JP2000239312A - Catalyst for polymerizing olefin and olefin polymerization using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prepare a catalyst for polymerizing olefins, having high polymerizing reactivity at a high temperature and useful for polymerizing ethylene or the like by including a specific transition metal compound. SOLUTION: This catalyst is prepared by including a transition metal compound [e.g. a compound of formula II (wherein, tBu is t-butyl; nOctadecyl is n-octadecyl) or the like] of formula I [wherein, M is a transition metal of group IV-V; (m) is 1-5; Q is N or C having a substituent R2; A is O, S, N having a substituent R5 or the like; R1 is an aromatic hydrocarbon, an (alicyclic hydrocarbon-substituted) aliphatic hydrocarbon or the like; R2 to R5 are each H, a hydrocarbon or the like; (n) is a number satisfying the valence of M; X is H, a halogen or the like] in which the net charge parameter of a central metal M is <=2.00. The compound of formula I is obtained e.g. by reacting a ligand precursor such as a compound of formula III with a compound [e.g. a compound of the formula: ZrCl(THF)2 (wherein, THF is tetrahydrofuran)] of the formula: MXk [wherein, (k) is a number satisfying the valence of M].

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a novel catalyst for olefin polymerization and a method for polymerizing olefins using the catalyst for olefin polymerization.

[0002]

BACKGROUND OF THE INVENTION Polyolefins are generally used in various fields such as for various molded articles because of their excellent mechanical properties. In recent years, demands for physical properties of polyolefins have been diversified, and polyolefins of various properties are desired, and improvement in productivity is also desired.

As a catalyst for producing a polyolefin, a titanium catalyst comprising a titanium compound and an organoaluminum compound and a vanadium catalyst comprising a vanadium compound and an organoaluminum compound have been known.

A Ziegler catalyst comprising a metallocene compound such as zirconocene and an organic aluminum oxy compound (aluminoxane) is known as a catalyst capable of producing a polyolefin with high polymerization activity.

[0005] 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. Further, as a new catalyst for olefin polymerization, the present applicant has proposed a transition metal compound having a salicylaldimine ligand in Japanese Patent Application Laid-Open No. 11-315109. The catalyst exhibits high olefin polymerization activity at temperatures around 25 ° C. However, when producing a polyolefin by an industrial process, higher temperatures are advantageous in that the heat of reaction is easier to remove, the viscosity of the reaction solution can be reduced, and productivity is improved. There is a need for a polymerization catalyst having higher polymerization activity at high temperatures.

[0006]

SUMMARY OF THE INVENTION The object of the present invention is to provide a catalyst for olefin polymerization having a high polymerization activity at high temperatures, which has been made in view of the above prior art. Another object of the present invention is to provide a method for polymerizing an olefin using such a catalyst having good properties.

[0007]

The catalyst for olefin polymerization according to the present invention is characterized by comprising a transition metal compound represented by the following general formula (I) and having a net charge parameter of the central metal M of 2.00 or less.

[0008]

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(Wherein, M represents a transition metal atom belonging to Groups 4 to 5 of the periodic table, m represents an integer of 1 to 5, Q represents a nitrogen atom or a carbon atom having a substituent R ²⁾ A represents an oxygen atom, a sulfur atom, a selenium atom or a nitrogen atom having a substituent R ⁵ , and R ¹ represents an aliphatic hydrocarbon group which may be substituted with an aromatic hydrocarbon group or an alicyclic hydrocarbon group. A hydrogen group, or an alicyclic hydrocarbon group which may be substituted with an aromatic hydrocarbon group or an aliphatic hydrocarbon group, and R ^{2 to} R ⁵ may be the same or different;
Hydrogen atom, hydrocarbon group, oxygen containing group, nitrogen containing group, sulfur containing group, boron containing group, aluminum containing group, phosphorus containing group, halogen containing group, heterocyclic compound residue, silicon containing group, germanium containing group or Indicates a tin-containing group,
Two or more of these may be connected to each other to form a ring, and when m is 2 or more, among the groups represented by R ^{2 to} R ⁵ belonging to any one of the ligands And at least one of the groups represented by R ^{2 to} R ⁵ belonging to another ligand may be linked to each other, and when m is 2 or more, , R ¹ , R ² , R
³ and R ⁴ and R ⁵ may be the same or different from each other, n is a number satisfying the valence of M, and X is
Hydrogen atom, halogen atom, hydrocarbon group, oxygen-containing group, sulfur-containing group, nitrogen-containing group, boron-containing group, aluminum-containing group, phosphorus-containing group, halogen-containing group, heterocyclic compound residue, silicon-containing group, germanium And 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 bond to each other to form a ring May be. ).

The transition metal compound represented by the general formula (I) is represented by the following general formula (Ia) and has a net charge parameter of the central metal M in the range of 1.70 to 2.00. There are transition metal compounds.

[0011]

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Wherein M, m, A, n and X have the same meanings as M, m, A, n and X in the general formula (I), respectively, and R ^1a represents an aromatic hydrocarbon group. Or an aliphatic hydrocarbon group which may be substituted with an alicyclic hydrocarbon group, wherein R ² and R ^{5 to} R ⁹ may be the same or different from each other, and include a hydrogen atom, a hydrocarbon group, and an oxygen-containing group. Group, a nitrogen-containing group, a sulfur-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, a halogen-containing group, a heterocyclic compound residue, a silicon-containing group, a germanium-containing group, or a tin-containing group. ^May be linked to each other to form a ring, and when m is 2 or more, among the groups represented by R ² and R ^{5 to} R ⁹ belonging to any one of the ligands, And at least one group represented by R ² and R ^{5 to} R ⁵ belonging to another ligand ^At least one of the groups represented by ⁹
And when m is 2 or more, R ^1a , R ² , R ⁵ , R ⁶ ,
⁷ to each other, R ⁸ together, each other R ⁹ may be the same or different from each other. In addition, the transition metal compound represented by the general formula (I) includes:
There is a transition metal compound represented by the following general formula (Ib) and having a net charge parameter of the central metal M in the range of 1.50 to 1.89.

[0013]

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Wherein M, m, A, n and X have the same meanings as M, m, A, n and X in the general formula (I), respectively, and R ^1b represents an aromatic hydrocarbon group. Or an alicyclic hydrocarbon group which may be substituted with an aliphatic hydrocarbon group, wherein R ² and R ^{5 to} R ⁹ may be the same or different from each other, and include a hydrogen atom, a hydrocarbon group, Group, a nitrogen-containing group, a sulfur-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, a halogen-containing group, a heterocyclic compound residue, a silicon-containing group, a germanium-containing group, or a tin-containing group. ^May be linked to each other to form a ring, and when m is 2 or more, among the groups represented by R ² and R ^{5 to} R ⁹ belonging to any one of the ligands, And at least one group represented by R ² and R ^{5 to} R ⁵ belonging to another ligand ^At least one of the groups represented by ⁹
And when m is 2 or more, R ^1b , R ² , R ⁵ , R ⁶ , R ⁷ , R ⁸ , and R ⁹ , May be the same or different. As the transition metal compound represented by the general formula (Ib), a compound in which A is -O- is preferable.

The above general formula (I), (Ia) or (I-
The transition metal compound (A-1) represented by b) reacts with (B-1) an organometallic compound, (B-2) an organoaluminum oxy compound, and (B-3) a transition metal compound to form an ion pair. Can be used as an olefin polymerization catalyst in combination with at least one compound (B) selected from the compounds forming

An olefin polymerization catalyst according to another embodiment of the present invention is characterized by comprising a transition metal compound represented by the following general formula (II).

[0017]

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[0018] (wherein, M, R ^1, n and X are, M respectively in the above formula (I), have the same meanings as R ^1, n and X, m represents 1 or 2, R ¹⁰ And R ^{11 to} R ¹³
May be the same or different from each other, and represent a hydrogen atom, a hydrocarbon group, a hydrocarbon-substituted silyl group, an oxygen-containing group, a nitrogen-containing group or a sulfur-containing group, and R ¹⁴ is a hydrocarbon group or a hydrocarbon-substituted silyl group. And when m is 2,
And at least one group of the groups represented by R ¹⁰ to R ¹⁴ belonging to one of the ligands, R belonging to other ligands
¹⁰ to R ¹⁴ may at least one group of the groups represented even has not been linked, and when m is 2, R ¹ together, R ¹⁰ together, R ¹¹ together, R ¹² to each other, R ¹³ and R ¹⁴ may be the same or different from each other. ) Of the transition metal compounds represented by the general formula (II), R
¹ is an aliphatic hydrocarbon group which may be substituted with an aromatic hydrocarbon group or an alicyclic hydrocarbon group and is a group having 5 or more carbon atoms, R ¹ is an aromatic hydrocarbon group or An alicyclic hydrocarbon group which may be substituted with an aliphatic hydrocarbon group and has 7 or more carbon atoms is one of preferred embodiments.

In the general formula (II), R ¹² is preferably an oxygen-containing group, a nitrogen-containing group or a sulfur-containing group. The transition metal compound (A-2) represented by the general formula (II) reacts with (B-1) an organometallic compound, (B-2) an organoaluminum oxy compound, and (B-3) a transition metal compound. Can be used as an olefin polymerization catalyst in combination with at least one compound (B) selected from compounds that form an ion pair.

The olefin polymerization method according to the present invention is characterized in that olefin is polymerized in the presence of the olefin polymerization catalyst.

[0021]

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. The term "polymer" means not only homopolymer but also homopolymer. , May also be used in a meaning including a copolymer.

The olefin polymerization catalyst according to the present invention is formed from a transition metal compound represented by the following general formula (I). (A-1) Transition metal compound The transition metal compound (A-1) is a compound represented by the following general formula (I).

[0024]

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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, specifically, titanium, zirconium, hafnium, vanadium, niobium, tantalum, etc., preferably titanium, zirconium, hafnium, and particularly preferably zirconium. is there.

M represents an integer of 1 to 5, preferably 1
To 3, more preferably 1 or 2. Q is
It represents a nitrogen atom (-N =) or a carbon atom having a substituent R ² (-C (R ² ) =), and is preferably a carbon atom having a substituent R ² .

A represents an oxygen atom (-O-), a sulfur atom (-
S-), selenium atom (-Se-) or a substituent nitrogen atom having ^{R 5 (-N (R 5)} -) indicates, more preferably an oxygen atom.

R ¹ is an aliphatic hydrocarbon group which may be substituted with an aromatic hydrocarbon group or an alicyclic hydrocarbon group,
And an alicyclic hydrocarbon group which may be substituted with an aromatic hydrocarbon group or an aliphatic hydrocarbon group.

In the definition of R ^1, the term “aliphatic hydrocarbon group” refers to the above general formula (I) even when it is substituted with an aromatic hydrocarbon group or an alicyclic hydrocarbon group.
Refers to those in which the carbon atom directly bonded to the nitrogen is an aliphatic skeleton, and when referred to as an alicyclic hydrocarbon group, it is the case where the carbon atom is substituted with an aromatic hydrocarbon group or an aliphatic hydrocarbon group. Even in this case, the carbon atom directly bonded to nitrogen in the general formula (I) is an alicyclic skeleton.

As R ¹ , specifically, for example, methyl,
Ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, tert-amyl, 1,2-dimethylpropyl, 1-ethylpropyl, isoamyl, 1-methylbutyl, 2- Methylbutyl, neopentyl, n-hexyl, 1,3-dimethylbutyl, 3,3-dimethylbutyl, n-heptyl, 1-ethylpentyl, 1-methylhexyl, n-octyl, 1,5-dimethylhexyl, 2-ethylhexyl , 1-methylheptyl, tert-octyl, n-nonyl, n
-Decyl, n-undecyl, n-dodecyl, n-tridecyl, n
-Tetradecyl, n-pentadecyl, n-hexadecyl, n-
Heptadecyl, n-octadecyl etc. have 1 to 1 carbon atoms
30 aliphatic hydrocarbon groups; cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 2-methylcyclohexyl, 2,2-dimethylcyclohexyl, 2,3-dimethylcyclohexyl, 2,6-dimethylcyclohexyl, 2,2,6,
An alicyclic hydrocarbon group which may be substituted with an aliphatic hydrocarbon group such as 6-tetramethylcyclohexyl and adamantyl and has 3 to 30 carbon atoms; cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl An aliphatic hydrocarbon group substituted with an alicyclic hydrocarbon group such as cyclohexylmethyl, and having 6 carbon atoms.
To 30; an aliphatic hydrocarbon group substituted with an aromatic hydrocarbon group such as benzyl and having 4 to 4 carbon atoms
30.

R ¹ is an aliphatic hydrocarbon group which may be substituted with an aromatic hydrocarbon group or an alicyclic hydrocarbon group, and has 1 to 30, preferably 5 to 30, carbon atoms.
30, more preferably 5 to 20, or an alicyclic hydrocarbon group which may be substituted with an aromatic hydrocarbon group or an aliphatic hydrocarbon group, having a total number of carbon atoms of 3 to 3
0, preferably 5 to 30, more preferably 5 to 20.

R ^{2 to} R ⁵ may be the same or different from each other and include a hydrogen atom, a hydrocarbon group, an oxygen-containing group, a nitrogen-containing group, a sulfur-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, It represents a halogen-containing group, a heterocyclic compound residue, a silicon-containing group, a germanium-containing group or a tin-containing group.

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; a cyclic unsaturated hydrocarbon group having 5 to 30 carbon atoms such as cyclopentadienyl, indenyl and fluorenyl; phenyl, benzyl, naphthyl, biphenylyl, terphenylyl, phenanthryl and anthryl Is an aryl group having 6 to 30, preferably 6 to 20 carbon atoms; tolyl, iso-propylphenyl, t-butylphenyl, dimethylphenyl, di-t
And alkyl-substituted aryl groups such as -butylphenyl.

The hydrocarbon group may have a hydrogen atom substituted with a halogen. Examples of the hydrocarbon group having a hydrogen atom substituted with a halogen atom include trifluoromethyl, pentafluorophenyl and chlorophenyl. Examples include 1 to 30, preferably 1 to 20, halogenated hydrocarbon groups.

The hydrocarbon group may be substituted with another hydrocarbon group. Examples of the hydrocarbon group substituted with another hydrocarbon group include an aryl-substituted alkyl group such as benzyl and cumyl. And the like.

Of these, methyl, ethyl,
n-propyl, isopropyl, n-butyl, isobutyl, se
a linear or branched alkyl group having 1 to 30, preferably 1 to 20 carbon atoms such as c-butyl, t-butyl, neopentyl and n-hexyl; phenyl, naphthyl, biphenylyl, terphenylyl, phenanthryl, anthryl and the like An aryl group having 6 to 30, preferably 6 to 20 carbon atoms; a halogen atom, an alkyl group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, and an aryl group having 1 to 30 carbon atoms, preferably 1 to 30 carbon atoms. Substitution in which 1 to 5 substituents such as an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms, and an aryloxy group having 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms are substituted. Aryl groups and the like are preferred.

The oxygen-containing group is a group containing 1 to 5 oxygen atoms in the group, and does not include a heterocyclic compound residue described later. Further, a group containing a nitrogen atom, a sulfur atom, a phosphorus atom, a halogen atom, or a silicon atom and in which these atoms are directly bonded to an oxygen atom is not included in the oxygen-containing group. Examples of the oxygen-containing group include a hydroxy group,
Alkoxy groups, aryloxy groups, arylalkoxy groups, acetoxy groups, carbonyl groups, ester groups, ether groups, acyl groups, carboxyl groups, carbonate groups, peroxy groups, carboxylic anhydride groups, and the like, hydroxy groups, alkoxy groups, Preferred are an aryloxy group, an arylalkoxy group, an acetoxy group, a carbonyl group and the like. Specific examples of preferred oxygen-containing groups include hydroxy groups; methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, and alkoxy groups such as tert-butoxy; phenoxy, methylphenoxy, 2,6-dimethylphenoxy, Aryloxy groups such as 2,4,6-trimethylphenoxy and naphthoxy; arylalkoxy groups such as phenylmethoxy and phenylethoxy; acetoxy groups; and carbonyl groups. When the oxygen-containing group contains a carbon atom, the number of carbon atoms is desirably in the range of 1 to 30, preferably 1 to 20.

The nitrogen-containing group is a group containing 1 to 5 nitrogen atoms in the group, and does not include a heterocyclic compound residue described later. Examples of the nitrogen-containing group include an amino group, an imino group, an amide group, an imide group, a nitro group, a hydrazino group,
Hydrazono group, nitroso group, cyano group, isocyano group,
Examples include a cyanate ester group, an amidino group, a diazo group, and a group in which an amino group is an ammonium salt, and an amino group, an imino group, an amide group, an imide group, and a nitro group are preferable. Specific examples of preferred nitrogen-containing groups include amino groups such as methylamino, dimethylamino, diethylamino, dipropylamino, dibutylamino, dicyclohexylamino, phenylamino, diphenylamino, ditolylamino, dinaphthylamino, and methylphenylamino; Imino groups such as ethylimino, propylimino, butylimino, and phenylimino; amide groups such as acetamide, N-methylacetamide and N-methylbenzamide; imide groups such as acetimide and benzimide; and nitro groups. When the nitrogen-containing group contains a carbon atom, the number of carbon atoms is 1 to 30, preferably 1 to 30.
It is desirably in the range of 20.

The sulfur-containing group has a sulfur atom in the group of 1 to 1.
It is a group containing 5 and does not include the heterocyclic compound residue described below. Examples of the sulfur-containing group include a sulfonate group, a sulfinate group, an alkylthio group, an arylthio group, a mercapto group, a thioester group, a dithioester group, a thioacyl group, a thioether group, a thiocyanate group, an isothiocyanate group, a sulfone ester group, and a sulfone group. Examples thereof include an amide group, a thiocarboxyl group, a dithiocarboxyl group, a sulfo group, a sulfonyl group, a sulfinyl group, and a sulfphenyl group, and a sulfonate group, a sulfinate group, an alkylthio group, and an arylthio group are preferable. Specific examples of preferred sulfur-containing groups include methyl sulfonate, trifluoromethane sulfonate, phenyl sulfonate, benzyl sulfonate, p-toluene sulfonate, trimethylbenzene sulfonate, and triisobutylbenzene sulfonate. , P-chlorobenzenesulfonate, pentafluorobenzenesulfonate and other sulfonate groups; methylsulfinate, phenylsulfinate,
Benzyl sulfinate, p-toluene sulfinate,
Sulfinate groups such as trimethylbenzenesulfinate and pentafluorobenzenesulfinate; alkylthio groups such as methylthio and ethylthio; and arylthio groups such as phenylthio, methylphenylthio and naphthylthio. When the sulfur-containing group contains carbon atoms, the number of carbon atoms is 1 to 30, preferably 1 to 20.
Is desirably within the range.

The boron-containing group has a boron atom in the group of 1 to 5.
It is a group containing 5 and does not include the heterocyclic compound residue described below. Examples of the boron-containing group include borandiyl, borantriyl, diboranyl, BR ₄ (R
Represents hydrogen, an alkyl group, an aryl group which may have a substituent, a halogen atom, or the like. And the like.

The aluminum-containing group is a group containing 1 to 5 aluminum atoms in the group. As the aluminum-containing group, specifically, a group in which one or two hydrocarbon groups each having 1 to 30, preferably 1 to 20 carbon atoms are substituted,
lR ₄ (R is a hydrogen atom, an alkyl group, an optionally substituted aryl group, etc. a halogen atom.) include groups represented by.

The phosphorus-containing group is a group containing 1 to 5 phosphorus atoms in the group, and does not include a heterocyclic compound residue described later. As the phosphorus-containing group, for example, a phosphoryl group,
Examples thereof include a thiophosphoryl group, a phosphine group, a phosphite group, a phosphonic acid group, and a phosphinic acid group. A phosphine group, a phosphite group, a phosphonic acid group, and a phosphinic acid group are preferable. Specific examples of the preferable phosphorus-containing group include trialkylphosphine groups such as trimethylphosphine, tributylphosphine and tricyclohexylphosphine; triarylphosphine groups such as triphenylphosphine and tolylphosphine; methylphosphite, ethylphosphite, Phosphite groups such as phenyl phosphite (phosphide groups); phosphonic acid groups; and phosphinic acid groups.

Examples of the halogen-containing group include fluorine, chlorine,
Examples include groups having at least one selected from bromine and iodine. Specific examples of the halogen-containing group include P
Fluorine-containing groups such as F ₆ and BF ₄ , ClO ₄ , SbCl
_And iodine-containing groups such as IO ₄ .

The heterocyclic compound residue has one heteroatom.
This is a group having a ring structure containing at least one ring structure, and examples of the hetero atom include oxygen, nitrogen, sulfur, phosphorus, and boron. The ring structure includes a 3- to 18-membered ring, preferably a 4- to 7-membered ring, and more preferably a 5- to 6-membered ring. Specifically, pyrrole, pyridine, pyrimidine,
A residue of a nitrogen-containing compound such as quinoline or triazine; a residue of an oxygen-containing compound such as furan or pyran; a residue of a sulfur-containing compound such as thiophene; ~ 30, preferably 1-2
0 alkyl group, having 1 to 30 carbon atoms, preferably 1
And a group further substituted with a substituent such as an alkoxy group of -20.

The silicon-containing group has one or more silicon atoms in the group.
It is a group containing five. Examples of the silicon-containing group include a silyl group, a siloxy group, a hydrocarbon-substituted silyl group, a hydrocarbon-substituted siloxy group, a hydrocarbon-substituted silyl ether group, a silicon-substituted alkyl group, and a silicon-substituted aryl group. Groups, hydrocarbon-substituted silyl ether groups, silicon-substituted alkyl groups, silicon-substituted aryl groups and the like. Specific examples of preferred silicon-containing groups include methylsilyl, dimethylsilyl, trimethylsilyl, ethylsilyl, diethylsilyl, triethylsilyl, tripropylsilyl, tricyclohexylsilyl,
Phenylsilyl, diphenylsilyl, triphenylsilyl, dimethyl-t-butylsilyl, dimethylphenylsilyl, methyldiphenylsilyl, tolylsilyl, trinaphthylsilyl, dimethyl (pentafluorophenyl)
Hydrocarbon-substituted silyl groups such as silyl; hydrocarbon-substituted silyl ether groups such as trimethylsilyl ether; silicon-substituted alkyl groups such as trimethylsilylmethyl; silicon-substituted aryl groups such as trimethylsilylphenyl; and hydrocarbon-substituted silyl groups are particularly preferred. . Among the hydrocarbon-substituted silyl groups, methylsilyl, dimethylsilyl, trimethylsilyl, ethylsilyl, diethylsilyl, triethylsilyl, dimethylphenylsilyl, triphenylsilyl and the like are preferable, and trimethylsilyl, triethylsilyl, triphenylsilyl and dimethylphenylsilyl are particularly preferable. . When the silicon-containing group contains a carbon atom, the number of carbon atoms is 1 to 30, preferably 1
It is desirably in the range of 20 to 20.

Specific examples of the germanium-containing group include groups in which silicon of the above-mentioned silicon-containing group is substituted with germanium. Specific examples of the tin-containing group include groups in which silicon in the silicon-containing group is substituted with tin.

R ⁴ is an oxygen-containing group such as an alkoxy group, an aryloxy group or a hydroxy group; a nitrogen-containing group such as an amino group, an imino group, an amide group, an imide group or a nitro group;
Sulfur-containing groups such as an alkylthio group and an arylthio group are preferred, and an alkoxy group, an aryloxy group and an amino group are more preferred. Particularly preferred is an alkoxy group.

The oxygen-containing group, the nitrogen-containing group, the sulfur-containing group, the boron-containing group, the aluminum-containing group, and the phosphorus-containing group are formed so that the atomic group characterizing the group is directly bonded to a nitrogen atom or a carbon atom. Preferably, the group is

R ^{1 to} R ⁵ represent two or more of these groups, preferably adjacent groups, being linked to each other to form an aliphatic ring, an aromatic ring, or a hydrocarbon ring containing a hetero atom such as a nitrogen atom. And these rings may further have a substituent. In the present invention, it is particularly preferable that the substituents R ³ and R ⁴ bond to form an aromatic ring.

In the above formula (I), when m is 2 or more, one group of R ^{2 to} R ⁵ contained in any one of the ligands and m And one of R ^{2 to} R ⁵ may be linked.

When m is 2 or more, R ¹ and R ²
Together, R ³ together, R ⁴ together, R ⁵ together may be the same or different from each other. n is a number that satisfies the valence of M, and is specifically an integer of 2 to 4, and is preferably 2.

X represents a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, a halogen-containing group, or a heterocyclic compound residue. , A silicon-containing group, a germanium-containing group or a tin-containing group.

A hydrocarbon group, an oxygen-containing group, a sulfur-containing group,
Examples of the boron-containing group, aluminum-containing group, phosphorus-containing group, halogen-containing group, heterocyclic compound residue, silicon-containing group, germanium-containing group or tin-containing group include R ^{2 to} R ⁵ in the above general formula (I). And the same as those exemplified above.

Examples of the halogen atom include fluorine, chlorine, bromine and iodine. 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, dinaphthylamino, and methylphenylamino. And an arylamino group or an alkylarylamino group.

Of these, X is preferably a hydrogen atom, a halogen atom, a hydrocarbon, an oxygen-containing group, or a nitrogen-containing group, and more preferably a hydrogen atom, a halogen atom, or a hydrocarbon 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.

The transition metal compound represented by the above general formula (I) has a net charge parameter of the central metal M of 2.0.
0, preferably in the range of 1.40 to 2.00.
The net charge parameter (hereinafter may be abbreviated as “NC”) of the central metal M as used herein refers to the structure of a complex in which all the substituents represented by X in the above general formula (I) are replaced by methyl groups. Semi-empirical molecular orbital method PM3
The structure obtained by optimizing using (tm) and removing one methyl group from the structure is defined as (I ′). The program used is SPARTANrel.5.0.3. Using the obtained structure of (I '), the ab initio molecular orbital program Gaussian
The RHF wave function is solved according to 98, and Mulliken charge is obtained as the charge of the central metal. For the central metal, Hay and Wadt's effective core potential was used for the inner core, their double zeta basis functions were used for the valence shell, and 3-21G was used for the other atoms. The value of the Mulliken charge thus obtained is defined as a net charge parameter. The following formula (Ia), (Ib) or (II)
Similarly, the net charge parameter of the compound represented by is calculated.

NC is a value of 2.0 or less, and when R ¹ is an aliphatic hydrocarbon group which may be substituted with an aromatic hydrocarbon group or an alicyclic hydrocarbon group, it is 1.70 to 1.
It is preferably in the range of 2.0. When R ¹ is an alicyclic hydrocarbon group which may be substituted with an aromatic hydrocarbon group or an aliphatic hydrocarbon group, 1.50 to 1.89
Is preferably within the range.

When the NC of the central metal M is 2.0 or less, the transition metal compound is excellent in polymerization activity especially at a high temperature when used as a catalyst for olefin polymerization. The transition metal compound represented by the general formula (I) includes the following general formula (I)
-a) or (Ib).

[0059]

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In the formula, M, m, A, n and X have the same meanings as M, m, A, n and X in the general formula (I), respectively. R ^1a represents an aliphatic hydrocarbon group which may be substituted with an aromatic hydrocarbon group or an alicyclic hydrocarbon group,
Specifically, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, tert-amyl, 1,2-dimethylpropyl, 1-ethylpropyl, isoamyl , 1-methylbutyl,
2-methylbutyl, neopentyl, n-hexyl, 1,3-dimethylbutyl, 3,3-dimethylbutyl, n-heptyl, 1-ethylpentyl, 1-methylhexyl, n-octyl, 1,5-dimethylhexyl, 2 -Ethylhexyl, 1-methylheptyl,
tert-octyl, n-nonyl, n-decyl, n-undecyl, n
An aliphatic hydrocarbon group having 1 to 30 carbon atoms such as -dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl;
Aliphatic hydrocarbons substituted with an aromatic hydrocarbon group such as benzyl and having a total of 6 to 30 carbon atoms; alicyclic hydrocarbons such as cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl and cyclohexylmethyl; Examples thereof include an aliphatic hydrocarbon group substituted with a hydrogen group and having a total number of carbon atoms of 4 to 30.

R^1aHas 1 to 30 carbon atoms, preferably
Preferably 5 to 30, more preferably 5 to 20
Good. R^TwoAnd R^Five~ R⁹Are the same or different
Hydrogen atom, hydrocarbon group, oxygen-containing group, nitrogen
Sulfur-containing group, sulfur-containing group, boron-containing group, aluminum
Containing group, phosphorus containing group, halogen containing group, heterocyclic compound
Residue, silicon-containing group, germanium-containing group or tin
Shows the contained groups. Specifically, R in the above general formula (I) ^Two~ R^Five
And the same as those exemplified above.

R ² and R ^{5 to} R ⁹ , two or more of these groups, preferably adjacent groups are linked to each other to form an aliphatic ring, an aromatic ring, or a hydrocarbon ring containing a hetero atom such as a nitrogen atom. May be formed, and these rings may further have a substituent.

In the above general formula (Ia), when m is 2 or more, at least one of R ² and R ^{5 to} R ⁹ belonging to any one of the ligands Group and
At least one of the groups represented by R ² and R ^{5 to} R ⁹ belonging to another ligand may be linked.

When m is 2 or more, R ^1a and R ^1a
2 s, R ⁵ each other, R ⁶ together, R ⁷ together, R ⁸ s, R
⁹ may be the same or different from each other. The transition metal compound represented by the general formula (Ia) has a central metal M
Is in the range of 1.70 to 2.00, preferably 1.895 to 1.912.

When the NC of the central metal M is in the above range, the transition metal compound is excellent in polymerization activity especially at a high temperature when used as a catalyst for olefin polymerization.

[0066]

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In the formula, M, m, A, n and X have the same meanings as M, m, A, n and X in the general formula (I), respectively. R ^1b represents an alicyclic hydrocarbon group which may be substituted with an aromatic hydrocarbon group or an aliphatic hydrocarbon group,
Specifically, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 2-methylcyclohexyl, 2,2-dimethylcyclohexyl, 2,6-dimethylcyclohexyl, 2,2,6,6-tetramethylcyclohexyl, adamantyl, cyclopropylmethyl An alicyclic hydrocarbon group which may be substituted with an aliphatic hydrocarbon group such as cyclobutylmethyl, cyclopentylmethyl and cyclohexylmethyl, having a total number of carbon atoms of 3 to 30, preferably 5
To 30, more preferably 5 to 20.

R^TwoAnd R^Five~ R⁹Are the same or different
May contain hydrogen atoms, hydrocarbon groups, oxygen-containing
Group, nitrogen-containing group, sulfur-containing group, boron-containing group, aluminum
Ium-containing group, phosphorus-containing group, halogen-containing group, heterocycle
Formula compound residue, silicon-containing group, germanium-containing group or
Represents a tin-containing group. Specifically, R in the above general formula (I)
^Two~ R^FiveAnd the same as those exemplified above.

R ² and R ^{5 to} R ⁹ are two of these
Two or more groups, preferably adjacent groups, may be linked to each other to form an aliphatic ring, an aromatic ring, or a hydrocarbon ring containing a hetero atom such as a nitrogen atom, and these rings further have a substituent. It may be.

In the above general formula (Ib), when m is 2 or more, at least one of R ² and R ^{5 to} R ⁹ belonging to any one of the ligands Group and
At least one of the groups represented by R ² and R ^{5 to} R ⁹ belonging to another ligand may be linked.

When m is 2 or more, R ^1b and R ^1b
2 s, R ⁵ each other, R ⁶ together, R ⁷ together, R ⁸ s, R
⁹ may be the same or different from each other. The transition metal compound represented by the above general formula (Ib) has a central metal M
Preferably has a net charge parameter of 1.50
1.89, more preferably in the range of 1.80 to 1.89.

When the NC of the central metal M is within the above range, the transition occurs.
When the metal compound is used as an olefin polymerization catalyst
In particular, it has excellent polymerization activity at high temperatures. Below, the above general
Specific examples of the transition metal compound represented by the formula (I) are shown.
However, the present invention is not limited to these. The following example
Is a compound represented by the above general formula (Ia) or (Ib)
Things are included. In addition, the following general formula (I) among the following examples
Wherein Q is a substituent R^TwoIs a carbon atom having
Is an oxygen atom, and R ^ThreeAnd R^FourAre combined with each other
Compounds having an aromatic ring include compounds represented by the following general formula (I
Includes those represented by I).

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[0074]

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[0076]

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In the above examples, Me represents a methyl group, E
t is an ethyl group, ⁿ Pr is an n-propyl group, ⁱ Pr is an isopropyl group, ⁿ Bu is an n-butyl group, ^t Bu is a t-butyl group, ⁿ Pentyl is an n-pentyl group, and ⁿ Hexyl Is n-hexyl group, ⁿ Heptyl is n-heptyl group, ⁿ Octyl is n-octyl group, ⁿ Nonyl is n-nonyl group, ⁿ Decyl is n-decyl group, ⁿ Undecyl is n-undecyl ^N Dodecyl represents an n-dodecyl group, ⁿ Octadecyl represents an n-octadecyl 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 above compounds may be used.

The olefin polymerization catalyst according to another embodiment of the present invention includes a catalyst comprising a transition metal compound represented by the following general formula (II).

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In the formula, M, n and X have the same meanings as M, n and X in the general formula (I), respectively. R ¹ is
An aliphatic hydrocarbon group which may be substituted with an aromatic hydrocarbon group or an alicyclic hydrocarbon group, or an aromatic hydrocarbon group or an aliphatic hydrocarbon group similar to R ¹ in the general formula (I). An alicyclic hydrocarbon group which may be substituted with a hydrogen group; an aliphatic hydrocarbon group which may be substituted with an aromatic hydrocarbon group or an alicyclic hydrocarbon group; It is preferably a number of 5 or more, more preferably 5 to 30, and is preferably an alicyclic hydrocarbon group which may be substituted with an aromatic hydrocarbon group or an aliphatic hydrocarbon group, and is preferably a total carbon atom. It is also desirable that the number is 7 or more, more preferably 7 to 30.

Examples of the aliphatic hydrocarbon group include those having 1 to 30 carbon atoms, and those having 4 to 30 carbon atoms.
Preferably those having 5 to 30 carbon atoms are preferred. Specifically, methyl, ethyl, n-propyl, isopropyl, n-
Butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, tert-amyl, 1,2-dimethylpropyl, 1-ethylpropyl, isoamyl, 1-methylbutyl, 2-methylbutyl, neopentyl, n-hexyl, 1, 3-dimethylbutyl, 3,3-dimethylbutyl, n-heptyl, 1-ethylpentyl, 1-methylhexyl, n-octyl, 1,5-dimethylhexyl, 2-ethylhexyl, 1-methylheptyl, tert-octyl , N-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl,
n-hexadecyl, n-heptadecyl, n-octadecyl and the like.

Among them, n-pentyl, tert-amyl, 1,2-
Dimethylpropyl, 1-ethylpropyl, isoamyl, 1-
Methylbutyl, 2-methylbutyl, neopentyl, n-hexyl, 1,3-dimethylbutyl, 3,3-dimethylbutyl, n-heptyl, 1-ethylpentyl, 1-methylhexyl, n-octyl, 1,5-dimethyl Hexyl, 2-ethylhexyl, 1-methylheptyl, tert-octyl, n-nonyl, n-decyl, n
-Undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl are preferred.

The aliphatic hydrocarbon group may be substituted with an aromatic hydrocarbon group or an alicyclic hydrocarbon group, and may be substituted with an aromatic hydrocarbon group or an alicyclic hydrocarbon group. Specific examples of the hydrogen group include benzyl, methylene naphthyl, methylene fluorenyl, methylene anthranyl, methylene cyclopropyl, methylene cyclobutyl,
Methylenecyclopentyl, methylenecyclohexyl, methylene-2-methylcyclohexyl, methylene-2,3-dimethylcyclohexyl, methylene-2,2-dimethylcyclohexyl, methylene-2,6-dimethylcyclohexyl, methylene-2,2,6,6- Examples thereof include those having 4 to 30 carbon atoms such as tetramethylcyclohexyl, methyleneadamantyl, methylenecyclopropylmethyl, methylenecyclobutylmethyl, and methylenecyclopentylmethyl.

Among them, benzyl, methylenenaphthyl, methylenefluorenyl, methyleneanthranyl, methylenecyclobutyl, methylenecyclopentyl, methylenecyclohexyl, methylene-2-methylcyclohexyl, methylene-2,3-dimethylcyclohexyl, methylene-2,2- 5 to 30 carbon atoms such as dimethylcyclohexyl, methylene-2,6-dimethylcyclohexyl, methylene-2,2,6,6-tetramethylcyclohexyl, methyleneadamantyl, methylenecyclopropylmethyl, methylenecyclobutylmethyl and methylenecyclopentylmethyl Are preferred.

The alicyclic hydrocarbon group includes, for example, those having 3 to 30 carbon atoms, preferably those having 7 to 30 carbon atoms. Specific examples include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, norbornyl and the like.

The alicyclic hydrocarbon group may have an aromatic hydrocarbon group or an aliphatic hydrocarbon group as a substituent, and may have an aromatic hydrocarbon group or an aliphatic hydrocarbon group as a substituent. As the alicyclic hydrocarbon group, specifically, 2-methylcyclohexyl, 2,3-dimethylcyclohexyl, 2,2-dimethylcyclohexyl, 2,6-dimethylcyclohexyl, 2,2,6,6,- Those having 7 to 30 carbon atoms such as tetramethylcyclohexyl, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclopropylphenyl, cyclobutylphenyl, cyclopentylphenyl, cyclohexylphenyl and the like can be mentioned.

M represents 1 or 2, and is preferably 2. R ¹⁰ and R ^{11 to} R ¹³ may be the same or different from each other, and represent a hydrogen atom, a hydrocarbon group, a hydrocarbon-substituted silyl group, an oxygen-containing group, a nitrogen-containing group, or a sulfur-containing group. Examples include the same hydrocarbon groups, hydrocarbon-substituted silyl groups, oxygen-containing groups, nitrogen-containing groups, and sulfur-containing groups as those exemplified as R ^{2 to} R ⁵ in the general formula (I).

As R ¹² , a hydrocarbon group, an oxygen-containing group,
Nitrogen-containing groups and sulfur-containing groups are preferred, and oxygen-containing groups, nitrogen-containing groups and sulfur-containing groups are particularly preferred. Specific examples include the same hydrocarbon groups, oxygen-containing groups, nitrogen-containing groups, and sulfur-containing groups as described above. Among these, alkoxy groups, alkylthio groups, aryloxy groups, arylthio groups, arylthio groups, amino groups, imino groups, An amide group, an imide group, a nitro group or a hydroxy group is preferred, and an alkoxy group is particularly preferred.

R ¹⁴ represents a hydrocarbon group or a hydrocarbon-substituted silyl group, and specifically, R ² to R ¹ in the above formula (I)
The same hydrocarbon groups and hydrocarbon-substituted silyl groups as those exemplified as R ⁵ can be mentioned.

Next, the above substituents will be described more specifically. R ¹² is an oxygen-containing group such as an alkoxy group, an aryloxy group or a hydroxy group; a nitrogen-containing group such as an amino group, an imino group, an amide group, an imide group or a nitro group;
Sulfur-containing groups such as an alkylthio group and an arylthio group are preferred, and an alkoxy group, an aryloxy group and an amino group are more preferred. Particularly preferred is an alkoxy group.

R ¹⁴ is a hydrocarbon group or a hydrocarbon-substituted silyl group. Preferred hydrocarbon groups as R ¹⁴ include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, neopentyl, and n-hexyl having 1 to 30 carbon atoms, preferably 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 ¹⁴ include methylsilyl, dimethylsilyl, trimethylsilyl, ethylsilyl, diethylsilyl, triethylsilyl, diphenylmethylsilyl, triphenylsilyl,
Dimethylphenylsilyl, dimethyl-t-butylsilyl,
Dimethyl (pentafluorophenyl) silyl and the like. Particularly preferred are trimethylsilyl, triethylphenylsilyl, diphenylmethylsilyl, isophenylsilyl, dimethylphenylsilyl, dimethyl-t-butylsilyl, dimethyl (pentafluorophenyl) silyl and the like.

In the present invention, R ¹⁴ particularly has 3 to 30 carbon atoms, preferably 3 to 2 carbon atoms, such as isopropyl, isobutyl, sec-butyl, tert-butyl and neopentyl.
A branched alkyl group of 0, a group in which a hydrogen atom of these groups is substituted with an aryl group having 6 to 30, preferably 6 to 20 carbon atoms (such as a cumyl group), adamantyl, cyclopropyl, cyclobutyl, cyclopentyl, Cyclohexyl or the like having 3 to 30, preferably 3 to 2 carbon atoms.
0 is preferably a group selected from cyclic saturated hydrocarbon groups, or phenyl, naphthyl, fluorenyl,
6 to 3 carbon atoms such as anthranil and phenanthryl
It is also preferably 0, preferably 6 to 20 aryl groups or hydrocarbon-substituted silyl groups.

Hereinafter, specific examples of the transition metal compound represented by the general formula (II) will be shown, but the invention is not limited thereto. The following examples include the compound represented by the general formula (I).

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[0097]

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[0098]

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[0099]

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[0100]

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[0101]

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[0102]

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In the above examples, Me represents a methyl group, E
t is an ethyl group, ⁿ Pr is an n-propyl group, ⁱ Pr is an isopropyl group, ⁿ Bu is an n-butyl group, ^t Bu is a t-butyl group, ⁿ Pentyl is an n-pentyl group, and ⁿ Hexyl Is n-hexyl group, ⁿ Heptyl is n-heptyl group, ⁿ Octyl is n-octyl group, ⁿ Nonyl is n-nonyl group, ⁿ Decyl is n-decyl group, ⁿ U
ndecyl represents an n-undecyl group, ⁿ Dodecyl represents an n-dodecyl group, ⁿ Octadecyl represents an n-octadecyl 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 above compounds may be used.

The method for producing the transition metal compound represented by the general formula (I) or (II) is not particularly limited, and can be produced, for example, as follows. The transition metal compound represented by the general formula (I) includes, for example, a compound (ligand precursor) which becomes a ligand when a transition metal compound is synthesized, and MX _k (M and X are represented by the above general formula ( I)
Synonymous with M and X in the formula, and k is a number satisfying the valence of M. The compound can be synthesized by reacting with a transition metal M-containing compound represented by the formula (1).

The ligand precursor includes β-diketones, β-ketoester compounds (including thioketones and thioketoesters), acetylacetone compounds and the like, and a compound represented by the formula R ¹ -N
H ₂ primary amine compounds (R ¹ is a compound of the above general formula (I)
The same meaning as that of R ¹ in. ) For example, it can be obtained by reacting with an aniline compound or an alkylamine compound. The above-mentioned β-diketones, β-ketoester compounds (including thioketones and thioketoesters), acetylacetone compounds and the like can be obtained commercially or by methods known in the literature.

To synthesize the ligand precursor, both starting compounds are first dissolved in a solvent, and the resulting solution is stirred at room temperature under reflux conditions for about 1 to 48 hours to give the corresponding ligand. The precursor is obtained in good yield.

As the solvent, those usually used in such a reaction are used, and among them, alcohol solvents such as methanol and ethanol, and hydrocarbon solvents such as toluene are preferable.

When synthesizing the ligand precursor, an acid catalyst such as formic acid, acetic acid or toluenesulfonic acid may be used as a catalyst. 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.

Preferred examples of the transition metal M-containing compound include TiCl ₃ , TiCl ₄ , TiBr ₃ , TiBr ₄ , T
i (benzyl) ₄ , Ti (NiMe ₂ ) ₄ , ZrCl ₄ , Zr
(NiMe ₂ ) ₄ , Zr (benzyl) ₄ , ZrBr ₄ , HfCl
_{4, HfBr 4, VCl 4,} VCl 5, VBr 4, VBr 5,
Ti (acac) ₃ , and these and tetrahydrofuran (T
HF), acetonitrile, complexes with diethyl ether and the like.

Next, by reacting the ligand precursor thus obtained with the transition metal M-containing compound, the corresponding transition metal compound can be synthesized. Specifically, the synthesized ligand precursor is dissolved in a solvent, and if necessary, contacted with a base to prepare a 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 commonly used in such reactions are used, and among them, polar solvents such as ether and tetrahydrofuran, and hydrocarbon solvents such as toluene are preferably used. Further, as the base used for preparing the phenoxide salt, a metal salt such as a lithium salt such as n-butyllithium, a sodium salt such as sodium hydride, and an organic base such as triethylamine and pyridine are preferable.

Depending on the properties of the transition metal M-containing compound, the corresponding transition metal compound may be synthesized by directly reacting the ligand precursor with the transition metal M-containing compound without going through salt preparation. Can also.

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

The transition metal compound represented by the general formula (Ia) or (Ib) is, for example, a compound forming a ligand such as a thiosalicylidene ligand or an anilino ligand (a ligand precursor). ) And a transition metal M-containing compound.

The ligand precursor forming the thiosalicylidene ligand is, for example, a thiosalicylic aldehyde compound,
It is obtained by reacting with an aniline compound or an amine compound.

The ligand precursor can also be obtained by reacting o-acylbenzenethiol with an aniline or amine compound. Specifically, for example, a thiosalicylaldehyde compound or o-acylbenzenethiol,
The compound is obtained by dissolving an aniline compound or a primary amine compound in which the nitrogen moiety is unsubstituted in a solvent, and stirring the solution at room temperature to reflux for about 1 to 48 hours. Preferred examples of the solvent used here include alcohol solvents such as methanol and ethanol and hydrocarbon solvents such as toluene. As the catalyst, an acid catalyst such as formic acid, acetic acid, and toluenesulfonic acid can be used. During the reaction, removing water in the system using Dean Stark is effective for the progress of the reaction. As the dehydrating agent, molecular sieve, magnesium sulfate, sodium sulfate and the like can be used.

The o-acylbenzenethiol used here can be obtained, for example, by converting the OH group of o-acylphenol to thiocarbamate with dimethylthiocarbamate and then performing a conversion reaction between oxygen atoms and sulfur atoms by heat or the like. Can be.

The anilino ligand precursor can be obtained by reacting an o-formaniline compound with an aniline compound or an amine compound. The ligand precursor is o-
It can also be obtained by reacting acylaniline with aniline or amines.

Specifically, for example, an o-formaniline compound having an unsubstituted nitrogen portion or an o-acylaniline having an unsubstituted nitrogen portion and an aniline compound or a primary amine compound having an unsubstituted nitrogen portion are used. And can be synthesized in the same manner as described above.

The o-acylaniline used here can be obtained, for example, by reducing the carboxylic acid group of an o-aminobenzoic acid compound. The anthranyl compounds, N-
Performing the alkylation reaction also gives the corresponding N-alkyl-o
-Acylaniline compounds can be obtained.

The corresponding transition metal compound can be synthesized by reacting the ligand precursor obtained as described above with the transition metal M-containing compound. Specifically, after dissolving a ligand precursor in a solvent and, if necessary, contacting with a base to prepare a thiophenoxide salt or an anilino salt, a metal halide, a transition metal M such as a metal alkylated compound is contained. The transition metal compound is obtained by mixing with the compound at a low temperature and stirring at -78 ° C to room temperature or under reflux conditions for about 1 hour to 24 hours.

The solvent used here is preferably a polar solvent such as ether or tetrahydrofuran, or a hydrocarbon solvent such as toluene, but is not limited thereto. Preferred examples of the base include, but are not limited to, lithium salts such as n-butyllithium; sodium salts such as sodium hydride; and nitrogen-containing compounds such as pyridine and triethylamine.

Depending on the transition metal compound, the corresponding compound can be synthesized by directly reacting the ligand precursor with the metal compound without preparing a thiophenoxide salt or an anilino salt.

The transition metal compound represented by the general formula (II) can be synthesized in the same manner as described above. The obtained transition metal compound is 270 MHz ¹ H-NMR (JEOL GSH-270), FT-IR (SHIMADZU FT-IR8200).
D), FD-mass spectrometry (JEOL SX-102A), metal content analysis (dry ashing and dilute nitric acid dissolution, analysis by ICP method:
The structure is determined using SHIMADZU ICPS-8000), carbon, hydrogen, and nitrogen content analysis (Heraus CHNO type).

The transition metal compound obtained by the above-described method is usually isolated and subjected to polymerization by a conventional method. However, the transition metal compound is not isolated, and the reaction solution of the ligand precursor and the metal compound is not isolated. Can be used for polymerization as it is.

The transition metal compounds represented by the above formula (I) are used alone or in combination of two or more as an olefin polymerization catalyst. In the present invention, the transition metal compound (A-1) or (A-2) is (B-1) an organometallic compound, (B-2) an organoaluminum oxy compound,
And (B-3) at least one compound (B) selected from compounds which react with a transition metal compound to form an ion pair
It is one of the preferable embodiments to use together with.

(B-1) Organometallic Compounds Specific examples of the (B-1) organometallic compounds that may be used in the present invention include the following Periodic Table Groups 1 and 2 and Groups 12 and 13 Organic metal compounds.

[0128] (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).

[0129] (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.

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

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

Further, compounds similar to (B-1a) can also be used, and examples thereof include an organic aluminum compound in which two or more aluminum compounds are bonded via a nitrogen atom. Specific examples of such a compound include (C ₂ H ₅ ) ₂ A
1N (C ₂ H ₅ ) Al (C ₂ H ₅ ) _{2 and the} like.

Compounds belonging to the above (B-1b) include Li
_{Al (C 2 H 5) 4} , LiAl (C 7 H 15) 4 and the like. In addition, as the (B-1) organometallic compound,
Methyl lithium, ethyl lithium, propyl lithium,
Butyllithium, methylmagnesium bromide, methylmagnesium chloride, ethylmagnesium bromide,
Ethyl magnesium chloride, propyl magnesium bromide, propyl magnesium chloride, butyl magnesium bromide, butyl magnesium chloride, dimethyl magnesium, diethyl magnesium, dibutyl magnesium, butyl ethyl magnesium and the like can also be used.

Further, a compound that forms the above-mentioned organoaluminum compound in the polymerization system, for example, a combination of an aluminum halide and an alkyl lithium, or a combination of an aluminum halide and an alkyl magnesium can also be used.

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

(B-2) Organoaluminum oxy compound The (A-2) organoaluminum oxy compound that may be used in the present invention may be a conventionally known aluminoxane, or disclosed in JP-A-2-78687. It may be a benzene-insoluble organic aluminum oxy compound as exemplified.

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

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

Specific examples of the organoaluminum compound used for preparing the aluminoxane include those described in the above (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 aluminoxanes include aromatic hydrocarbons such as benzene, toluene, xylene, cumene and cymene; and aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane and octadecane. Alicyclic hydrocarbons such as cyclopentane, cyclohexane, cyclooctane and methylcyclopentane; petroleum fractions such as gasoline, kerosene and light oil or halides of the above aromatic hydrocarbons, aliphatic hydrocarbons and alicyclic hydrocarbons (E.g., chlorinated products, brominated products, etc.). Further, ethers such as ethyl ether and tetrahydrofuran can also be used. Among these solvents, aromatic hydrocarbons and aliphatic hydrocarbons are particularly preferred.

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

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

[0145]

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In the formula, R ²⁰ represents a hydrocarbon group having 1 to 10 carbon atoms. R ²¹ may be the same or different from each other, and have 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 (III) is represented by the following general formula (I)
The alkylboronic acid represented by V) and R ²⁰ -B- (OH) ₂ ... (IV) (in the formula, R ²⁰ 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 (IV) include methylboronic acid, ethylboronic acid, isopropylboronic acid, n-propylboronic acid, n-butylboronic acid, isobutylboronic acid, and n -Hexylboronic acid, cyclohexylboronic acid, phenylboronic acid, 3,5-difluoroboronic acid, pentafluorophenylboronic acid, 3,5-bis (trifluoromethyl) phenylboronic acid and the like. Among these, methylboronic acid, n-butylboronic acid, isobutylboronic acid, 3,5-difluorophenylboronic acid, and pentafluorophenylboronic acid are preferred. These are used alone or in combination of two or more.

Specific examples of the organoaluminum compound to be reacted with the alkylboronic acid include those described in (B-1a) above.
And the same organoaluminum compounds as those exemplified as the organoaluminum compounds belonging to the above.

Of these, trialkylaluminum and tricycloalkylaluminum are preferable, and trimethylaluminum, triethylaluminum and triisobutylaluminum are particularly preferable. These are used alone or in combination of two or more.

The above-mentioned organoaluminum oxy compounds (B-2) are used alone or in combination of two or more. (B-3) Reaction with a transition metal compound to form an ion pair
Compound capable of reacting with the transition metal compound that may be used in compound present invention to form an ion pair (B-3) (hereinafter, referred to as "ionizing ionic compound".), The above general formula (I) or ( A compound that forms an ion pair by reacting with the transition metal compound represented by II).
JP-A-1-501950, JP-A-1-50203
No. 6, JP-A-3-179005, JP-A-3-179005
JP 179006, JP-A-3-207703,
JP-A-3-207704, USP-532110
No. 6, etc., Lewis acids, ionic compounds, borane compounds and carborane compounds. Furthermore, heteropoly compounds and isopoly compounds can also be mentioned.

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

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

[0154]

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In the formula, R ²² includes H ⁺ , carbonium cation, oxonium cation, ammonium cation, phosphonium cation, cycloheptyltrienyl cation, and ferrocenium cation having a transition metal.

R ^{23 to} R ²⁶ may be the same or different and 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-dimethylanilyl. 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 ²² , a carbonium cation, an ammonium cation and the like are preferable, and particularly, a triphenylcarbonium cation, an N, N-dimethylanilinium cation and an N, N-diethylanilinium cation are 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-dimethylanilinium tetra (phenyl) boron, N, N-diethylanilinium tetra (phenyl) boron, N, N-2, 4,6-pentamethylanilinium tetra (phenyl) boron and the like.

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

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

[0165]

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

[0167]

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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-carbadecaborate, tri (n-butyl) Ammonium bromo-1-carbadodecaborate, tri (n-butyl) ammonium 6-carbadecaborate (14), tri (n-butyl) ammonium 6-carbadecaborate (1
2), tri (n-butyl) ammonium 7-carboundecaborate (13), tri (n-butyl) ammonium 7,8-
Dicarboundecaborate (12), tri (n-butyl)
Ammonium 2,9-dicarboundecaborate (12),
Tri (n-butyl) ammonium dodecahydride-8-
Methyl-7,9-dicarboundecaborate, tri (n-butyl) ammonium undecahydride-8-ethyl-7,9-
Dicarbaune decaborate, tri (n-butyl) ammonium undecahydride-8-butyl-7,9-dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-8-allyl-7,9-dicarbaune Decaborate, tri (n-butyl) ammonium undecahydride-9-trimethylsilyl-7,8-dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-4,6-dibromo-7-carboundecaborate Salts of anions such as tri (n-butyl) ammonium bis (nonahydride-1,3-dicarbanonaborate) cobaltate (III), tri (n-butyl) ammonium bis (undecahydride-7,8 -Dicarboundecaborate) ferrate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarboundecaborate) co Belt salt (III), tri (n- butyl) ammonium bis (undecapeptide 7,8-dicarbaundecaborate deca borate)
Nickelate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarboundecaborate) cuprate (III), tri (n-butyl) ammonium bis (undecahydride-7) , 8-Dicarboundecaborate) aurate (III), tri (n-butyl) ammonium bis (nonahydride-7,8-dimethyl-7,8-dicarboundecaborate) ferrate (III) (N-butyl) ammonium bis (nonahydride-7,8-dimethyl-7,8-dicarboundecaborate) chromate (III), tri (n-butyl) ammonium bis (tribromooctahydride-7,8 -Dicarboundecaborate) cobaltate (II
I), tris [tri (n-butyl) ammonium] bis (undecahydride-7-carboundecaborate) chromate (III), bis [tri (n-butyl) ammonium]
Bis (undecahydride-7-carboundecaborate) manganate (IV), bis [tri (n-butyl) ammonium] bis (undecahydride-7-carboundecaborate) cobaltate (III), Bis [tri (n-butyl) ammonium] bis (undecahydride-7-
Metal carborane anions such as (carboundecaborate) nickelate (IV).

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

The above-mentioned (B-3) ionized ionic compounds are used alone or in combination of two or more. In the present invention, the above transition metal compound (A-1) or (A-2) may be used alone in the polymerization of the olefin,
Reacts with the transition metal compound (A-1) or (A-2), (B-1) the organometallic compound (B-2) the organoaluminum oxy compound, and (B-3) the transition metal compound to form an ion pair. At least one compound (B) selected from the compounds to be formed may be used.

When, for example, the compound represented by the above general formula (II) is used as the transition metal compound and the component (B) is used in combination, the transition metal compound (A) is converted into the following general formula (II- The compound represented by a) is formed.

[0173]

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(Wherein, R ¹ , R ^{10 to} R ¹⁴ , M, m, n and X each represent R ¹ , R ¹⁰
~R ^14, M, m, has the same meaning as n, and X, Y represents a so-called weakly coordinating anion. In the general formula (II-a), the bond between the metal M and Y may be a covalent bond or an ionic bond.

Examples of Y include a weakly coordinating anion described in Chemical Review, vol. 88, p. 1405 (1988), Chemical Review, vol. 93, p. 927 (1993), WO 98/30612, p. Specifically, AlR ₄ ⁻ (R may be the same or different from each other, and may be an oxygen atom, a nitrogen atom, a phosphorus atom, a hydrogen atom, a halogen atom or a substituent containing these, an aliphatic hydrocarbon group, an aromatic A hydrocarbon or alicyclic hydrocarbon group, or an aliphatic, aromatic, or alicyclic hydrocarbon group substituted with an oxygen, nitrogen, phosphorus, or halogen atom, Group hydrocarbon group,
A group in which a substituent having an oxygen atom, a nitrogen atom, a phosphorus atom, or a halogen atom is substituted for an aromatic hydrocarbon group or an alicyclic hydrocarbon group. BR ₄ ⁻ (R may be the same or different and each represents an oxygen atom, a nitrogen atom, a phosphorus atom, a hydrogen atom, a halogen atom or a substituent containing these, or an aliphatic hydrocarbon group or an aromatic hydrocarbon. Or an alicyclic hydrocarbon group, or an aliphatic, aromatic, or alicyclic hydrocarbon group substituted with an oxygen, nitrogen, phosphorus, or halogen atom, or an aliphatic hydrocarbon Hydrogen group,
A group in which a substituent having an oxygen atom, a nitrogen atom, a phosphorus atom, or a halogen atom is substituted for an aromatic hydrocarbon group or an alicyclic hydrocarbon group. ) Or PF ^6- , Sb
F ^5- , trifluoromethanesulfonate, p-toluenesulfonate and the like.

The catalyst for olefin polymerization according to the present invention comprises the above-mentioned transition metal compound (A-1) or (A-2) (hereinafter sometimes referred to as “component (A)”). At least one compound (B) selected from B-1) an organometallic compound, (B-2) an organoaluminum oxy compound and (B-3) an ionized ionic compound (hereinafter referred to as "component (B)")
There is that. ) Together with the following carrier (C) and / or organic compound (D) as described below, if necessary.

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

Among these, inorganic oxides include porous oxides.
Material, inorganic halide, clay, clay mineral or ion exchange
Exchangeable layered compounds are preferred. As a porous oxide,
In general, SiO_Two, Al_TwoO_Three, MgO, ZrO, TiO_Two,
B_TwoO_Three, CaO, ZnO, BaO, ThO_Two And so on
Are composites or mixtures containing them, such as natural or
Synthetic zeolite, SiO_Two-MgO, SiO _Two-Al_TwoO_Three,
SiO_Two-TiO_Two, SiO_Two-V_TwoO_Five, SiO_Two-Cr
_TwoO_Three, SiO_Two-TiO_Two-It is possible to use MgO etc.
Wear. Of these, SiO_TwoAnd / or Al_TwoO_Three
The main component is preferably.

[0179] The above inorganic oxide is composed of a small amount of Na ₂ C
O ₃ , K ₂ CO ₃ , CaCO ₃ , MgCO ₃ , Na ₂ SO ₄ ,
Al ₂ (SO ₄ ) ₃ , BaSO ₄ , KNO ₃ , Mg (NO ₃ ) ₂ ,
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 porous oxides vary depending on the kind and the production method, the carrier preferably used in the present invention has a particle diameter of 10 to 300 μm, preferably 20 to 300 μm.
And a specific surface area of 50 to 1000 m ^2.
/ G, preferably in the range of 100 to 700 m ² / g, and the pore volume is desirably in the range of 0.3 to 3.0 cm ³ / g. Such a carrier may be used, if necessary, for 10 hours.
It is used by firing at 0 to 1000 ° C, preferably 150 to 700 ° C.

Examples of inorganic halides include MgCl ₂ ,
MgBr ₂ , MnCl ₂ , MnBr _{2 and the} like are used. The inorganic halide may be used as it is, or may be used after being pulverized by a ball mill or a vibration mill. Also,
A solution obtained by dissolving an inorganic halide in a solvent such as alcohol and then precipitating in a fine particle state with a precipitant can also be used.

[0182] Clay is usually composed mainly of clay minerals. Further, the ion-exchangeable layered compound is a compound having a crystal structure in which surfaces formed by ionic bonds and the like are stacked in parallel with a weak bonding force, and the ions contained therein 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. Examples of the ion-exchange layered compound include α-Zr (HAsO ₄ ) ₂ .H ₂ O,
α-Zr (HPO ₄ ) ₂ , α-Zr (KPO ₄ ) ₂ .3H ₂ O, α-Zr
Ti (HPO ₄ ) ₂ , α-Ti (HAsO ₄ ) ₂ .H ₂ O, α-S
n (HPO ₄ ) ₂ .H ₂ O, γ-Zr (HPO ₄ ) ₂ , γ-Ti (H
PO ₄ ) ₂ and crystalline acidic salts of polyvalent metals such as γ-Ti (NH ₄ PO ₄ ) ₂ .H ₂ O.

The clay, clay mineral or ion-exchangeable layered compound preferably has a pore volume of 0.1 cc / g or more at a radius of 20 ° or more measured by a mercury intrusion method.
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. Clay and clay minerals are also preferably subjected to chemical treatment.

As the chemical treatment, any of a surface treatment for removing impurities adhering to the surface, a treatment that affects the crystal structure of clay, and the like 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 may be a layered compound in which the interlayer is expanded by utilizing the ion-exchange property and exchanging the exchangeable ion between the layers with another large bulky ion. 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. As the intercalating guest compound, TiC
l ₄ , a cationic inorganic compound such as ZrCl ₄ , Ti (O
Metal alkoxides such as R) ₄ , Zr (OR) ₄ , PO (OR) ₃ , B (OR) ₃ (R is a hydrocarbon group, etc.), [Al ₁₃ O
₄ (OH) ₂₄ ] ⁷⁺ , [Zr ₄ (OH) ₁₄ ] ²⁺ , [Fe ₃ O (OCOC
H _{3) 6]} ⁺ and metal hydroxide ions such as.
These compounds are used alone or in combination of two or more. When intercalating these compounds, Si (OR) ₄ , Al (OR) ₃ , Ge (OR) ₄
And a polymer obtained by hydrolyzing a metal alkoxide (R is a hydrocarbon group, etc.), a colloidal inorganic compound such as SiO _2, and the like. Examples of the pillars include oxides formed by intercalating the metal hydroxide ions between layers and then heating and dehydrating the layers.

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

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, 1-
Butene, 4-methyl-1-pentene, etc. having 2 to 2 carbon atoms
Produced mainly with 14 α-olefins (co)
Examples thereof include a polymer or a (co) polymer formed mainly of vinylcyclohexane and styrene, and modified products thereof.

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

As the alcohols and phenolic compounds, those represented by R ³⁰ —OH are usually used.
Here, R ³⁰ 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 ³⁰ is a halogenated hydrocarbon are preferred. Further, as the phenolic compound, a compound in which the α, α′-position of the hydroxyl group is substituted by a hydrocarbon having 1 to 20 carbon atoms is preferable.

As the carboxylic acid, R is usually³¹-COO
The one represented by H is used. R ³¹Represents 1 to 1 carbon atoms
50 hydrocarbon groups or halogens having 1 to 50 carbon atoms
A halo group having 1 to 50 carbon atoms.
Genated hydrocarbon groups are preferred.

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

[0197]

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In the formula, M is an element belonging to groups 1 to 14 of the periodic table. R ³³ is hydrogen, a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group having 1 to 20 carbon atoms.

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

FIG. 1 shows a process for preparing the olefin polymerization catalyst according to the present invention. During polymerization, the usage of each component,
Although the order of addition is arbitrarily selected, the following method is exemplified. (1) A method in which the component (A) and the component (B) are added to a polymerization vessel in an arbitrary order. (2) A method in which the catalyst 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 in contact with each other in advance. (3) and (4) above in which the component (B) is supported.
In each of the above methods, the unsupported component (B) may be added in an arbitrary order, if necessary. In this case, the components (B) may be the same or different.

The solid catalyst component in which the component (A) and the component (B) are supported on the carrier (C) may be prepolymerized with an olefin. Further, a catalyst component may be supported.

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. If necessary, a specific organic compound component (D) (component (D)) as described later can also be contained together with the carrier (C).

The component (B-1) has a molar ratio [(B-1) / M] between the component (B-1) and all the transition metal atoms (M) in the component (A).
Usually 0.01 to 100,000, preferably 0.05 to 5
0000 is used. Component (B-2) is
The molar ratio [(B-2) / M] of the aluminum atom in the component (B-2) to the transition metal atom (M) in the component (A) is usually 1
It is used in such an amount as to be 0 to 500,000, preferably 20 to 100,000. Component (B-3) is composed of component (B-3) and
The molar ratio with the transition metal atom (M) in the component (A) [(B-3)
/ M] is generally used in an amount of 1 to 10, preferably 1 to 5.

In the component (D), the component (B) is the 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 0.005.
When the component (B) is the component (B-3) in an amount such that the molar ratio [(D) / (B-3)] is usually 0.01 to 1
It is used in an amount such that it becomes 10, preferably 0.1 to 5.

The polymerization temperature of olefin using such an olefin polymerization catalyst is usually -50 to +250.
° C, preferably 0 to 200 ° C, particularly preferably 60 to 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 normal pressure to 50 kg / cm ² , and the polymerization reaction can be carried out by any of a batch system, a semi-continuous system, and a continuous system. Further, the polymerization can be performed in two or more stages having different reaction conditions.

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

In the present invention, by using the olefin polymerization catalyst, it is possible to produce an olefin polymer having high activity and high molecular weight even at a high temperature. Examples of the olefin that can be polymerized by such an olefin polymerization catalyst include linear or branched α-olefins having 2 to 30 carbon atoms, preferably 2 to 20 carbon atoms, such as ethylene, propylene, and 1-butene. , 2-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-
Methyl-1-pentene, 3-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene; having 3 to 30 carbon atoms; Preferably from 3 to 20 cyclic olefins, such as cyclopentene, cycloheptene, norbornene,
5-methyl-2-norbornene, tetracyclododecene, 2-
Methyl 1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene; polar monomers such as acrylic acid, methacrylic acid, fumaric acid, maleic anhydride, itacone Acid, itaconic anhydride, bicyclo (2,2,1) -5-heptene-
Α, β-unsaturated carboxylic acids such as 2,3-dicarboxylic anhydride and α, β-unsaturated carboxylic acid metals such as sodium, potassium, lithium, zinc, magnesium, and calcium salts thereof Salt; methyl acrylate,
Ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, Α, β-unsaturated carboxylic esters such as isopropyl methacrylate, n-butyl methacrylate and isobutyl methacrylate; vinyl acetate, vinyl propionate, vinyl caproate, vinyl caprate, vinyl laurate, vinyl stearate, trifluoro Vinyl esters such as vinyl acetate; unsaturated glycidyls such as glycidyl acrylate, glycidyl methacrylate, and monoglycidyl itaconate; halogenated olefins such as vinyl fluoride, vinyl chloride, vinyl bromide, and vinyl iodide. Ceremony I can do it.

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

[0212]

Industrial Applicability The olefin polymerization catalyst and the polymerization method according to the present invention can produce a polyolefin with high polymerization activity at a high temperature.

[0213]

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 limiting viscosity [η]
Was measured in 135 ° C decalin. The structure of the compound obtained in the synthesis example is 270 MHz ¹ H-NMR (JEOL GSH-270), FD-mass spectrometry (JEOL SX-102A)
And so on.

[0215]

[Synthesis Example 1] 500ml sufficiently dried and purged with argon
7.51 g of 2-tert-butylphenol (5.
(0 mmol) and 54 ml of THF, and 18.53 ml of an ether solution containing 55.6 mmol of ethylmagnesium bromide was added dropwise at 0 ° C over 15 minutes, and then slowly heated to room temperature and stirred at room temperature for 1 hour. 180 ml of toluene was added, the mixture was heated to 100 ° C., and about 40 ml of a mixed solution of ether and THF was distilled off to obtain a cloudy slurry. After cooling to room temperature, 3.75 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, it is quenched with 10% hydrochloric acid, and the organic layer is concentrated and purified by a silica gel column to give 6.22 g of 3-t-butylsalicylaldehyde.
(70% yield).

¹ H-NMR (CDCl ₃ ): 1.42 (s, 9H) 6.94 (t, 1H)
7.25-7.54 (m, 2H) 9.86 (s, 1H) 11.79 (s, 1H)
0 ml, n-octadecylamine 6.06 g (22.5 m
mol) and 3-t-butylsalicylaldehyde 2.84
g (15.0 mmol), and a small amount of acetic acid was added.
Stirring was continued at room temperature for 24 hours. The reaction solution was concentrated under reduced pressure to remove the solvent, thereby obtaining 4.56 g (yield 70.7%) of a compound (A) as a yellow crystal represented by the following formula (A).

¹ H-NMR (CDCl ₃ ): 0.89 (t, 3H) 1.26 (s, 30H)
1.44 (s, 9H) 1.53-1.75 (m, 2H) 3.57 (t, 2H) 6.79 (t, 1H)
7.08-7.11 (dd, 1H) 7.26-7.32 (dd, 1H) 8.32 (s, 1H) 14.22
(s, 1H)

[0218]

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100 ml sufficiently dried and purged with argon
0.86 g (2.0 mmol) of compound (A)
l) and 20 ml of ether were charged, cooled to -78 ° C and stirred. It contains 2.2 mmol of n-butyllithium
1.43 ml of an n-hexane solution was added dropwise over 10 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 0.38 g (1.0 g) of a ZrCl ₄ (THF) ₂ complex.
(mmol) in a THF solution (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. By recrystallizing the obtained solid with a mixed solution of ether and hexane, 0.220 g of compound (1) of a bright yellow crystal represented by the following formula (1) (yield: 21.6%)
Obtained.

¹ H-NMR (CDCl ₃ ): 0.88 (t, 6H) 1.25 (s, 78H)
1.57 (s, 4H) 3.59 (t, 4H) 6.92 (t, 2H) 7.20-7.26 (dd, 2H)
7.55-7.62 (dd, 2H) 8.15 (s, 1H) FD-MS: 1018

[0221]

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[0222]

Synthesis Example 2 50 ml of ethanol and cyclohexanemethylamine were placed in a 100 ml reactor sufficiently purged with nitrogen.
28 g (20.14 mmol) and 2.98 g (16.73 mmol) of 3-t-butylsalicylaldehyde were charged, and stirring was continued at room temperature for 20 hours. The reaction solution was concentrated under reduced pressure to remove the solvent, and the resulting liquid was purified by silica gel column chromatography to obtain 3.38 g (yield 74%) of a yellow liquid compound (B) represented by the following formula (B). I got

¹ H-NMR (CDCl ₃ ): 0.95-1.82 (m, 11H) 1.44
(s, 9H) 3.42 (d, 2H) 6.76-7.32 (m, 3H) 8.28 (s, 1H) 14.19
(s, 1H)

[0224]

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100 ml sufficiently dried and purged with argon
0.97 g (3.55 mmol) of compound (B)
l) and 20 ml of ether were charged, cooled to -78 ° C and stirred. To this, 2.40 ml of an n-hexane solution containing 3.84 mmol of n-butyllithium was added dropwise over 10 minutes.
Thereafter, the temperature was slowly raised to room temperature, and stirring was continued at room temperature for 4 hours to prepare a lithium salt solution. -78 ° C
0.66 g of ZrCl ₄ (THF) ₂ complex cooled to
(1.75 mmol) was added dropwise to 30 ml of a THF solution. 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 methylene chloride 120 ml.
Then, the filtrate was concentrated and then washed again with ether to obtain 0.57 g (yield 46%) of a yellow powdered compound (2) represented by the following formula (2).

¹ H-NMR (CDCl ₃ ): 0.50-1.74 (m, 22H) 1.58
(s, 18H) 3.32 (m, 4H) 6.90-7.60 (m, 6H) 8.01 (s, 2H) FD-Mass Spec: 706

[0227]

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[0228]

[Synthesis Example 3] 50 ml of ethanol, 2.27 g (20.05 mmol) of 2-methylcyclohexylamine and 2.89 g (16.23 mmol) of 3-t-butylsalicylaldehyde were charged into a 100 ml reactor sufficiently purged with nitrogen. Then, a small amount of acetic acid was added, and stirring was continued at room temperature for 24 hours. The reaction solution was concentrated under reduced pressure to remove the solvent, and the resulting liquid was purified by silica gel column chromatography,
Compound (C) 3.6 as a yellow liquid represented by the following formula (C):
5 g (82% yield) were obtained.

¹ H-NMR (CDCl ₃ ): 0.81-0.85 (m, 3H) 1.03-1.
83 (m, 9H) 1.44 (s, 9H) 2.65-2.74 (td, 1H) 6.78-7.32 (m, 3
H) 8.30,8.33 (s, s, 1H) 14.19,14.24 (s, s, 1H)

[0230]

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100 ml sufficiently dried and purged with argon
Into a reactor of 0.96 g (3.51 mmol) of compound (C).
l) and 20 ml of ether were charged, cooled to -78 ° C and stirred. 2.41 ml of an n-hexane solution containing 3.86 mmol of n-butyllithium was added dropwise thereto over 10 minutes,
Thereafter, the temperature was slowly raised to room temperature, and stirring was continued at room temperature for 2 hours to prepare a lithium salt solution. -78 ° C
0.66 g of ZrCl ₄ (THF) ₂ complex cooled to
(1.75 mmol) in 20 ml of a THF solution. 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 washed with 50 ml of ether, the filtrate was concentrated, and then recrystallized with a mixed solution of methylene chloride and hexane to obtain a yellow powder compound (3) represented by the following formula (3). .47 g (38% yield) were obtained.

¹ H-NMR (CDCl ₃ ): 0.69-1.90 (m, 24H) 1.62
(s, 18H) 3.65-3.90 (m, 2H) 6.86-7.64 (m, 6H) 8.14-8.27
(m, 2H) FD-Mass Spec: 706

[0233]

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[0234]

Synthesis Example 4 50 ml of ethanol, 2.31 g (18.16 mmol) of 2,3-dimethylcyclohexylamine and 3.11 g (17.45 mmol) of 3-t-butylsalicylaldehyde were placed in a 100 ml reactor which was sufficiently purged with nitrogen.
And stirring was continued at room temperature for 24 hours. The reaction solution was concentrated under reduced pressure to remove the solvent, and 4.97 g (yield 99.1%) of a yellow liquid compound (D) represented by the following formula (D) was obtained.

¹ H-NMR (CDCl ₃ ): 0.75-1.00 (m, 6H) 1.00-1.
95 (m, 8H) 1.44 (s, 9H) 2.73-3.30 (m, 1H) 6.77-7.32 (m, 3
H) 8.30-8.36 (m, 1H) 14.20-14.33 (m, 1H)

[0236]

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100 ml sufficiently dried and purged with argon
1.20 g of compound (D) (4.18 mmol)
l) and 20 ml of ether were charged, cooled to -78 ° C and stirred. To this, 2.70 ml of an n-hexane solution containing 4.24 mmol of n-butyllithium was added dropwise over 10 minutes.
Thereafter, the temperature was slowly raised to room temperature, and stirring was continued at room temperature for 4 hours to prepare a lithium salt solution. -78 ° C
0.79 g of ZrCl ₄ (THF) ₂ complex cooled to
(2.09 mmol) in 30 ml of a THF solution. 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 washed with 30 ml of ether and 70 ml of methylene chloride, the filtrate was concentrated, and then washed again with a mixed solution of ether and hexane to obtain a yellow powdered compound (4) represented by the following formula (4). 0.37
g (24% yield).

¹ H-NMR (CDCl ₃ ): 0.10-1.90 (m, 28H) 1.61
(s, 18H) 2.55-2.75 (m, 2H) 6.70-7.70 (m, 6H) 8.10-8.40
(m, 2H) FD-Mass Spec: 734

[0239]

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[0240]

Synthesis Example 5 Ethanol 40 ml and benzylamine 0.90 g (0.
84 mmol) and 1.50 g (8.42 mmol) of 3-t-butylsalicylaldehyde, and while stirring at room temperature, a small amount of molecular sieve was added.
Stirred at 5 ° C for 4 hours. After the reaction solution was filtered, the filtrate was concentrated under reduced pressure. 40 ml of cold MeOH was added thereto, and the mixture was cooled at −78 ° C. with stirring to obtain 1.80 g of a compound (E) as a yellow solid represented by the following formula (E).
(80% yield).

¹ H-NMR (CDCl ₃ ): 1.45 (s, 9H) 4.82 (s, 2H)
6.78-7.45 (m, 8H) 8.47 (s, 1H) 13.89 (bs, 1H)

[0242]

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100 ml sufficiently dried and purged with argon
0.50 g (1.87 mmol) of compound (E)
l) and 40 ml of ether, cool to −78 ° C. and stir
Stirred. This contains 1.93 mmol of n-butyllithium.
N-hexane solution 1.20 ml was added dropwise over 10 minutes,
Then slowly warm to room temperature and stir at room temperature for 15 hours
And a lithium salt solution was prepared. This solution was -78
ZrCl cooled to ℃ _Four(THF)_Two0.352 g of complex
(1.87 mmol) in 50 ml of THF solution
Was. After the completion of dropping, the temperature is allowed to rise slowly and stir at room temperature overnight.
Stirred. After stirring this solution at 60 ° C. for 3 hours, the reaction solution
Was evaporated. The obtained solid was mixed with 100 ml of ether.
Reslurry with 100 ml of hexane mixed solvent, filter
Was. This was washed with 100 ml of hexane, and the residue was dried under reduced pressure.
By drying, a pale yellow-white solid represented by the following formula (5) is obtained.
0.30 g (yield 46%) of the compound (5) was obtained.

¹ H-NMR (CDCl ₃ ): 1.60 (s, 18H) 4.65 (d, 2H)
4.95 (d, 2H) 6.70-7.70 (m, 16H) 7.85 (s, 2H) FD-Mass Spec: 694

[0245]

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[0246]

[Synthesis Example 6] Ethyl magnesium bromide was placed in a 1 liter reactor which had been thoroughly dried and purged with argon and charged with 110 mm.
ol containing ether solution 36.6 ml and ether 73.4
Then, 18.39 g (100 mmol) of 2-tert-butyl-4-methoxyphenol was added at 0 ° C. in THF 90m.
The solution diluted with 1 was added dropwise over 30 minutes, and then slowly warmed to room temperature and stirred at room temperature for 1 hour. After adding 350 ml of toluene, the mixture was heated to 100 ° C., and about 180 ml of a mixed solution of ether and THF was distilled off to obtain a cloudy slurry. After cooling to 50 ° C., 4.50 g (150 mmol) of paraformaldehyde and 21.0 ml (150 mmol) of triethylamine were added, and
The mixture was stirred at 90 ° C. for 1.5 hours. After cooling to room temperature, 10
The organic layer was concentrated, and the precipitated solid was dried under reduced pressure to obtain 11.66 g (yield: 56%) of 3-t-butyl-5-methoxysalicylaldehyde.

¹ H-NMR (CDCl ₃ ): 1.4 (s, 9H) 3.8 (t, 3H) 6.8
(s, 1H) -7.2 (d, 1H) 9.9 (s, 1H) 11.5 (s, 1H)
56 ml, 2.53 g of n-hexylamine (25 mmo
l) and 5.20 g (25 mmol) of 3-t-butyl-5-methoxysalicylaldehyde were added and stirring was continued at room temperature for 24 hours. The reaction solution was concentrated under reduced pressure to remove the solvent, and a yellow crystalline compound (F) 6.96 represented by the following formula (F) was obtained.
g (yield 97%) was obtained.

¹ H-NMR (CDCl ₃ ): 0.9 (t, 3H) 1.3 (s, 6H) 1.4
(s, 9H) 1.7-1.8 (m, 2H) 3.6 (t, 2H) 3.8 (s, 3H) 6.6 (s, 1H)
7.0 (s, 1H) 8.3 (s, 1H) 13.8 (s, 1H)

[0249]

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100 ml sufficiently dried and purged with argon
1.17 g of compound (F) (4.0 mmol)
l) and 40 ml of ether, cool to −78 ° C. and stir
Stirred. It contains 4.2 mmol of n-butyllithium
2.61 ml of n-hexane solution was slowly dropped, and then
Slowly warm to room temperature, continue stirring at room temperature for 4 hours,
A lithium salt solution was prepared. Cool this solution to -78 ° C
ZrCl_Four(THF)_Two 0.755 g (2.0 m
mol) in a THF solution (40 ml). Drip end
Thereafter, stirring was continued while slowly raising the temperature to room temperature. Sa
After stirring at room temperature for 15 hours, the reaction solution was evaporated.
Was. 20 ml of ether was added to the obtained solid, and slurry was added.
After washing with ether (10 ml × 2),
Filtered. After concentrating the filtrate to 10 ml, overnight at 0 ° C
By standing, a yellow-orange color represented by the following formula (6) is formed.
0.85 g (yield 58%) of crystalline compound (6) was obtained.

¹ H-NMR (CDCl ₃ ): 0.9 (t, 6H) 1.0-1.4 (s, 12
H) 1.6 (s, 18H) 3.6 (t, 4H) 3.8 (s, 6H) 6.7 (s, 2H) 7.2 (s, 2
H) 8.2 (s, 1H) FD-Mass Spec: 742

[0252]

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[0253]

[Synthesis Example 7] 50 ml of ethanol and 1.23 g of cyclohexylamine were placed in a 200 ml reactor which was sufficiently purged with nitrogen.
(12.4 mmol) and 2.55 g (12.2 mmol) of 3-t-butyl-5-methoxysalicylaldehyde were added, and stirring was continued at room temperature for 24 hours. The precipitated solid was separated by filtration, washed with ethanol, and dried under reduced pressure to obtain 2.34 g (yield 66%) of a yellow-orange crystal compound (G) represented by the following formula (G). .

¹ H-NMR (CDCl ₃ ): 1.20-1.85 (m, 19H) 3.18-
3.23 (m, 1H) 3.77 (s, 3H) 6.59-6.60 (d, 1H) 6.95-6.96 (d,
1H) 8.33 (s, 1H) 13.75 (s, 1H) FD-Mass Spec: 289

[0255]

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100 ml sufficiently dried and purged with argon
0.86 g (2.99 mmol) of compound (G)
l) and 20 ml of ether were charged, cooled to -78 ° C and stirred. To this, 2.15 ml of an n-hexane solution containing 3.31 mmol of n-butyllithium was slowly dropped, and then the temperature was slowly raised to room temperature, and stirring was continued at room temperature for 1 hour to prepare a lithium salt solution. This solution was cooled to −78 ° C., and 0.566 g of ZrCl ₄ (THF) ₂ complex was added.
(1.50 mmol) was added dropwise to a THF solution (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 washed with 100 ml of ether and 90 ml of methylene chloride, and the filtrate was concentrated to obtain 0.27 g (yield: 25%) of a compound (7) as a yellow powder represented by the following formula (7). .

¹ H-NMR (CDCl ₃ ): 0.98-2.12 (m, 38H) 3.46-
3.87 (m, 8H) 6.63-6.64 (d, 2H) 7.19-7.20 (d, 2H) 8.20 (s,
2H) FD-Mass Spec: 738

[0258]

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[0259]

Synthesis Example 8 Ethanol (30 ml) and cyclohexanemethylamine were placed in a 100 ml reactor sufficiently purged with nitrogen.
05g (9.27 mmol) and 1.92 g (9.23 mmol) of 3-t-butyl-5-methoxysalicylaldehyde
1) and stirring was continued at room temperature for 73 hours. The precipitated solid was separated by filtration, washed with ethanol, and dried under reduced pressure to obtain 2.70 g (96% yield) of an orange liquid compound (H) represented by the following formula (H).

¹ H-NMR (CDCl ₃ ): 0.93-1.86 (m, 11H) 1.43
(s, 9H) 3.42 (d, 2H) 3.77 (s, 3H) 6.60 (d, 1H) 6.96 (d, 1H)
8.25 (s, 1H) 13.71 (bs, 1H)

[0261]

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100 ml sufficiently dried and purged with argon
0.84 g (2.57 mmol) of compound (H)
l) and 20 ml of ether were charged, cooled to -78 ° C and stirred. To this, 1.90 ml of an n-hexane solution containing 3.04 mmol of n-butyllithium was slowly dropped, and then the temperature was slowly raised to room temperature, and stirring was continued at room temperature for 1.5 hours to prepare a lithium salt solution. -78 ° C
0.52 g of ZrCl ₄ (THF) ₂ complex cooled to
(1.34 mmol) was added dropwise to a THF solution (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 solvent of the reaction solution was distilled off. The obtained solid was washed with 40 ml of ether and 100 ml of methylene chloride, the filtrate was concentrated, and then washed again with a mixed solution of ether and hexane to obtain a yellow powder compound represented by the following formula (8). .67g
(63% yield).

¹ H-NMR (CDCl ₃ ): 0.53-1.85 (m, 22H) 1.55
(s, 18H) 3.22-3.40 (m, 4H) 3.80 (s, 6H) 6.64-6.67 (m, 2H)
7.10-7.26 (m, 2H) 7.96 (s, 2H) FD-Mass Spec: 766

[0264]

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[0265]

Synthesis Example 9 Ethanol (30 ml), 2-methylcyclohexylamine (1.72 g, 15.19 mmol) and 3-t-butyl-5 were placed in a 100 ml reactor which was sufficiently purged with nitrogen.
-Methoxysalicylaldehyde 2.64 g (12.68
mmol) and stirring was continued at room temperature for 24 hours. The precipitated solid was separated by filtration, washed with ethanol, and dried under reduced pressure to obtain 2.82 g (yield 73%) of a yellow powdery compound (I) represented by the following formula (I).

¹ H-NMR (CDCl ₃ ): 0.83 (d, 3H) 1.00-1.89 (m,
9H) 1.43 (s, 9H) 2.64-2.73 (td, 1H) 3.78 (s, 3H) 6.60 (d, 1
H) 6.96 (d, 1H) 8.27 (s, 1H) 13.7 (s, 1H)

[0267]

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100 ml sufficiently dried and purged with argon
Of the compound (I) (3.00 mmol)
l) and 20 ml of ether were charged, cooled to -78 ° C and stirred. To this, 2.10 ml of an n-hexane solution containing 3.36 mmol of n-butyllithium was slowly dropped, and then the temperature was slowly raised to room temperature, and stirring was continued at room temperature for 2 hours to prepare a lithium salt solution. This solution was cooled to −78 ° C. and 0.57 g of ZrCl ₄ (THF) ₂ complex (1.
(51 mmol) in a THF solution (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. After the obtained solid was washed with 10 ml of ether and 60 ml of methylene chloride, the filtrate was concentrated and washed again with a mixture of ether and hexane to obtain a yellow powdered compound represented by the following formula (9) ( 9) 0.54g
(46% yield).

¹ H-NMR (CDCl ₃ ): 0.60-2.90 (m, 24H) 1.60
(s, 18H) 2.50-2.70 (m, 2H) 3.47 (m, 6H) 6.61-6.64 (m, 2H)
7.21,7,22 (s, s, 2H) 8.15-8.23 (m, 2H) FD-Mass Spec: 766

[0270]

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[0271]

Synthesis Example 10 In a 100-ml reactor purged with nitrogen, 40 ml of ethanol and 1.61 g of benzylamine (1
5.0 mmol) and 3.12 g (15.0 mmol) of 3-t-butyl-5-methoxysalicylaldehyde, and stirring was continued at room temperature for 1.5 hours. The precipitated solid was separated by filtration, washed with methanol, and dried under reduced pressure to obtain 3.25 g (yield 73%) of a yellow-orange crystal compound (J) represented by the following formula (J). .

¹ H-NMR (CDCl ₃ ): 1.42 (s, 9H) 3.78 (s, 3H)
4.80 (s, 2H) 6.62-7.43 (m, 7H) 8.41 (s, 1H) 13.52 (s, 1H)

[0273]

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In a 50 ml reactor which was sufficiently dried and purged with argon, 0.89 g of compound (J) (3.00 mmol) was added.
l) and 30 ml of ether were charged, cooled to -78 ° C and stirred. 2.01 ml of an n-hexane solution containing 3.15 mmol of n-butyllithium was slowly added dropwise thereto, 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 0.57 g of ZrCl ₄ (THF) ₂ complex (1.
The solution was dropped into 30 ml of a THF solution containing 50 mmol). 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 solvent of the reaction solution was distilled off. After the obtained solid was washed with 30 ml of ether and 20 ml of methylene chloride, the filtrate was concentrated and washed again with 20 ml of ether to obtain 0.58 g of compound (10) as a yellow powder represented by the following formula (10). (51% yield).

¹ H-NMR (CDCl ₃ ): 1.51 (s, 18H) 3.75 (s, 6H)
4.60-5.10 (m, 4H) 6.35-7.25 (m, 14H) 7.82 (s, 2H) FD-Mass Spec: 754

[0276]

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[0277]

Synthesis Example 11 2-tert-butyl-4-methylphenol 9.68 was placed in a 1-liter reactor which had been sufficiently dried and purged with nitrogen.
g (58.93 mmol) and 100 ml of THF were charged, and at 0 ° C., 69.00 of ethyl magnesium bromide was added.
23.00 ml of an ether solution containing 3 mmol was dropped over 30 minutes, and then the temperature was slowly raised to room temperature.
Stirred for hours. 100 ml of toluene was added, the mixture was heated to 95 ° C., and a mixed solution of ether and THF was distilled off to obtain a cloudy slurry. After cooling to room temperature, toluene 100
ml, paraformaldehyde 4.50 g (149.90
mmol) and 12.50 ml of triethylamine (8
9.93 mmol) and stirred at 95 ° C. for 2 hours. After allowing to cool to room temperature, the mixture was quenched with 1N hydrochloric acid (300 ml), and the organic layer was concentrated and purified by a silica gel column to give 3-t-butyl-5-methylsalicylaldehyde.
36 g (65% yield) were obtained.

¹ H-NMR (CDCl ₃ ): 1.41 (s, 9H) 2.32 (s, 3H)
7.19 (d, 1H) 7.33 (d, 1H) 9.83 (s, 1H) 11.60 (s, 1H)
0 ml, n-hexylamine 1.52 g (15.02 mm
ol) and 2.86 g (14.90 mmol) of 3-t-butyl-5-methylsalicylaldehyde and 2
Stirring was continued for 4 hours. The reaction solution was concentrated under reduced pressure to remove the solvent, thereby obtaining 4.14 g (yield 100%) of a yellow liquid compound (K) represented by the following formula (K).

¹ H-NMR (CDCl ₃ ): 0.89 (t, 3H) 1.25-1.43 (m,
4H) 1.43 (s, 9H) 1.60-1.77 (m, 2H) 2.28 (s, 3H) 3.56 (t, 2
H) 6.89 (s, 1H) 7.11 (d, 1H) 8.27 (s, 1H) 13.94 (s, 1H)

[0280]

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300 ml sufficiently dried and purged with argon
4.16 g of the compound (K) (15.10 mm
ol) and 70 ml of ether, cooled to -78 ° C and stirred. To this, add 15.04 mmol of n-butyl lithium.
Then, 9.40 ml of an n-hexane solution containing 1 was dropped over 30 minutes, and 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
2.85 g of ZrCl ₄ (THF) ₂ complex cooled to 8 ° C.
(7.56 mmol) was added dropwise to a THF solution (80 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. After the obtained solid was washed with 50 ml of ether and 200 ml of methylene chloride, the filtrate was concentrated and washed again with 20 ml of ether to obtain the following formula (1)
4.30 g of compound (11) as a yellow powder shown in 1)
(80% yield).

¹ H-NMR (CDCl ₃ ): 0.74-1.54 (m, 18H) 1.55
(s, 18H) 2.31 (s, 6H) 3.37-3.68 (m, 4H) 6.99 (s, 2H) 7.36
(s, 2H) 8.09 (s, 2H) FD-Mass Spec: 710

[0283]

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[0284]

Synthesis Example 12 70 ml of ethanol, 1.83 g (16.17 mmol) of 2-methylcyclohexylamine and 3-t-butyl-5 were placed in a 200 ml reactor sufficiently purged with nitrogen.
-Methyl salicylaldehyde 3.06 g (15.92 m
mol), and stirring was continued at room temperature for 24 hours. The precipitated solid was separated by filtration and then dried under reduced pressure to obtain a yellow crystalline compound (L) represented by the following formula (L).
3.00 g (66% yield) was obtained.

¹ H-NMR (CDCl ₃ ): 0.79-0.83 (m, 3H) 0.96-1.
88 (m, 9H) 1.43 (s, 9H) 2.28 (s, 3H) 2.63-2.72 (td, 1H) 6.
90 (d, 1H) 7.11 (d, 1H) 8.26 (s, 1H) 13.93 (s, 1H)

[0286]

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100 ml sufficiently dried and purged with argon
0.87 g (3.03 mmol) of compound (L)
l) and 20 ml of ether were charged, cooled to -78 ° C and stirred. To this, 1.90 ml of an n-hexane solution containing 2.98 mmol of n-butyllithium was added dropwise over 10 minutes.
Thereafter, the temperature was slowly raised to room temperature, and stirring was continued at room temperature for 2 hours to prepare a lithium salt solution. -78 ° C
0.57 g of ZrCl ₄ (THF) ₂ complex cooled to
(1.50 mmol) was added dropwise to a THF solution (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. After the obtained solid was washed with 80 ml of ether, the filtrate was concentrated and recrystallized with a mixed solution of ether and hexane to obtain a yellow powdered compound (12) represented by the following formula (12). .44 g (yield 40
%)Obtained.

¹ H-NMR (CDCl ₃ ): 0.65-1.90 (m, 24H) 1.60
(s, 18H) 2.32 (s, 6H) 3.68-3.90 (m, 2H) 6.98 (s, 2H) 7.37
(s, 2H) 8.14-8.22 (m, 2H) FD-Mass Spec: 734

[0289]

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[0290]

Synthesis Example 13 In a 200 ml reactor which was sufficiently dried and purged with nitrogen, 34.15 g (316.0 m) of paracresol was placed.
mol), 2.50 g of Amberlyst-15E (trade name, manufactured by Organo) and 20 ml of toluene, and charged at 80 ° C.
14.40 g of 4-cumylphenol (105.0 mm
ol) diluted with 30 ml of toluene was added dropwise, and 1
Stir for 7 hours. After cooling to room temperature and filtering while washing with hexane, the obtained liquid was purified by silica gel column chromatography to obtain 10.52 g (44%) of 2-cumyl-4-methylphenol.

¹ H-NMR (CDCl ₃ ): 1.75 (s, 6H) 2,40 (s, 3H)
7.10-7.30 (m, 8H) 11.17 (s, 1H) Ether solution containing 63.1 mmol of ethylmagnesium bromide in a 500 ml reactor purged with nitrogen sufficiently.
1.0 ml and THF 40 ml were charged, and 13.61 g (60.1 mmol) of 2-cumyl-4-methylphenol was added at 0 ° C.
A solution of l) diluted with 20 ml of THF was added dropwise over 1 hour, and then the temperature was slowly raised to room temperature, followed by stirring at room temperature for 30 minutes. After adding 220 ml of toluene, the mixture was heated to 100 ° C., and about 50 ml of a mixed solution of ether and THF was distilled off to obtain a cloudy slurry. After cooling to 24 ° C,
4.37 g of paraformaldehyde (145.5 mmol
1) and 12.0 ml of triethylamine (86.0 m
mol) was added and stirred at 90 ° C. for 1 hour. After cooling to room temperature, the mixture was quenched with 42 ml of 18% hydrochloric acid, the organic layer was concentrated, and the resulting liquid was purified by silica gel column chromatography to give 3-cumyl-5-.
14.13 g of methyl salicylaldehyde (92% yield)
I got

¹ H-NMR (CDCl ₃ ): 1.75 (s, 6H) 2.40 (s, 3H)
7.10-7.42 (m, 7H) 8.55 (s, 1H) 13.18 (s, 1H) Ethanol was added to a 100 ml reactor which was sufficiently purged with nitrogen.
0 ml, n-hexylamine 1.82 g (18.0 mmol
l) and 3-cumyl-5-methylsalicylaldehyde
81 g (15.0 mmol) were charged and stirring was continued at room temperature for 3 hours. The reaction solution was concentrated under reduced pressure to remove the solvent, and the obtained liquid was purified by silica gel column chromatography to obtain 3.97 g (yield 78%) of a compound (M) represented by the following formula (M). Was.

¹ H-NMR (CDCl ₃ ): 0.85 (t, 3H) 1.27 (s, 6H)
1.52-1.70 (m, 2H) 1.71 (s, 6H) 2.34 (s, 3H) 3.45 (t, 2H)
6.92-7.35 (m, 7H) 8.22 (s, 1H) 13.49 (s, 1H)

[0294]

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In a 50 ml reactor which was sufficiently dried and purged with argon, 1.01 g of compound (M) (3.00 mmol) was added.
l) and 30 ml of ether were charged, cooled to -78 ° C and stirred. To this, 2.20 ml of an n-hexane solution containing 3.45 mmol of n-butyllithium was slowly dropped, and 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., and 0.622 g of ZrCl ₄ (THF) ₂ complex (1.
(65 mmol) in 30 ml of a THF solution. 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. 20 ml of ether was added to the obtained solid to form a slurry, which was filtered while washing with 10 ml of ether. The filtrate was concentrated and washed again with a mixed solution of hexane and ether to obtain 0.53 g (yield 42%) of compound (13) as a pale yellow powder represented by the following formula (13).

¹ H-NMR (CDCl ₃ ): 0.50-2.00 (m, 34H) 2.25-
2.45 (m, 6H) 2.50-2.75 (m, 4H) 6.90-7.55 (m, 14H) 8.85
(s, 2H) FD-Mass Spec: 832

[0297]

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[0298]

Synthetic Example 14 Ethanol (40 ml) and cyclohexylamine (0.99) were placed in a 100 ml reactor sufficiently purged with nitrogen.
g (10.0 mmol) and 2.54 g (10.0 mmol) of 3-cumyl-5-methylsalicylaldehyde were added, and stirring was continued at room temperature for 20 hours. The precipitated solid was separated by filtration, washed with cold methanol, and dried under reduced pressure to obtain 2.85 g (yield: 85%) of a compound (N) as a pale yellow crystal represented by the following formula (N). .

¹ H-NMR (CDCl ₃ ): 1.10-1.65 (m, 6H) 1.65-1.
82 (m, 4H) 1.75 (s, 6H) 2.35 (s, 3H) 3.12 (m, 1H) 6.95-7.3
3 (m, 7H) 8.28 (s, 1H) 13.42 (s, 1H)

[0300]

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In a 50 ml reactor which had been sufficiently dried and purged with argon, 1.01 g of compound (N) (3.00 mmol) was added.
l) and 30 ml of ether were charged, cooled to -78 ° C and stirred. 2.01 ml of an n-hexane solution containing 3.15 mmol of n-butyllithium was slowly added dropwise thereto, and 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., and 0.566 g of ZrCl ₄ (THF) ₂ complex (1.
The solution was dropped into 30 ml of a THF solution containing 50 mmol). 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. 30 ml of ether was added to the obtained solid to form a slurry, which was filtered while washing with ether (10 ml × 2). The filtrate was concentrated and washed again with a mixed solution of hexane and ether to obtain 0.91 g (yield 73%) of a pale yellow powdered compound (14) represented by the following formula (14).

¹ H-NMR (CDCl ₃ ): 0.85-2.10 (m, 32H) 2.28,
2.38 (s, s, 6H) 3.62 (m, 2H) 6.95-7.50 (m, 14H) 8.10 (s, 2
H) FD-Mass Spec: 830

[0303]

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[0304]

Synthesis Example 15 Ethanol (30 ml), 2-methylcyclohexylamine (0.91 g, 8.04 mmol) and 3-cumyl-5-methylsalicylaldehyde (1.96 g, 7.71 mmol) were placed in a 100 ml reactor which was sufficiently purged with nitrogen.
1) and stirring was continued at room temperature for 15 hours. The precipitated solid was separated by filtration and dried under reduced pressure to obtain 2.65 g (yield 98%) of a yellow crystal compound represented by the following formula (O).

¹ H-NMR (CDCl ₃ ): 0.70-0.80 (m, 3H) 0.85-1.
90 (m, 15H) 2.33,2.34 (s, s, 3H) 2.60,3.23 (m, 1H) 6.95-
7.30 (m, 7H) 8.20-8.30 (m, 1H) 13.35 (s, 1H)

[0306]

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100 ml sufficiently dried and purged with argon
1.08 g (3.08 mmol) of compound (O)
l) and 20 ml of ether were charged, cooled to -78 ° C and stirred. To this, 2.00 ml of an n-hexane solution containing 3.14 mmol of n-butyllithium was slowly dropped, and then the temperature was slowly raised to room temperature, and stirring was continued at room temperature for 1 hour to prepare a lithium salt solution. This solution was cooled to −78 ° C. and 0.58 g of ZrCl ₄ (THF) ₂ complex (1.
(54 mmol) in a THF solution (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 20 hours, the reaction solution was evaporated. After adding 30 ml of ether and 50 ml of methylene chloride to the obtained solid and filtering, the filtrate was concentrated and recrystallized with ether to obtain 0.39 g of compound (15) as a yellow powder represented by the following formula (15). (30% yield).

¹ H-NMR (CDCl ₃ ): 0.20-2.50 (m, 42H) 3.38-
3.65 (m, 2H) 6.90-7.70 (m, 14H) 8.05-8.25 (m, 2H) FD-Mass Spec: 858

[0309]

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[0310]

[Synthesis Example 16] 100 m sufficiently dried and purged with argon
In a 1 l reactor, 11.22 g (46.30 mmol) of 2- (1-adamantyl) -4-methyl-phenol and 10 parts of THF
0 ml was charged, and 16.20 ml of an ether solution containing 48.60 mmol of ethylmagnesium bromide at 0 ° C.
Was added dropwise over 30 minutes, and then slowly warmed to room temperature and stirred at room temperature for 2.5 hours. 300 ml of toluene was added, and the mixture was heated to 100 ° C. to obtain a cloudy slurry.
After cooling to room temperature, 3.80 g of paraformaldehyde (1
26.54 mmol) and triethylamine 7.10.
g (70.17 mmol) was added and stirred at 85 ° C. for 30 minutes. After cooling to room temperature, the mixture was quenched with 10% hydrochloric acid, the organic layer was concentrated, and the precipitated solid was dried under reduced pressure.
(1-adamantyl) -5-methylsalicylaldehyde 1
0.51 g (yield 84%) was obtained.

¹ H-NMR (CDCl ₃ ): 2.2-1.8 (s, 16H) 2.3 (s, 3
H) 7.5-7.0 (m, 2H) 9.8 (s, 1H) 11.6 (s, 1H)
0 ml, cyclohexylamine 0.55 g (5.55 m
mol) and 1.51 g (5.57 mmol) of 3- (1-adamantyl) -5-methylsalicylaldehyde, and stirring was continued at room temperature for 18 hours. The precipitated solid is separated by filtration and then dried under reduced pressure to obtain the following formula (P)
1.73 g (yield 8) of the compound (P) of yellow crystals represented by
9%).

¹ H-NMR (CDCl ₃ ): 1.18-1.70 (m, 10H) 1.79
(t, 6H) 2.11 (s, 3H) 2.30 (s, 6H) 2.31 (s, 3H) 3.12-3.28
(m, 1H) 6.97 (d, 1H) 7.02 (s, 1H) 8.17 (s, 1H) 13.98 (s, 1
H)

[0313]

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100 ml sufficiently dried and purged with argon
1.01 g of compound (P) (2.88 mmol)
l) and 20 ml of THF were charged, cooled to -78 ° C and stirred. It contains 2.87 mmol of n-butyllithium
1.83 ml of n-hexane solution was slowly added dropwise, and then the temperature was slowly raised to room temperature, and stirring was continued at room temperature for 1 hour.
A lithium salt solution was prepared. This solution was cooled to −78 ° C., and 0.54 g (1.44 m ₂ ) of ZrCl ₄ (THF) ₂ complex was cooled.
mol) in a THF solution (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. 30 ml of ether and 7 ml of methylene chloride were added to the obtained solid.
After adding 0 ml to make a slurry, the mixture was filtered. The filtrate was concentrated and recrystallized from a mixed solution of hexane and ether to give a yellow powdered compound (1) represented by the following formula (16).
0.99 g (yield 79%) of 6) was obtained.

¹ H-NMR (CDCl ₃ ): 0.70-2.20 (m, 50H) 2.27
(s, 6H) 3.80-3.95 (m, 2H) 6.87 (d, 2H) 7.04 (d, 2H) 8.31
(s, 2H) FD-Mass Spec: 862

[0316]

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[0317]

Synthesis Example 17 Ethanol (30 ml), 2-methylcyclohexylamine (0.67 g, 5.92 mmol) and 3- (1-adamantyl) -5-methylsalicylaldehyde 1.50 g (5 .
(55 mmol) and stirring was continued at room temperature for 18 hours. The precipitated solid was separated by filtration and dried under reduced pressure to obtain 1.67 g (yield: 82%) of a compound (Q) as a yellow powder represented by the following formula (Q).

¹ H-NMR (CDCl ₃ ): 0.81 (d, 3H) 0.95-1.75 (m,
9H) 1.79 (d, 6H) 2.08 (s, 3H) 2.18 (d, 6H) 2.28 (s, 3H) 2.
60-2.75 (td, 1H) 6.89 (s, 1H) 7.05 (d, 1H) 8.25,8.28 (s,
(s, 1H) 13.88,13.90 (s, s, 1H)

[0319]

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100 ml sufficiently dried and purged with argon
1.00 g (2.74 mmol) of compound (Q)
l) and 20 ml of THF were charged, cooled to -78 ° C and stirred. It contains 2.75 mmol of n-butyllithium
1.75 ml of an n-hexane solution was slowly dropped, and then the temperature was slowly raised to room temperature, and stirring was continued at room temperature for 1.5 hours to prepare a lithium salt solution. This solution was cooled to −78 ° C. and 0.52 g of ZrCl ₄ (THF) ₂ complex (1.
(37 mmol) in a THF solution (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 20 hours, the reaction solution was evaporated. 30 ml of ether and 70 ml of methylene chloride were added to the obtained solid to form a slurry, which was then filtered. The filtrate was concentrated, and recrystallized from a mixed solution of hexane and ether to obtain 0.50 g (yield 41%) of a yellow powdered compound (17) represented by the following formula (17).

¹ H-NMR (CDCl ₃ ): 0.60-2.20 (m, 54H) 2.32
(s, 6H) 3.70-3.92 (m, 2H) 6.90-7.00 (m, 2H) 7.26,7.31
(s, s, 2H) 8.00-8.30 (m, 2H) FD-Mass Spec: 890

[0322]

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[0323]

Synthesis Example 18 25.31 g (203.90 mm) of anisole was placed in a 200 ml reactor which had been sufficiently dried and purged with nitrogen.
), 2.00 g of Amberlyst-15 (trade name, manufactured by Organo) and 30 ml of toluene, and 15.52 g of 1-adamantyl alcohol (101.
A solution of 9 mmol) in 20 ml of toluene was added dropwise, and the mixture was stirred for 5.5 hours. After cooling to room temperature, the precipitated crystals were washed with hexane, and dried under reduced pressure,
2- (1-adamantyl) -4-methoxyphenol 12.2
0 g (46%) were obtained.

¹ H-NMR (CDCl ₃ ): 1.78 (s, 6H) 2.09 (s, 3H)
2.12 (s, 6H) 3.76 (s, 3H) 4.30 (bs, 1H) 6.58 (s, 2H) 6.83
(s, 1H) A 500 ml reactor sufficiently purged with nitrogen was charged with 16.50 ml of an ether solution containing 49.60 mmol of ethylmagnesium bromide and 10 ml of THF.
(1-adamantyl) -4-methoxyphenol 12.31
g (47.20 mmol) in 50 ml of THF was added dropwise over 15 minutes.
After adding 1, the mixture was heated to 95 ° C., and about 40 ml of a mixed solution of ether and THF was distilled off to obtain a cloudy slurry. After cooling to 20 ° C., 3.43 of paraformaldehyde
g (114.30 mmol) and 9.40 ml (67.50 mmol) of triethylamine,
For 30 minutes. After cooling to room temperature, 18% hydrochloric acid 3
After quenching with 2 ml, the organic layer was treated with 100 ml of water, 50 ml of an aqueous sodium hydrogen carbonate solution,
After washing with 00 ml, the mixture was concentrated, and the obtained solid was purified by silica gel column chromatography to obtain 4.95 g of 3- (1-adamantyl) -5-methoxysalicylaldehyde (37% yield).

¹ H-NMR (CDCl ₃ ): 1.78 (s, 6H) 2.09 (s, 3H)
2.12 (s, 6H) 3.82 (s, 3H) 6.80 (s, 1H) 7.13 (s, 1H) 9.87 (s,
1H) 11.57 (s, 1H) Ethanol 3 in a 100 ml reactor purged with nitrogen
0 ml, cyclohexylamine 0.37 g (3.73 m
mol) and 3- (1-adamantyl) -5-methoxysalicylaldehyde (1.03 g, 3.59 mmol), and stirring was continued at room temperature for 5.5 hours. The precipitated solid was separated by filtration, and dried under reduced pressure to obtain 1.24 g of a compound (R) represented by the following formula (R) (yield: 94).
%).

¹ H-NMR (CDCl ₃ ): 1.20-1.80 (m, 10H) 1.80
(s, 6H) 2.08 (s, 3H) 2.15 (s, 6H) 3.15-3.30 (m, 1H) 3.77
(s, 3H) 6.58 (d, 1H) 6.89 (d, 1H) 8.32 (s, 1H) 13.76 (s, 1
H)

[0327]

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In a 50 ml reactor which was sufficiently dried and purged with argon, 1.00 g (2.72 mmol) of compound (R) was added.
l) and 10 ml of THF were charged, cooled to -78 ° C and stirred. It contains 2.83 mmol of n-butyllithium
1.80 ml of an n-hexane solution was slowly added dropwise, and then the temperature was slowly raised to room temperature, and stirring was continued at room temperature for 1.5 hours to prepare a lithium salt solution. This solution was cooled to −78 ° C., and 0.51 g of ZrCl ₄ (THF) ₂ complex (1.
The solution was dropped into 20 ml of a THF solution containing 36 mmol). After completion of the dropwise addition, stirring was continued while slowly raising the temperature to room temperature. After further stirring at room temperature for 20 hours, the reaction solution was evaporated. After adding 30 ml of ether and 70 ml of methylene chloride to the obtained solid, the mixture was filtered. The filtrate was concentrated and washed again with a mixed solution of ether and hexane to obtain a yellow powdered compound (1) represented by the following formula (18).
8) (0.16 g, yield 13%) was obtained.

¹ H-NMR (CDCl ₃ ): 0.50-2.40 (m, 50H) 3.80
(s, 6H) 3.80-4.00 (m, 2H) 6.62 (d, 2H) 7.14 (d, 2H) 8.18
(s, 2H) FD-Mass Spec: 894

[0330]

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[0331]

Synthesis Example 19 Ethanol (30 ml), 2-methylcyclohexylamine (0.44 g, 3.89 mmol) and 3- (1-adamantyl) -5-methoxysalicylaldehyde (1.06 g) were placed in a 100 ml reactor which was sufficiently purged with nitrogen.
(3.70 mmol) and stirring was continued at room temperature for 5 hours. The precipitated solid is separated by filtration and then dried under reduced pressure to obtain a compound (S) represented by the following formula (S).
1.27 g (90% yield) were obtained.

¹ H-NMR (CDCl ₃ ): 0.82 (d, 3H) 1.00-1.80 (m,
9H) 1.79 (s, 6H) 2.07 (s, 3H) 2.17 (d, H) 2.65-2.75 (m, 1
H) 3.77 (s, 3H) 6.59 (d, 1H) 6.90 (d, 1H) 8.27,8,30 (s, s,
1H) 13.66,13.88 (s, s, 1H)

[0333]

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In a 50 ml reactor which was sufficiently dried and purged with argon, 1.00 g (2.63 mmol) of the compound (S) was placed.
l) and 20 ml of THF were charged, cooled to -78 ° C and stirred. It contains 2.67 mmol of n-butyllithium
1.70 ml of an n-hexane solution was slowly added dropwise, and then the temperature was slowly raised to room temperature, and stirring was continued at room temperature for 1.5 hours to prepare a lithium salt solution. This solution was cooled to −78 ° C. to obtain 0.50 g of ZrCl ₄ (THF) ₂ complex (1.
32 mmol) in 20 ml of a THF solution. After completion of the dropwise addition, stirring was continued while slowly raising the temperature to room temperature. After further stirring at room temperature for 20 hours, the reaction solution was evaporated. After adding 30 ml of ether and 70 ml of methylene chloride to the obtained solid, the mixture was filtered. The filtrate was concentrated and washed again with ether to obtain 0.65 g of a yellow powdered compound (19) represented by the following formula (19) (yield: 54).
%)Obtained.

¹ H-NMR (CDCl ₃ ): 0.20-2.40 (m, 54H) 3.65-
3.95 (m, 2H) 3.80 (s, 6H) 6.59-6.65 (m, 2H) 7.13-7.16 (m, 2
H) 8.14-8.23 (m, 2H) FD-Mass Spec: 923

[0336]

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[0337]

Synthesis Example 20 43.00 g (346.4 mmol) of anisole was placed in a 200 ml reactor which was sufficiently dried and purged with nitrogen.
l), Amberlist-15 (trade name, manufactured by Organo Corporation)
4.30 g and 50 ml of toluene were charged and 81.88 g of α-methylstyrene (692.8 mmol
6. A solution of 1) diluted with 50 ml of toluene was added dropwise.
Stir for 5 hours. After cooling to room temperature and filtering while washing with toluene, the obtained liquid was purified by silica gel column chromatography to obtain 24.28 g (28%) of 2-cumyl-4-methoxyphenol.

¹ H-NMR (CDCl ₃ ): 1.67 (s, 6H) 3.82 (s, 3H)
3.96 (s, 1H) 6.72-7.38 (m, 8H) Into a 1-liter reactor sufficiently purged with nitrogen, 43.5 ml of an ether solution containing 130.7 mmol of ethylmagnesium bromide and 70 ml of THF were charged, and 2-cumyl was added at 0 ° C. 30.16 g of 4-methoxyphenol (124.5
(mmol) was added dropwise over 30 minutes, and then 500 ml of toluene was added.
The mixture was heated to 100 ° C., and about 40 ml of a mixed solution of ether and THF was distilled off to obtain a cloudy slurry. After cooling to 15 ° C., 9.04 g of paraformaldehyde (301.
3 mmol) and 24.8 ml of triethylamine (1
(78.0 mmol) and stirred at 90 ° C. for 15 minutes. After cooling to room temperature, the mixture was quenched with 84% of 18% hydrochloric acid.
After washing in 2), the mixture is concentrated, and the obtained liquid is purified by silica gel column chromatography to obtain
27.27 g of 3-cumyl-5-methoxysalicylaldehyde
(81% yield).

¹ H-NMR (CDCl ₃ ): 1.82 (s, 6H) 3.85 (s, 3H)
7.15-7.38 (m, 7H) 9.80 (s, 1H) 11.3 (s, 1H)
0 ml, cyclohexylamine 1.09 g (11.0 m
mol) and 2.85 g (10.0 mmol) of 3-cumyl-5-methoxysalicylaldehyde.
Stirring was continued for hours. The precipitated solid was separated by filtration and dried under reduced pressure to obtain 2.54 g (yield: 72%) of a compound (T) represented by the following formula (T).

¹ H-NMR (CDCl ₃ ): 1.11-1.55 (m, 6H) 1.55-1.
85 (m, 4H) 1.75 (s, 6H) 3.11 (m, 1H) 3.82 (s, 3H) 6.63-7.2
9 (m, 7H) 8.28 (s, 1H) 13.20 (s, 1H)

[0341]

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In a 50 ml reactor which had been sufficiently dried and purged with argon, 1.05 g of compound (T) (3.00 mmol) was added.
l) and 30 ml of ether were charged, cooled to -78 ° C and stirred. 2.01 ml of an n-hexane solution containing 3.15 mmol of n-butyllithium was slowly added dropwise thereto, 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 0.57 g (1.5%) of ZrCl ₄ (THF) ₂ complex was added.
0 mmol) in 30 ml of a THF solution. After completion of the dropwise addition, stirring was continued while slowly raising the temperature to room temperature. After further stirring at room temperature for 20 hours, the reaction solution was evaporated. 30 ml of ether was added to the obtained solid to form a slurry, which was filtered while washing with 50 ml of methylene chloride. The filtrate was concentrated and washed again with a mixed solution of methylene chloride and ether to obtain 0.67 g of a yellow powdered compound (20) represented by the following formula (20) (yield 5
2%).

¹ H-NMR (CDCl ₃ ): 0.90-2.10 (m, 32H) 3.67
(m, 2H) 3.77,3.85 (s, s 6H) 6.60-7.41 (m, 14H) 8.11 (s, 2
H) FD-Mass Spec: 863

[0344]

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[0345]

Synthesis Example 21 In a 100 ml reactor purged with nitrogen, 40 ml of ethanol, 1.25 g (11.0 mmol) of 2-methylcyclohexylamine, and 2.85 g (10.0 mmol) of 3-cumyl-5-methoxysalicylaldehyde
1) and stirring was continued at room temperature for 3 hours. The precipitated solid was separated by filtration, and dried under reduced pressure to obtain 2.73 g of a compound (U) represented by the following formula (U) (yield: 7).
5%).

¹ H-NMR (CDCl ₃ ): 0.70-0.80 (d, 3H) 0.9-1.8
3 (m, 9H) 1.75 (s, 6H) 2.62 (m, 1H) 3.82 (s, 3H) 6.68-7.31
(m, 7H) 8.23 (s, 1H) 13.13 (s, 1H)

[0347]

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In a 50 ml reactor which was sufficiently dried and purged with argon, 1.10 g of compound (U) (3.00 mmol) was added.
l) and 30 ml of ether were charged, cooled to -78 ° C and stirred. 2.01 ml of an n-hexane solution containing 3.15 mmol of n-butyllithium was slowly added dropwise thereto, and then the temperature was slowly raised to room temperature, and stirring was continued at room temperature for 2 hours to prepare a lithium salt solution. This solution was cooled to −78 ° C. and 0.57 g of ZrCl ₄ (THF) ₂ complex (1.
The solution was dropped into 30 ml of a THF solution containing 50 mmol). After completion of the dropwise addition, stirring was continued while slowly raising the temperature to room temperature. After further stirring at room temperature for 20 hours, the reaction solution was evaporated. After adding 10 ml of ether and 30 ml of methylene chloride to the obtained solid to form a slurry, methylene chloride 2
It was filtered while washing with 0 ml. The filtrate was concentrated and washed again with a mixed solution of methylene chloride and ether to obtain a yellow powdered compound (2) represented by the following formula (21).
0.78 g (yield 58%) of 1) was obtained.

¹ H-NMR (CDCl ₃ ): 0.60-0.80 (m, 36H) 3.52
(m, 2H) 3.77 (s, 6H) 6.50-7.60 (m, 14H) 8.12 (s, 2H) FD-Mass Spec: 891

[0350]

Embedded image

[0351]

Synthesis Example 22 In a 300 ml reactor which was sufficiently dried and purged with nitrogen, 34.04 g of 4-phenylphenol (20
0.0mmol), Amberlyst-15E (trade name,
3.40 g of toluene (manufactured by Organo Corporation) and 150 ml of toluene were charged, and 148.20 g of t-butyl alcohol was added at 105 ° C.
A solution of (200.0 mmol) diluted with 10 ml of toluene was added dropwise, and the mixture was stirred for 16 hours. After cooling to room temperature, the solution was transferred into 500 ml of hexane and filtered while washing with hexane. After concentration, the obtained liquid was purified by silica gel column chromatography to obtain 31.15 g (69%) of 2-t-butyl-4-phenylphenol.

¹ H-NMR (CDCl ₃ ): 1.48 (s, 9H) 4.78 (s, 1H)
6.70-6.58 (m, 8H) Into a 1-liter reactor which was sufficiently purged with nitrogen, 66.80 ml of an ether solution containing 200.4 mmol of ethylmagnesium bromide and 100 ml of THF were charged.
43.16 g of 2-t-butyl-4-phenylphenol (19
0.7 mmol) in 90 ml of THF.
The mixture was added dropwise over 0 minutes, and then slowly heated to room temperature and stirred at room temperature for 30 minutes. After adding 700 ml of toluene, the mixture was heated to 100 ° C., and 52 ml of a mixed solution of ether and THF was distilled off to obtain a cloudy slurry. −
After cooling to 20 ° C., 13.84 g of paraformaldehyde
(460.9 mmol) and triethylamine
Add 1 ml (273.4 mmol) and add 3
Stirred for 0 minutes. After cooling with ice, quenching is performed with 133 ml of 18% hydrochloric acid, and the organic layer is washed with 300 ml of water, 300 ml of an aqueous sodium hydrogen carbonate solution and 300 ml of an aqueous sodium chloride solution, and then concentrated. The obtained liquid is purified by silica gel column chromatography. As a result, 37.73 g (yield 78%) of 3-t-butyl-5-phenylsalicylaldehyde was obtained.

¹ H-NMR (CDCl ₃ ): 1.47 (s, 9H) 7.29-7.79 (m,
7H) 9.70 (s, 1H) 11.78 (s, 1H)
0 ml, n-hexylamine 1.21 g (12.0 mmol
l) and 2.54 g (10.0 mmol) of 3-t-butyl-5-phenylsalicylaldehyde were added, and stirring was continued at room temperature for 1 hour. The reaction solution was concentrated under reduced pressure to remove the solvent,
The obtained liquid was purified by silica gel column chromatography to obtain 3.38 g (yield 94%) of a compound (V) represented by the following formula (V).

¹ H-NMR (CDCl ₃ ): 0.90 (t, 3H) 1.20-1.50 (m,
6H) 1.48 (s, 9H) 1.72 (m, 2H) 3.61 (t, 2H) 7.27-7.56 (m, 7
H) 8.40 (s, 1H) 14.29 (s, 1H)

[0355]

Embedded image

In a 50 ml reactor that was sufficiently dried and purged with argon, 1.01 g of compound (V) (3.00 mmol) was added.
l) and 30 ml of ether were charged, cooled to -78 ° C and stirred. 1.97 ml of an n-hexane solution containing 3.15 mmol of n-butyllithium was slowly added dropwise thereto, and 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. and 0.57 g (1.5%) of ZrCl ₄ (THF) ₂ complex was added.
0 mmol) in 30 ml of a THF solution. After completion of the dropwise addition, stirring was continued while slowly raising the temperature to room temperature. After further stirring at room temperature for 20 hours, the reaction solution was evaporated. 20 ml of ether was added to the obtained solid to form a slurry, which was filtered while washing with 10 ml of methylene chloride. The filtrate was concentrated and washed again with 30 ml of ether to obtain 0.49 g (yield: 39%) of a yellow powdered compound (22) represented by the following formula (22).

¹ H-NMR (CDCl ₃ ): 0.7-0.9 (m, 6H) 1.1-2.0
(s, 34H) 3.8-4.1 (m, 4H) 7.2-8.1 (m, 14H) 8.3,8.8 (brs,
(s, 2H) FD-Mass Spec: 834

[0358]

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Table 1 shows the NC value of the obtained compound.

[0360]

[Table 1]

[0361]

Examples 1 to 17 Stainless steel 1 sufficiently substituted with nitrogen
A liter autoclave was charged with 500 ml of heptane, heated to 75 ° C., and the liquid and gas phases were saturated with ethylene. Thereafter, methylaluminoxane 1.25mmol aluminum atoms terms, the amounts described the compounds shown in Table 2 in Tables 2 addition, ethylene pressure 8 kg / cm ² -
Polymerization was performed at G for 15 minutes.

The obtained polymer suspension was added to a large amount of acetone: methanol = 1: 1 containing a small amount of hydrochloric acid to precipitate a polymer, which was filtered with a glass filter, and after removing the solvent, the polymer was washed with methanol. Polymer at 80 ° C 1
After drying under reduced pressure for 0 hours, polyethylene was obtained. The results are shown in Table 2 below.

[0363]

Comparative Example 1 In the polymerization of Examples 1 to 22, the following zirconium compound (23) (N
C = 2.01) and the addition amount is 0.00005 mmo.
As a result of performing polymerization in the same manner except that the amount was changed to 1, the obtained polyethylene was 2.61 g, and the polymerization activity was 20.
It was 9 kg / mmol-Zr · hr. The intrinsic viscosity [η] of the obtained polyethylene was 1.95 dl / g. The results are shown in Table 2 below.

[0364]

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[0365]

[Table 2]

[0366]

Examples 18 to 29 In the polymerization of Examples 1 to 17,
Polymerization was carried out in the same manner except that the polymerization temperature was 90 ° C. and the amount of the catalyst was the amount shown in Table 3. The results are shown in Table 3 below.

[0367]

Comparative Example 2 Polymerization was carried out in the same manner as in Examples 18 to 29 except that the zirconium compound was changed to the zirconium compound (23) and the addition amount was changed to 0.00025 mmol. .87
g, and the polymerization activity is 62 kg / mmol-Zr · hr.
Met. The intrinsic viscosity [η] of the obtained polyethylene
Was 4.19 dl / g. The results are shown in Table 3 below.

[0368]

[Table 3]

[Brief description of the drawings]

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

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Masatoshi Nitahara 1-2-1, Waki, Waki-cho, Kuga-gun, Yamaguchi Prefecture Inside Mitsui Chemicals, Inc. (72) Junji Saito, Waki-cho, Kuga-gun, Yamaguchi Prefecture 6-1-2 Waki, Mitsui Chemicals, Inc. (72) Inventor Tetsuhiro Matsumoto 1-2-1, Waki, Waki-cho, Kuga-gun, Yamaguchi Pref. Mitsui Chemicals, Inc. (72) Tetsuo Hayashi, Yamaguchi Inventor Mitsui Chemicals Co., Ltd. (72) Inventor Takashi Nakano 6-1-2 Waki, Waki-machi, Kuga-gun, Yamaguchi Prefecture Mitsui Chemicals, Inc. (72) Invention Person Eiji Tanaka 6-1, 1-2 Waki, Waki-machi, Kuga-gun, Yamaguchi Prefecture Inside Mitsui Chemicals, Inc. (72) Inventor Makoto Mitani 6-1-2, Waki, Waki-machi, Kuga-gun, Yamaguchi Mitsui Chemicals, Inc. (72) Inventor Fujita Scripture Yamaguchi Prefecture Kuga District Waki-cho Waki 6-chome No. 1 No. 2 Mitsui Chemicals Co., Ltd. in

Claims (11)

[Claims] 1. An olefin polymerization catalyst represented by the following general formula (I), comprising a transition metal compound having a net charge parameter of the central metal M of 2.00 or less; (Wherein, M represents a transition metal atom of Groups 4 to 5 of the periodic table, m represents an integer of 1 to 5, Q represents a nitrogen atom or a carbon atom having a substituent R ² , and A represents Represents an oxygen atom, a sulfur atom, a selenium atom or a nitrogen atom having a substituent R ⁵ , R ¹ is an aliphatic hydrocarbon group which may be substituted with an aromatic hydrocarbon group or an alicyclic hydrocarbon group, Or an alicyclic hydrocarbon group which may be substituted with an aromatic hydrocarbon group or an aliphatic hydrocarbon group; R ^{2 to} R ⁵ may be the same or different; Group, oxygen-containing group, nitrogen-containing group, sulfur-containing group, boron-containing group, aluminum-containing group, phosphorus-containing group, halogen-containing group, heterocyclic compound residue, silicon-containing group, germanium-containing group or tin-containing group , Two or more of these are To form a ring, and when m is 2 or more, at least one of the groups represented by R ^{2 to} R ⁵ belonging to any one of the ligands; At least one of the groups represented by R ^{2 to} R ⁵ belonging to another ligand may be connected to each other. When m is 2 or more, R ¹ and R ^{2 are} , R ³
R, R ⁴ and R ⁵ may be the same or different from each other, n is a number satisfying the valency of M, X is a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, A sulfur-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, a halogen-containing group, a heterocyclic compound residue, a silicon-containing group, a germanium-containing group or a tin-containing group, wherein n is 2 or more In this case, a plurality of groups represented by X may be the same or different from each other, and a plurality of groups represented by X may be bonded to each other to form a ring. ). 2. A metal represented by the following general formula (Ia):
A catalyst for olefin polymerization, characterized by comprising a transition metal compound having a net charge parameter in the range of 1.70 to 2.00; (Wherein, M represents a transition metal atom of Groups 4 to 5 of the periodic table, m represents an integer of 1 to 5, A represents an oxygen atom, a sulfur atom, a selenium atom, or a nitrogen atom having a substituent R ^5. R ^1a represents an aliphatic hydrocarbon group which may be substituted with an aromatic hydrocarbon group or an alicyclic hydrocarbon group, and R ² and R ^{5 to} R ⁹ are the same or different. May be a hydrogen atom, a hydrocarbon group, an oxygen-containing group, a nitrogen-containing group, a sulfur-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, two or more of which may be linked to each other to form a ring, and when m is 2 or more, R belonging to any one of the ligands at least one of the groups represented by ² and R ⁵ to R ⁹ And number of groups may be at least one group of the groups represented by R ² and R ⁵ to R ⁹ belonging to other ligands are linked, and when m is 2 or more , R ^1a , R ² , R ⁵
R ⁶ , R ⁷ , R ⁸ , and R ⁹ may be the same or different from each other, n is a number satisfying the valence of M, X is a hydrogen atom, a 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 tin-containing group In the case where 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 may be bonded to each other to form a ring. ). 3. A compound represented by the following general formula (Ib):
An olefin polymerization catalyst comprising a transition metal compound having a net charge parameter in the range of 1.50 to 1.89. (Wherein, M represents a transition metal atom of Groups 4 to 5 of the periodic table, m represents an integer of 1 to 5, A represents an oxygen atom, a sulfur atom, a selenium atom, or a nitrogen atom having a substituent R ^5. R ^1b represents an alicyclic hydrocarbon group which may be substituted with an aromatic hydrocarbon group or an aliphatic hydrocarbon group, and R ² and R ^{5 to} R ⁹ are the same or different. May be a hydrogen atom, a hydrocarbon group, an oxygen-containing group, a nitrogen-containing group, a sulfur-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, two or more of which may be linked to each other to form a ring, and when m is 2 or more, R belonging to any one of the ligands at least one of the groups represented by ² and R ⁵ to R ⁹ And number of groups may be at least one group of the groups represented by R ² and R ⁵ to R ⁹ belonging to other ligands are linked, and when m is 2 or more , R ^1b , R ² , R ⁵
R ⁶ , R ⁷ , R ⁸ , and R ⁹ may be the same or different from each other, n is a number satisfying the valence of M, X is a hydrogen atom, a 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 tin-containing group In the case where 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 may be bonded to each other to form a ring. ). 4. The olefin polymerization catalyst according to claim 3, wherein in the general formula (Ib), A is an oxygen atom. (A-1) The transition metal compound according to any one of (1) to (4), (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 which form an ion pair by reacting with a transition metal compound. 6. An olefin polymerization catalyst comprising a transition metal compound represented by the following general formula (II): (Wherein, M represents a transition metal atom of Groups 4 to 5 of the periodic table, m represents 1 or 2, R ¹ is substituted with an aromatic hydrocarbon group or an alicyclic hydrocarbon group, An aliphatic hydrocarbon group, or an alicyclic hydrocarbon group which may be substituted with an aromatic hydrocarbon group or an aliphatic hydrocarbon group, and R ¹⁰ and R ^{11 to} R ¹³ may be the same as each other. They may be different and represent a hydrogen atom, a hydrocarbon group, a hydrocarbon-substituted silyl group, an oxygen-containing group, a nitrogen-containing group or a sulfur-containing group, and two or more of these are linked to each other to form a ring. R ¹⁴ represents a hydrocarbon group or a hydrocarbon-substituted silyl group; and when m is 2, R ¹⁰ belongs to any one of the ligands.
And at least one group of the groups represented by to R ^14, it may be at least one group of the groups represented by R ¹⁰ to R ¹⁴ belonging to other ligands are linked, When m is 2, R ^{1 s} , R ^{10 s} , R ^{11 s} , R ^{12 s} , R ^{13 s} , and R ^{14 s} may be the same as or different from each other. X represents a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, a halogen-containing group, and a heterocyclic group. A compound residue, a silicon-containing group, a germanium-containing group or a tin-containing group, and when n is 2 or more, a plurality of groups represented by X may be the same or different from each other; The groups may be linked together to form a ring. ). 7. In the above general formula (II), R ¹ is an aliphatic hydrocarbon group which may be substituted by an aromatic hydrocarbon group or an alicyclic hydrocarbon group and has a total carbon number of 5 or more. The olefin polymerization catalyst according to claim 6, which is a group. 8. In the above general formula (II), R ¹ is an alicyclic hydrocarbon group which may be substituted by an aromatic hydrocarbon group or an aliphatic hydrocarbon group and has a total carbon atom number of 7 or more. The olefin polymerization catalyst according to claim 6, which is a group. 9. In the general formula (II), R ¹² is an oxygen-containing group, a nitrogen-containing group or a sulfur-containing group.
9. The catalyst for olefin polymerization according to any one of items 1 to 8. (A-2) The transition metal compound according to any one of (6) to (9), (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 which form an ion pair by reacting with a transition metal compound. 11. A method for polymerizing olefins, comprising polymerizing olefins in the presence of the catalyst for olefin polymerization according to any one of claims 1 to 10.