition, stirring was continued while slowly raising the temperature to room temperature. After further stirring at room temperature for 16 hours, the reaction solution was evaporated. The obtained solid is ether 20 ml, methylene chloride 10 m
And insolubles were removed with a glass filter. After the filtrate was concentrated under reduced pressure, it was again dissolved in 20 ml of ether, and insolubles were removed with a glass filter. After the filtrate was concentrated, 10 ml of hexane was added and the mixture was filtered. The obtained solid was dried under reduced pressure to obtain 0.19 g (0.20 mmol, yield: 19%) of a compound as a yellow powder represented by the following formula (6). ¹ H-NMR (CDCl ₃ ): 1.74-2.30 (s, 36H) 3.66 (s, 6H) 6.57-
6.91 (m, 12H) 8.02 (s, 2H) FD-Mass spectrometry: 910

[0179]

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[0180]

Synthesis Example 7 1.10 g (2.37 mmol) of compound L-7 and diethyl ether were placed in a 30 ml reactor which was sufficiently dried and purged with argon.
20 ml was charged, cooled to -78 ° C and stirred. Add 1.69 ml of n-butyllithium (n-hexane solution, 1.54M, 2.61mmo
l) was added dropwise over 5 minutes, then the temperature was slowly raised to room temperature, and stirring was continued at room temperature for 5 hours to prepare a lithium salt solution. This solution was cooled to −78 ° C. with a ZrCl ₄ (THF) ₂ complex of _0.45.
g (1.19 mmol) was slowly added dropwise to a solution of THF (20 ml). After completion of the dropwise addition, stirring was continued while slowly raising the temperature to room temperature. After further stirring at room temperature for 16 hours, the reaction solution was evaporated. The obtained solid was dissolved in 20 ml of ether, and insolubles were removed with a glass filter. After concentrating the filtrate under reduced pressure,
It was again dissolved in 30 ml of ether, and insolubles were removed with a glass filter. After the filtrate was concentrated, 40 ml of hexane was added and the mixture was filtered. The obtained solid was dried under reduced pressure to obtain 0.10 g (0.09 mmo) of a yellow powdered compound represented by the following formula (7).
1, yield 7.5%). ¹ H-NMR (CDCl ₃ ): 1.65 (s, 12H) 1.78 (s, 12H) 3.81 (s, 6H)
6.91-7.85 (m, 32H) 8.68 (s, 2H) FD-Mass Spec: 1086

[0181]

Embedded image (3) Olefin polymerization using transition metal compounds

EXAMPLE 1 500 ml of heptane was charged into a 1 liter autoclave made of SUS which had been sufficiently purged with nitrogen, heated to 75 ° C., and the liquid phase and the gas phase were saturated with ethylene. Thereafter, 1.25 mmol of methylaluminoxane in terms of aluminum atom and 0.0001 of zirconium compound (1) were added.
mmol and added at ethylene pressure of 8 kg / cm2-G.
Polymerization was carried out for 5 minutes.

To the obtained polymer suspension was added 1.5 liter of methanol containing a small amount of hydrochloric acid to precipitate a polymer. The polymer was filtered with a glass filter, the solvent was removed, and the polymer was washed with methanol and heated to 80 ° C. And dried under reduced pressure for 10 hours.
The obtained polyethylene was 6.143 g, and the polymerization activity was 246.
kg / mmol-Zr · hr. The intrinsic viscosity [η] of the obtained polyethylene was 6.45 dl / g, and the value of the molecular weight distribution (Mw / Mn) determined by GPC was 39.5.

Example 2 The polymerization was carried out in the same manner as in Example 1, except that the zirconium compound (1) was changed to the zirconium compound (2). As a result, the resulting polyethylene was 5.51 g, and the polymerization activity was 5.5%. Was 220 kg / mmol-Zr · hr. The intrinsic viscosity [η] of the obtained polyethylene is 3.
45dl / g, and the value of the molecular weight distribution (Mw / Mn) determined from GPC is
43.9.

Example 3 In the polymerization of Example 1, the addition amount of the zirconium compound (1) to the zirconium compound (3) was 0.00
As a result of performing polymerization in the same manner except that the amount was changed to 5 mmol, the obtained polyethylene was 1.68 g, and the polymerization activity was
1.34 kg / mmol-Zr · hr. The intrinsic viscosity [η] of the obtained polyethylene was 9.75 dl / g, and the value of the molecular weight distribution (Mw / Mn) determined by GPC was 48.3.

Example 4 Polymerization was carried out in the same manner as in Example 1 except that the zirconium compound (1) was changed to the zirconium compound (4). As a result, the obtained polyethylene was 6.80 g, and the polymerization activity was Was 272 kg / mmol-Zr · hr. The intrinsic viscosity [η] of the obtained polyethylene is 5.
20dl / g, and the value of the molecular weight distribution (Mw / Mn) obtained from GPC is
Was 42.1.

Example 5 In the polymerization of Example 1, the addition amount of the zirconium compound (1) to the zirconium compound (5) was 0.00
Polymerization was performed in the same manner except that the amount was changed to 05 mmol, and the obtained polyethylene was 6.68 g, and the polymerization activity was
It was 53 kg / mmol-Zr · hr. The intrinsic viscosity [η] of the obtained polyethylene was 4.60 dl / g, and the value of the molecular weight distribution (Mw / Mn) determined by GPC was 44.6.

Example 6 Polymerization was carried out in the same manner as in Example 1, except that the zirconium compound (1) was changed to the zirconium compound (6). As a result, the obtained polyethylene was 5.32 g, and the polymerization activity was 5.3%. Was 213 kg / mmol-Zr · hr. The intrinsic viscosity [η] of the obtained polyethylene was 7.
90dl / g, and the value of the molecular weight distribution (Mw / Mn) determined from GPC is
51.1.

Example 7 In the polymerization of Example 1, the addition amount of the zirconium compound (1) to the zirconium compound (7) was 0.00
Polymerization was performed in the same manner except that the amount was changed to 02 mmol, and the obtained polyethylene was 3.05 g, and the polymerization activity was
It was 61 kg / mmol-Zr · hr. The intrinsic viscosity [η] of the obtained polyethylene was 14.3 dl / g, and the value of the molecular weight distribution (Mw / Mn) determined by GPC was 46.3.

Comparative Example 1 In the polymerization of Example 1, the zirconium compound (1) was added to the following zirconium compound (8) in an amount of
Polymerization was performed in the same manner except that 0.0002 mmol, the ethylene pressure was changed to 1 kg / cm ² -G, and the polymerization time was changed to 5 minutes. As a result, the obtained polyethylene was 1.17 g, and the polymerization activity was 1.17 g.
It was 70.2 kg / mmol-Zr · hr. The intrinsic viscosity [η] of the obtained polyethylene was 0.46 dl / g, and the value of the molecular weight distribution (Mw / Mn) determined by GPC was 2.90.

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[Brief description of the drawings]

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

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Masatoshi Nitahara 6-1-2, Waki, Waki-machi, Kuga-gun, Yamaguchi Prefecture Inside Mitsui Chemicals Co., Ltd. (72) Inventor Kazutaka Tsuru Waki, Waki-cho, Yamaguchi 6-1-2, Mitsui Chemicals Co., Ltd. (72) Inventor Nariwa Matsui 6-1-2, Mitsui Chemicals Co., Ltd. 6-1-2, Waki, Waki-machi, Kuga-gun, Yamaguchi Prefecture (72) Inventor Terunori Fujita Yamaguchi 6-1-2, Waki, Waki-machi, Kuga-gun Mitsui Chemicals Co., Ltd. F-term (reference) 4J028 AA01A AB00A AB01A AC01A AC02A AC09A AC22A AC27A AC31A BA03B BB01B BB02B BC01B BC04B BC12B BC14B BC15B BC16B BC19B BC02B BC19B BC19B BC19B BC01B EB03 EB04 EB05 EB07 EB08 EB09 EB10 EB12 EB13 EB14 EB21 EB25 FA01 FA02 FA03 FA04 FA07 GA04 GA06 4J100 AA02P AA03P AA04P AA07P AA09P AA15P AA16P AA18P AA19P AA11P AC03P AJ02P AJ09P AL02P AR02P AR04P AR11P AR21P CA01 CA04 FA10

Claims (5)

[Claims] (A) a transition metal compound represented by the following general formula (I), (B) (B-1) an organometallic compound, (B-2) an organoaluminum oxy compound, and (B-3) An olefin polymerization catalyst comprising: at least one compound selected from compounds that form an ion pair by reacting with a transition metal compound (A). Embedded image (Wherein, M represents a transition metal atom belonging to Groups 4 to 5 of the periodic table,
m represents an integer of 1 to 2, R ¹ is one or more optionally substituted aromatic hydrocarbon group, R ²
To R ⁵ may be the same or different, and each represents a hydrogen atom, a halogen atom, a hydrocarbon group, a hydrocarbon-substituted silyl group, a hydrocarbon-substituted siloxy group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group. , A halogen-containing group, a group selected from heterocyclic compound residues, wherein at least one or more selected from the group consisting of a substituent of R ¹ and R ^{2 to} R ⁵ is a halogen atom, Group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, a halogen-containing group, or a group selected from heterocyclic compound residues, or a hydrocarbon group or a hydrocarbon-substituted silyl group containing those groups, R ⁶ represents a hydrocarbon group or a hydrocarbon-substituted silyl group, and two or more of R ^{1 to} R ⁶ may be connected to each other to form a ring, and n is a valence of M X is a hydrogen atom, Halogen atom, hydrocarbon group, oxygen-containing group, sulfur-containing group, nitrogen-containing group, boron-containing group, aluminum-containing group, phosphorus-containing group, halogen-containing group, heterocyclic compound residue, silicon-containing group, germanium-containing group, Or a tin-containing group, and when n is 2 or more, X
May be the same or different from each other, and the groups represented by X may be bonded to each other to form a ring. ) In the general formula (I), at least one or more selected from the group consisting of a substituent of R ¹ and R ^{2 to} R ⁵ is a heterocyclic compound residue, an alkylthio group, 2. The olefin polymerization catalyst according to claim 1, which is a group selected from an aryloxy group, an arylthio group, an amino group, an imino group, a cyano group, or a nitro group, or a hydrocarbon group containing such a group. 3. In the general formula (I), at least one or more selected from the group consisting of a substituent of R ¹ and R ^{2 to} R ⁵ is an alkoxy group, and At least one of them is a heterocyclic compound residue, an alkoxy group, an alkylthio group, an aryloxy group, an arylthio group, an amino group, an imino group, a cyano group, or a group selected from nitro groups or contains these groups. 2. The olefin polymerization catalyst according to claim 1, which is a hydrocarbon group. 4. The olefin polymerization catalyst according to claim 1, wherein an organic aluminum oxy compound (B-2) is used as the component (B). 5. An olefin is polymerized in the presence of the catalyst for olefin polymerization according to any one of claims 1 to 4, having an intrinsic viscosity [η] of 2.0 dl / g or more and an Mw / Gw determined by GPC. A method for polymerizing an olefin, comprising producing a polyolefin having a Mn value of 5.0 or more.