JPH11315109A - Catalyst for polymerizing olefin, transition metal compound, polymerization of olefin and alpha-olefin-conjugated diene copolymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject catalyst capable of providing an α-olefin-conjugated diene copolymer having excellent olefin polymerization activity, a narrow distribution of molecular weight and scarcely containing a cyclopentane skeleton in the polymer chain by using a specific transition metal compound. SOLUTION: This catalyst comprises (A) a transition metal compound represented by the formula [M is a group 3 to 11 transition metal; (m) is 1-6; R<1> to R<6> are each H, a halogen or the like; (n) is a number satisfying the valence of M; X is H, a hydrocarbon or the like] and (B) a compound selected from an organometallic compound, an organoaluminumoxy compound and a compound reactive with the component A and forming an ion pair. Compounds, or the like, in which M is a group 4 or 5 transition metal; (m) is 1-3; R<1> is a hydrocarbon; R<2> to R<5> are each H; R<6> and X are each a halogen are new compounds in the compound represented by the formula. The compound represented by the formula is obtained by reacting, e.g. salicylaldehydes with a primary amine compound represented by the formula R<1> -NH2 and then reacting the produced ligand with a transition metal-containing compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

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

Another object of the present invention is to provide an α-olefin / conjugated diene copolymer which has a narrow molecular weight distribution and is suitably used as a rubber.

[0003]

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

In general, polyolefins have excellent mechanical properties and are used in various fields such as various molded articles. In recent years, however, demands for physical properties of polyolefins have been diversified, and polyolefins having various properties have been developed. Is desired. It is also desired to improve productivity.

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

It is well known that the use of a Ziegler-Natta polymerization catalyst promotes the copolymerization of several types of α-olefins with non-conjugated dienes. Since this copolymer is useful as a rubber, various types are produced. However, the non-conjugated diene used here is
Since they are generally expensive and have low reactivity, there has been a demand for an inexpensive and highly reactive diene component.

[0007] Examples of such a diene component include conjugated dienes such as 1,3-butadiene and isoprene. These conjugated dienes are cheaper and more reactive than the conventionally used non-conjugated dienes.
When copolymerization is carried out using a Natta polymerization catalyst, there have been problems that the activity is greatly reduced and that only a heterogeneous copolymer having a wide composition distribution and molecular weight distribution can be obtained. In the Ziegler-Natta catalyst system using a vanadium compound, a relatively uniform copolymer was obtained, but the polymerization activity was at a very low level. Therefore, in recent years, studies have been actively conducted, and a copolymerization of ethylene and butadiene using a so-called metallocene catalyst, which is known to exhibit high polymerization activity, has been studied (Japanese Patent Application Laid-Open No. 1-501633).
No.).

However, in this case, it has been reported that a cyclopentane skeleton is formed in the polymer chain from the diene unit incorporated in the polymer and ethylene, and the ratio thereof is 50% or more of the total diene units. The conversion of the double bond of the diene unit into a cyclopentane skeleton is extremely disadvantageous in an operation called vulcanization which is indispensable when this copolymer is used as a rubber. Further, this cyclopentane skeleton has an effect of increasing the glass transition temperature of the copolymer and impairs the low-temperature properties of the rubber, so that it is an undesirable skeleton.

Under these circumstances, it has been strongly desired that a copolymer of an α-olefin and a conjugated diene having a narrow molecular weight distribution, a uniform composition, and substantially containing no cyclopentane skeleton in a polymer chain be produced. I have.

[0010]

An object of the present invention is to provide an olefin polymerization catalyst having excellent olefin polymerization activity, a novel transition metal compound useful for such a catalyst, and a method for polymerizing olefins using the catalyst. I have.

Another object of the present invention is to provide an α-olefin / conjugated diene copolymer having a narrow molecular weight distribution and containing almost no cyclopentane skeleton in a polymer chain.

[0012]

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

[0013]

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(Wherein, M represents a transition metal atom belonging to Groups 3 to 11 of the periodic table, m represents an integer of ^{1 to 6} , and R ^{1 to} R ⁶
May be the same or different from each other, and include a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, and a silicon-containing group. A group, a germanium-containing group, or a tin-containing group, two or more of which may be linked to each other to form a ring, and when m is 2 or more, R ^{1 to} R ⁶ Two of the groups shown may be connected (however, R ¹ is not bonded to each other), n is a number satisfying the valence of M, X is a hydrogen atom, Halogen atom, hydrocarbon group, oxygen-containing group, sulfur-containing group, nitrogen-containing group, boron-containing group, aluminum-containing group, phosphorus-containing group, halogen-containing group, heterocyclic compound residue, silicon-containing group, germanium-containing group, Or a tin-containing group, wherein n is 2 or more In the above case, the groups represented by X may be the same or different from each other, and the groups represented by X may be bonded to each other to form a ring. In the present invention, in the general formula (I), R ⁶ represents a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, It is preferably a silicon-containing group, a germanium-containing group, or a tin-containing group.

In the present invention, the transition metal compound represented by the general formula (I) is preferably a transition metal compound represented by the following general formula (Ia).

[0016]

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(Wherein M represents a transition metal atom belonging to Groups 3 to 11 of the periodic table, m represents an integer of 1 to 3, and R ^{1 to} R
⁶ may be the same or different from each other, and represent a hydrogen atom,
Halogen atom, hydrocarbon group, heterocyclic compound residue, hydrocarbon substituted silyl group, hydrocarbon substituted siloxy group, alkoxy group, alkylthio group, aryloxy group, arylthio group, acyl group, ester group, thioester group, amide group, An imide group, an amino group, an imino group, a sulfone ester group, a sulfonamide group, a cyano group, a nitro group, a carboxyl group, a sulfo group, a mercapto group or a hydroxy group, two or more of which are linked to each other to form a ring May be formed, and when m is 2 or more, R ¹ to
Two of the groups represented by R ⁶ may be linked (provided that R ¹ is not bonded to each other), and n is
X is a number satisfying the valence of M, and X is a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, a halogen-containing group. Represents a heterocyclic compound residue, a silicon-containing group, a germanium-containing group, or a tin-containing group,
When n is 2 or more, a plurality of groups represented by X may be the same or different, and a plurality of groups represented by X may be bonded to each other to form a ring. In the general formula (Ia), R ⁶ represents a halogen atom, a hydrocarbon group, a heterocyclic compound residue, a hydrocarbon-substituted silyl group, a hydrocarbon-substituted siloxy group, an alkoxy group, an alkylthio group, an aryloxy group, an arylthio group, Acyl group,
It is preferably an ester group, a thioester group, an amide group, an imide group, an amino group, an imino group, a sulfone ester group, a sulfonamide group, a cyano group, a nitro group, a carboxyl group, a sulfo group, a mercapto group or a hydroxy group.

The transition metal compound represented by the general formula (I) is preferably a transition metal compound represented by the following general formula (Ia-1).

[0019]

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(Wherein, M represents a transition metal atom belonging to Groups 3 to 11 of the periodic table, m represents an integer of 1 to 3, and R ^{1 to} R
⁶ may be the same or different from each other, and represent a hydrogen atom,
Halogen atom, hydrocarbon group, heterocyclic compound residue, hydrocarbon substituted silyl group, hydrocarbon substituted siloxy group, alkoxy group, alkylthio group, aryloxy group, arylthio group, acyl group, ester group, thioester group, amide group, An imide group, an amino group, an imino group, a sulfone ester group, a sulfonamide group, a cyano group, a nitro group or a hydroxy group, two or more of which may be linked to each other to form a ring; , When m is 2 or more, two of the groups represented by R ^{1 to} R ⁶ may be linked (however, R ¹ is not bonded to each other), and n is M X is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms,
Represents a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group, a sulfur-containing group or a silicon-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 Also, a plurality of groups represented by X may combine with each other to form a ring. In the general formula (Ia-1), R ⁶ represents a halogen atom, a hydrocarbon group, a heterocyclic compound residue, a hydrocarbon-substituted silyl group, a hydrocarbon-substituted siloxy group, an alkoxy group, an alkylthio group, an aryloxy group, an arylthio group. Group, acyl group,
It is preferably an ester group, a thioester group, an amide group, an imide group, an amino group, an imino group, a sulfone ester group, a sulfonamide group, a cyano group, a nitro group or a hydroxy group.

In the present invention, the transition metal compound represented by the general formula (I) is preferably a transition metal compound represented by the following general formula (Ib).

[0022]

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(Wherein M represents a transition metal atom belonging to Groups 3 to 11 of the periodic table, m represents an integer of ^{1 to 6} , and R ^{1 to} R ⁶
May be the same or different from each other, and include a hydrogen atom, a halogen atom, a hydrocarbon group, a hydrocarbon-substituted silyl group, an alkoxy group, an aryloxy group, an ester group, an amide group, an amino group, a sulfonamide group, a nitrile group, or a nitro group. Two or more of these groups may be connected to each other to form a ring, and when m is 2 or more, two of the groups represented by R ^{1 to} R ⁶ May be linked (however, R ¹ is not bonded to each other). In the formula (Ib), R ⁶ is a halogen atom, a hydrocarbon group, a hydrocarbon-substituted silyl group, an alkoxy group, an aryloxy group, an ester group, an amide group, an amino group, an amino group, a sulfonamide group, a cyano group or a nitro group. Preferably, there is.

In the transition metal compound (A), M is preferably at least one transition metal atom selected from Groups 3 to 5 and Group 9 of the periodic table.

In the first catalyst for olefin polymerization according to the present invention, the transition metal compound (A), (B-1) an organometallic compound, (B-2) an organoaluminum oxy compound and (B-
3) A carrier (C) may be contained in addition to at least one compound (B) selected from compounds that form an ion pair by reacting with a transition metal compound.

The first method for polymerizing olefins according to the present invention is characterized in that olefins are polymerized or copolymerized in the presence of the above-mentioned catalyst. Further, the second olefin polymerization catalyst according to the present invention comprises (A ′) a transition metal compound represented by the following general formula (II), and (B) (B-1)
At least one compound selected from an organometallic compound, (B-2) an organoaluminum oxy compound, and (B-3) a compound which forms an ion pair by reacting with the transition metal compound (A ′). And

[0027]

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(Wherein M represents a transition metal atom belonging to Groups 3 to 11 of the periodic table, and R ^{1 to} R ¹⁰ may be the same or different from each other, and may be a hydrogen atom, a halogen atom, a hydrocarbon group,
Heterocyclic compound residue, oxygen-containing group, nitrogen-containing group, boron-containing group, sulfur-containing group, phosphorus-containing group, silicon-containing group,
A germanium-containing group or a tin-containing group, two or more of which may be connected to each other to form a ring, n is a number satisfying the valence of M, and X is a hydrogen atom , Halogen atom, hydrocarbon group, oxygen-containing group, sulfur-containing group, nitrogen-containing group, boron-containing group, aluminum-containing group, phosphorus-containing group, halogen-containing group, heterocyclic compound residue, silicon-containing group, germanium-containing group Or, when n is 2 or more, a plurality of groups represented by X may be the same or different from each other, and a plurality of groups represented by X are bonded to each other to form a ring. May be, Y
Is oxygen, sulfur, carbon, nitrogen, phosphorus, silicon, selenium,
It represents a divalent bonding group containing at least one element selected from the group consisting of tin and boron. In the case of a hydrocarbon group, it is a group having three or more carbon atoms. In the general formula (II), at least one of R ^{6 and} R ¹⁰ is a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group. It is preferably a containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group.

The transition metal compound represented by the general formula (II) is preferably a transition metal compound represented by the following general formula (II-a).

[0030]

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(Wherein, M represents a transition metal atom belonging to Groups 3 to 11 of the periodic table, and R ^{1 to} R ¹⁰ may be the same or different from each other, and represent a hydrogen atom, a halogen atom, a hydrocarbon group,
A hydrocarbon-substituted silyl group, alkoxy group, aryloxy group, ester group, amide group, amino group, sulfonamide group, nitrile group or nitro group, two or more of which are connected to each other to form a ring. May be n
Is a number satisfying the valence of M, and X is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group, sulfur, When n is 2 or more, a plurality of groups represented by X may be the same or different from each other, and two or more Xs are connected to each other to form a ring Y may be oxygen, sulfur, carbon, nitrogen,
It represents a divalent linking group containing at least one element selected from the group consisting of phosphorus, silicon, selenium, tin and boron. When it is a hydrocarbon group, it is a group having three or more carbon atoms. In the formula (II-a), at least one of R ^{6 and} R ¹⁰ is a halogen atom, a hydrocarbon group, a hydrocarbon-substituted silyl group, an alkoxy group, an aryloxy group, an ester group, an amide group, an amino group, a sulfone. It is preferably an amide group, a cyano group or a nitro group.

In the transition metal compound (A ′), M
Is preferably a transition metal atom belonging to Group 4 or 5 of the periodic table. In the second olefin polymerization catalyst according to the present invention, the transition metal compound (A ^′ ), (B-1) an organometallic compound, (B-2) an organoaluminum oxy compound, and (B-3)
The carrier (C) may be contained in addition to at least one compound (B) selected from ionized ionic compounds.

The second olefin polymerization method according to the present invention is characterized in that olefin is polymerized or copolymerized in the presence of the olefin polymerization catalyst. The novel transition metal compound according to the present invention is represented by the following general formula (III).

[0034]

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(Wherein M represents a transition metal atom belonging to Group 4 or 5 of the periodic table, m represents an integer of 1 to 3,
¹ represents a hydrocarbon group, a hydrocarbon-substituted silyl group, a hydrocarbon-substituted siloxy group, an alkoxy group, an alkylthio group, an aryloxy group, an arylthio group, an ester group, a thioester group, a sulfone ester group or a hydroxy group;
^{2 to} R ⁵ may be the same or different from each other, and represent a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, a hydrocarbon-substituted silyl group, a hydrocarbon-substituted siloxy group,
Alkoxy group, alkylthio group, aryloxy group, arylthio group, ester group, thioester group, amide group,
Imide group, amino group, imino group, sulfone ester group,
A sulfonamide group, a cyano group, a nitro group, a carboxyl group, a sulfo group, a mercapto group or a hydroxy group, and R ⁶ represents a halogen atom, a hydrocarbon group, a hydrocarbon-substituted silyl group, a hydrocarbon-substituted siloxy group, an alkoxy group, An alkylthio group, an aryloxy group, an arylthio group, an ester group, a thioester group, an amide group, an imide group, an imino group, a sulfone ester group, a sulfonamide group or a cyano group, and two or more of R ^{1 to} R ⁶ May be linked to form a ring, and when m is 2 or more, two of the groups represented by R ^{1 to} R ⁶ may be linked (provided that R ¹ is Are not combined),
n is a number that satisfies the valence of M, X is 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;
Is two or more, the plurality of groups represented by X may be the same or different, and the plurality of groups represented by X may be bonded to each other to form a ring. The transition metal compound is preferably represented by the following general formula (III-a).

[0036]

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(Wherein M represents a transition metal atom belonging to Group 4 or 5 of the periodic table, m represents an integer of ¹ to 3, and R ¹ to
R ⁵ may be the same or different, and represents a hydrocarbon group, an alkoxy group or a hydrocarbon-substituted silyl group;
R ⁶ represents a halogen atom, a hydrocarbon group, a hydrocarbon-substituted silyl group, an alkoxy group, an alkylthio group or a cyano group, and two or more of R ^{1 to} R ⁶ are connected to each other to form a ring. And when m is 2 or more, R ¹
To R ⁶ , two of which may be linked (however, R ¹ is not bonded to each other), and n
Is a number satisfying the valence of M, X is a halogen atom,
Hydrocarbon groups, oxygen-containing groups, sulfur-containing groups, nitrogen-containing groups,
A halogen-containing group or a silicon-containing group, and when n is 2 or more, a plurality of groups represented by X may be the same or different from each other, and a plurality of groups represented by X are bonded to each other to form a ring It may be formed. In the general formula (III-a), m is preferably 2.

The third olefin polymerization catalyst according to the present invention comprises the above-mentioned transition metal compound (A "), (B) (B-1) an organometallic compound, (B-2) an organoaluminum oxy compound, and B-3) At least one compound selected from compounds which form an ion pair by reacting with the transition metal compound (A).

The third olefin polymerization catalyst comprises the above-mentioned transition metal compound (A ″), (B-1) an organometallic compound, (B-2) an organoaluminum oxy compound and (B-3) a transition metal compound. The carrier (C) may be contained in addition to at least one compound (B) selected from compounds that react to form an ion pair.

The third olefin polymerization method according to the present invention is characterized in that olefin is polymerized or copolymerized in the presence of the olefin polymerization catalyst. The α-olefin / conjugated diene copolymer according to the present invention has a molecular weight distribution (Mw / Mn) of 3.5 or less, and the content of the structural unit derived from the α-olefin is 1 to 99.9 mol%.
And the content of the structural unit derived from the conjugated diene is in the range of 99 to 0.1 mol%, and the content of the 1,2-cyclopentane skeleton derived from the conjugated diene in the polymer chain is 1%. It is characterized in that it contains substantially no mol% or less, preferably no 1,2-cyclopentane skeleton.

In the α-olefin / conjugated diene copolymer according to the present invention, the content of the constituent unit derived from the α-olefin is in the range of 50 to 99.9 mol%, and the constituent unit derived from the conjugated diene is contained. Is preferably in the range of 50 to 0.1 mol%.

Further, in the α-olefin / conjugated diene copolymer according to the present invention, the α-olefin is ethylene and / or
Alternatively, it is preferably propylene, and the conjugated diene is butadiene and / or isoprene.

[0043]

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.

First Olefin Polymerization Catalyst The first olefin polymerization catalyst according to the present invention comprises (A) a transition metal compound represented by the following general formula (I) and (B) (B)
-1) an organic metal compound, (B-2) an organic aluminum oxy compound, and (B-3) at least one compound selected from compounds which react with a transition metal compound to form an ion pair. .

First, each catalyst component forming the olefin polymerization catalyst of the present invention will be described. (A) Transition metal compound The (A) transition metal compound used in the present invention is a compound represented by the following general formula (I).

[0047]

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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 formula (I) , M represent transition metal atoms of Groups 3 to 11 of the periodic table (Group 3 also includes lanthanoids), preferably metal atoms of Groups 3 to 9 (Group 3 also includes lanthanoids), More preferably, they are metal atoms of groups 3 to 5 and 9, and particularly preferably metal atoms of group 4 or 5. Specifically, scandium, titanium, zirconium, hafnium, vanadium, niobium, tantalum, cobalt, rhodium, yttrium, chromium, molybdenum, tungsten, manganese, rhenium, iron, ruthenium, etc., preferably scandium, titanium, zirconium, Hafnium, vanadium, niobium, tantalum, cobalt, rhodium, etc., more preferably,
Titanium, zirconium, hafnium, cobalt, rhodium, vanadium, niobium, tantalum and the like are particularly preferable, and titanium, zirconium and hafnium are particularly preferable.

M represents an integer of 1 to 6, preferably 1 to 4. R ^{1 to} R ⁶ may be the same or different from each other, and represent a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group,
A sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group;
More than one may be connected to each other to form a ring.

Examples of the halogen atom include fluorine, chlorine, bromine and iodine. Specific examples of the hydrocarbon group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, neopentyl, and n-hexyl having 1 to 30 carbon atoms, preferably A linear or branched alkyl group having 1 to 20 carbon atoms, such as vinyl, allyl, and isopropenyl;
30, preferably 2 to 20 linear or branched alkenyl groups; ethynyl, propargyl and the like having 2 carbon atoms
A linear or branched alkynyl group having a carbon number of 3 to 30, preferably 2 to 20; a cyclic saturated hydrocarbon group having a carbon number of 3 to 30, preferably 3 to 20, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and adamantyl. A cyclic unsaturated hydrocarbon group having 5 to 30 carbon atoms such as cyclopentadienyl, indenyl and fluorenyl; phenyl, benzyl, naphthyl, biphenyl, terphenyl,
6 carbon atoms such as phenanthryl and anthracenyl
To 30, preferably 6 to 20 aryl groups; tolyl, is
Examples include alkyl-substituted aryl groups such as o-propylphenyl, t-butylphenyl, dimethylphenyl, di-t-butylphenyl, and the like.

The above-mentioned hydrocarbon group may have a hydrogen atom substituted by a halogen atom. For example, a halogenated carbon atom having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms such as trifluoromethyl, pentafluorophenyl and chlorophenyl. And a hydrogen group.

The hydrocarbon group may be substituted with another hydrocarbon group, for example, an aryl-substituted alkyl group such as benzyl and cumyl. Furthermore, the hydrocarbon group is a heterocyclic compound residue;
Alkoxy groups, aryloxy groups, ester groups, ether groups, acyl groups, carboxyl groups, carbonate groups, hydroxy groups, peroxy groups, oxygen-containing groups such as carboxylic anhydride groups; amino groups, imino groups, amide groups, imide groups,
Hydrazino group, hydrazono group, nitro group, nitroso group,
A nitrogen-containing group such as a cyano group, an isocyano group, a cyanate ester group, an amidino group, a diazo group, or an amino group having an ammonium salt; a boron-containing group such as a borandiyl group, a borantriyl group, or a diboranyl group; a mercapto group;
Thioester group, dithioester group, alkylthio group,
Arylthio group, thioacyl group, thioether group, thiocyanate group, isothiocyanate group, sulfone ester group, sulfonamide group, thiocarboxyl group, dithiocarboxyl group, sulfo group, sulfonyl group,
Sulfur-containing groups such as a sulfinyl group and a sulfenyl group;
It may have a phosphorus-containing group such as a phosphide group, a phosphoryl group, a thiophosphoryl group, a phosphato group, a silicon-containing group, a germanium-containing group, or a tin-containing group.

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

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

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

Examples of the germanium-containing group and the tin-containing group include those obtained by substituting silicon in the silicon-containing group with germanium and tin. Next, the examples of R ^{1 to} R ⁶ described above will be described more specifically.

Specific examples of the alkoxy group include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy and the like. Specific examples of the alkylthio group include methylthio and ethylthio.

Specific examples of the aryloxy group include phenoxy, 2,6-dimethylphenoxy, and 2,4,6-trimethylphenoxy. Specific examples of the arylthio group include phenylthio, methylphenylthio, and naphthylthio.

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

Specific examples of the thioester group include acetylthio, benzoylthio, methylthiocarbonyl, phenylthiocarbonyl and the like. As the amide group, specifically, acetamido, N-methylacetamido, N-
Methyl benzamide and the like.

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

Specific examples of the imino group include methylimino, ethylimino, propylimino, butylimino, phenylimino and the like. Specific examples of the sulfone ester group include methyl sulfonate, ethyl sulfonate, and phenyl sulfonate.

Specific examples of the sulfonamide group include phenylsulfonamide, N-methylsulfonamide, N-methyl-p-toluenesulfonamide and the like. Note that R ⁶ is preferably a substituent other than hydrogen. That is, R ⁶ is preferably a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a boron-containing group, a sulfur-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group. In particular, R ⁶ is a halogen atom, a hydrocarbon group, a heterocyclic compound residue, a hydrocarbon-substituted silyl group, a hydrocarbon-substituted siloxy group, an alkoxy group, an alkylthio group, an aryloxy group, an arylthio group, an acyl group, an ester group, a thioester. Preferred are a group, an amide group, an amino group, an imide group, an imino group, a sulfone ester group, a sulfonamide group, a cyano group, a nitro group and a hydroxy group.

Preferred hydrocarbon groups for R ⁶ include:
Methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, thiopentyl, n-hexyl, etc. having 1 to 30, preferably 1 to 20 linear or branched carbon atoms Alkyl group; a cyclic saturated hydrocarbon group having 3 to 30, preferably 3 to 20 carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and adamantyl; carbon atoms such as phenyl, benzyl, naphthyl, biphenylyl and triphenylyl An aryl group having 6 to 30, preferably 6 to 20; and an alkyl or alkoxy group having 1 to 30, preferably 1 to 20, carbon atoms in these groups, and having 1 to 30, preferably 1 to 30 carbon atoms. Is a halogenated alkyl group of 1 to 20, having 6 to 30 carbon atoms, preferably 6 to 2 carbon atoms.
A group further substituted with a substituent such as an aryl group or an aryloxy group of 0, a halogen, a cyano group, a nitro group, a hydroxy group and the like are preferable.

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

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

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

When m is 2 or more, R ^{1 to} R ⁶
And two groups may be linked to each other.
However, R ¹ is not bonded to each other. Furthermore, m
Is 2 or more, R ¹ and R ² , R ³ and R ^3
4 together, R ⁵ each other, R ⁶ to each other may be the same or different from each other.

N is a number that satisfies the valence of M, and is specifically 0 to 5, preferably 1 to 4, more preferably 1 to 3.
Is an integer. X represents a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, a halogen-containing group, a heterocyclic compound residue, or a silicon-containing residue. Group, germanium-containing group, or tin-containing group. When n is 2 or more, they may be the same or different.

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

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

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

Examples of the sulfur-containing group include the same ones as those exemplified above in R ^{1 to} R ⁶ , and specifically, methyl sulfonate, trifluoromethane sulfonate, phenyl sulfonate, benzyl sulfonate and the like. Sulfonate groups such as phonate, p-toluenesulfonate, trimethylbenzenesulfonate, triisobutylbenzenesulfonate, p-chlorobenzenesulfonate, and pentafluorobenzenesulfonate; methylsulfinate, phenylsulfate Sulfonate groups such as carboxylate, benzylsulfinate, p-toluenesulfinate, trimethylbenzenesulfinate, pentafluorobenzenesulfinate; alkylthio; arylthio; and the like, but are not limited thereto. .

Specific examples of the nitrogen-containing group include the aforementioned R ¹ to
The same ones as those exemplified for R ⁶ can be mentioned, and specifically, an amino group; an alkylamino group such as methylamino, dimethylamino, diethylamino, dipropylamino, dibutylamino, dicyclohexylamino; phenylamino, diphenylamino , Ditolylamino, dinaphthylamino, an arylamino group such as methylphenylamino or an alkylarylamino group.
It is not limited to these.

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

Specific examples of the silicon-containing group include the aforementioned R ¹
To R ⁶ , and specifically include phenylsilyl, diphenylsilyl, trimethylsilyl, triethylsilyl, tripropylsilyl, tricyclohexylsilyl, triphenylsilyl, methyldiphenylsilyl, and tolylsilyl. A hydrocarbon-substituted silyl group such as trinaphthylsilyl; a hydrocarbon-substituted silyl ether group such as trimethylsilyl ether; a silicon-substituted alkyl group such as trimethylsilylmethyl; a silicon-substituted aryl group such as trimethylsilylphenyl.

Specific examples of the germanium-containing group include the same ones as those exemplified above in R ^{1 to} R ⁶ , and specific examples include a group in which silicon of the silicon-containing group is replaced with germanium. .

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

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

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

When n is 2 or more, a plurality of groups represented by X may be the same or different from each other.
May be bonded to each other to form a ring. Transition metal compound (Ia) As such a transition metal compound represented by the formula (I), a compound represented by the following general formula (Ia) is preferable.

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In the formula (Ia), M represents a transition metal atom belonging to Groups 3 to 11 of the periodic table, and examples thereof include those described above. m is an integer of 1 to 3, and is preferably 2.

R ^{1 to} R ⁶ may be the same or different, and each represents a hydrogen atom, a halogen atom, a hydrocarbon group, a residue of a heterocyclic compound, a hydrocarbon-substituted silyl group, a hydrocarbon-substituted siloxy group, or an alkoxy group. , Alkylthio group, aryloxy group, arylthio group, acyl group, ester group, thioester group, amide group, imide group, amino group, imino group, sulfone ester group, sulfonamide group, cyano group, nitro group, carboxyl group, sulfo group , A mercapto group or a hydroxy group, two or more of which may be linked to each other to form a ring. Examples of these groups include the same as those described above.

When m is 2 or more, two of the groups represented by R ^{1 to} R ⁶ may be linked. However, R ¹ is not bonded to each other. n is a number that satisfies the valence of M, and specifically, is 0 to 5, preferably 1
To 4, more preferably an integer of 1 to 3.

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. Specifically, the same as described above can be used.

When n is 2 or more, a plurality of groups represented by X may be the same or different from each other.
May be bonded to each other to form a ring. As such a transition metal compound, a compound represented by the following general formula (Ia-1) is particularly preferable.

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In the formula (Ia-1), R ^{1 to} R ⁶ , M and X are the same as described above, but the following are particularly preferable. M represents a transition metal atom of Groups 3 to 11 of the periodic table, preferably a metal atom of Groups 3 to 5 and 9, preferably scandium, titanium, zirconium, hafnium, vanadium, niobium, tantalum, cobalt, Rhodium and the like, more preferably titanium, zirconium, hafnium, cobalt and rhodium, and particularly preferably titanium, zirconium and hafnium.

M is an integer of 1 to 3. R ^{1 to} R
⁶ may be the same or different from each other, and represent a hydrogen atom,
Halogen atom, hydrocarbon group, heterocyclic compound residue, hydrocarbon-substituted silyl group, hydrocarbon-substituted siloxy group, alkoxy group, alkylthio group, aryloxy group, arylthio group, thioester group, ester group, acyl group, amide group, Examples include an imide group, an amino group, an imino group, a sulfone ester group, a sulfonamide group, a cyano group, a nitro group, and a hydroxy group. Among these, a hydrogen atom, a halogen atom, a hydrocarbon group, a hydrocarbon-substituted silyl group, an alkoxy group, an aryloxy group, an ester group, an amide group, an amino group, a sulfonamide group, a cyano group or a nitro group are particularly preferred.

Examples of the halogen atom include fluorine, chlorine, bromine and iodine. Specific examples of the hydrocarbon group include straight-chain or 1 to 20 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, and hexyl. A branched alkyl group; a linear or branched alkenyl group having 2 to 20 carbon atoms such as vinyl, allyl, and isopropenyl; a linear or branched alkenyl group having 2 to 20 carbon atoms such as ethynyl and propargyl An alkynyl group; a cyclic saturated hydrocarbon group having 3 to 20 carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and adamantyl; and a cyclic saturated hydrocarbon group having 6 to 2 carbon atoms such as phenyl, benzyl, naphthyl, biphenylyl, and triphenylyl.
An aryl group of 0; cyclopentadienyl, indenyl,
A cyclic unsaturated hydrocarbon group having 5 to 20 carbon atoms such as fluorenyl; and these groups have 1 to 2 carbon atoms.
0 alkyl group, halogenated alkyl group having 1 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, alkoxy group having 1 to 20 carbon atoms, 6 to 20 carbon atoms
And a group further substituted with a substituent such as an aryloxy group, a halogen, a cyano group, a nitro group or a hydroxy group. Among them, particularly, straight-chain or branched alkyl having 1 to 20 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl and hexyl. An aryl group having 6 to 20 carbon atoms such as phenyl and naphthyl; an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms. 1 to 20 alkoxy groups having 6 to 2 carbon atoms
A substituted aryl group substituted with 1 to 5 substituents such as 0 aryloxy group is preferable.

Examples of the heterocyclic compound residues include nitrogen-containing compounds such as pyrrole, pyridine, pyrimidine, quinoline and triazine; oxygen-containing compounds such as furan and pyran;
Residues such as sulfur-containing compounds such as thiophene; and groups obtained by further substituting these heterocyclic compound residues with a substituent such as an alkyl group or an alkoxy group having 1 to 20 carbon atoms.

Specific examples of the hydrocarbon-substituted silyl group include:
Examples include methylsilyl, dimethylsilyl, trimethylsilyl, ethylsilyl, diethylsilyl, triethylsilyl, diphenylmethylsilyl, triphenylsilyl, dimethylphenylsilyl, dimethyl-t-butylsilyl, and dimethyl (pentafluorophenyl) silyl.
Among these, methylsilyl, dimethylsilyl,
Preferred are trimethylsilyl, ethylsilyl, diethylsilyl, triethylsilyl, triphenylsilyl and the like.

Specific examples of the hydrocarbon-substituted siloxy group include trimethylsiloxy. Specific examples of the alkoxy group include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, ter
t-butoxy and the like.

Specific examples of the alkylthio group include methylthio, ethylthio and the like. Specifically as the aryloxy group, phenoxy, 2,6-dimethylphenoxy,
2,4,6-trimethylphenoxy and the like.

Specific examples of the arylthio group include phenylthio, methylphenylthio, naphthylthio and the like. Specific examples of the acyl group include a formyl group, an acetyl group, a benzoyl group, a p-chlorobenzoyl group, and a p-methoxybenzoyl group.

Specific examples of the ester group include acetyloxy, benzoyloxy, methoxycarbonyl, phenoxycarbonyl, p-chlorophenoxycarbonyl and the like.

Specific examples of the thioester group include acetylthio, benzoylthio, methylthiocarbonyl, phenylthiocarbonyl and the like. As the amide group, specifically, acetamido, N-methylacetamido, N-
Methyl benzamide and the like.

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

Specific examples of the imino group include methylimino, ethylimino, propylimino, butylimino, phenylimino and the like. Specific examples of the sulfone ester group include methyl sulfonate, ethyl sulfonate, and phenyl sulfonate.

Specific examples of the sulfonamide group include phenylsulfonamide, N-methylsulfonamide, N-methyl-p-toluenesulfonamide and the like. Note that R ⁶ is preferably a substituent other than hydrogen. That is, R ⁶ is a halogen atom, a hydrocarbon group, a heterocyclic compound residue, a hydrocarbon-substituted silyl group, a hydrocarbon-substituted siloxy group, an alkoxy group, an alkylthio group, an aryloxy group, an arylthio group, an acyl group, an ester group, a thioester. It is preferably a group, amide group, imide group, amino group, imino group, sulfone ester group, sulfonamide group, cyano group, nitro group or hydroxy group.

Preferred hydrocarbon groups for R ⁶ include:
A linear or branched alkyl group having 1 to 20 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl; A cyclic saturated hydrocarbon group having 3 to 20 carbon atoms such as cyclobutyl, cyclopentyl, cyclohexyl and adamantyl; an aryl group having 6 to 20 carbon atoms such as phenyl, benzyl, naphthyl, biphenylyl and triphenylyl; and these groups An alkyl group having 1 to 20 carbon atoms,
A halogenated alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group, an aryloxy group, a halogen, a group further substituted with a substituent such as a cyano group, a nitro group, a hydroxy group, and the like; Are preferred.

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

In the present invention, R ⁶ is preferably a branched alkyl group having 3 to 20 carbon atoms such as isopropyl, isobutyl, sec-butyl, tert-butyl and the like. May be a group selected from a cyclic saturated hydrocarbon group having 3 to 20 carbon atoms such as a group substituted with an aryl group having 6 to 20 (such as a cumyl group), adamantyl, cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. Preferably, it is also a hydrocarbon-substituted silyl group.

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

When m is 2 or more, R ^{1 to} R ⁶
And two groups may be linked to each other.
However, R ¹ is not bonded to each other. Furthermore, m
Is 2 or more, R ¹ and R ² , R ³ and R ^3
4 together, R ⁵ each other, R ⁶ to each other may be the same or different from each other.

N is a number that satisfies the valence of M, and is specifically an integer of 1 to 3. X is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms,
20 represents a halogenated hydrocarbon group, an oxygen-containing group, a sulfur-containing group, a silicon-containing group, etc., and when n is 2 or more, they may be the same or different.

The halogen atom includes fluorine, chlorine, bromine and iodine. Examples of the hydrocarbon group having 1 to 20 carbon atoms include an alkyl group, a cycloalkyl group, an alkenyl group, an arylalkyl group, and an aryl group. More specifically, methyl, ethyl, propyl, butyl, and hexyl Alkyl groups such as octyl, nonyl, dodecyl and eicosyl; cycloalkyl groups such as cyclopentyl, cyclohexyl, norbornyl and adamantyl; alkenyl groups such as vinyl, propenyl and cyclohexenyl; arylalkyl groups such as benzyl, phenylethyl and phenylpropyl; Phenyl, tolyl, dimethylphenyl, trimethylphenyl, ethylphenyl,
And aryl groups such as propylphenyl, biphenyl, naphthyl, methylnaphthyl, anthryl, and phenanthryl.

Examples of the halogenated hydrocarbon group having 1 to 20 carbon atoms include groups in which the aforementioned hydrocarbon group having 1 to 20 carbon atoms is substituted with halogen. Examples of the oxygen-containing group include a hydroxy group; an alkoxy group such as methoxy, ethoxy, propoxy, and butoxy; an aryloxy group such as phenoxy, methylphenoxy, dimethylphenoxy, and naphthoxy; and an arylalkoxy group such as phenylmethoxy and phenylethoxy.

Examples of the sulfur-containing group include a substituent in which oxygen of the above-mentioned oxygen-containing group is substituted by sulfur, methyl sulfonate, trifluoromethane sulfonate, phenyl sulfonate, benzyl sulfonate, p-toluene sulfonate. Sulfonate groups such as benzoate, trimethylbenzenesulfonate, triisobutylbenzenesulfonate, p-chlorobenzenesulfonate and pentafluorobenzenesulfonate; methylsulfinate, phenylsulfinate, benzylsulfinate, p -Sulfinate groups such as toluenesulfinate, trimethylbenzenesulfinate and pentafluorobenzenesulfinate.

Examples of the silicon-containing group include monohydrocarbon-substituted silyl groups such as methylsilyl and phenylsilyl; dihydrocarbon-substituted silyl groups such as dimethylsilyl and diphenylsilyl; trimethylsilyl, triethylsilyl, tripropylsilyl, tricyclohexylsilyl, Trihydrocarbon-substituted silyl groups such as phenylsilyl, dimethylphenylsilyl, methyldiphenylsilyl, tolylsilyl, and trinaphthylsilyl; silyl ether groups of hydrocarbon-substituted silyls such as trimethylsilyl ether; silicon-substituted alkyl groups such as trimethylsilylmethyl; trimethylsilyl And a silicon-substituted aryl group such as phenyl.

As the group represented by X, of these,
It is preferably a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a sulfonate group. When n is 2 or more, the groups represented by X may be the same or different from each other, or may be linked to each other to form a ring.

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

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In the formula (Ia-2), M, R ^{1 to} R ⁶ and X are
Each is the same as in the case of the general formula (I), and R ¹¹ to
R ¹⁶ is the same as R ^{1 to} R ⁶ . Particularly preferred are the following groups.

R ^{1 to} R ¹⁶ may be the same or different, and each represents a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, a hydrocarbon-substituted silyl group, a hydrocarbon-substituted siloxy group, or an alkoxy group. , An alkylthio group, an aryloxy group, an arylthio group, an acyl group, an ester group, a thioester group, an amide group, an imide group, an amino group, an imino group, a sulfone ester group, a sulfonamide group, a cyano group, and a nitro group. Represents the same atom or group as R ^{1 to} R ⁶ . Two or more groups, preferably adjacent groups, of R ^{1 to} R ¹⁶ are connected to each other to form an aliphatic ring,
It may form an aromatic ring or a hydrocarbon ring containing a hetero atom such as a nitrogen atom.

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

Examples of the bonding group represented by Y ′ include groups containing at least one element selected from oxygen, sulfur, carbon, nitrogen, phosphorus, silicon, selenium, tin, boron and the like. the -O -, - S -, - chalcogen atom-containing groups such as Se-; -NH -, - N ( CH 3) 2 -, -
_{PH -, - P (CH 3} ) 2 - a nitrogen or phosphorus atom-containing groups such _{as; -CH 2 -, - CH 2} -CH 2 -, - C (CH 3)
- ₂ hydrocarbon group having 1 to 20 carbon atoms such as; benzene, naphthalene, carbon atoms, such as anthracene 6
20 cyclic unsaturated hydrocarbon residues; pyridine, quinoline,
A heterocyclic compound residue having 3 to 20 carbon atoms including a hetero atom such as thiophene or furan; -SiH ₂ -,-
Si (CH _{3) 2} - silicon atom-containing group such as, -SnH
_{2 -, - Sn (CH 3} ) 2 - tin atom-containing groups such as; -BH
-, -B (CH ₃ )-, -BF- and the like, or a single bond.

Hereinafter, specific examples of the transition metal compound represented by the general formula (Ia-1) will be shown, but the invention is not limited thereto. In the following specific examples, M is a transition metal element, and is individually Sc (III), Ti (III),
Ti (IV), Zr (III), Zr (IV), Hf (IV), V (IV),
Nb (V), Ta (V), Co (II), Co (III), Rh (I
I), Rh (III), and Rh (IV) are shown, but not limited thereto. Among these, Ti (IV),
Zr (IV) and Hf (IV) are preferred.

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

N is determined by the valence of the metal M. For example, if two monoanion species are bound to a metal,
N = 0 for a divalent metal, n = 1 for a trivalent metal, n = 2 for a tetravalent metal, and n = 3 for a pentavalent metal. For example, when the metal is Ti (IV), n = 2, when Zr (IV), n = 2, and when Hf (IV), n = 2.

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

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In the olefin polymerization catalyst according to the present invention, it is particularly preferable to use a novel transition metal compound represented by the following general formula (III) as the component (A). Transition metal compound (Ib) In the present invention, as the transition metal compound (A), a transition metal compound represented by the following general formula (Ib) can also be used.

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In the formula (Ib), M represents a transition metal atom belonging to groups 3 to 11 of the periodic table, preferably a group 3 to 5 or 9
Group, particularly preferably a group 4 or group 5 transition metal atom, especially titanium, zirconium, hafnium, cobalt or rhodium.

M is an integer of 1 to 6, preferably 1 to 4. R ^{1 to} R ⁶ may be the same or different, and each represents a hydrogen atom, a halogen atom, a hydrocarbon group, a hydrocarbon-substituted silyl group, an alkoxy group, an aryloxy group, an ester group, an amide group, an amino group, or a sulfonamide group. , A cyano group and a nitro group.

Of these groups, particularly, a halogen atom,
Preferred are a hydrocarbon group, a hydrocarbon-substituted silyl group, an alkoxy group, an aryloxy group, an ester group, an amide group, an amino group, a sulfonamide group, a cyano group, and a nitro group.

Examples of the groups R ^{1 to} R ⁶ are the same as those exemplified for the transition metal compounds represented by the aforementioned general formulas (I) and (Ia). Further, when m is 2 or more, R ^{1 to} R ⁶ may form a ring by connecting two or more of these groups, preferably adjacent groups, to each other. However, R ¹ is not connected to each other.

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

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In the present invention, a transition metal compound in which cobalt metal is replaced with a metal such as titanium, zirconium, hafnium, iron, copper, or rhodium in the above compounds may be used.

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

Other Transition Metal Compounds As the transition metal compounds other than the above transition metal compound (A), specifically, the following transition metal compounds can be used, but not limited thereto. (a-1) Transition metal imide compound represented by the following formula (Ic)

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In the formula, M represents a transition metal atom belonging to Groups 8 to 10 of the periodic table, and is preferably nickel, palladium or platinum. R ^{21 to} R ²⁴ may be the same or different from each other, and may be a hydrocarbon group having 1 to 50 carbon atoms, 1 to 5 carbon atoms.
0 represents a halogenated hydrocarbon group, a hydrocarbon-substituted silyl group, or a hydrocarbon group substituted with a substituent containing at least one element selected from nitrogen, oxygen, phosphorus, sulfur and silicon.

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

X represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group, a sulfur-containing group, a silicon-containing group or a nitrogen-containing group. Represents a group, and when q is 2 or more,
A plurality of groups represented by X may be the same or different. (a-2) Transition metal amide compound represented by the following formula (Id)

[0169]

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In the formula, M represents a transition metal atom belonging to Groups 3 to 6 of the periodic table, and is preferably titanium, zirconium or hafnium. R ′ and R ″ may be the same or different, and each represents a hydrogen atom, a hydrocarbon group having 1 to 50 carbon atoms, a halogenated hydrocarbon group having 1 to 50 carbon atoms, a hydrocarbon-substituted silyl group, or nitrogen. And a substituent having at least one element selected from oxygen, phosphorus, sulfur and silicon.

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

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

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

[0174]

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

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

N is a number satisfying the valence of M. X is
A hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group, a sulfur-containing group, a silicon-containing group or a nitrogen-containing group; In the case of two or more, a plurality of groups represented by X may be the same or different from each other, or may be bonded to each other to form a ring. (A-4) transition metal compound containing a ligand having a cyclopentadienyl skeleton containing at least one hetero atom represented by the following formula (If)

[0178]

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

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

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

Y is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group, a sulfur-containing group, a silicon-containing group or a nitrogen-containing group. Represents a group.

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

N is a number that satisfies the valence of M. X is
It represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group, a sulfur-containing group, a silicon-containing group or a nitrogen-containing group. When n is 2 or more, a plurality of groups represented by X may be the same or different from each other, or may be bonded to each other to form a ring. (a-6) a transition metal compound represented by the following formula (Ig)

[0185]

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

[0187]

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In the formula, R ^{31 to} R ³⁴ may be the same or different, and each represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon having 1 to 20 carbon atoms. And two or more of these may be connected to each other to form a ring. (a-8) a transition metal compound represented by the following formula (Ii)

[0189]

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

R ^{41 to} R ⁴⁸ may be the same or different from each other, and represent a hydrogen atom, a halogen atom,
A hydrocarbon group of 20; a halogenated hydrocarbon group having 1 to 20 carbon atoms; an oxygen-containing group; a sulfur-containing group; a silicon-containing group; or a nitrogen-containing group. May be formed.

X is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group, a sulfur-containing group, a silicon-containing group or a nitrogen-containing group. A group, and when q is 2 or more, X
May be the same as or different from each other, or the groups represented by X may be bonded to each other to form a ring.

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

(B-1) Organometallic Compounds As the (B-1) organometallic compounds used in the present invention, specifically, the following groups 1 and 2 and 12 of the periodic table:
Group 13 organometallic compounds are used.

[0195] (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).

[0196] (B-1b) In the general formula M ² AlR ^a ₄ (wherein, M ² represents a Li, Na or K, R ^a is the number of carbon atoms 1 to 15, preferably 1 to 4 hydrocarbon groups A complex alkylated product of a metal of Group 1 of the periodic table represented by the formula (1) 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, preferably 1 to 4 carbon atoms) A dialkyl compound of a metal of Group 2 or 12 of the periodic table represented by a hydrocarbon group, wherein M ³ is Mg, Zn or Cd.

As the organoaluminum compound belonging to (B-1a), the following compounds can be exemplified. In the general formula _{^{R a m Al (OR b)}} 3-m ( wherein, R ^a and R ^b may be the same or different, 1 to 15, preferably 1 to 4 hydrocarbon group having carbon atoms are shown, m is preferably a number 1.5 ≦ m ≦ 3.) an organoaluminum compound represented by the general formula R ^a _m AlX _3-m (wherein, R ^a is 1 to carbon atoms 15, preferably 1
4 represents a hydrocarbon group, X represents a halogen atom, and m is preferably 0 <m <3. An 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 specifically, the organoaluminum compounds belonging to (B-1a) include trimethylaluminum, triethylaluminum, trin-butylaluminum, tripropylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum. Tri-n-alkyl aluminum such as triisopropyl aluminum, triisobutyl aluminum, tri sec-butyl aluminum, tri tert-
Butylaluminum, tri2-methylbutylaluminum, tri3-methylbutylaluminum, tri2-methylpentylaluminum, tri3-methylpentylaluminum, tri4-methylpentylaluminum, tri2-methylhexylaluminum, tri3-methylhexyl Aluminum, tribranched alkyl aluminum such as tri-2-ethylhexyl aluminum; tricycloalkyl aluminum such as tricyclohexyl aluminum and tricyclooctyl aluminum; triaryl aluminum such as triphenyl aluminum and tritolyl aluminum; dialkyl aluminum such as diisobutyl aluminum hydride Hydride; (i-C ₄ H ₉ ) _x
Trialkenyl aluminum such as triisoprenyl aluminum represented by Al _y (C ₅ H ₁₀ ) _z (where x, y and z are positive numbers and z ≧ 2x); isobutylaluminum methoxy Alkyl aluminum alkoxides such as isobutylaluminum ethoxide and isobutylaluminum isopropoxide; dialkylaluminum alkoxides such as dimethylaluminum methoxide, diethylaluminum ethoxide and dibutylaluminum butoxide; alkyls such as ethylaluminum sesquiethoxide and butylaluminum sesquibutoxide Aluminum sesquialkoxide; ^Ra
_2.5 Al (OR ^b ) _0.5 partially alkylated alkyl aluminum having an average composition such as _0.5 ; diethyl aluminum phenoxide, diethyl aluminum (2,6-di-t-butyl-4-methylphenoxide), ethyl Aluminum bis (2,6-di-t-butyl-4-methylphenoxide), diisobutylaluminum (2,6-di-t-butyl-4-)
Dialkylaluminum aryloxides such as methylphenoxide) and isobutylaluminum bis (2,6-di-t-butyl-4-methylphenoxide); dimethylaluminum chloride, diethylaluminum chloride, dibutylaluminum chloride, diethylaluminum bromide, diisobutylaluminum chloride Alkyl aluminum sesquihalides such as ethyl aluminum sesquichloride, butyl aluminum sesquichloride and ethyl aluminum sesquibromide; partially such as alkyl aluminum dihalides such as ethyl aluminum dichloride, propyl aluminum dichloride and butyl aluminum dibromide Alkylaluminum halides; diethylaluminum hydride Dialkylaluminum hydrides such as dibutylaluminum hydride; other partially hydrogenated alkylaluminums such as ethylaluminum dihydride and alkylaluminum dihydride such as propylaluminum dihydride; ethylaluminum ethoxycyclolide, butylaluminum butoxycyclolide, ethylaluminum Partially alkoxylated and halogenated alkyl aluminums such as ethoxy bromide can be mentioned.

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

Compounds belonging to the above (B-1b) include Li
Al (C ₂ H ₅ ) ₄ and LiAl (C ₇ H ₁₅ ) ₄ can be exemplified. In addition, (B-1) as the organometallic compound, methyl lithium, ethyl lithium, propyl lithium, butyl lithium, methyl magnesium bromide, methyl magnesium chloride, ethyl magnesium bromide, ethyl magnesium chloride, propyl magnesium bromide, propyl magnesium Chloride, butylmagnesium bromide, butylmagnesium chloride, dimethylmagnesium, diethylmagnesium, dibutylmagnesium, butylethylmagnesium and the like can also be used.

Further, a compound which forms the above-mentioned organoaluminum compound in the polymerization system, for example, a combination of aluminum halide and alkyllithium or a combination of aluminum halide and alkylmagnesium may be used.

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

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

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 water of adsorption or salts containing water of crystallization such as hydrated magnesium chloride, hydrated copper sulfate, hydrated aluminum sulfate, hydrated nickel sulfate, hydrated cerium chloride A method of adding an organoaluminum compound such as a trialkylaluminum to a suspension of a hydrocarbon medium of the above, and reacting the water of adsorption or water of crystallization with the organoaluminum compound. (2) A method in which water, ice or steam is allowed to directly act on an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether or tetrahydrofuran. (3) A method of reacting an organoaluminum compound such as trialkylaluminum with an organotin oxide such as dimethyltin oxide or dibutyltin oxide in a medium such as decane, benzene or toluene.

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

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

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

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

[0212]

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In the formula, R ¹⁷ represents a hydrocarbon group having 1 to 10 carbon atoms. R ¹⁸ may be the same or different, and each has a hydrogen atom, a halogen atom, and 1 to 10 carbon atoms.
Represents a hydrocarbon group.

The organoaluminum oxy compound containing boron represented by the above general formula (IV) is represented by the following general formula (V)
And R ¹⁷ -B- (OH) ₂ ... (V) (wherein R ¹⁷ represents the same group as above) under an inert gas atmosphere. It can be produced by reacting in a 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 (V) 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 preferred, and trimethylaluminum, triethylaluminum and triisobutylaluminum are particularly preferred. These are used alone or in combination of two or more.

The above-mentioned (B-2) organoaluminum oxy compounds are used alone or in combination of two or more. (B-3) Reaction with transition metal compound to form ion pair
Compound capable of reacting with the transition metal compound used in the compound the present invention to form an ion pair (B-3) (hereinafter, referred to as "ionizing ionic compound".) Is reacted with the transition metal compound (A) These compounds form an ion pair. Examples of such a compound are described in JP-A-1-501950 and JP-A-1-501950.
JP-5020236, JP-A-3-179005, JP-A-3-179006, JP-A-3-207
703, JP-A-3-207704, USP
And Lewis acids, ionic compounds, borane compounds and carborane compounds described in US Pat. No. 5,321,106. Furthermore, 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 (VI).

[0221]

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

R ^{20 to} R ²³ may be the same or different and are an organic group, preferably an aryl group or a substituted aryl group. Specific examples of the carbonium cation include trisubstituted carbonium cations such as triphenylcarbonium cation, tri (methylphenyl) carbonium cation, and tri (dimethylphenyl) carbonium cation.

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

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

As R ¹⁹ , a carbonium cation, an ammonium cation and the like are preferable, and a triphenylcarbonium cation, an N, N-dimethylanilinium cation and an N, N-diethylanilinium cation are particularly preferable.

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

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

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

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

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

[0232]

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

[0234]

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

Specific examples of the carborane compound include, for example, 4-carbanonaborane (14), 1,3-dicarbanonaborane (13), 6,9-dicarbadecaborane (14), dodecahydride-1-phenyl- 1,3-dicarbanonaborane,
Dodecahydride-1-methyl-1,3-dicarbanonaborane, undecahydride-1,3-dimethyl-1,3-dicarbanonaborane, 7,8-dicarboundecaborane (13), 2,
7-dicarboundecaborane (13), undecahydride-7,8-dimethyl-7,8-dicarboundecaborane, dodecahydride-11-methyl-2,7-dicarboundecaborane, tri (n-butyl ) Ammonium 1-carbadecaborate, tri (n-butyl) ammonium 1-carboundecaborate, tri (n-butyl) ammonium 1-carbadodecaborate, tri (n-butyl) ammonium 1-trimethylsilyl-1-carbadeca Borate, tri (n-butyl) ammonium bromo-1-carbadecaborate, tri (n-butyl) ammonium 6-carbadecaborate (14), tri (n-butyl) ammonium 6-carbadecaborate (1
2), tri (n-butyl) ammonium 7-carboundecaborate (13), tri (n-butyl) ammonium 7,8-
Dicarboundecaborate (12), tri (n-butyl)
Ammonium 2,9-dicarboundecaborate (12),
Tri (n-butyl) ammonium dodecahydride-8-
Methyl-7,9-dicarboundecaborate, tri (n-butyl) ammonium undecahydride-8-ethyl-7,9-
Dicarbaune decaborate, tri (n-butyl) ammonium undecahydride-8-butyl-7,9-dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-8-allyl-7,9-dicarbaune Decaborate, tri (n-butyl) ammonium undecahydride-9-trimethylsilyl-7,8-dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-4,6-dibromo-7-carboundecaborate Salts of anions such as tri (n-butyl) ammonium bis (nonahydride-1,3-dicarbanonaborate) cobaltate (III), tri (n-butyl) ammonium bis (undecahydride-7,8 -Dicarboundecaborate) ferrate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarboundecaborate) co Belt salt (III), tri (n- butyl) ammonium bis (undecapeptide 7,8-dicarbaundecaborate deca borate)
Nickelate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarboundecaborate) cuprate (III), tri (n-butyl) ammonium bis (undecahydride-7) , 8-Dicarboundecaborate) aurate (III), tri (n-butyl) ammonium bis (nonahydride-7,8-dimethyl-7,8-dicarboundecaborate) ferrate (III) (N-butyl) ammonium bis (nonahydride-7,8-dimethyl-7,8-dicarboundecaborate) chromate (III), tri (n-butyl) ammonium bis (tribromooctahydride-7,8 -Dicarboundecaborate) cobaltate (II
I), tris [tri (n-butyl) ammonium] bis (undecahydride-7-carboundecaborate) chromate (III), bis [tri (n-butyl) ammonium]
Bis (undecahydride-7-carboundecaborate) manganate (IV), bis [tri (n-butyl) ammonium] bis (undecahydride-7-carboundecaborate) cobaltate (III), Bis [tri (n-butyl) ammonium] bis (undecahydride-7-
Metal carborane anions such as (carboundecaborate) nickelate (IV).

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

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

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

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

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

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

[0243] 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 size of 10 to 300 μm, preferably 20 to 300 μm.
And a specific surface area of 50 to 1000 m ^2.
/ G, preferably in the range of 100 to 700 m ² / g, and the pore volume is desirably in the range of 0.3 to 3.0 cm ³ / g. Such a carrier may be used, if necessary, for 10 hours.
It is used by firing at 0 to 1000 ° C, preferably 150 to 700 ° C.

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

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

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

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

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

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

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

Of these, preferred are clay or clay mineral, 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 α-olefin of 14 (co)
Examples thereof include polymers or (co) polymers formed mainly of vinylcyclohexane and styrene, and modified products thereof.

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

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

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

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

As the carboxylic acid, R ³² —COO is usually used.
The one represented by H is used. R ³² has 1 to 1 carbon atoms
A hydrocarbon group having 50 or a halogenated hydrocarbon group having 1 to 50 carbon atoms is shown, and a halogenated hydrocarbon group having 1 to 50 carbon atoms is particularly preferable.

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

[0261]

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In the formula, M is an element belonging to Group 1-14 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 first olefin polymerization catalyst according to the present invention. During polymerization, use of each component,
Although the order of addition is arbitrarily selected, the following method is exemplified.

(1) Component (A), (B-1) an organometallic compound, (B-2) an organoaluminum oxy compound and (B-3)
A method in which at least one component (B) selected from ionized ionic compounds (hereinafter, simply referred to as “component (B)”) is added to a polymerization vessel in an arbitrary order.

(2) A method in which the catalyst in which the component (A) and the component (B) are brought into contact in advance is added to the polymerization reactor. (3) A method in which the catalyst component in which the component (A) and the component (B) are brought into contact in advance, and the component (B) are added to the polymerization reactor in an arbitrary order. In this case, the components (B) may be the same or different.

(4) A method in which the catalyst component in which the component (A) is supported on the carrier (C) and the component (B) are added to the polymerization vessel in an arbitrary order. (5) A method in which a catalyst in which the component (A) and the component (B) are supported on a carrier (C) is added to a polymerization reactor.

(6) A method in which the catalyst component in which the component (A) and the component (B) are supported on the carrier (C) and the component (B) are added to the polymerization reactor in any order. In this case, component (B)
May be the same or different.

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

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

(11) A method in which the component (A), the component (B), and the organic compound component (D) are added to the polymerization reactor in any order. (12) a component in which the component (B) and the component (D) are brought into contact in advance,
And adding the component (A) to the polymerization reactor in any order.

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

(15) A method in which the catalyst component in which the component (A) and the component (B) are brought into contact in advance, and the component (B) and the component (D) are added to the polymerization reactor in an arbitrary order. (16) A method in which the catalyst component in which the component (A) and the component (B) are brought into contact in advance and the component in which the component (B) and the component (D) are brought into contact in advance are added to the polymerization reactor in an arbitrary order.

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

(19) A method of adding a catalyst component in which the component (A), the component (B), and the component (D) are brought into contact in an arbitrary order in advance, and then adding the catalyst component to a polymerization reactor. (20) A method in which the catalyst component in which the component (A), the component (B) and the component (D) are brought into contact in advance, and the component (B) are added to the polymerization reactor in an arbitrary order. In this case, the components (B) may be the same or different.

(21) A method in which a catalyst in which the components (A), (B) and (D) are supported on a carrier (C) is added to a polymerization vessel. (22) A method in which the catalyst component in which the component (A), the component (B) and the component (D) are supported on the carrier (C), and the component (B) are added to the polymerization reactor in an arbitrary order. In this case, the components (B) may be the same or different.

The solid catalyst component in which the component (A) and the component (B) are supported on the carrier (C) may be preliminarily polymerized with an olefin. In the first olefin polymerization method according to the present invention, an olefin polymer is obtained by polymerizing or copolymerizing an olefin in the presence of the olefin polymerization catalyst as described above.

In the present invention, the polymerization can be carried out by any of 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. In the present invention, the olefin can be polymerized with high polymerization activity even when the component (A) is used at a relatively low concentration.

The component (B-1) is composed of the component (B-1) and the component (A)
The molar ratio with the transition metal atom (M) in [(B-1) / M] is
Usually 0.01 to 100,000, preferably 0.05 to 5
0000 is used. Component (B-2) is
The molar ratio of the aluminum atom in the component (B-2) to the transition metal atom (M) in the component (A) [(B-2) / M] 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 replaced by Component (B-3)
And the molar ratio of the transition metal atom (M) in the component (A) [(B
-3) / M] is usually used in an amount of 1 to 10, preferably 1 to 5.

Component (D) is different from component (B) in component (B-1)
In the case of the above, the molar ratio [(D) / (B-1)] is usually 0.01 to
Component (B) in an amount such that it is 10, preferably 0.1 to 5
In the case of -2), the molar ratio of the component (D) to the aluminum atom in the component (B-2) [(D) / (B-2)] is usually 0.001.
In the case of the component (B-3), the molar ratio [(D) / (B-3)] is usually 0.1 to 2, preferably 0.005 to 1.
It is used in such an amount as to be from 01 to 10, preferably from 0.1 to 5.

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

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.

The olefin which can be polymerized with such an olefin polymerization catalyst has 2 carbon atoms.
-30, preferably 2-20 linear or branched α
Olefins, such as ethylene, propylene, 1-butene, 2-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene,
1-octene, 1-decene, 1-dodecene, 1-tetradecene,
1-hexadecene, 1-octadecene, 1-eicosene; a cyclic olefin having 3 to 30, preferably 3 to 20 carbon atoms, for example, cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, 2 -Methyl 1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-
Octahydronaphthalene; a polar monomer such as acrylic acid, methacrylic acid, fumaric acid, maleic anhydride,
Α, β-unsaturated carboxylic acids such as itaconic acid, itaconic anhydride, bicyclo (2,2,1) -5-heptene-2,3-dicarboxylic anhydride, and their sodium and potassium salts,
Metal salts such as lithium salt, zinc salt, magnesium salt and calcium salt; methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, ter acrylate
α, β-unsaturated carboxylic esters such as t-butyl, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate and isobutyl methacrylate; acetic acid Vinyl esters such as vinyl, vinyl propionate, vinyl caproate, vinyl caprate, vinyl laurate, vinyl stearate, and vinyl trifluoroacetate; unsaturated glycidyl such as glycidyl acrylate, glycidyl methacrylate, and monoglycidyl itaconate And the like. Further, vinylcyclohexane, diene, polyene, or the like can be used. As the diene or polyene, a cyclic or chain compound having 4 to 30, preferably 4 to 20 carbon atoms and having two or more double bonds is used. Specifically, butadiene, isoprene, 4-methyl-1,3-pentadiene, 1,3-pentadiene, 1,4-pentadiene, 1,5-hexadiene, 1,4-hexadiene, 1,3-
Hexadiene, 1,3-octadiene, 1,4-octadiene,
1,5-octadiene, 1,6-octadiene, 1,7-octadiene, ethylidene norbornene, vinylnorbornene, dicyclopentadiene; 7-methyl-1,6-octadiene, 4-
Ethylidene-8-methyl-1,7-nonadiene, 5,9-dimethyl-
1,4,8-decatriene; further aromatic vinyl compounds such as styrene, o-methylstyrene, m-methylstyrene,
mono- or polyalkylstyrenes such as p-methylstyrene, o, p-dimethylstyrene, o-ethylstyrene, m-ethylstyrene, p-ethylstyrene; methoxystyrene,
Styrene derivatives having functional groups 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.

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

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

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

In the present invention, when the α-olefin and the conjugated diene are copolymerized, a non-conjugated diene or polyene can be further used. As the non-conjugated diene or polyene, 1,4-pentadiene, 1,5- Hexadiene,
1,4-hexadiene, 1,4-octadiene, 1,5-octadiene, 1,6-octadiene, 1,7-octadiene, ethylidene norbornene, vinylnorbornene, dicyclopentadiene, 7-methyl-1,6-octadiene, 4-ethylidene-8-
Methyl-1,7-nonadiene, 5,9-dimethyl-1,4,8-decatriene and the like can be mentioned.

Next, the second olefin polymerization catalyst according to the present invention will be described. The second olefin polymerization catalyst according to the present invention comprises (A ′) a transition metal compound represented by the following general formula (II), (B) (B-1) an organometallic compound, and (B-2) an organic metal compound. It is formed from an aluminum oxy compound and (B-3) at least one compound selected from compounds which react with the transition metal compound (A ') to form an ion pair.

First, each component forming the olefin polymerization catalyst of the present invention will be described. (A ′) Transition metal compound The (A ′) transition metal compound used in the present invention is a transition metal compound represented by the following general formula (II).

[0291]

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(In the formula, M represents a transition metal atom belonging to Groups 3 to 11 of the periodic table, and R ^{1 to} R ¹⁰ may be the same or different from each other, and represent a hydrogen atom, a halogen atom, a hydrocarbon group, A cyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group; two or more of these May be linked to form a ring, n is a number satisfying the valence of M, X is a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, Represents a boron-containing group, an aluminum-containing group, a phosphorus-containing group, a halogen-containing group, a heterocyclic compound residue, a silicon-containing group, a germanium-containing group, or a tin-containing group, and is represented by X when n is 2 or more. Multiple groups may be the same or different It may have I, and a plurality of groups represented by X may be bonded to each other to form a ring, Y
Is oxygen, sulfur, carbon, nitrogen, phosphorus, silicon, selenium,
It represents a divalent bonding group containing at least one element selected from the group consisting of tin and boron. In the case of a hydrocarbon group, it is a group having three or more carbon atoms.

In the general formula (II), at least one of R ^{6 and} R ¹⁰ , particularly both, are a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group,
It is preferably a boron-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group.

In formula (II), M, R ^{1 to} R ¹⁰ and X can be the same groups as M, R ^{1 to} R ⁶ and X described for the compound of formula (I).
Specific examples of Y will be described later.

The transition metal compound represented by the general formula (II) is preferably a transition metal compound represented by the following general formula (II-a).

[0296]

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In the formula, M represents a transition metal atom of Groups 3 to 11 of the periodic table, preferably Group 4 or Group 5, more preferably Group 4 such as titanium, zirconium, hafnium and the like. It is titanium.

R ^{1 to} R ¹⁰ may be the same or different, and each represents a hydrogen atom, a halogen atom, a hydrocarbon group, a hydrocarbon-substituted silyl group, an alkoxy group, an aryloxy group, an ester group, an amide group, an amino group, It represents a sulfonamide group, a nitrile group or a nitro group, and two or more of them, preferably adjacent groups, may be connected to each other to form a ring.

N is a number satisfying the valency of M, and is generally an integer of 0 to 4, preferably 1 to 4, more preferably 1 to 3. X represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group, a sulfur-containing group, or a silicon-containing group; In the case of two or more, a plurality of groups represented by X may be the same or different from each other, and two or more Xs may be connected to each other to form a ring.

Y represents a divalent linking group containing at least one element selected from the group consisting of oxygen, sulfur, carbon, nitrogen, phosphorus, silicon, selenium, tin and boron, and is a hydrocarbon group. In this case, it is a group consisting of 3 or more carbon atoms.

These bonding groups preferably have a structure in which the main chain is composed of 3 or more atoms, more preferably 4 to 20 atoms, and particularly preferably 4 to 10 atoms. In addition, these bonding groups may have a substituent.

In the formula (II-a), R ⁶ or R ¹⁰
It is preferable that at least one, particularly both, are a halogen atom, a hydrocarbon group, a hydrocarbon-substituted silyl group, an alkoxy group, an aryloxy group, an ester group, an amide group, an amino group, a sulfonamide group, a nitrile group, or a nitro group. .

In the general formula (II-a), X and R ¹ to
Specific examples of R ¹⁰ include the same groups as X and R ¹ to R ⁶ described in the general formula (I) and (Ia). X is, in particular, a halogen atom, having 1 carbon atom.
Up to 20 hydrocarbon or sulfonate groups are preferred.
When n is 2 or more, the ring formed by linking two or more Xs to each other may be an aromatic ring or an aliphatic ring.

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

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

[0306]

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[0307]

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

In the second olefin polymerization catalyst according to the present invention, the transition metal compound (A ′) may be used in combination with another transition metal compound as in the case of the transition metal compound (A). It is possible, and specific examples include the compounds (a-1) to (a-8) exemplified above.

Further, it reacts with the organometallic compound (B-1), the organoaluminum oxy compound (B-2) and the transition metal compound (A ') used in the second olefin polymerization catalyst according to the present invention. As the compound (B-3) forming an ion pair, the same compounds as described above can be mentioned.

In the second olefin polymerization catalyst according to the present invention, as in the first olefin polymerization catalyst, the transition metal compound (A ′), the organometallic compound (B-1) and the (B-1) -2) Organoaluminum oxy compound, and (B-
3) At least one selected from ionized ionic compounds
The carrier (C) as described above can be used together with the seed compound (B), if necessary. Further, if necessary, the specific organic compound (D) as described above can be used.

FIG. 2 shows a process for preparing the second olefin polymerization catalyst according to the present invention. The second olefin polymerization catalyst according to the present invention can be used for the polymerization of the same monomer under the same conditions as those described for the first olefin polymerization catalyst according to the present invention.

In the second olefin polymerization method according to the present invention, the method of using each component and the order of addition are arbitrarily selected, but the same method as in the first olefin polymerization method is exemplified.

Novel transition metal compound The novel transition metal compound according to the present invention has the following general formula (II)
I).

[0315]

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In the formula (III), M is the fourth or fifth periodic table.
Represents a group transition metal atom, m represents an integer of 1 to 3,
R ¹ represents a hydrocarbon group, a hydrocarbon-substituted silyl group, a hydrocarbon-substituted siloxy group, an alkoxy group, an alkylthio group, an aryloxy group, an arylthio group, an ester group, a thioester group, a sulfone ester group or a hydroxy group,
R ^{2 to} R ⁵ may be the same or different from each other, and represent a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, a hydrocarbon-substituted silyl group, a hydrocarbon-substituted siloxy group,
Alkoxy group, alkylthio group, aryloxy group, arylthio group, ester group, thioester group, amide group,
Imide group, amino group, imino group, sulfone ester group,
A sulfonamide group, a cyano group, a nitro group, a carboxyl group, a sulfo group, a mercapto group or a hydroxy group, and R ⁶ represents a halogen atom, a hydrocarbon group, a hydrocarbon-substituted silyl group, a hydrocarbon-substituted siloxy group, an alkoxy group, An alkylthio group, an aryloxy group, an arylthio group, an ester group, a thioester group, an amide group, an imide group, an imino group, a sulfone ester group, a sulfonamide group or a cyano group, and two or more of R ^{1 to} R ⁶ May be linked to form a ring, and when m is 2 or more, two of the groups represented by R ^{1 to} R ⁶ may be linked (provided that R ¹ is Are not combined),
n is a number that satisfies the valence of M, X is 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;
Is two or more, the plurality of groups represented by X may be the same or different, and the plurality of groups represented by X may be bonded to each other to form a ring.

Among the transition metal compounds of the general formula (III),
Those represented by the following general formula (III-a) are preferred.

[0318]

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In the formula (III-a), M represents a transition metal atom belonging to Group 4 or 5 of the periodic table, and specifically includes titanium, zirconium, hafnium, vanadium, niobium and tantalum.

M represents an integer of 1 to 3, preferably 2, and R ^{1 to} R ⁵ may be the same or different;
Hydrocarbon group, an alkoxy group or a hydrocarbon-substituted silyl group, R ⁶ is a halogen atom, a hydrocarbon group, a hydrocarbon-substituted silyl group, an alkoxy group, an alkylthio group or a cyano group, among R ¹ to R ⁶ May be linked to each other to form a ring, and when m is 2 or more, two of the groups represented by R ^{1 to} R ⁶ may be linked to each other. (However, R ¹ is not bonded to each other), n is a number satisfying the valence of M, X is a halogen atom, a hydrocarbon group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, Represents a halogen-containing group or a silicon-containing group;
Is two or more, the plurality of groups represented by X may be the same or different, and the plurality of groups represented by X may be bonded to each other to form a ring. Of these, X
Is preferably a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group, a sulfur-containing group, or a silicon-containing group.

Examples of each of R ^{1 to} R ⁶ and X in the general formula (III-a) include the same groups as those described in the general formula (I). The following are illustrated as a novel transition metal compound.

[0322]

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[0323]

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[0324]

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General Method for Producing Transition Metal Compounds The transition metal compounds represented by the general formulas (I), (II) and (III) are not particularly limited, and can be produced, for example, as follows. it can.

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

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

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

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

Further, the metal M in the synthesized transition metal compound can be exchanged for another transition metal by a conventional method. Further, for example, when any of R ^{1 to} R ⁶ is H, a substituent other than H can be introduced at any stage of the synthesis.

Formula (III), preferably Formula (III-a)
The novel transition metal compound according to the present invention represented by the formula (1) can be suitably used, for example, as a catalyst for olefin polymerization.

When a novel transition metal compound is used as an olefin polymerization catalyst, an olefin (co) polymer having a high polymerization activity and a narrow molecular weight distribution can be synthesized. α-olefin / conjugated diene copolymer The α-olefin / conjugated diene copolymer according to the present invention is:
The structural unit derived from an α-olefin is from 1 to 99.9.
Mol%, the constitutional unit derived from the conjugated diene is 99 to
0.1 mol%, preferably 50 to 99.9 mol% of the structural unit derived from the α-olefin, and 50 to 0.1 mol% of the structural unit derived from the conjugated diene.

In the polymer chain of the α-olefin / conjugated diene copolymer according to the present invention, 1,1 derived from a conjugated diene is contained.
The content of the 2-cyclopentane skeleton is 1 mol% or less, preferably, the content (0.1 mol%
Less). If the content of the 1,2-cyclopentane skeleton is less than 0.1 mol%, it is considered to be below the detection limit and is not included in the calculation of all conjugated diene units.

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

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

In the present invention, when the α-olefin and the conjugated diene are copolymerized, a non-conjugated diene or polyene can be further used. As the non-conjugated diene or polyene, 1,4-pentadiene, 1,5- Hexadiene,
1,4-hexadiene, 1,4-octadiene, 1,5-octadiene, 1,6-octadiene, 1,7-octadiene, ethylidene norbornene, vinylnorbornene, dicyclopentadiene, 7-methyl-1,6-octadiene, 4-ethylidene-8-
Methyl-1,7-nonadiene, 5,9-dimethyl-1,4,8-decatriene and the like can be mentioned.

Further, in the polymer chain of the α-olefin / conjugated diene copolymer according to the present invention, the ratio of the 1,2-cyclopentane skeleton to the total diene unit content is 20 mol% or less, preferably 10 mol% or less. It is. Further, the ratio of other insertion forms of diene (1,4-cis, 1,4-trans, 1,2-vinyl) in the α-olefin / conjugated diene copolymer is arbitrary. This ratio is based on Die Makromolek
It can be measured by ¹³ C-NMR and ¹ H-NMR according to the method described in ulare Chemie, vol. 192, p. 2591 (1991).

The α-olefin / conjugated diene copolymer has a molecular weight distribution (Mw / Mn) of 3.5 or less, has a uniform composition distribution, and has a molecular weight expressed by weight average molecular weight (Mw). It is 1000 or more, preferably 5000 or more.

In the present invention, the α-olefin / conjugated diene copolymer can be variously modified by having a double bond in a main chain or a side chain. For example, a double bond can be epoxidized by peroxide modification to introduce a highly reactive epoxy group into the copolymer. This makes it possible to use it as a thermosetting resin or as a reactive resin. Further, a double bond can be used for a Diels-Alder reaction, a Michael addition reaction, and the like. In addition, when the main chain has a double bond, heat resistance and ozone resistance are further improved by selectively hydrogenating and saturating the double bond.

In the present invention, a part or the whole of the α-olefin / conjugated diene copolymer may be an unsaturated carboxylic acid,
It may be modified with a derivative thereof or an aromatic vinyl compound, and the modification amount is preferably in the range of 0.01 to 30% by weight.

Examples of the monomer used for the modification (hereinafter referred to as “graft monomer”) include unsaturated carboxylic acids, derivatives thereof, and aromatic vinyl compounds. Specific examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, maleic acid, fumaric acid, and itaconic acid. Examples of the unsaturated carboxylic acid derivatives include acid anhydrides, esters, amides, imides, and metal salts, and specifically, maleic anhydride, citraconic anhydride, itaconic anhydride, methyl acrylate, and methacrylic acid. Methyl, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, glycidyl acrylate, glycidyl methacrylate, monoethyl maleate, diethyl maleate, monomethyl fumarate, dimethyl fumarate,
Itaconic acid monomethyl ester, itaconic acid diethyl ester, acrylamide, methacrylamide, maleic acid monoamide, maleic acid diamide, maleic acid-N-monoethylamide, maleic acid-N, N-diethylamide, maleic acid-N-monobutylamide, Maleic acid-N, N-dibutylamide, fumaric acid monoamide, fumaric acid diamide, fumaric acid-N-monoethylamide, fumaric acid-N, N-diethylamide, fumaric acid-N-monobutylamide, fumaric acid-N, N-
Dibutylamide, maleimide, N-butylmaleimide, N-
Examples include phenylmaleimide, sodium acrylate, sodium methacrylate, potassium acrylate, potassium methacrylate and the like. It is preferable to use maleic anhydride among these graft monomers.

As the aromatic vinyl compound, specifically, styrene; o-methylstyrene, m-methylstyrene, p-methylstyrene, o, p-dimethylstyrene, o-ethylstyrene, m-ethylstyrene, p-ethyl Mono- or polyalkylstyrenes such as styrene; methoxystyrene, ethoxystyrene, vinylbenzoic acid, methyl vinylbenzoate, vinylbenzyl acetate, hydroxystyrene,
Functional group-containing styrene derivatives such as o-chlorostyrene, p-chlorostyrene and divinylbenzene; 3-phenylpropylene, 4-phenylbutene, α-methylstyrene and the like. Of these, styrene or 4-methoxystyrene is preferred.

In order to produce a modified copolymer by graft copolymerizing a graft monomer with an α-olefin / conjugated diene copolymer, various known methods can be employed. For example, a method of performing graft copolymerization by heating an α-olefin / conjugated diene-based copolymer and a graft monomer at a high temperature with or without a radical initiator in the presence or absence of a solvent. There is. In the reaction, two or more graft monomers may be used in combination.

A graft modified α-olefin having a graft ratio of 0.01 to 30% by weight, partially or wholly modified.
In order to produce a conjugated diene-based copolymer, a graft-modified α-olefin / conjugated diene-based copolymer having a higher graft ratio is produced from an industrial viewpoint, and then an unmodified α-olefin. A method of adjusting the graft ratio by mixing the graft-modified α-olefin / conjugated diene copolymer with the conjugated diene copolymer is a preferable method because the concentration of the graft monomer in the composition can be appropriately adjusted. However, the α-olefin / conjugated diene copolymer may be graft-modified from the beginning with a predetermined amount of a graft monomer.

The modification amount of the α-olefin / conjugated diene copolymer with the graft monomer is such that the graft ratio in the entire resin composition as described above is 0.01 to 30% by weight, particularly 0.05 to 10% by weight. Is preferably within the range.

The α-olefin / conjugated diene copolymer (including the above-mentioned modified product) according to the present invention is blended with (i) a polyolefin resin and, if necessary, (ii) a filler to form a resin composition. Can be used for various applications.

(I) Polyolefin Resin The (i) polyolefin resin that can be blended with the α-olefin / conjugated diene copolymer according to the present invention may be a crystalline polyolefin or an amorphous polyolefin. Alternatively, a mixture of a plurality of types of polyolefin resins may be used.

As the crystalline polyolefin, a homopolymer or copolymer of an α-olefin or a cyclic olefin having 2 to 20 carbon atoms can be used. Further, as the amorphous polyolefin, one or more kinds of carbon atoms having 2 or more carbon atoms
To 20 α-olefins and one or more cyclic olefins.

The α-olefin having 2 to 20 carbon atoms includes ethylene, propylene, 1-butene, 2-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene,
4,4-dimethyl-1-pentene, 3-methyl-1-pentene, 4-methyl-1-hexene, 3-ethyl-1-hexene, 4-ethyl-1-
Hexene, 4,4-dimethyl-1-hexene, 1-octene, 3-
Methyl-1-butene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-
Octadecene, 1-eicosene and the like.

As the cyclic olefin, cyclopentene, cycloheptene, cyclohexene, norbornene,
5-ethyl-2-norbornene, tetracyclododecene, 2-
Ethyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene and the like.

Specific examples of the crystalline polyolefin resin include (co) polymers shown in the following (1) to (11), and the following (3) and (5) are particularly preferable. (1) Ethylene homopolymer (manufacturing method may be either low-pressure method or high-pressure method) (2) Ethylene and 20 mol% or less of other α-olefin or vinyl monomer (eg, vinyl acetate, ethyl acrylate, etc.) Or a copolymer with a cyclic olefin; (3) a propylene homopolymer; (4) a random copolymer of propylene with 20 mol% or less of another α-olefin; and (5) a propylene and 30 mol% or less of other α-olefin. Block copolymer with olefin (6) 1-butene homopolymer (7) Random copolymer of 1-butene and other α-olefin of 20 mol% or less (8) 4-methyl-1-pentene alone Polymer (9) 4-methyl-1-pentene and up to 20 mol% of other α
-Random copolymer with olefin (10) Cyclopentene homopolymer (11) Random copolymer of cyclopentene and 20 mol% or less of other α-olefin and the like.

In the above (1) to (11), “other α-
As the olefin, among the α-olefins exemplified above, ethylene, propylene, 1-butene,
4-Methyl-1-pentene, 1-hexene, 1-octene are used. Further, as the cyclic olefin, preferably,
Cyclopentene, cyclohexene, norbornene and tetracyclododecene are used.

Such a crystalline polyolefin resin is
Melt flow rate (23 according to ASTM D1238-65T)
0 ° C., measured under the condition of a load of 2.16 kg) is 0.01 to
It is desirably in the range of 100 g / 10 min, preferably 0.3 to 70 g / 10 min. The crystallinity determined by the X-ray diffraction method is usually 5 to 100%, preferably 20 to 80%.
% Is desirable.

Such a crystalline polyolefin resin is
It can be manufactured by a conventionally known method. Specific examples of the amorphous polyolefin resin include the following (co) polymers. (1) a homopolymer of norbornene (2) a copolymer of ethylene and norbornene, or a copolymer of ethylene, norbornene, and another α-olefin (3) a copolymer of ethylene and tetracyclododecene, or ethylene And a copolymer of tetracyclododecene and another α-olefin.

(Ii) Filler The filler which can be blended with the α-olefin / conjugated diene copolymer according to the present invention is not particularly limited, and a commonly used filler can be used as needed.

Specific examples of the inorganic filler include fine powder of talc, kaolinite, calcined clay, pyrophyllite,
Silicates such as sericite and wollastonite, carbonates such as precipitated calcium carbonate, heavy calcium carbonate and magnesium carbonate, hydroxides such as marine aluminum and magnesium hydroxide, zinc oxide, zinc oxide and magnesium oxide Powdered fillers such as oxides, hydrous calcium silicates, hydrous aluminum silicates, hydrous silicic acid, anhydrous silicic acid and other synthetic silicic acids or silicates; flake-like fillers such as mica;
Fibrous filler such as basic magnesium sulfate whisker, calcium titanate whisker, aluminum borate whisker, sepiolite, PMF (Processed Mineral Fiber), zonotolite, potassium titanate, elestadite; balun filler such as glass balun, fly ash balun And the like.

These fillers can be used alone or in combination of two or more. When blending the (i) polyolefin resin and (ii) a filler with the α-olefin / conjugated diene copolymer according to the present invention, when the total amount of the obtained composition is 100 parts by weight, α-olefin The olefin / conjugated diene copolymer is 10 to 90 parts by weight, preferably 15 to 80 parts by weight, and more preferably 20 to 7 parts by weight.
Desirably, it is contained in an amount of 5 parts by weight.

When the α-olefin / conjugated diene copolymer is used in an amount within the above range, impact resistance, weather resistance,
An α-olefin / conjugated diene-based copolymer composition having excellent moldability and capable of providing a molded article having excellent heat stability and excellent rigidity, strength and heat resistance can be obtained.

(I) The polyolefin resin is used in an amount of 1 to 99 parts by weight, preferably 10 to 85 parts by weight, more preferably 2 to 100 parts by weight, when the total amount of the obtained composition is 100 parts by weight.
Desirably, it is contained in an amount of 0 to 80 parts by weight.

(I) When the polyolefin resin is used in an amount within the above range, it is excellent in impact resistance and cold resistance, and is excellent in rigidity, strength, heat resistance and moldability. A united composition is obtained.

(Ii) The filler is desirably contained in an amount of 0 to 40 parts by weight, preferably 0 to 30 parts by weight, when the total amount of the obtained composition is 100 parts by weight. . When (ii) the filler is used in such an amount, a composition excellent in rigidity, surface appearance, heat resistance and the like can be obtained.

The α-olefin / conjugated diene copolymer according to the present invention may further include a nucleating agent, an antioxidant, a hydrochloric acid absorber, a heat stabilizer, and a light stabilizer as long as the object of the present invention is not impaired. , UV absorbers, lubricants, antistatic agents, flame retardants, pigments, dyes, dispersants, copper damage inhibitors, neutralizing agents, foaming agents, plasticizers, foam inhibitors, crosslinking agents, crosslinking aids, crosslinking accelerators Further, additives such as a flow improver such as a peroxide, a weld strength improver, a processing aid, a weather resistance stabilizer, and a blooming inhibitor may be added. These optional additives may be used in combination of two or more.

[0363]

The catalyst for olefin polymerization according to the present invention comprises:
Has high polymerization activity for olefins.

According to the olefin polymerization method of the present invention, an olefin (co) polymer having a high polymerization activity and a narrow molecular weight distribution can be produced. Further, when the α-olefin and the conjugated diene are copolymerized, a copolymer having no 1,2-cyclopentane skeleton in the polymer chain can be produced.

The novel transition metal compound according to the present invention is useful as a catalyst for olefin polymerization, and provides an olefin (co) polymer having a high polymerization activity and a narrow molecular weight distribution. The α-olefin / conjugated diene copolymer according to the present invention has a narrow molecular weight distribution and almost no cyclopentane skeleton in the polymer chain.

[0366]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited to these Examples.

The structure of the compound obtained in the synthesis example is 27
0MHz ¹ H-NMR (JEOL GSH-270), FT-IR (SHIMAZU FTIR)
-8200D), FD-Mass spectrometry (JEOL SX-102A), Metal content analysis (Dry incineration, dissolving in diluted nitric acid, analysis by ICP method; SHI
MAZU ICPS-8000), carbon, hydrogen, and nitrogen content analysis (Helaus CHNO type) and the like.

The structures of Compound A-1 and Compound B-1 obtained in Synthesis Examples 1 and 2 were further determined by X-ray crystal structure analysis. The measurement was performed by Mo-Kα irradiation using a Rigaku AFC7R four-axis diffractometer. The direct analysis (SIR92) was used for the structural analysis, and the structural optimization was performed using the TeXan crystal structure analysis program.

In this example, the limiting viscosity [η]
Was measured in 135 ° C decalin. Molecular weight distribution (Mw
/ Mn) is 140 using o-dichlorobenzene as a solvent.
It measured and measured by gel permeation chromatography (GPC) in ° C.

Specific examples of the synthesis of ligands are shown below.

[0371]

[Synthesis example 1 of ligand ] Synthesis of ligand (L1) 40 ml of ethanol was placed in a 100 ml reactor which was sufficiently purged with nitrogen.
0.71 g (7.62 mmol) of aniline and 1.35 g (7.58 mmol) of 3-t-butylsalicylaldehyde were charged, and stirring was continued at room temperature for 24 hours. The reaction solution was concentrated under reduced pressure to remove the solvent, ethanol (40 ml) was added again, and stirring was continued at room temperature for 12 hours. The reaction solution was concentrated under reduced pressure to obtain 1.83 g (7.23 mmol, yield 95%) of an orange oil compound represented by L1.

[0372]

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¹ H-NMR (CDCl ₃ ): 1.47 (s, 9H) 6.88 (dd, 1H)
7.24-7.31 (m, 4H) 7.38-7.46 (m, 3H) 8.64 (s, 1H) 13.95
(s, 1H) IR (neat): 1575, 1590, 1610 cm ^-1 FD-Mass spectrometry: 253

[0374]

[Ligand synthesis example 2] Synthesis of ligand (L2) 30 ml of ethanol was placed in a 100 ml reactor which was sufficiently purged with nitrogen.
After charging 1.43 g (9.99 mmol) of α-naphthylamine and 1.40 g (7.86 mmol) of 3-t-butylsalicylaldehyde, adding 5 g of molecular sieves 3A, the mixture was stirred under reflux for 8 hours, and further stirred at room temperature for 12 hours. Continued. The reaction solution was concentrated under reduced pressure and purified by a silica gel column to obtain 2.35 g (7.75 mmol, yield 98%) of an orange oil compound represented by L2.

[0375]

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¹ H-NMR (CDCl ₃ ): 1.50 (s, 9H) 6.90-7.90 (m, 1
1H) 8.30-8.50 (m, 1H) 13.90 (s, 1H) FD-Mass spectrometry: 303

[0377]

[Ligand Synthesis Example 3] Synthesis of Ligand (L3) 30 ml of ethanol was placed in a 100 ml reactor sufficiently purged with nitrogen.
0.90 g (12.0 mmol) of t-butylamine and 1.78 g (10.0 mmol) of 3-t-butylsalicylaldehyde were charged, and 5 g of Molecular Sieves 3A was added, followed by stirring at room temperature for 12 hours. The reaction solution was concentrated under reduced pressure, and purified by a silica gel column to give a compound of a fluorescent yellow oil represented by L3.
2.17 g (9.3 mmol, 93% yield) was obtained.

[0378]

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¹ H-NMR (CDCl ₃ ): 1.20 (s, 9H) 1.42 (s, 9H)
6.50-7.50 (m, 3H) 8.38 (s, 1H) 13.80 (s, 1H) FD-Mass spectrometry: 233

[0380]

[Ligand synthesis examples 4 to 42] The following ligands L4 to L42 were synthesized in the same manner as in the above ligand synthesis examples. The structure was identified by ¹ H-NMR and FD-mass spectrometry.

[0381]

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[0382]

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[0383]

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Hereinafter, specific synthetic examples of the transition metal compound according to the present invention will be described.

[0385]

[Synthesis Example 1] Synthesis of compound A-1 : 1.785 g (7.05 g) of compound L1 was placed in a 300 ml reactor which had been thoroughly dried and purged with argon.
mmol) and 100 ml of diethyl ether, cooled to -78 ° C, and stirred. 4.78 ml of n-butyl lithium (1.55 mm
ol / ml n-hexane solution, 7.40 mmol) was added dropwise over 5 minutes, then the temperature was slowly raised to room temperature, and stirring was continued at room temperature for 4 hours to prepare a lithium salt solution. Add this solution to -7
The mixture was gradually dropped into a mixed solution of 7.05 ml of a titanium tetrachloride solution (0.5 mmol / ml heptane solution, 3.53 mmol) and 40 ml of diethyl ether cooled to 8 ° C.

[0386] After the completion of the dropwise addition, stirring was continued while the temperature was slowly raised to room temperature. After further stirring at room temperature for 8 hours, the reaction solution was filtered with a glass filter, and the obtained solid was dissolved and washed with 50 ml of methylene chloride to remove insolubles. The filtrate was concentrated under reduced pressure.
and pentane (70 ml) was added slowly with stirring. The mixture was allowed to stand at room temperature to precipitate reddish brown crystals. The crystals were collected by filtration with a glass filter, washed with pentane, and dried under reduced pressure to obtain 1.34 g (2.15 mmol, 61%) of compound A-1 as red-brown crystals represented by the following formula.

[0387]

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¹ H-NMR (CDCl ₃ ): 1.35 (s, 18H) 6.82-7.43
(m, 16H) 8.07 (s, 2H) IR (KBr): 1550, 1590, 1600 cm ^-1 FD-Mass Spectrometry: 622 (M +) Elemental Analysis: Ti; 7.7% (7.7) C; 65.8% (65.5) H; 6.0% (5.8) N; 4.5% (4.5) (): Calculated values Melting point: 265 ° C. X-ray crystal structure analysis: FIG. 3 shows the structure of the obtained compound A-1.

[0389]

[Synthesis Example 2] Synthesis of compound B-1 : 1.53 g (6.04 mmol) of compound L1 was placed in a 200 ml reactor sufficiently dried and purged with argon.
l) and 60 ml of tetrahydrofuran were charged, cooled to -78 ° C and stirred. 4.1 ml of n-butyl lithium (1.55 mmol / ml
An n-hexane solution, 6.34 mmol) was added dropwise over 5 minutes, and then the temperature was slowly raised to room temperature, followed by stirring at room temperature for 4 hours. A mixture of 10 ml of tetrahydrofuran and 0.70 g of zirconium tetrachloride cooled to -78 ° C (purity
(99.9% product, 3.02 mmol) in 30 ml of tetrahydrofuran. After the addition, the temperature was slowly raised to room temperature.
After stirring at room temperature for 2 hours, stirring was continued for 4 hours under reflux.

This reaction solution was concentrated under reduced pressure, and the precipitated solid was washed with 50 ml of methylene chloride, and insolubles were removed with a glass filter. The filtrate was concentrated under reduced pressure, the precipitated solid was dissolved in 30 ml of diethyl ether, and the mixture was allowed to stand at −20 ° C. under nitrogen for 1 day to precipitate yellow crystals. The solid was separated by filtration, washed with hexane, and dried under reduced pressure to give 1.09 g (1.63 mmol, yield 5) of compound B-1 as a fluorescent yellow crystal represented by the following formula.
4%).

[0391]

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¹ H-NMR (CDCl ₃ ): 1.33 (s, 18H) 6.78-7.42
(m, 16H) 8.12 (s, 2H) IR (KBr): 1550, 1590, 1605 cm ^-1 FD-Mass spectrometry: 664 (M +) Elemental analysis: Zr; 13.5% (13.7) C; 61.0% (61.2) H; 5.5% (5.4) N; 4.2% (4.2) (): Calculated values Melting point: 287 ° C. X-ray crystallography: The structure of the obtained compound B-1 is shown in FIG.

[0393]

[Synthesis Example 3] Synthesis of compound C-1 : Compound L1; 0.66 g (2.60 mmol
l) and 8 ml of diethyl ether were charged, cooled to -78 ° C and stirred. 1.81 ml of n-butyl lithium (1.55 mmol / ml n-
(Hexane solution, 2.80 mmol) was added dropwise over 5 minutes, then the temperature was slowly raised to room temperature, and the mixture was further stirred at room temperature for 2 hours. A mixed solution of 10 ml of tetrahydrofuran and 0.385 g of hafnium tetrachloride cooled to −78 ° C. (purity 99.9
% Product, 3.02 mmol) was slowly added to a 10 ml solution of tetrahydrofuran. After the addition, the temperature was slowly raised to room temperature. After stirring at room temperature for 2 hours, stirring was continued for another 2 hours while heating at 50 ° C.

The reaction solution was concentrated under reduced pressure, and the precipitated solid was washed with 20 ml of methylene chloride, and insolubles were removed with a glass filter. The filtrate was concentrated under reduced pressure, and the precipitated solid was reslurried in 10 ml of diethyl ether at room temperature for 1 hour, and the solid was separated by filtration. The solid was washed with hexane and dried under reduced pressure to give a fluorescent white compound C-1 represented by the following formula.
33 g (0.40 mmol, yield 33%) were obtained.

[0395]

Embedded image

¹ H-NMR (CDCl ₃ ): 1.30 (s, 18H) 6.70-7.50
(m, 16H) 8.18 (s, 2H) FD-Mass Spectroscopy: 754 (M +) Elemental Analysis: Hf; 23.5% (23.7) C; 54.4% (54.2) H; 4.8% (4.8) N; 3.6% (3.7 ) Calculations in parentheses are calculated values. Melting point: 277 ℃

[0397]

Synthesis Example 4 Synthesis of Compound D-1 : Compound L1; 0.61 g (2.40 mmol) was placed in a 100 ml reactor which was sufficiently dried and purged with argon.
l) and 10 ml of diethyl ether were charged, cooled to -78 ° C and stirred. 1.61 ml of n-butyl lithium (1.55 mmol / ml
An n-hexane solution (2.50 mmol) was added dropwise over 5 minutes, and then the temperature was slowly raised to room temperature, followed by stirring at room temperature for 4 hours. 0.385 g of hafnium tetrachloride cooled to -78 ° C (purity 9
(9.9% product, 3.02 mmol) was slowly added to a solution of 10 ml of anhydrous diethyl ether. After the addition, slowly raise the temperature to room temperature,
Stirring was further continued at room temperature for 4 hours.

After the reaction solution was concentrated under reduced pressure, the precipitated solid was washed with 20 ml of methylene chloride and insolubles were removed with a glass filter. The filtrate was concentrated under reduced pressure, and the precipitated solid was dissolved in 1 ml of diethyl ether. Then, 10 ml of hexane was slowly added to this solution with stirring, whereby a black-green solid precipitated. The solid was filtered off, washed with hexane for 1 hour at room temperature, and then dried under reduced pressure to obtain 0.55 g (0.88 mmol, yield 733) of a dark blue powdered compound D-1 represented by the following formula.
%)Obtained.

[0399]

Embedded image

¹ H-NMR (CDCl ₃ ): (cannot be measured due to paramagnetic metal complex) FD-mass spectrometry: 625 (M +) Elemental analysis: V; 8.4% (8.1) C; 65.3% (65.2) H; 5.5% (5.8) N; 4.5% (4.8) () is calculated value

[0401]

[Synthesis Example 5] Synthesis of Compound E-1 : Compound L1; 0.61 g (2.40 mmol
l) and 10 ml of diethyl ether were charged, cooled to -78 ° C and stirred. Add 1.60 ml of n-butyl lithium (1.55 mmol / ml
An n-hexane solution (2.50 mmol) was added dropwise over 5 minutes, and then the temperature was slowly raised to room temperature, followed by stirring at room temperature for 4 hours. A mixed solution obtained by adding 5 ml of tetrahydrofuran to this was cooled to −78 ° C. and 0.34 g of niobium pentachloride (purity 95%, 1.
(20 mmol) in 10 ml of tetrahydrofuran. After the addition, the temperature was slowly raised to room temperature, and then stirring was continued at room temperature for 15 hours.

The reaction solution was concentrated under reduced pressure, and the precipitated solid was washed with 20 ml of methylene chloride, and insolubles were removed with a glass filter. The filtrate was concentrated under reduced pressure, and the precipitated solid was dissolved in 3 ml of diethyl ether. 12 ml of hexane was slowly dropped into this solution at room temperature with stirring, and a black solid precipitated. This solid was separated by filtration, washed with hexane for 1 hour at room temperature, and dried under reduced pressure to obtain 0.36 g (0.51 mmol, yield 43%) of a fluorescent white compound E-1 represented by the following formula. .

[0403]

Embedded image

¹ H-NMR (CDCl ₃ ): 1.46 (s, 18H) 7.20-7.50
(m, 16H) 8.65 (s, 2H) FD-Mass Spectroscopy: 702 (M +) Elemental Analysis: Nb; 13.0% (13.2) C; 58.4% (58.0) H; 5.0% (5.2) N; 3.9% (4.0 ) () Is the calculated value

[0405]

Synthesis Example 6 Synthesis of Compound F-1 : Compound L1; 0.61 g (2.40 mmo) was placed in a 100 ml reactor which had been thoroughly dried and purged with argon.
l) and 10 ml of toluene were charged, cooled to −40 ° C., and stirred.
0.43 g of tantalum pentachloride (purity 99.99%, 1.20 mmol)
Was added slowly as a solid. After the addition, the temperature was slowly raised to room temperature, and then further heated to 60 ° C., and stirring was continued for 16 hours.

[0406] To this reaction solution was added 30 ml of methylene chloride, and the insoluble matter was filtered. The filtrate was concentrated under reduced pressure.
Upon addition of 8 ml, an orange viscous oil separated. The oil was separated and dissolved in 1 ml of diethyl ether.
9 ml of hexane was slowly added dropwise while stirring the solution, and a bright yellow solid precipitated. This solid was separated by filtration, washed with hexane for 1 hour at room temperature, and dried under reduced pressure to obtain a compound of the following formula.
g (0.26 mmol, yield 22%) was obtained.

[0407]

Embedded image

¹ H-NMR (CDCl ₃ ): 1.50 (s, 9H) 6.80-7.75 (m,
8H) 8.23 (s, 1H) FD-Mass Spectrometry: 575 (M +) Elemental Analysis: Ta; 31.0% (31.5) C; 58.4% (58.0) H; 3,3% (3.2) N; 4.5% (4.8) Figures in parentheses are calculated values

[0409]

[Synthesis Example 7] Synthesis of compound A-2 : Compound L2; 0.91 g (3.0 mm
ol) and 20 ml of diethyl ether, cooled to -78 ° C,
Stirred. 1.90 ml of n-butyl lithium (1.54 mmol / m
(In-hexane solution, 3.3 mmol) was added dropwise over 5 minutes, then the temperature was slowly raised to room temperature, and stirring was continued at room temperature for 4 hours to prepare a lithium salt solution. After cooling this solution to −78 ° C., it was gradually added dropwise to a mixture of 3.0 ml of titanium tetrachloride solution (0.5 mmol / ml heptane solution, 1.50 mmol) and 10 ml of diethyl ether. After completion of the dropwise addition, stirring was continued while slowly raising the temperature to room temperature. After further stirring at room temperature for 8 hours,
This reaction solution was filtered with a glass filter. The obtained solid was dissolved and washed with 50 ml of methylene chloride, and insolubles were removed by filtration. The filtrate was concentrated under reduced pressure, and the precipitated solid was reprecipitated with diethyl ether and hexane, and dried under reduced pressure to obtain 0.53 g of compound A-2 of brown crystals represented by the following formula.
(0.73 mmol yield 49%) was obtained.

[0410]

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¹ H-NMR (CDCl ₃ ): 0.86 (s, 18H) 6.85-7.05 (m,
6H) 7.15-7.30 (m, 4H) 7.35-7.90 (m, 10H) 8.45 (s, 2H) FD-Mass Spectrometry: 722 (M +) Elemental Analysis: Ti; 6.6% (6.6) C; 69.9% (69.7) H; 5.5% (5.6) N; 3.4% (3.9) () is calculated value

[0412]

[Synthesis Example 8] Synthesis of compound B-2 : 0.91 g (3.0 mm) of compound L2 was placed in a 100 ml reactor which had been thoroughly dried and purged with argon.
ol) and 20 ml of diethyl ether, cooled to -78 ° C,
Stirred. 1.94 ml of n-butyl lithium (1.55 mmol / m
(n-hexane solution, 3.0 mmol) was added dropwise over 5 minutes, then the temperature was slowly raised to room temperature, and stirring was continued at room temperature for 4 hours to prepare a lithium salt solution. This solution was gradually added dropwise to a solution of zirconium tetrachloride (0.35 g, 1.50 mmol) in 10 ml of tetrahydrofuran cooled to -78 ° C. After completion of the dropwise addition, stirring was continued while slowly raising the temperature to room temperature. After further stirring at room temperature for 8 hours, the reaction solution was concentrated to dryness, and the solid was dissolved and washed with 50 ml of methylene chloride, and insolubles were removed by filtration. The filtrate was concentrated under reduced pressure, and the precipitated solid was reprecipitated with diethyl ether and hexane, and dried under reduced pressure to give a yellow crystalline compound B-2 represented by the following formula.
0.21 g (0.73 mmol, 18% yield) was obtained.

[0413]

Embedded image

¹ H-NMR (CDCl ₃ ): 1.11-1.70 (m, 18H) 6.80-8.
30 (m, 20H) 8.33-8.48 (m, 2H) FD-Mass spectrometry: 766 (M +) Elemental analysis: Zr; 12.1% (11.9)
Figures in parentheses are calculated values

[0415]

[Synthesis Example 9] Synthesis of compound A-3 : 0.70 g (3.0 mm
ol) and 30 ml of diethyl ether, cooled to -78 ° C,
Stirred. 1.90 ml of n-butyl lithium (1.54 mmol / m
(In-hexane solution, 3.3 mmol) was added dropwise over 5 minutes, then the temperature was slowly raised to room temperature, and stirring was continued at room temperature for 4 hours to prepare a lithium salt solution. After the solution was cooled to −78 ° C., 3.0 ml of a titanium tetrachloride solution (0.5 mmol / ml heptane solution, 1.50 mmol) was gradually added dropwise. After completion of the dropwise addition, stirring was continued while slowly raising the temperature to room temperature. At room temperature
After stirring for 15 hours, the reaction solution was filtered with a glass filter. The obtained solid was dissolved and washed with 50 ml of methylene chloride, and insolubles were removed by filtration. The filtrate was concentrated under reduced pressure, the precipitated solid was reprecipitated with diethyl ether and hexane, and dried under reduced pressure to obtain 0.15 g (0.26 mmol, 17% yield) of a yellow-brown crystal compound A-3 represented by the following formula. Was.

[0416]

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¹ H-NMR (CDCl ₃ ): 1.20 (s, 18H) 1.41 (s, 18H)
6.85-7.05 (m, 2H) 7.20-7.80 (m, 4H) 8.58 (s, 2H) FD-Mass Spectrometry: 582 (M +) Elemental Analysis: Ti; 8.2% (8.2) C; 62.1% (61.8) H; 7.1% (7.6) N; 4.7% (4.8) () is calculated value

[0418]

Synthesis Example 10 Synthesis of compound B-3 : In a 100 ml reactor which was sufficiently dried and purged with argon, 0.70 g (3.0 g) of compound L3 was added.
mmol) in 30 ml of tetrahydrofuran, cooled to -78 ° C and stirred. Add 1.90ml of n-butyl lithium (1.54mm
ol / ml n-hexane solution, 3.3 mmol) was added dropwise over 5 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. The solution was cooled to −78 ° C. and zirconium tetrachloride (0.38 g, 1.65 mmol) was added as a solid. After completion of the addition, stirring was continued while the temperature was slowly raised to room temperature. After further stirring at room temperature for 15 hours, the reaction solution was evaporated, and the obtained solid was methylene chloride (50 ml).
, And insolubles were removed by filtration. The filtrate was concentrated under reduced pressure, the precipitated solid was reprecipitated with methylene chloride and hexane, and dried under reduced pressure to obtain 0.31 g (0.50 mmol, 30% yield) of a yellow powdered compound B-3 represented by the following formula. .

[0419]

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¹ H-NMR (CDCl ₃ ): 1.34 (s, 18H) 1.44 (s, 18H)
6.79 (dd, 2H) 7.11 (d, 2H) 7.27 (d, 2H) 8.34 (s, 2H) FD-Mass Spectroscopy: 626 (M +) Elemental Analysis: Zr; 15.0% (14.6) C; 52.9 (57.5) H ; 7.2 (7.1) N; 4.7 (4.8) () is calculated value

[0421]

Synthesis Example 11 Synthesis of Compound A-4 : In a 100 ml reactor which was thoroughly dried and purged with argon, compound L4;
2 mmol) and 30 ml of diethyl ether were charged, cooled to -78 ° C, and stirred. 1.36 ml of n-butyl lithium (1.54 mm
ol / ml n-hexane solution 2.09 mmol) was added dropwise over 5 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. The solution was cooled to −78 ° C., and 2.00 ml of a titanium tetrachloride solution (0.5 mmol / ml heptane solution, 1.00 mmol) was gradually added dropwise. After completion of the dropwise addition, stirring was continued while slowly raising the temperature to room temperature. After further stirring at room temperature for 8 hours, the reaction solution was filtered with a glass filter. The obtained solid was dissolved and washed with 50 ml of methylene chloride, and insolubles were removed by filtration. The filtrate was concentrated under reduced pressure, and the precipitated solid was reprecipitated with methylene chloride and hexane, and dried under reduced pressure to obtain 0.34 g (0.56 mmol, 56% yield) of compound A-4 as a dark brown powder represented by the following formula. Was.

[0422]

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¹ H-NMR (CDCl ₃ ): 7.00-7.90 (m, 22H) 8.35-
8.55 (m, 2H) FD-Mass spectrometry: 610 (M +) Elemental analysis: Ti; 7.8% (7.8) C; 62.4% (66.8) H; 4.9% (4.4) N; 4.2% (4.6) Calculated value

[0424]

Synthesis Example 12 Synthesis of Compound B-4 : 0.46 g (1.8%) of Compound L4 was placed in a 100 ml reactor which had been thoroughly dried and purged with argon.
6 mmol) and 30 ml of diethyl ether, cooled to -78 ° C, and stirred. Add 1.30 ml of n-butyl lithium (1.54 mm
ol / ml n-hexane solution, 2.00 mmol) was added dropwise over 5 minutes, then the temperature was slowly raised to room temperature, and stirring was continued at room temperature for 4 hours to prepare a lithium salt solution. Add this solution to -78
C., and zirconium tetrachloride (0.21 g, 0.91 mmol) was added as a solid. After completion of the addition, stirring was continued while the temperature was slowly raised to room temperature. After further stirring at room temperature for 16 hours, 20 ml of diethyl ether was added, and insolubles were removed with a glass filter. The obtained filtrate was concentrated under reduced pressure, and the precipitated solid was reprecipitated with diethyl ether and hexane, and dried under reduced pressure to obtain 0.25 g of a yellow-brown powdered compound B-4 represented by the following formula (0.38 mmol, 42% yield). )Obtained.

[0425]

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¹ H-NMR (CDCl ₃ ): 6.90-7.95 (m, 22H) 8.40-
8.60 (m, 2H) FD-Mass spectrometry: 652 (M +) Elemental analysis: Zr; 14.3% (13.9)
Figures in parentheses are calculated values

[0427]

[Synthesis Example 13] Synthesis of compound A-5 : 0.83 g (3.0
0 mmol) and 30 ml of diethyl ether, cooled to -78 ° C, and stirred. Add 2.00 ml of n-butyl lithium (1.54 mm
ol / ml n-hexane solution 3.08 mmol) was added dropwise over 5 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. This solution is heated to -78 ° C
The solution was gradually dropped into 3.00 ml of a titanium tetrachloride solution (0.5 mmol / ml heptane solution, 1.50 mmol) which had been cooled. 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 filtered with a glass filter. The filtrate was concentrated under reduced pressure, the precipitated solid was reprecipitated with methylene chloride and hexane, and dried under reduced pressure to obtain 0.07 g (0.10 mmol, 7% yield) of compound A-5 as an ocher powder represented by the following formula. .

[0428]

Embedded image

FD-mass spectrometry: 666 (M +) Elemental analysis: Ti; 7.3% (7.2)

[0430]

Synthesis Example 14 Synthesis of Compound B-5 : In a 100 ml reactor which was sufficiently dried and purged with argon, 0.50 g (1.8 g) of Compound L5 was added.
2 mmol) and 15 ml of tetrahydrofuran were charged, cooled to -78 ° C, and stirred. 1.36 ml of n-butyl lithium (1.54
mmol / ml n-hexane solution, 2.09 mmol) was added dropwise over 5 minutes, then the temperature was slowly raised to room temperature, and stirring was continued at room temperature for 4 hours to prepare a lithium salt solution. Add this solution to -78
C. and cooled to zirconium tetrachloride / 2THF complex (0.38
g, 1.00 mmol) in 10 ml of tetrahydrofuran was added dropwise. After completion of the dropwise addition, stirring was continued while slowly raising the temperature to room temperature. After further stirring at room temperature for 10 hours and at 50 ° C. for 4 hours, insoluble materials were removed with a glass filter. The obtained solution was concentrated under reduced pressure, and the precipitated solid was reprecipitated with methylene chloride, diethyl ether and hexane, and dried under reduced pressure to obtain a yellow powder powder compound B-5 represented by the following formula at a concentration of 0.04.
g (0.05 mmol yield 5%) was obtained.

[0431]

Embedded image

FD-Mass spectrometry: 710 (M +) Elemental analysis: Zr; 13.3% (12.8)
Figures in parentheses are calculated values

[0433]

Synthesis Example 15 Synthesis of Compound A-6 : In a 100 ml reactor which was thoroughly dried and purged with argon, was placed 0.93 g (3.0 g) of compound L6.
1 mmol) and 30 ml of diethyl ether, and the mixture was cooled to -78 ° C and stirred. Add 2.1 ml of n-butyl lithium (1.54 mmo
l / ml n-hexane solution (3.23 mmol) was added dropwise over 5 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. The solution was cooled to −78 ° C., and 3.0 ml of a titanium tetrachloride solution (0.5 mmol / ml heptane solution, 1.50 mmol) was gradually added dropwise. After completion of the dropwise addition, stirring was continued while slowly raising the temperature to room temperature. At room temperature
After stirring for 15 hours, the reaction solution was filtered with a glass filter. The filtrate was concentrated under reduced pressure, and the precipitated solid was recrystallized from hexane at -78 ° C and dried under reduced pressure to obtain 0.41 g (0.56 mmol, 37% yield) of brown powder Compound A-6 represented by the following formula.

[0434]

Embedded image

¹ H-NMR (CDCl ₃ ): 1.21 (s, 18H) 1.30 (s, 18H)
6.70-7.70 (m, 14H) 8.08 (s, 2H) FD-Mass Spectrometry: 734 (M +) Elemental Analysis: Ti; 6.6% (6.5) C; 67.9% (68.6) H; 7.4% (7.1) N; 3.9 % (3.8) () is calculated value

[0436]

Synthesis Example 16 Synthesis of Compound B-6 : In a 100 ml reactor which was sufficiently dried and purged with argon, compound L6; 0.93 g (3.0
1 mmol) and 30 ml of diethyl ether, and the mixture was cooled to -78 ° C and stirred. Add 2.1 ml of n-butyl lithium (1.54 mmo
l / ml n-hexane solution, 3.23 mmol) was added dropwise over 5 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. The solution was cooled to −78 ° C. and zirconium tetrachloride (0.35 g, 1.50 mmol) was added as a solid. After completion of the addition, stirring was continued while the temperature was slowly raised to room temperature. After further stirring at room temperature for 14 hours, 20 ml of methylene chloride was added, and insoluble materials were removed with a glass filter. The filtrate was concentrated under reduced pressure.
The crystals were recrystallized from hexane and dried under reduced pressure to obtain 0.55 g (0.71 mmol, 47% yield) of a yellow powdery compound B-6 represented by the following formula.

[0437]

Embedded image

¹ H-NMR (CDCl ₃ ): 1.20-1.80 (m, 36H) 6.70-
7.70 (m, 14H) 7.80-7.90 (m, 2H) FD-Mass spectrometry: 776 (M +) Elemental analysis: Zr; 11.2% (11.7)
Figures in parentheses are calculated values

[0439]

[Synthesis Example 17] Synthesis of compound A-7 : In a 100 ml reactor which was thoroughly dried and purged with argon, compound L7;
mmol) and 20 ml of diethyl ether, cooled to -78 ° C and stirred. 2.48 ml of n-butyl lithium (1.55 mmol / m
(In-hexane solution 3.84 mmol) was added dropwise over 5 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 gradually added dropwise to a mixture of 3.66 ml of a titanium tetrachloride solution (0.5 mmol / ml heptane solution, 1.83 mmol) cooled to −78 ° C. and 20 ml of diethyl ether. 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 filtered with a glass filter. The filtrate was concentrated under reduced pressure, and the precipitated solid was reslurried in hexane.
The compound was washed by filtering off hexane and dried under reduced pressure to give a brown powdered compound A-7 represented by the following formula.
0.95 g (1.43 mmol, 78% yield) was obtained.

[0440]

Embedded image

¹ H-NMR (CDCl ₃ ): 6.90-7.90 (m, 26H) 8.00
(s, 2H) FD-Mass spectrometry: 662 (M +) Elemental analysis: Ti; 6.5% (6.5) C; 62.0% (62.2) H; 3.7% (3.8) N; 3.8% (3.8) (Calculated in parentheses) value

[0442]

Synthesis Example 18 Synthesis of Compound B-7 : In a 100 ml reactor which had been thoroughly dried and purged with argon, compound L7; 1.0 g (3.66
mmol) and 20 ml of diethyl ether, cooled to -78 ° C and stirred. 2.48 ml of n-butyl lithium (1.55 mmol / m
(In-hexane solution, 3.84 mmol) was added dropwise over 5 minutes, then the temperature was slowly raised to room temperature, and stirring was continued at room temperature for 4 hours to prepare a lithium salt solution. This solution was added dropwise to a mixture of zirconium tetrachloride (0.41 g, 1.77 mmol) in 30 ml of diethyl ether cooled to -78 ° C. 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, 20 ml of methylene chloride was added, and insolubles were removed with a glass filter. The filtrate was concentrated under reduced pressure, the precipitated solid was reslurried in hexane, washed by filtering off hexane, and dried under reduced pressure to obtain 0.94 g of compound B-7 as a yellow-green powder represented by the following formula.
(1.33 mmol, 73% yield).

[0443]

Embedded image

¹ H-NMR (CDCl ₃ ): 7.00-7.90 (m, 26H) 8.20
(s, 2H) FD-Mass Spectroscopy: 704 (M +) Elemental Analysis: Zr; 11.5% (11.7)
Figures in parentheses are calculated values

[0445]

[Synthesis Example 19] Synthesis of compound A-8 : In a 100 ml reactor sufficiently dried and purged with argon, compound L8; 1.0 g (2.93
mmol) and 20 ml of diethyl ether, cooled to -78 ° C and stirred. 2.0 ml of n-butyl lithium (1.55 mmol / ml
An n-hexane solution (3.10 mmol) was added dropwise over 5 minutes, then the temperature was slowly raised to room temperature, and stirring was continued at room temperature for 4 hours to prepare a lithium salt solution. 2.9 ml of a titanium tetrachloride solution cooled to −78 ° C. (0.5 mmol / ml heptane solution,
1.45 mmol) and 20 ml of diethyl ether were gradually added dropwise. After completion of the dropwise addition, stirring was continued while slowly raising the temperature to room temperature. After further stirring at room temperature for 15 hours, the reaction solution was filtered with a glass filter. The filtrate was concentrated under reduced pressure, and the precipitated solid was reslurried in hexane. Then, the hexane was filtered off, washed and dried under reduced pressure to obtain 1.06 g (1.33m) of brown powdered compound A-8 represented by the following formula.
mol yield 91%).

[0446]

Embedded image

¹ H-NMR (CDCl ₃ ): 0.90-1.70 (m, 18H) 3.40-
3.80 (m, 4H) 7.00-7.70 (m, 20H) 7.80-8.20 (m, 2H) FD-Mass Spectrometry: 798 (M +) Elemental Analysis: Ti; 6.0% (6.0) ()

[0448]

[Synthesis Example 20] Synthesis of compound B-8 : In a 100 ml reactor sufficiently dried and purged with argon, compound L8;
mmol) and 20 ml of diethyl ether, cooled to -78 ° C and stirred. 2.0 ml of n-butyl lithium (1.55 mmol / ml
An n-hexane solution, 3.10 mmol) was added dropwise over 5 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 added dropwise to a mixture of zirconium tetrachloride (0.34 g, 1.44 mmol) in 20 ml of diethyl ether cooled to -78 ° C. After completion of the dropwise addition, stirring was continued while slowly raising the temperature to room temperature. After further stirring at room temperature for 8 hours, 20 ml of diethyl ether was added, and insolubles were removed with a glass filter. The filtrate is concentrated under reduced pressure, the precipitated solid is reslurried in hexane, and then the hexane is separated by filtration, washed and dried under reduced pressure to obtain a yellow-green powder compound represented by the following formula.
1.02 g (1.21 mmol, 83% yield) of B-8 was obtained.

[0449]

Embedded image

¹ H-NMR (CDCl ₃ ): 0.90-1.80 (m, 18H) 3.40-
3.90 (m, 4H) 6.40-7.90 (m, 20H) 8.00-8.30 (m, 2H) FD-Mass spectrometry: 842 (M +) Elemental analysis: Zr; 11.1% (10.8)
Figures in parentheses are calculated values

[0451]

Synthesis Example 21 Synthesis of Compound A-9 : In a 100 ml reactor which was thoroughly dried and purged with argon, 0.50 g (1.20 g) of Compound L9 was added.
3 mmol) and 15 ml of diethyl ether were charged, cooled to -78 ° C and stirred. 0.84 ml of n-butyl lithium (1.55 mmol
/ ml n-hexane solution 1.30 mmol) was added dropwise over 5 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 gradually added dropwise to a mixed solution of 1.2 ml of a titanium tetrachloride solution (0.5 mmol / ml heptane solution, 0.60 mmol) and 15 ml of diethyl ether cooled to -78 ° C. After completion of the dropwise addition, stirring was continued while slowly raising the temperature to room temperature. After further stirring at room temperature for 8 hours, the reaction solution was filtered with a glass filter. The filtrate is concentrated under reduced pressure, and the precipitated solid is reslurried in hexane, washed by filtering off hexane, and dried under reduced pressure to obtain a brown powder compound represented by the following formula.
0.39 g (0.36 mmol, 58% yield) of A-9 was obtained.

[0452]

Embedded image

¹ H-NMR (CDCl ₃ ): 1.70-1.90 (m, 18H) 6.60-
7.80 (m, 34H) FD-Mass spectrometry: 926 (M +) Elemental analysis: Ti; 5.3% (5.2) ()

[0454]

Synthesis Example 22 Synthesis of Compound B-9 : In a 100 ml reactor which was thoroughly dried and purged with argon, 0.50 g (1.20 g) of Compound L9 was added.
3 mmol) and 15 ml of diethyl ether were charged, cooled to -78 ° C and stirred. 0.84 ml of n-butyl lithium (1.55 mmol
/ ml n-hexane solution, 1.30 mmol) was added dropwise over 5 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. This solution is heated to -78 ° C
A cooled mixed solution of zirconium tetrachloride (0.14 g, 0.60 mmol) and diethyl ether (15 ml) was added dropwise. After completion of the dropwise addition, stirring was continued while slowly raising the temperature to room temperature. After further stirring at room temperature for 15 hours, the solvent was distilled off, and the obtained solid was dissolved in methylene chloride (50 ml) and diethyl ether (10 ml), and the insoluble matter was removed with a glass filter. The filtrate was concentrated under reduced pressure, and the precipitated solid was reslurried in hexane, washed by filtering off hexane, and dried under reduced pressure to give a pale yellow powder compound represented by the following formula.
0.19 g (0.20 mmol, 32% yield) of B-9 was obtained.

[0455]

Embedded image

¹ H-NMR (CDCl ₃ ): 1.28-1.52 (m, 18H) 6.70-
7.76 (m, 34H) FD-Mass Spectrometry: 970 (M +) Elemental Analysis: Zr; 9.6% (9.4)
Figures in parentheses are calculated values

[0457]

Synthesis Example 23 Synthesis of Compound A-10 : In a 100 ml reactor which was sufficiently dried and purged with argon, compound L10; 0.32 g (1.
03 mmol) and 10 ml of diethyl ether, and the mixture was cooled to -78 ° C and stirred. 0.77 ml of n-butyl lithium (1.55 mmol
/ ml n-hexane solution 1.19 mmol) was added dropwise over 5 minutes, then the temperature was slowly raised to room temperature, and stirring was continued at room temperature for 4 hours to prepare a lithium salt solution. This solution was gradually added dropwise to a mixed solution of 1.0 ml of titanium tetrachloride solution (0.5 mmol / ml heptane solution, 0.50 mmol) and 10 ml of diethyl ether cooled to -78 ° C. 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,
This reaction solution was filtered with a glass filter. The filtrate was concentrated under reduced pressure, and the precipitated solid was reprecipitated with methylene chloride and hexane and dried under reduced pressure to obtain 0.16 g (0.22 mmol, 43%) of a brown powdered compound A-10 represented by the following formula. .

[0458]

Embedded image

¹ H-NMR (CDCl ₃ ): 0.40-0.90 (m, 30H) 6.60-
7.80 (m, 18H) FD-mass spectrometry: 739 (M +) Elemental analysis: Ti; 5.3% (5.2) ()

[0460]

Synthesis Example 24 Synthesis of Compound A-11 : In a 100 ml reactor which was thoroughly dried and purged with argon, 0.68 g of Compound L11 (2.
40 mmol) and 30 ml of diethyl ether were charged, cooled to -78 ° C and stirred. 1.49 ml of n-butyl lithium (1.61 mmol
/ ml n-hexane solution (2.40 mmol) was added dropwise over 5 minutes, then the temperature was slowly raised to room temperature, and stirring was continued at room temperature for 4 hours to prepare a lithium salt solution. This solution was gradually added dropwise to a mixture of 2.4 ml of a titanium tetrachloride solution (0.5 mmol / ml heptane solution, 1.20 mmol) and 15 ml of diethyl ether cooled to −78 ° C. 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 this reaction solution was distilled off, and the precipitated solid was methylene chloride.
It was dissolved in 50 ml, and the insoluble matter was filtered with a glass filter.
The filtrate was concentrated under reduced pressure, and the precipitated solid was reprecipitated with methylene chloride and hexane at 0 ° C. and dried under reduced pressure to obtain 0.37 g (0.54 mmol, 45% yield) of compound A-11 as a reddish brown powder.

[0461]

Embedded image

¹ H-NMR (CDCl ₃ ): 1.20-1.40 (m, 9H) 1.50-1.
55 (m, 9H) 3.70-3.85 (m, 6H) 6.52-7.40 (m, 14H) 8.05-8.20 (m, 2H) FD-Mass spectrometry: 682 (M +) Elemental analysis: Ti; 7.0% (7.0) ( Figures in parentheses are calculated values

[0463]

Synthesis Example 25 Synthesis of Compound B-11 : In a 100 ml reactor which was thoroughly dried and purged with argon, 0.64 g of Compound L11 (2.
26 mmol) and 20 ml of diethyl ether were charged, cooled to -78 ° C and stirred. 1.40 ml of n-butyl lithium (1.61 mmol
/ ml n-hexane solution, 2.26 mmol) was added dropwise over 5 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. This solution is heated to -78 ° C
Zirconium tetrachloride / 2THF (0.42 g, 1.10
(mmol) in 20 ml of tetrahydrofuran. 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. Dissolve the resulting solid in 50 ml of methylene chloride,
The insoluble matter was removed with a glass filter. The filtrate was concentrated under reduced pressure, and the precipitated solid was reprecipitated with methylene chloride and hexane and dried under reduced pressure to obtain 0.25 g (0.34 mmol, 31% yield) of a yellow-green powdered compound B-11 represented by the following formula. Was.

[0464]

Embedded image

¹ H-NMR (CDCl ₃ ): 1.20-1.60 (m, 18H) 3.66-
3.86 (m, 6H) 6.50-7.50 (m, 14H) 8.05-8.20 (m, 2H) FD-Mass spectrometry: 726 (M +) Elemental analysis: Zr; 12.4% (12.6)
Figures in parentheses are calculated values

[0466]

Synthesis Example 26 Synthesis of Compound A-12 : In a 100 ml reactor which was sufficiently dried and purged with argon, compound L12;
1 mmol) and 20 ml of diethyl ether were charged, cooled to -78 ° C and stirred. 1.56 ml of n-butyl lithium (1.55 mmol
/ ml n-hexane solution (2.42 mmol) was added dropwise over 5 minutes, then the temperature was slowly raised to room temperature, and stirring was continued at room temperature for 4 hours to prepare a lithium salt solution. This solution was gradually added dropwise to a mixed solution of 2.3 ml of a titanium tetrachloride solution (0.5 mmol / ml heptane solution, 1.15 mmol) and 20 ml of diethyl ether cooled to −78 ° C. 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, insolubles were filtered with a glass filter. The filtrate was concentrated under reduced pressure, and the precipitated solid was reslurried in hexane. The hexane was filtered off, washed and dried under reduced pressure to obtain 0.45 g of compound A-12 as a reddish brown powder (0.45 mmol yield: 40%). )Obtained.

[0467]

Embedded image

¹ H-NMR (CDCl ₃ ): 1.30-2.20 (m, 24H) 6.20-
7.40 (m, 34H) 7.50-7.70 (m, 2H) FD-Mass spectrometry: 982 (M +) Elemental analysis: Ti; 5.0% (4.9)

[0469]

Synthesis Example 27 Synthesis of compound B-12 : In a 100 ml reactor which was sufficiently dried and purged with argon, compound L12;
1 mmol) and 20 ml of diethyl ether were charged, cooled to -78 ° C and stirred. 1.56 ml of n-butyl lithium (1.55 mmol
/ ml n-hexane solution, 2.42 mmol) was added dropwise over 5 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. This solution is heated to -78 ° C
The mixture was slowly added dropwise to a cooled mixture of zirconium tetrachloride (0.27 g, 1.15 mmol) and diethyl ether (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 insolubles were removed with a glass filter. The filtrate was concentrated under reduced pressure, and the precipitated solid was reprecipitated with diethyl ether, hexane, heptane, and pentane, washed with reslurry, and dried under reduced pressure to obtain 0.02 g of a compound B-12 as a yellow-green powder represented by the following formula.
(0.02 mmol yield 1%) was obtained.

[0470]

Embedded image

¹ H-NMR (CDCl ₃ ): 1.20-2.10 (m, 24H) 6.20-
7.40 (m, 34H) 7.50-8.00 (m, 2H) FD-Mass spectrometry: 1026 (M +) Elemental analysis: Zr; 9.1% (8.9)
Figures in parentheses are calculated values

[0472]

Synthesis Example 28 Synthesis of Compound A-13 : 1.10 g of Compound L13 (3.
26 mmol) and 22 ml of diethyl ether were charged, cooled to -78 ° C and stirred. 2.2 ml of n-butyl lithium (1.55 mmol /
ml n-hexane solution (3.41 mmol) was added dropwise over 5 minutes, then the temperature was slowly raised to room temperature, and stirring was continued at room temperature for 4 hours to prepare a lithium salt solution. This solution was gradually added dropwise to a mixture of 3.26 ml of a titanium tetrachloride solution (0.5 mmol / ml heptane solution, 1.13 mmol) and 22 ml of diethyl ether cooled to −78 ° C. 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 insoluble material of the reaction solution was filtered with a glass filter. The filtrate was concentrated under reduced pressure, and the precipitated solid was reprecipitated with diethyl ether and pentane, and dried under reduced pressure to obtain 0.22 g (0.28 mmol, 17% yield) of compound A-13 as a reddish brown powder.

[0473]

Embedded image

¹ H-NMR (CDCl ₃ ): 0.60-2.41 (m, 44H) 6.70-
7.60 (m, 34H) 7.91-8.10 (m, 2H) FD-Mass spectrometry: 790 (M +) Elemental analysis: Ti; 6.3% (6.1) () is calculated value

[0475]

Synthesis Example 29 Synthesis of Compound B-13 : 1.03 g of Compound L13 (3.
02 mmol) and 20 ml of diethyl ether, cooled to −78 ° C., and stirred. 2.0 ml of n-butyl lithium (1.55 mmol /
ml n-hexane solution, 3.10 mmol) was added dropwise over 5 minutes, then the temperature was slowly raised to room temperature, and stirring was continued at room temperature for 4 hours to prepare a lithium salt solution. This solution was slowly added dropwise to a mixture of zirconium tetrachloride (0.35 g, 1.50 mmol) in 20 ml of diethyl ether cooled to -78 ° C. 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, insolubles were removed with a glass filter. The filtrate was concentrated under reduced pressure, and the precipitated solid was recrystallized from pentane and dried under reduced pressure to obtain 0.27 g (0.32 mmol, 21% yield) of a yellow-green powdered compound B-13 represented by the following formula.

[0476]

Embedded image

¹ H-NMR (CDCl ₃ ): 0.30-2.32 (m, 44H) 6.70-
7.60 (m, 14H) 7.90-8.20 (m, 2H) FD-Mass spectrometry: 834 (M +) Elemental analysis: Zr; 10.9% (10.9)
Figures in parentheses are calculated values

[0478]

Synthesis Example 30 Synthesis of Compound A-14 : 0.98 g of Compound L14 (2.
97 mmol) and 30 ml of diethyl ether were charged, cooled to -78 ° C and stirred. 2.0 ml of n-butyl lithium (1.61 mmol /
(3.22 mmol of n-hexane solution) was added dropwise over 5 minutes, then the temperature was slowly raised to room temperature, and stirring was continued at room temperature for 4 hours to prepare a lithium salt solution. This solution was gradually added dropwise to a mixture of 3.0 ml of titanium tetrachloride solution (0.5 mmol / ml heptane solution, 1.50 mmol) and 15 ml of diethyl ether cooled to -78 ° C. 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 insoluble portion of the reaction solution was filtered off, and the residue was filtered with diethyl ether 30
The residue was dissolved in 50 ml of methylene chloride and 50 ml of methylene chloride, and the insoluble matter was filtered with a glass filter. The filtrate was concentrated under reduced pressure, and the precipitated solid was recrystallized from diethyl ether and dried under reduced pressure to obtain 0.66 g of a black-brown powder of Compound A-14 (0.85 mmol, yield 57%).
Obtained.

[0479]

Embedded image

¹ H-NMR (CDCl ₃ ): 1.41 (s, 18H) 6.70-7.90
(m, 24H) 8.18 (s, 2H) FD-Mass spectrometry: 774 (M +) Elemental analysis: Ti; 6.2% (6.2)

[0481]

Synthesis Example 31 Synthesis of Compound B-14 : In a 100 ml reactor that was sufficiently dried and purged with argon, 1.01 g of Compound L14 (3.
05 mmol) and 20 ml of diethyl ether, cooled to -78 ° C and stirred. 2.0 ml of n-butyl lithium (1.61 mmol /
ml n-hexane solution, 3.22 mmol) was added dropwise over 5 minutes, then the temperature was slowly raised to room temperature, and stirring was continued at room temperature for 4 hours to prepare a lithium salt solution. This solution was slowly added dropwise to a solution of zirconium tetrachloride (0.36 g, 1.52 mmol) in tetrahydrofuran cooled to -78 ° C. After dropping,
The stirring was continued while slowly raising the temperature to room temperature. After further stirring at room temperature for 8 hours, the insoluble portion was removed with a glass filter. The filtrate was concentrated to dryness, the precipitated solid was reprecipitated with methylene chloride and hexane, and dried under reduced pressure to obtain 0.61 g (0.74m) of a fluorescent yellow powdered compound B-14 represented by the following formula.
mol yield 49%).

[0482]

Embedded image

¹ H-NMR (CDCl ₃ ): 1.41 (s, 18H) 6.80-7.90
(m, 24H) 8.24 (s, 2H) FD-Mass Spectrometry: 818 (M +) Elemental Analysis: Zr; 11.0% (11.1)
Figures in parentheses are calculated values

[0484]

Synthesis Example 32 Synthesis of Compound A-15 : In a 100 ml reactor which was sufficiently dried and purged with argon, 0.40 g of Compound L15 (1.
01 mmol) and 10 ml of diethyl ether, cooled to −78 ° C., and stirred. 0.77 ml of n-butyl lithium (1.55 mmol
/ ml n-hexane solution 1.19 mmol) was added dropwise over 5 minutes, then the temperature was slowly raised to room temperature, and stirring was continued at room temperature for 4 hours to prepare a lithium salt solution. This solution was gradually added dropwise to a mixture of 1.0 ml of titanium tetrachloride solution (0.5 mmol / ml heptane solution, 0.50 mmol) and 10 ml of diethyl ether cooled to -78 ° C. 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, insolubles were filtered with a glass filter. The filtrate was concentrated under reduced pressure.
0.19 g (0.21 mmol, yield 42%) was obtained.

[0485]

Embedded image

¹ H-NMR (CDCl ₃ ): 0.60-1.30 (m, 6H) 6.50-
7.80 (m, 36H) 7.80-7.90 (m, 2H) FD-Mass Spectrometry: 900 (M +) Elemental Analysis: Ti; 5.5% (5.3) () is calculated value

[0487]

Synthesis Example 33 Synthesis of Compound B-15 : In a 100 ml reactor which was sufficiently dried and purged with argon, 0.40 g of Compound L15 (1.
02 mmol) and 10 ml of tetrahydrofuran, and the mixture was cooled to -78 ° C and stirred. 0.77ml of n-butyl lithium (1.55mm
ol / ml n-hexane solution, 1.19 mmol) was added dropwise over 5 minutes, then the temperature was slowly raised to room temperature, and stirring was continued at room temperature for 4 hours to prepare a lithium salt solution. Add this solution to -78
After cooling to ° C., zirconium tetrachloride (0.12 g, 0.50 mmol) was added as a solid. After completion of the addition, stirring was continued while the temperature was slowly raised to room temperature. After further stirring at room temperature for 15 hours, the reaction solution was evaporated. The obtained solid was dissolved in 50 ml of methylene chloride, and the insoluble matter was removed with a glass filter. The filtrate was concentrated under reduced pressure, and the precipitated solid was reprecipitated with diethyl ether and hexane, and dried under reduced pressure to obtain 0.20 g of a compound B-15 as an off-white powder represented by the following formula.
(0.21 mmol yield 42%) was obtained.

[0488]

Embedded image

¹ H-NMR (CDCl ₃ ): 0.70-1.00 (m, 6H) 6.60-
7.60 (m, 36H) 7.70-7.80 (m, 2H) FD-Mass spectrometry: 944 (M +) Elemental analysis: Zr; 9.4% (9.6)
Figures in parentheses are calculated values

[0490]

Synthesis Example 34 Synthesis of compound A-16 : In a 100 ml reactor which was thoroughly dried and purged with argon, 1.0 g of compound L16 (4.7 g) was added.
3 mmol) and 20 ml of diethyl ether were charged, cooled to -78 ° C and stirred. 3.2 ml of n-butyl lithium (1.55 mmol /
(n-hexane solution 4.96 mmol) was added dropwise over 5 minutes, then the temperature was slowly raised to room temperature, and stirring was continued at room temperature for 4 hours to prepare a lithium salt solution. This solution was gradually added dropwise to a mixture of 4.7 ml of a titanium tetrachloride solution (0.5 mmol / ml heptane solution, 2.35 mmol) and 20 ml of diethyl ether cooled to -78 ° C. 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 filtered, and the residue was dissolved in 50 ml of methylene chloride.
After removing insolubles in the solution, the solution was concentrated under reduced pressure to precipitate a solid, which was reprecipitated with methylene chloride and hexane,
The compound A-16 as a light brown powder was dried by drying under reduced pressure to obtain a compound A.
96 g (1.78 mmol, 75% yield) were obtained.

[0490]

Embedded image

¹ H-NMR (CDCl ₃ ): 1.90 (s, 6H) 6.50-7.30
(m, 16H) 7.90 (s, 2H) FD-Mass spectrometry: 538 (M +) Elemental analysis: Ti; 9.0% (8.9) () is calculated value

[0493]

Synthesis Example 35 Synthesis of Compound B-16 : In a 100 ml reactor which was sufficiently dried and purged with argon, compound L16;
3 mmol) and 20 ml of diethyl ether were charged, cooled to -78 ° C and stirred. 3.2 ml of n-butyl lithium (1.55 mmol /
ml n-hexane solution, 4.96 mmol) was added dropwise over 5 minutes, then slowly heated to room temperature, and stirred at room temperature for 4 hours to prepare a lithium salt solution. This solution was added dropwise to a mixture of zirconium tetrachloride (0.55 g, 2.36 mmol) and 20 ml of diethyl ether cooled to -78 ° C. 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 filtered. The solvent from the filtrate was distilled off to precipitate a solid, which was recrystallized with diethyl ether, methylene chloride and hexane, and dried under reduced pressure to obtain 0.49 g of a compound B-16 as a yellow-green powder represented by the following formula.
(0.84 mmol yield 36%) was obtained.

[0494]

Embedded image

¹ H-NMR (CDCl ₃ ): 2.00 (s, 6H) 6.40-7.40
(m, 16H) 8.10 (s, 2H) FD-Mass Spectrometry: 582 (M +) Elemental Analysis: Zr; 15.9% (15.7)
Figures in parentheses are calculated values

[0496]

Synthesis Example 36 Synthesis of Compound A-17 : Compound L17; 1.0 g (2.7 g)
7 mmol) and 20 ml of diethyl ether were charged, cooled to −78 ° C., and stirred. 1.87 ml of n-butyl lithium (1.55 mmol
/ ml n-hexane solution (2.90 mmol) was added dropwise over 5 minutes, then the temperature was slowly raised to room temperature, and stirring was continued at room temperature for 4 hours to prepare a lithium salt solution. This solution was gradually added dropwise to a mixture of 2.76 ml of a titanium tetrachloride solution (0.5 mmol / ml heptane solution, 1.38 mmol) and 20 ml of diethyl ether cooled to −78 ° C. 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, insolubles were filtered with a glass filter. The filtrate was concentrated under reduced pressure, and the precipitated solid was reslurried in hexane. The hexane was separated by filtration, washed, and dried under reduced pressure to obtain 0.15 g of a brown powder of Compound A-17 (0.18 mmol yield 1).
3%).

[0497]

Embedded image

¹ H-NMR (CDCl ₃ ): 3.20-3.80 (m, 4H) 6.90-
7.81 (m, 30H) 8.15 (s, 2H) FD-Mass spectrometry: 838 (M +) Elemental analysis: Ti; 5.9% (5.7)

[0499]

Synthesis Example 37 Synthesis of compound B-17 : In a 100 ml reactor which was sufficiently dried and purged with argon, compound L17; 1.0 g (2.7 g)
7 mmol) and 20 ml of diethyl ether were charged, cooled to −78 ° C., and stirred. 1.87 ml of n-butyl lithium (1.55 mmol
/ ml n-hexane solution, 2.90 mmol) was added dropwise over 5 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. This solution is heated to -78 ° C
Was added dropwise to a cooled mixture of zirconium tetrachloride (0.32 g, 1.37 mmol) and diethyl ether (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 filtered with a glass filter to remove insolubles. The filtrate was concentrated under reduced pressure, and the precipitated solid was reslurried in hexane. Then, the hexane was separated by filtration, washed, and dried under reduced pressure to obtain 0.71 g (0.88 g) of a yellow-green powder compound B-17 represented by the following formula. mmol yield 58
%)Obtained.

[0500]

Embedded image

¹ H-NMR (CDCl ₃ ): 3.30-3.80 (m, 4H) 6.71-
7.72 (m, 30H) 8.25 (s, 2H) FD-Mass spectrometry: 882 (M +) Elemental analysis: Zr; 10.6% (10.3)
Figures in parentheses are calculated values

[0502]

Synthesis Example 38 Synthesis of Compound A-18 : In a 100 ml reactor sufficiently dried and purged with argon, 0.59 g of compound L18 (2.
20 mmol) and 10 ml of diethyl ether were charged, cooled to -78 ° C and stirred. 1.49 ml of n-butyl lithium (1.55 mmol
/ ml n-hexane solution (2.31 mmol) was added dropwise over 5 minutes, then the temperature was slowly raised to room temperature, and stirring was continued at room temperature for 4 hours to prepare a lithium salt solution. This solution was gradually added dropwise to a mixture of 2.2 ml of a titanium tetrachloride solution (0.5 mmol / ml heptane solution, 1.10 mmol) and 10 ml of tetrahydrofuran cooled to −78 ° C. 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,
Concentrate to dryness and dissolve the resulting solid in 20 ml of methylene chloride. The insoluble material was filtered through a glass filter, the solution was concentrated under reduced pressure, and the precipitated solid was reprecipitated with diethyl ether and hexane at −78 ° C. and dried under reduced pressure to obtain 0.27 g (0.41 mmol yield) of brown powdered compound A-18. Rate 37%).

[0503]

Embedded image

¹ H-NMR (CDCl ₃ ): 1.22 (s, 18H) 2.40 (s, 6H)
6.44-7.80 (m, 14H) 8.21 (s, 2H) FD-Mass Spectrometry: 650 (M +) Elemental Analysis: Ti; 7.1% (7.4) () Calculated value

[0505]

Synthesis Example 39 Synthesis of compound B-18 : In a 100 ml reactor which was sufficiently dried and purged with argon, compound L18; 0.60 g (2.
25 mmol) and 10 ml of diethyl ether were charged, cooled to -78 ° C and stirred. 1.52 ml of n-butyl lithium (1.55 mmol
/ ml n-hexane solution, 2.36 mmol) was added dropwise over 5 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. This solution was added dropwise to a solution of zirconium tetrachloride (0.26 g, 1.12 mmol) in 10 ml of tetrahydrofuran cooled to −78 ° C. After completion of the dropwise addition, stirring was continued while slowly raising the temperature to room temperature. After further stirring at room temperature for 8 hours, the reaction solution was evaporated. The obtained solid was dissolved in 20 ml of methylene chloride, and insolubles were removed with a glass filter. The filtrate was concentrated under reduced pressure, the precipitated solid was reprecipitated with diethyl ether and hexane, and dried under reduced pressure to obtain a yellow-green powder compound B-18 represented by the following formula.
16 g (0.24 mmol, 21% yield) was obtained.

[0506]

Embedded image

¹ H-NMR (CDCl ₃ ): 1.13 (s, 18H) 2.39 (s, 6H)
6.50-7.75 (m, 14H) 8.26 (s, 2H) FD-Mass spectrometry: 694 (M +) Elemental analysis: Zr; 13.1% (13.1)
Figures in parentheses are calculated values

[0508]

Synthesis Example 40 Synthesis of compound B-19 : In a 100 ml reactor which was sufficiently dried and purged with argon, 0.70 g of compound L19 (2.
25 mmol) and 10 ml of diethyl ether were charged, cooled to -78 ° C and stirred. 1.52 ml of n-butyl lithium (1.55 mmol
/ ml n-hexane solution, 2.36 mmol) was added dropwise over 5 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. This solution was added dropwise to a solution of zirconium tetrachloride (0.26 g, 1.12 mmol) in 10 ml of tetrahydrofuran cooled to −78 ° C. 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 was distilled off from the reaction solution. The obtained solid was dissolved in 20 ml of methylene chloride, and insolubles were removed with a glass filter. The filtrate was concentrated under reduced pressure, and the precipitated solid was reprecipitated with diethyl ether and hexane, and dried under reduced pressure to give a yellow-green powder compound represented by the following formula.
0.16 g (0.20 mmol, 18% yield) of B-19 was obtained.

[0509]

Embedded image

¹ H-NMR (CDCl ₃ ): 1.43 (s, 18H) 1.47 (s, 18H)
6.90-7.60 (m, 14H) 8.40 (s, 2H) FD-Mass spectrometry: 778 (M +) Elemental analysis: Zr; 12.1% (11.7)
Figures in parentheses are calculated values

[0511]

Synthesis Example 41 Synthesis of Compound B-20 : In a 100 ml reactor which was thoroughly dried and purged with argon, 0.63 g of Compound L20 (2.
25 mmol) and 10 ml of diethyl ether were charged, cooled to -78 ° C and stirred. 1.52 ml of n-butyl lithium (1.55 mmol
/ ml n-hexane solution, 2.36 mmol) was added dropwise over 5 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. This solution was added dropwise to a solution of zirconium tetrachloride (0.26 g, 1.12 mmol) in 10 ml of tetrahydrofuran cooled to −78 ° C. After completion of the dropwise addition, stirring was continued while slowly raising the temperature to room temperature. After further stirring at room temperature for 15 hours, the reaction solution was evaporated. The obtained solid was dissolved in 25 ml of methylene chloride, and insolubles were removed with a glass filter. The filtrate was concentrated under reduced pressure, and the precipitated solid was reprecipitated with diethyl ether and hexane, and dried under reduced pressure to obtain a yellow powdered compound B-20 represented by the following formula by 0.35.
g (0.48 mmol, 43% yield) was obtained.

[0512]

Embedded image

¹ H-NMR (CDCl ₃ ): 1.40 (s, 18H) 1.50 (s, 18H)
2.21 (s, 12H) 6.70-7.40 (m, 12H) 8.33 (s, 2H) FD-Mass spectrometry: 720 (M +) Elemental analysis: Zr; 12.8% (12.6)
Figures in parentheses are calculated values

[0514]

Synthesis Example 42 Synthesis of Compound A-21 : 0.80 g of compound L21 (2.
50 mmol) and 10 ml of diethyl ether were charged, cooled to -78 ° C and stirred. 1.7 ml of n-butyl lithium (1.55 mmol /
ml n-hexane solution 2.64 mmol) was added dropwise over 5 minutes, then the temperature was slowly raised to 0 ° C, and stirring was continued at 0 ° C for 4 hours.
A lithium salt solution was prepared. This solution was gradually dropped into a mixture of 2.5 ml of a titanium tetrachloride solution (0.5 mmol / ml heptane solution, 1.25 mmol) and 10 ml of diethyl ether cooled to -78 ° C. After completion of the dropwise addition, stirring was continued while slowly raising the temperature to room temperature. After further stirring at room temperature for 8 hours, the mixture was concentrated to dryness, and the obtained solid was dissolved in 50 ml of diethyl ether and 60 ml of methylene chloride. After filtering the insoluble matter with a glass filter, the filtrate was concentrated under reduced pressure, and the precipitated solid was recrystallized from diethyl ether and dried under reduced pressure to obtain 0.07 g of a red-brown powder of Compound A-21 (0.09 mmol, yield 8%). )Obtained.

[0515]

Embedded image

¹ H-NMR (CDCl ₃ ): 1.34 (s, 18H) 6.75-7.75
(m, 14H) 8.10 (s, 2H) FD-Mass spectrometry: 758 (M +) Elemental analysis: Ti; 6.5% (6.3) ()

[0517]

Synthesis Example 43 Synthesis of Compound B-21 : In a 100 ml reactor which was sufficiently dried and purged with argon, 1.03 g of Compound L21 (3.
20 mmol) and 10 ml of diethyl ether were charged, cooled to -78 ° C and stirred. 2.0 ml of n-butyl lithium (1.61 mmol /
ml n-hexane solution, 3.22 mmol) was added dropwise over 5 minutes, then the temperature was slowly raised to -15 ° C, and stirring was continued at -15 ° C for 2 hours to prepare a lithium salt solution. This solution was added dropwise to a solution of zirconium tetrachloride (0.36 g, 1.54 mmol) in 10 ml of tetrahydrofuran cooled to -78 ° C. 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. This was dissolved in 20 ml of toluene, and the reaction was further continued for 3 hours under reflux conditions. The solvent was distilled off from the reaction solution, and the obtained solid was dissolved in 50 ml of methylene chloride, and the insoluble matter was removed with a glass filter. The filtrate was concentrated under reduced pressure, and the precipitated solid was reprecipitated with diethyl ether and hexane, and dried under reduced pressure to obtain 0.33 g (0.41 mmol) of compound B-21 as an ocher powder represented by the following formula.
l yield 27%).

[0518]

Embedded image

¹ H-NMR (CDCl ₃ ): 1.24 (s, 18H) 6.80-7.78
(m, 14H) 8.15 (s, 2H) FD-Mass spectrometry: 802 (M +) Elemental analysis: Zr; 11.7% (11.4)
Figures in parentheses are calculated values

[0520]

Synthesis Example 44 Synthesis of Compound A-22 : In a 100 ml reactor which was thoroughly dried and purged with argon, 0.50 g of Compound L22 (1.
77 mmol) and 40 ml of diethyl ether were charged, cooled to -78 ° C and stirred. 1.20 ml of n-butyl lithium (1.55 mmol
/ ml n-hexane solution 1.86 mmol) was added dropwise over 5 minutes, then the temperature was slowly raised to room temperature, and stirring was continued at room temperature for 4 hours to prepare a lithium salt solution. This solution was gradually added dropwise to a mixture of 1.77 ml (0.5 mmol / ml heptane solution, 0.89 mmol) of a titanium tetrachloride solution cooled to −78 ° C. and 50 ml of diethyl ether.

[0521] After completion of the dropwise addition, stirring was continued while the temperature was slowly raised to room temperature. After further stirring at room temperature for 15 hours, the reaction solution was filtered with a glass filter, and the residue was washed with diethyl ether and dissolved in methylene chloride. After removing insolubles in the solution, the solution was concentrated under reduced pressure, and the precipitated solid was reprecipitated with diethyl ether and hexane at -78 ° C, and dried under reduced pressure to obtain 0.31 g of compound A-22 as a brown powder.
(0.45 mmol, 51% yield) was obtained.

[0522]

Embedded image

¹ H-NMR (CDCl ₃ ): 0.70-1.80 (m, 18H) 3.50-
4.00 (m, 6H) 6.40-7.70 (m, 14H) 8.05 (s, 2H) FD-Mass Spectrometry: 682 (M +) Elemental Analysis: Ti; 7.3% (7.0) ()

[0524]

Synthesis Example 45 Synthesis of Compound B-22 : In a 100 ml reactor which was sufficiently dried and purged with argon, 0.50 g of Compound L22 (1.
77 mmol) and 25 ml of diethyl ether were charged, cooled to -78 ° C and stirred. 1.20 ml of n-butyl lithium (1.55 mmol
/ ml n-hexane solution, 1.86 mmol) was added dropwise over 5 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. This solution was added dropwise to a mixed solution of zirconium tetrachloride (0.21 g, 0.99 mmol) in 10 ml of diethyl ether and 60 ml of tetrahydrofuran cooled to -78 ° C. 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 reslurried with 70 ml of hexane, and insolubles were separated with a glass filter. The filter cake is dissolved in 100 ml of diethyl ether and 70 ml of hexane to remove insolubles in the solution, and the solution is concentrated under reduced pressure. The precipitated solid was washed with hexane and dried under reduced pressure to give a yellow-green powdered compound B-22 represented by the following formula.
0.08 g (0.11 mmol, 11% yield) was obtained.

[0525]

Embedded image

¹ H-NMR (CDCl ₃ ): 1.40 (s, 18H) 3.75 (s, 6H)
6.40-7.70 (m, 14H) 8.10 (s, 2H) FD-Mass Spectroscopy: 726 (M +) Elemental Analysis: Zr; 12.3% (12.6)
Figures in parentheses are calculated values

[0527]

Synthesis Example 46 Synthesis of Compound A-23 : Compound L23; 1.01 g (4.
33 mmol) and 22 ml of diethyl ether were charged, cooled to -78 ° C and stirred. 2.9 ml of n-butyl lithium (1.55 mmol /
ml n-hexane solution 4.50 mmol) was added dropwise over 5 minutes, then the temperature was slowly raised to room temperature, and stirring was continued at room temperature for 4 hours to prepare a lithium salt solution. This solution was gradually added dropwise to a mixture of 4.25 ml of a titanium tetrachloride solution (0.5 mmol / ml heptane solution, 2.13 mmol) and 20 ml of diethyl ether cooled to −78 ° C. 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 separated by filtration, and the filtrate was concentrated to dryness to obtain a solid. The resulting solid was reprecipitated with methylene chloride, diethyl ether and hexane and dried under reduced pressure to give a brown powdered compound.
0.26 g (0.44 mmol, 21% yield) of A-23 was obtained.

[0528]

Embedded image

¹ H-NMR (CDCl ₃ ): 0.82-1.40 (m, 12H) 2.90-
3.30 (m, 2H) 6.60-7.40 (m, 16H) 8.10 (s, 2H) FD-Mass Spectrometry: 594 (M +) Elemental Analysis: Ti; 8.0% (8.0) ()

[0530]

Synthesis Example 47 Synthesis of Compound B-23 : 1.02 g of Compound L23 (4.
25 mmol) and 20 ml of diethyl ether were charged, cooled to -78 ° C and stirred. 3.43 ml of n-butyl lithium (1.55 mmol
/ ml n-hexane solution, 5.32 mmol) was added dropwise over 5 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. This solution was added dropwise to a mixture of zirconium tetrachloride (0.50 g, 2.15 mmol) and 20 ml of diethyl ether cooled to -78 ° C. 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, insolubles were removed with a glass filter. The filtrate was concentrated under reduced pressure, and the precipitated solid was reprecipitated with diethyl ether, methylene chloride and hexane, and dried under reduced pressure to obtain a yellow-green powdered compound B-23 represented by the following formula.
0.61 g (0.96 mmol, yield 45%) was obtained.

[0531]

Embedded image

¹ H-NMR (CDCl ₃ ): 0.80-1.30 (m, 12H) 2.90-
3.25 (m, 2H) 6.72-7.43 (m, 16H) 8.20 (s, 2H) FD-Mass Spectrometry: 638 (M +) Elemental Analysis: Zr; 14.0% (14.3)
Figures in parentheses are calculated values

[0533]

[Synthesis Example 48] Synthesis of compound A-24 : 0.52 g of compound L24 (2.
05 mmol) and 40 ml of diethyl ether, cooled to -78 ° C and stirred. 1.36 ml of n-butyl lithium (1.55 mmol
/ ml n-hexane solution (2.11 mmol) was added dropwise over 5 minutes, then the temperature was slowly raised to room temperature, and stirring was continued at room temperature for 4 hours to prepare a lithium salt slurry. -78 ° C
Was slowly added dropwise to a mixture of 2.04 ml of a titanium tetrachloride solution (0.5 mmol / ml heptane solution, 1.02 mmol), 40 ml of diethyl ether and 20 ml of tetrahydrofuran. After dropping,
The 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 reslurried with 100 ml of diethyl ether, the insolubles were separated with a glass filter, the filter cake was washed with diethyl ether, dissolved in methylene chloride, and the insolubles in the solution were removed. The mixture was concentrated under reduced pressure, and the precipitated solid was washed with hexane and dried under reduced pressure to obtain 0.12 g (0.19 mmol, yield: 19%) of compound A-24 as an orange powder.

[0534]

Embedded image

¹ H-NMR (CDCl ₃ ): 0.80-2.30 (m, 18H) 6.30-
9.20 (m, 14H) 8.35 (brs, 2H) FD-Mass spectrometry: 624 (M +) Elemental analysis: Ti; 8.1% (7.7) () is calculated value

[0536]

Synthesis Example 49 Synthesis of Compound B-24 : In a 100 ml reactor which was sufficiently dried and purged with argon, 0.76 g of compound L24 (2.
99 mmol) and 40 ml of diethyl ether were charged, cooled to -78 ° C and stirred. 1.91 ml of n-butyl lithium (1.61 mmol
/ ml n-hexane solution, 3.08 mmol) was added dropwise over 5 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 slurry. Add this solution to -78
Zirconium tetrachloride / 2THF complex (0.56
(3 g, 1.49 mmol) in a mixed solution of 80 ml of tetrahydrofuran. 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, 50 ml of toluene was added, and the mixture was heated and stirred at 80 ° C. for 10 hours and at 90 ° C. for 30 hours. The solvent was distilled off from the reaction solution, and the obtained solid was reslurried with 150 ml of diethyl ether, and insolubles were separated by a glass filter. After washing the residue with diethyl ether, dissolving with methylene chloride and removing insolubles in the solution,
The lysate is concentrated under reduced pressure. The precipitated solid was washed with hexane and dried under reduced pressure to obtain 0.43 g (0.64 mmol, 43% yield) of a yellow powdered compound B-24 represented by the following formula.

[0537]

Embedded image

¹ H-NMR (CDCl ₃ ): 0.60-2.30 (m, 18H) 6.30-
9.40 (m, 14H) 8.35 (brs, 2H) FD-Mass spectrometry: 668 (M +) Elemental analysis: Zr; 13.2% (13.6)
Figures in parentheses are calculated values

[0539]

Synthesis Example 50 Synthesis of Compound A-25 : In a 100 ml reactor which was sufficiently dried and purged with argon, 0.50 g of Compound L25 (1.
93 mmol) and 20 ml of diethyl ether were charged, cooled to -78 ° C and stirred. 1.42 ml of n-butyl lithium (1.55 mmol
/ ml n-hexane solution 2.20 mmol) was added dropwise over 5 minutes, then the temperature was slowly raised to room temperature, and stirring was continued at room temperature for 4 hours to prepare a lithium salt solution. This solution was gradually added dropwise to a mixture of 1.93 ml of titanium tetrachloride solution (0.5 mmol / ml heptane solution, 0.97 mmol) and 50 ml of diethyl ether cooled to -78 ° C. 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 filtered with a glass filter, and the residue was washed with diethyl ether and dissolved in methylene chloride. After removing the insolubles in the solution, the solution was concentrated under reduced pressure, and the precipitated solid was washed with hexane and dried under reduced pressure to obtain 0.11 g of a red-brown powder of Compound A-25 (0.17 mmol, 18% yield). )Obtained.

[0540]

Embedded image

¹ H-NMR (CDCl ₃ ): 1.65 (s, 18H) 0.50-2.40
(m, 20H) 3.85 (brdt, 2H) 6.90-7.70 (m, 6H) 8.20 (s, 2H) FD-Mass Spectrometry: 634 (M +) Elemental Analysis: Ti; 7.6% (7.5) ()

[0542]

Synthesis Example 51 Synthesis of Compound B-25 : In a 100 ml reactor which was sufficiently dried and purged with argon, 0.50 g of Compound L25 (1.
93 mmol) and 20 ml of diethyl ether were charged, cooled to -78 ° C and stirred. 1.42 ml of n-butyl lithium (1.55 mmol
/ ml n-hexane solution, 2.20 mmol) was added dropwise over 5 minutes, then the temperature was slowly raised to room temperature, and stirring was continued at room temperature for 4 hours to prepare a lithium salt solution. This solution was added dropwise to a solution of zirconium tetrachloride (0.23 g, 0.99 mmol) in 50 ml of diethyl ether cooled to -78 ° C. After completion of the dropwise addition, stirring was continued while slowly raising the temperature to room temperature. 15 at room temperature
After stirring for hours, the reaction solution was filtered through a glass filter,
The filtrate was concentrated under reduced pressure. The precipitated solid was washed with hexane and dried under reduced pressure to obtain 0.28 g (0.41 mmol, 43% yield) of compound B-25 as an ocher powder represented by the following formula.

[0543]

Embedded image

¹ H-NMR (CDCl ₃ ): 1.65 (s, 18H) 0.70-2.50
(m, 20H) 3.85 (brdt, 2H) 6.70-7.70 (m, 6H) 8.25 (s, 2H) FD-Mass spectrometry: 678 (M +) Elemental analysis: Zr; 13.3% (13.4)
Figures in parentheses are calculated values

[0545]

Synthesis Example 52 Synthesis of Compound A-26 : In a 100 ml reactor which was thoroughly dried and purged with argon, 0.61 g of Compound L26 (2.
28 mmol) and 10 ml of diethyl ether were charged, cooled to -78 ° C and stirred. 1.6 ml of n-butyl lithium (1.55 mmol /
ml n-hexane solution 2.48 mmol) was added dropwise over 5 minutes, then the temperature was slowly raised to room temperature, and stirring was continued at room temperature for 4 hours to prepare a lithium salt solution. 2.2 ml of a titanium tetrachloride solution (0.5 mmol / ml heptane solution, cooled to −78 ° C.)
1.10 mmol) and 10 ml of tetrahydrofuran were gradually added dropwise. After completion of the dropwise addition, stirring was continued while slowly raising the temperature to room temperature. After further stirring at room temperature for 12 hours, the insolubles in the reaction solution were filtered with a glass filter, the obtained filtrate was concentrated under reduced pressure, and the precipitated solid was reprecipitated with diethyl ether and hexane at -78 ° C and dried under reduced pressure. This gave 0.36 g (0.55 mmol, 51% yield) of compound A-26 as a brown powder.

[0546]

Embedded image

¹ H-NMR (CDCl ₃ ): 1.33 (s, 18H) 2.14 (s, 6H)
6.60-7.68 (m, 14H) 8.03 (s, 2H) FD-Mass spectrometry: 650 (M +) Elemental analysis: Ti; 7.4% (7.3)

[0548]

Synthesis Example 53 Synthesis of Compound B-26 : 0.61 g of Compound L26 (2.
28 mmol) and 10 ml of diethyl ether were charged, cooled to -78 ° C and stirred. 1.6 ml of n-butyl lithium (1.55 mmol /
ml n-hexane solution, 2.48 mmol) was added dropwise over 5 minutes, then the temperature was slowly raised to room temperature, and stirring was continued at room temperature for 4 hours to prepare a lithium salt solution. This solution was added dropwise to a solution of zirconium tetrachloride (0.27 g, 1.15 mmol) in 10 ml of diethyl ether cooled to -78 ° C. After completion of the dropwise addition, stirring was continued while slowly raising the temperature to room temperature. 12 at room temperature
After stirring for an hour, insolubles were removed with a glass filter. The filtrate was concentrated under reduced pressure, and the precipitated solid was reprecipitated with diethyl ether and hexane, and dried under reduced pressure to obtain 0.14 g (0.20 m) of yellow-green powdered compound B-26 represented by the following formula.
mol yield 18%).

[0549]

Embedded image

¹ H-NMR (CDCl ₃ ): 1.31 (s, 18H) 2.14 (s, 6H)
6.69-7.65 (m, 14H) 8.09 (s, 2H) FD-Mass spectrometry: 694 (M +) Elemental analysis: Zr; 13.1% (13.1)
Figures in parentheses are calculated values

[0551]

Synthesis Example 54 Synthesis of Compound A-27 : In a 100 ml reactor sufficiently dried and purged with argon, 0.30 g of Compound L27 (1.
(00 mmol) and 10 ml of diethyl ether, cooled to -78 ° C and stirred. 0.65 ml of n-butyl lithium (1.55 mmol
/ 1.00 mmol of n-hexane solution) was added dropwise over 5 minutes, then the temperature was slowly raised to room temperature, and stirring was continued at room temperature for 4 hours to prepare a lithium salt solution. This solution was gradually added dropwise to a mixture of 1.0 ml of titanium tetrachloride solution (0.5 mmol / ml heptane solution, 0.50 mmol) and 10 ml of diethyl ether cooled to -78 ° C. After completion of the dropwise addition, stirring was continued while slowly raising the temperature to room temperature. Stir at room temperature for 12 hours, then reflux under 1
After stirring for an hour, insolubles in the reaction solution were filtered with a glass filter. The filtrate was concentrated under reduced pressure, and the precipitated solid was reprecipitated with diethyl ether and hexane, and dried under reduced pressure to obtain 0.18 g (0.25 mmol, 50% yield) of orange powder of Compound A-27.

[0552]

Embedded image

¹ H-NMR (CDCl ₃ ): 1.13 (s, 18H) 1.25 (brd, 6
H) 1.28 (brd, 6H) 3.29 (brdq, 2H) 6.45-6.70 (m, 2H) 6.80
-7.20 (m, 4H) 7.20-7.50 (m, 8H) 8.23 (s, 2H) FD-Mass spectrometry: 706 (M +) Elemental analysis: Ti; 6.8% (6.8) ()

[0554]

Synthesis Example 55 Synthesis of Compound B-27 : In a 100 ml reactor sufficiently dried and purged with argon, 0.95 g of Compound L27 (3.
20 mmol) and 10 ml of diethyl ether were charged, cooled to -78 ° C and stirred. 2.08 ml of n-butyl lithium (1.55 mmol
/ ml n-hexane solution, 3.22 mmol) was added dropwise over 5 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. This solution was added dropwise to a solution of zirconium tetrachloride (0.37 g, 1.60 mmol) in 10 ml of tetrahydrofuran cooled to -78 ° C. After completion of the dropwise addition, stirring was continued while slowly raising the temperature to room temperature. After stirring at room temperature for 12 hours and then under reflux for 6 hours, the reaction solution was evaporated. The obtained solid was dissolved in 50 ml of methylene chloride, and the insoluble matter was removed with a glass filter. The filtrate was concentrated under reduced pressure, and the precipitated solid was reprecipitated with methylene chloride and hexane, and dried under reduced pressure to obtain a yellow powder compound represented by the following formula.
0.18 g (0.24 mmol, 15% yield) of B-27 was obtained.

[0555]

Embedded image

¹ H-NMR (CDCl ₃ ): 1.10 (s, 18H) 1.10-1.40
(m, 12H) 3.20-3.30 (m, 2H) 6.30-6.60 (m, 2H) 6.70-7.10-
7.60 (m, 8H) 8.28 (s, 2H) FD-Mass Spectroscopy: 750 (M +) Elemental Analysis: Zr; 12.0% (12.2) C; 63.5% (64.0) H; 6.6% (6.4) N; 3.5% ( 3.7) Values in () are calculated values

[0557]

Synthesis Example 56 Synthesis of Compound A-28 : In a 100 ml reactor sufficiently dried and purged with argon, 0.50 g of Compound L28 (1.
37 mmol) and 40 ml of diethyl ether were charged, cooled to -78 ° C and stirred. 0.92 ml of n-butyl lithium (1.55 mmol
/ ml n-hexane solution (1.43 mmol) was added dropwise over 5 minutes, then the temperature was slowly raised to room temperature, and stirring was continued at room temperature for 4 hours to prepare a lithium salt solution. This solution was gradually added dropwise to a mixture of 1.37 ml of a titanium tetrachloride solution (0.5 mmol / ml heptane solution, 0.69 mmol) cooled to -78 ° C and 40 ml of diethyl ether. After completion of the dropwise addition, stirring was continued while slowly raising the temperature to room temperature. After further stirring at room temperature for 8 hours, the reaction solution was filtered through a glass filter, the residue was washed with diethyl ether, insolubles were removed by filtration, the filtrate was concentrated under reduced pressure, and the precipitated solid was washed with hexane. The residue was dried under reduced pressure to obtain 0.17 g (0.20 mmol, 29% yield) of a brown powder of compound A-28.

[0558]

Embedded image

¹ H-NMR (CDCl ₃ ): 0.70-1.40 (m, 54H) 6.65-
7.75 (m, 12H) 8.35 (s, 2H) FD-mass spectrometry: 846 (M +) Elemental analysis: Ti; 5.5% (5.7)

[0560]

Synthesis Example 57 Synthesis of Compound B-28 : In a 100 ml reactor which was sufficiently dried and purged with argon, 0.50 g of Compound L28 (1.
37 mmol) and 40 ml of diethyl ether were charged, cooled to -78 ° C and stirred. 0.92 ml of n-butyl lithium (1.55 mmol
/ ml n-hexane solution, 1.43 mmol) was added dropwise over 5 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. This solution was added dropwise to a mixed solution of zirconium tetrachloride (0.16 g, 0.69 mmol) in anhydrous diethyl ether (20 ml) and tetrahydrofuran (50 ml) cooled to -78 ° C. After completion of the dropwise addition, stirring was continued while slowly raising the temperature to room temperature. After further stirring at room temperature for 12 hours, the solvent was distilled off from the reaction solution. The obtained solid was reslurried with diethyl ether, the insoluble matter was removed with a glass filter, and the filtrate was concentrated under reduced pressure. The precipitated solid was reprecipitated with hexane at -78 ° C, and dried under reduced pressure to obtain a yellow powdered compound B-28 represented by the following formula by 0.26
g (0.29 mmol yield 43%) was obtained.

[0561]

Embedded image

¹ H-NMR (CDCl ₃ ): 0.80-1.30 (m, 54H) 6.65
(m, 12H) 8.35 (s, 2H) FD-Mass spectrometry: 890 (M +) Elemental analysis: Zr; 9.9% (10.2)
Figures in parentheses are calculated values

[0563]

Synthesis Example 58 Synthesis of Compound A-29 : In a 100 ml reactor sufficiently dried and purged with argon, compound L29; 0.60 g (1.
79 mmol) and 40 ml of diethyl ether were charged, cooled to -78 ° C and stirred. 1.17 ml of n-butyl lithium (1.55 mmol
/ ml n-hexane solution (1.81 mmol) was added dropwise over 5 minutes, then the temperature was slowly raised to room temperature, and stirring was continued at room temperature for 4 hours to prepare a lithium salt solution. This solution was gradually added dropwise to a mixture of 1.79 ml of a titanium tetrachloride solution (0.5 mmol / ml heptane solution, 0.90 mmol) and 50 ml of diethyl ether cooled to −78 ° C. After completion of the dropwise addition, stirring was continued while slowly raising the temperature to room temperature. After further stirring at room temperature for 12 hours, the reaction solution was filtered through a glass filter to remove insolubles,
The filtrate was concentrated under reduced pressure, and the precipitated solid was washed with hexane,
Dry under reduced pressure to obtain 0.10 g (0.13 mmo) of compound A-29 as a red-brown powder.
l yield 14%).

[0564]

Embedded image

¹ H-NMR (CDCl ₃ ): 0.80-2.30 (m, 20H) 1.55
(s, 18H) 3.65 (brdt, 2H) 6.60-8.10 (m, 16H) FD-Mass Spectrometry: 786 (M +) Elemental Analysis: Ti; 6.4% (6.1) ()

[0566]

Synthesis Example 59 Synthesis of Compound B-29 : Compound L29; 0.50 g (1.
48 mmol) and 40 ml of diethyl ether were charged, cooled to -78 ° C and stirred. 1.02 ml (1.61 mmol) of n-butyl lithium
/ ml n-hexane solution, 1.64 mmol) was added dropwise over 5 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. This solution was cooled to −78 ° C. and a zirconium tetrachloride · 2THF complex (0.26 g, 0.1%) was added.
(69 mmol) in 40 ml of tetrahydrofuran. After completion of the dropwise addition, stirring was continued while slowly raising the temperature to room temperature. After further stirring at room temperature for 8 hours, 70 ml of toluene was added, and the mixture was heated and stirred at 80 ° C. for 20 hours. The solvent was distilled off from the reaction solution, and the obtained solid was reslurried with 50 ml of diethyl ether, filtered through a glass filter to remove insolubles, and then the filtrate was concentrated under reduced pressure to precipitate a solid again.
The precipitated solid was reprecipitated with hexane at -78 ° C,
By drying under reduced pressure, 0.04 g (0.05 mmol, yield: 7%) of a yellow-white powdered compound B-29 represented by the following formula was obtained.

[0567]

Embedded image

¹ H-NMR (CDCl ₃ ): 0.90-1.90 (m, 20H) 1.55
(s, 18H) 3.25 (brdt, 2H) 6.40-7.90 (m, 16H) FD-Mass spectrometry: 830 (M +) Elemental analysis: Zr; 11.3% (11.0)
Figures in parentheses are calculated values

[0569]

Synthesis Example 60 Synthesis of Compound A-30 : In a 100 ml reactor which was sufficiently dried and purged with argon, 0.51 g of Compound L30 (1.
86 mmol) and 50 ml of diethyl ether were charged, cooled to -78 ° C and stirred. 1.20 ml of n-butyl lithium (1.61 mmol
/ ml n-hexane solution 1.93 mmol) was added dropwise over 5 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 gradually dropped into 1.85 ml of titanium tetrachloride solution (0.5 mmol / ml heptane solution, 0.93 mmol) and 60 ml of tetrahydrofuran cooled to −78 ° C. After completion of the dropwise addition, stirring was continued while slowly raising the temperature to room temperature. After further stirring at room temperature for 8 hours, the reaction solution was heated to 60 ° C. and heated and stirred for 8 hours.

The solvent was distilled off from the reaction solution to precipitate a solid. The obtained solid was reslurried with diethyl ether, filtered through a glass filter, and the residue was washed with diethyl ether and dissolved in methylene chloride. . After insoluble matter in the solution was removed by filtration, the filtrate was concentrated under reduced pressure, and the precipitated solid was washed with hexane and dried under reduced pressure to obtain 0.14 g (0.21 mmol yield) of compound A-30 as a red-orange powder. Rate 23%)
Obtained.

[0571]

Embedded image

¹ H-NMR (CDCl ₃ ): 1.10-2.10 (m, 20H) 1.45
(s, 18H) 2.40 (s, 6H) 3.85 (brdt, 2H) 6.70-7.70 (m, 6H) FD-Mass spectrometry: 662 (M +) Elemental analysis: Ti; 7.1% (7.2) ()

[0573]

Synthesis Example 61 Synthesis of Compound B-30 : 0.51 g of Compound L30 (1.
86 mmol) and 50 ml of diethyl ether were charged, cooled to -78 ° C and stirred. 1.20 ml of n-butyl lithium (1.61 mmol
/ ml n-hexane solution, 1.93 mmol) was added dropwise over 5 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. This solution was added dropwise to a solution of zirconium tetrachloride (0.22 g, 0.94 mmol) in 60 ml of tetrahydrofuran cooled to -78 ° C. After completion of the dropwise addition, stirring was continued while slowly raising the temperature to room temperature. After further stirring at room temperature for 12 hours, 60 ml of toluene was added, and the mixture was heated and stirred at 85 ° C. for 12 hours.

The solvent was distilled off from the reaction solution, and the obtained solid was reslurried with 100 ml of diethyl ether, filtered with a glass filter to remove insolubles, and the filtrate was concentrated under reduced pressure. The precipitated solid is washed with hexane and dried under reduced pressure to obtain a milky white compound B- represented by the following formula.
0.10 g (0.14 mmol, 15% yield) of 30 was obtained.

[0575]

Embedded image

¹ H-NMR (CDCl ₃ ): 0.80-2.10 (m, 20H) 1.45
(s, 18H) 2.40 (s, 6H) 3.75 (brdt, 2H) 6.50-7.80 (m, 6H) FD-Mass spectrometry: 704 (M +) Elemental analysis: Zr; 13.3% (12.9)
Figures in parentheses are calculated values

[0577]

Synthesis Example 62 Synthesis of Compound A-31 : 1.00 g of Compound L31 (4.
22 mmol) and 20 ml of diethyl ether were charged, cooled to -78 ° C and stirred. 2.75 ml of n-butyl lithium (1.61 mmol
/ ml n-hexane solution (4.43 mmol) was added dropwise over 5 minutes, then the temperature was slowly raised to room temperature, and stirring was continued at room temperature for 4 hours to prepare a lithium salt solution. This solution was gradually added dropwise to a mixture of 4.22 ml of a titanium tetrachloride solution (0.5 mmol / ml heptane solution, 2.11 mmol) cooled to -78 ° C and 20 ml of diethyl ether.

After the completion of the dropwise addition, stirring was continued while slowly raising the temperature to room temperature. After stirring at room temperature for 12 hours, the reaction solution was filtered with a glass filter. Filter residue is methylene chloride 50ml
After removing insolubles in the solution, the solution was evaporated to dryness under reduced pressure, and the obtained solid was reprecipitated with methylene chloride and diethyl ether, and dried under reduced pressure to obtain a brown powder of compound A-. 0.90 g (1.55 mmol, yield 72%) of 31 was obtained.

[0579]

Embedded image

¹ H-NMR (CDCl ₃ ): 6.70-7.40 (m, 16H) 7.90-
8.20 (m, 2H) FD-Mass spectrometry: 578 (M +) Elemental analysis: Ti; 8.0% (8.3)

[0581]

Synthesis Example 63 Synthesis of Compound B-31 : In a 100 ml reactor which was sufficiently dried and purged with argon, 1.20 g of Compound L31 (5.
18 mmol) and 24 ml of diethyl ether were charged, cooled to -78 ° C and stirred. 3.38 ml of n-butyl lithium (1.61 mmol
/ ml n-hexane solution, 5.44 mmol) was added dropwise over 5 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. This solution was added dropwise to a mixture of zirconium tetrachloride (0.60 g, 2.57 mmol) and diethyl ether 24 ml cooled to -78 ° C. After completion of the dropwise addition, stirring was continued while slowly raising the temperature to room temperature. After stirring at room temperature for 12 hours, the reaction solution was filtered with a glass filter.
After the filtrate was dissolved in 60 ml of methylene chloride, insolubles in the solution were removed, the solution was concentrated under reduced pressure, and the precipitated solid was reprecipitated with methylene chloride and hexane, dried under reduced pressure, and represented by the following formula. 0.20 g (0.3
(2 mmol yield 12%).

[0582]

Embedded image

¹ H-NMR (CDCl ₃ ): 6.70-7.45 (m, 16H) 7.90-
8.25 (m, 2H) FD-Mass spectrometry: 621 (M +) Elemental analysis: Zr; 14.9% (14.6)

[0584]

Synthesis Example 64 Synthesis of Compound A-32 : 1.00 g of Compound L32 (5.
05 mmol) and 50 ml of diethyl ether were added, cooled to -78 ° C and stirred. 3.25 ml of n-butyl lithium (1.63 mmol
/ ml n-hexane solution (5.30 mmol) was added dropwise over 5 minutes, then the temperature was slowly raised to room temperature, and stirring was continued at room temperature for 4 hours to prepare a lithium salt solution. The solution was cooled to −78 ° C., and 2.52 ml of a titanium tetrachloride solution (0.5 mmol / ml heptane solution, 1.26 mmol) was gradually added dropwise. After completion of the dropwise addition, stirring was continued while slowly raising the temperature to room temperature. At room temperature
After stirring for 12 hours, the reaction solution was filtered through a glass filter, the residue was washed with diethyl ether, dissolved in methylene chloride, and after removing insolubles in the solution, the solution was concentrated under reduced pressure to precipitate. The solid was washed with hexane and dried under reduced pressure to obtain 0.23 g of an orange powder of compound A-32 (0.45 mmol, 18% yield).
Obtained.

[0585]

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FD-Mass Spectrometry: 512 (M +)

[0587]

Synthesis Example 65 Synthesis of Compound A-33 : 1.09 g of compound L33 (4.
39 mmol) and 70 ml of diethyl ether were charged, cooled to -78 ° C and stirred. 2.80 ml of n-butyl lithium (1.63 mmol
/ ml n-hexane solution 4.56 mmol) was added dropwise over 5 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. The solution was cooled to −78 ° C., and 8.78 ml of a titanium tetrachloride solution (0.5 mmol / ml heptane solution, 4.39 mmol) was gradually added dropwise. After completion of the dropwise addition, stirring was continued while slowly raising the temperature to room temperature. At room temperature
After stirring for 12 hours, the reaction solution was filtered through a glass filter, the residue was washed with diethyl ether, dissolved in methylene chloride, and after removing insolubles in the solution, the solution was concentrated under reduced pressure to precipitate. The solid was washed with diethyl ether and dried under reduced pressure to obtain 0.22 g (0.36 mmol) of compound A-33 as a brown powder.
Yield 16%).

[0588]

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FD-mass spectrometry: 612 (M +)

[0590]

Synthesis Example 66 Synthesis of compound A-34 : In a 100 ml reactor which was thoroughly dried and purged with argon, 0.60 g of compound L34 (2.
13 mmol) and 40 ml of diethyl ether were charged, cooled to -78 ° C and stirred. 2.75 ml of n-butyl lithium (1.63 mmol
/ ml n-hexane solution 4.48 mmol) was added dropwise over 5 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 cooled to -78 ° C, and titanium tetrachloride / tetrahydrofuran complex 0.71 g
(2.13 mmol) was added slowly. After completion of the dropwise addition, stirring was continued while slowly raising the temperature to room temperature. 8 at room temperature
After stirring for hours, the reaction solution was filtered through a glass filter,
The residue was washed with diethyl ether and dissolved in methylene chloride. After removing insolubles in the solution, the solution was concentrated under reduced pressure, and the precipitated solid was washed with hexane and dried under reduced pressure to obtain 0.19 g (0.48 mmol, 23% yield) of compound A-34 as a red powder. Was.

[0591]

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FD-Mass Spec: 398 (M +)

[0593]

Synthesis Example 67 Synthesis of compound A-35 : 0.1 ml of sodium hydride was placed in a 100 ml reactor which had been thoroughly dried and purged with argon.
9 g (60 wt% product, 4.75 mmol) and tetrahydrofuran (50 ml) were charged, and compound L35: 1.00 g (2.30 mmol) with stirring at room temperature.
And a 20 ml solution of tetrahydrofuran were added dropwise over 5 minutes, then the temperature was slowly raised to room temperature, and stirring was continued at 50 ° C. for 2 hours to prepare a sodium salt solution. This solution was stirred at room temperature and titanium tetrachloride / tetrahydrofuran complex 0.77 g
(2.31 mmol) and 50 ml of tetrahydrofuran were gradually added dropwise. After completion of the dropwise addition, stirring was continued while slowly raising the temperature to room temperature. After further stirring at room temperature for 8 hours, the reaction solution was filtered through a glass filter, the residue was washed with diethyl ether, the insolubles were removed by filtration, and the filtrate was concentrated under reduced pressure. The reaction solution was filtered with a glass filter, and the residue was washed with diethyl ether and dissolved in methylene chloride. After removing impurities in the solution, the solution was concentrated under reduced pressure, and the precipitated solid was washed with hexane and dried under reduced pressure to obtain 1.10 g of compound A-35 as a red-orange powder (2.00 mmol yield 87
%)Obtained.

[0594]

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FD-Mass spectrometry: 550 (M +)

[0596]

Synthesis Example 68 Synthesis of Compound A-36 : 0.1 ml of sodium hydride was placed in a 100 ml reactor which had been thoroughly dried and purged with argon.
9 g (4.75 mmol of a 60 wt% product) and 50 ml of tetrahydrofuran are charged, and while stirring at room temperature, compound L36; 1.00 g (2.23 mmol)
And a 20 ml solution of tetrahydrofuran were added dropwise over 5 minutes, then the temperature was slowly raised to room temperature, and stirring was continued at 50 ° C for 2 hours to prepare a sodium salt solution. The solution was cooled to −78 ° C., and 4.50 ml of a titanium tetrachloride solution (0.5 mmol / ml heptane solution, 2.25 mmol) was gradually added dropwise. After completion of the dropwise addition, stirring was continued while slowly raising the temperature to room temperature. After further stirring at room temperature for 8 hours, the reaction solution was filtered through a glass filter, and the residue was washed with diethyl ether and dissolved in methylene chloride. After removing insolubles in the solution, the solution was concentrated under reduced pressure, and the precipitated solid was washed with hexane and dried under reduced pressure to obtain 0.55 g of compound A-36 as an orange powder.
(0.97 mmol, 44% yield).

[0597]

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FD-Mass Spec: 564 (M +)

[0599]

Synthesis Example 69 Synthesis of Compound B-37 : A 0.3 ml sodium hydride was placed in a 100 ml reactor which had been thoroughly dried and purged with argon.
0 g (7.50 mmol of a 60 wt% product) and 50 ml of tetrahydrofuran are charged, and while stirring at room temperature, compound L37; 1.00 g (3.16 mmol)
And a 20 ml solution of tetrahydrofuran were added dropwise over 5 minutes, then the temperature was slowly raised to room temperature, and stirring was continued at 60 ° C. for 2 hours to prepare a sodium salt solution. The solution was stirred at room temperature and zirconium tetrachloride / 2THF complex 1.19 g (3.15 m
mol) and a 50 ml solution of tetrahydrofuran. After completion of the dropwise addition, stirring was continued while slowly raising the temperature to room temperature. After further stirring at room temperature for 8 hours, the reaction solution was filtered through a glass filter, the residue was washed with tetrahydrofuran, and the insoluble material was removed by filtration.
The precipitate was filtered through a glass filter, and the precipitate was washed with cold tetrahydrofuran and dried under reduced pressure to obtain 1.00 g (2.10 mmol) of yellow powdered compound B-37.
Yield 66%).

[0600]

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FD-Mass Spectroscopy: 474 (M +)

[0602]

Synthesis Example 70 Synthesis of Compound B-38 : A 0.2 ml sodium hydride was placed in a 100 ml reactor which had been thoroughly dried and purged with argon.
3 g (5.75 mmol of 60 wt% product) and 50 ml of tetrahydrofuran are charged, and while stirring at room temperature, compound L38; 1.00 g (2.73 mmol)
And a 20 ml solution of tetrahydrofuran were added dropwise over 5 minutes, then the temperature was slowly raised to room temperature, and stirring was continued at 50 ° C. for 2 hours to prepare a sodium salt solution. The solution was stirred at room temperature and zirconium tetrachloride / 2THF complex 1.03 g (2.73 m
mol) and a 50 ml solution of tetrahydrofuran. After completion of the dropwise addition, stirring was continued while slowly raising the temperature to room temperature. After further stirring at room temperature for 8 hours, the reaction solution was filtered with a glass filter, the residue was washed with tetrahydrofuran, and the insoluble matter was removed by filtration. Then, the filtrate was allowed to stand for 2 hours to precipitate a solid. . The precipitated solid was filtered through a glass filter, and the residue was washed with cold tetrahydrofuran and dried under reduced pressure to give a yellow powder of compound B-38 as 1.15.
g (2.18 mmol yield: 80%) was obtained.

[0603]

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FD-mass spectrometry: 524 (M +)

[0605]

Synthesis Example 71 Synthesis of Compound A-39 : A compound L39; 0.50 g (1.
87 mmol) and 50 ml of diethyl ether were charged, cooled to -78 ° C and stirred. 1.20 ml of n-butyl lithium (1.61 mmol
/ ml n-hexane solution 1.93 mmol) was added dropwise over 5 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 gradually added dropwise to a mixture of 1.87 ml of titanium tetrachloride solution (0.5 mmol / ml heptane solution, 0.94 mmol) and 70 ml of diethyl ether cooled to −78 ° C. After completion of the dropwise addition, stirring was continued while slowly raising the temperature to room temperature. After further stirring at room temperature for 8 hours, the reaction solution was filtered with a glass filter, and the residue was washed with diethyl ether and dissolved in methylene chloride. After removing insolubles in the solution, the solution was concentrated under reduced pressure, and the precipitated solid was washed with hexane and dried under reduced pressure to obtain 0.11 g of compound A-39 as a red powder (0.17 mmol, 18% yield). Obtained.

[0606]

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¹ H-NMR (CDCl ₃ ): 1.65 (s, 18H) 4.65 (d, 2H)
5.00 (d, 2H) 6.75-7.70 (m, 16H) 7.75 (s, 2H) FD-Mass Spectrometry: 650 (M +) Elemental Analysis: Ti; 7.2% (7.3) ()

[0608]

Synthesis Example 72 Synthesis of compound B-39 : In a 100 ml reactor which was thoroughly dried and purged with argon, 0.50 g of compound L39 (1.
87 mmol) and 40 ml of diethyl ether were charged, cooled to -78 ° C and stirred. 1.20 ml of n-butyl lithium (1.61 mmol
/ ml n-hexane solution, 1.93 mmol) was added dropwise over 5 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. This solution was cooled to −78 ° C. and zirconium tetrachloride · 2THF complex (0.352 g,
(0.93 mmol) in a mixed solution of 50 ml of tetrahydrofuran. After completion of the dropwise addition, stirring was continued while slowly raising the temperature to room temperature. After further stirring at room temperature for 8 hours, the reaction solution was
After heating and stirring at 3 ° C for 3 hours, the solvent was distilled off from the reaction solution. The obtained solid was reslurried with 50 ml of diethyl ether, and insolubles were separated by a glass filter. The filtrate was washed with 100 ml of diethyl ether, dissolved in methylene chloride to remove insolubles, and the filtrate was concentrated under reduced pressure. The precipitated solid was washed with hexane, and dried under reduced pressure to obtain 0.30 g of a compound B-39 as a yellowish white powder represented by the following formula.
(0.43 mmol, 46% yield).

[0609]

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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 spectrometry: 694 (M +) Elemental analysis: Zr; 12.9% (13.1)
Figures in parentheses are calculated values

[0611]

Synthesis Example 73 Synthesis of Compound A-40 : In a 100 ml reactor which was thoroughly dried and purged with argon, 0.58 g of Compound L40 (2.
02 mmol) and 40 ml of diethyl ether, cooled to -78 ° C and stirred. 1.50 ml of n-butyl lithium (1.61 mmol
/ ml n-hexane solution (2.42 mmol) was added dropwise over 5 minutes, then the temperature was slowly raised to room temperature, and stirring was continued at room temperature for 4 hours to prepare a lithium salt solution. This solution was gradually added dropwise to a mixture of 2.00 ml of titanium tetrachloride solution (0.5 mmol / ml heptane solution, 1.00 mmol) and 80 ml of diethyl ether cooled to -78 ° C. After completion of the dropwise addition, stirring was continued while slowly raising the temperature to room temperature. After further stirring at room temperature for 8 hours, the reaction solution was filtered through a glass filter to remove insolubles,
The filtrate was concentrated under reduced pressure, and the precipitated solid was reprecipitated with hexane at -78 ° C, and dried under reduced pressure to obtain compound A-40 as a red-orange powder.
0.19 g (0.28 mmol, 28% yield) was obtained.

[0612]

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¹ H-NMR (CDCl ₃ ): 0.80-1.80 (m, 18H) 6.50-
7.90 (m, 14H) 8.00-8.20 (m, 2H) FD-Mass spectrometry: 692 (M +) Elemental analysis: Ti; 7.0% (6.9)

[0614]

Synthesis Example 74 Synthesis of Compound B-40 : In a 100 ml reactor which was thoroughly dried and purged with argon, 0.58 g of Compound L40 (2.
02 mmol) and 40 ml of diethyl ether, cooled to -78 ° C and stirred. 1.50 ml of n-butyl lithium (1.61 mmol
/ ml n-hexane solution, 2.42 mmol) was added dropwise over 5 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. This solution was cooled to −78 ° C. and zirconium tetrachloride · 2THF complex (0.38 g, 1.
(00 mmol) in a mixed solution of 80 ml of tetrahydrofuran. After completion of the dropwise addition, stirring was continued while slowly raising the temperature to room temperature. After further stirring at room temperature for 8 hours, the solvent was distilled off from the reaction solution. The obtained solid is treated with diethyl ether 15
After reslurrying with 0 ml and removing insolubles with a glass filter, the filtrate was concentrated under reduced pressure. The precipitated solid is -78 ° C
In hexane, and dried under reduced pressure to obtain 0.23 g (0.31 m
mol yield 31%).

[0615]

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¹ H-NMR (CDCl ₃ ): 0.80-1.70 (m, 18H) 6.50
-7.90 (m, 14H) 8.20 (s, 2H) FD-Mass spectrometry: 734 (M +) Elemental analysis: Zr; 12.2% (12.4)
Figures in parentheses are calculated values

[0617]

Synthesis Example 75 Synthesis of Compound A-41 : In a 100 ml reactor which was thoroughly dried and purged with argon, 0.50 g of Compound L41 (1.
15 mmol) and 10 ml of diethyl ether were charged, cooled to -78 ° C and stirred. 1.47 ml of n-butyl lithium (1.61 mmol
/ ml n-hexane solution (2.36 mmol) was added dropwise over 5 minutes, then the temperature was slowly raised to room temperature, and stirring was continued at room temperature for 4 hours to prepare a lithium salt solution. This solution was gradually added dropwise to a mixture of 2.3 ml of a titanium tetrachloride solution (0.5 mmol / ml heptane solution, 1.15 mmol) cooled to -78 ° C and 10 ml of diethyl ether. After completion of the dropwise addition, stirring was continued while slowly raising the temperature to room temperature. After stirring at room temperature for 8 hours, the solvent was distilled off from the reaction solution, and the obtained solid was dissolved in 25 ml of methylene chloride. After filtering the insolubles in the solution using a glass filter, the solution was concentrated under reduced pressure, and the precipitated solid was reprecipitated with diethyl ether, methylene chloride and hexane,
The compound A-41 as an orange powder was dried under reduced pressure to give 0.49
g (0.93 mmol yield 76%) was obtained.

[0618]

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FD-mass spectrometry: 525 (M +) Elemental analysis: Ti; 8.9% (9.1) (): calculated value

[0620]

Synthesis Example 76 Synthesis of compound B-41 : In a 100 ml reactor which was sufficiently dried and purged with argon, 0.50 g of compound L41 (1.
15 mmol) and 10 ml of diethyl ether were charged, cooled to -78 ° C and stirred. 1.47 ml of n-butyl lithium (1.61 mmol
/ ml n-hexane solution, 2.36 mmol) was added dropwise over 5 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. This solution was cooled to −78 ° C. and zirconium tetrachloride · 2THF complex (0.43 g, 1.
(15 mmol) in 10 ml of tetrahydrofuran. After completion of the dropwise addition, stirring was continued while slowly raising the temperature to room temperature. After stirring for 8 hours at room temperature and then for 12 hours under reflux,
The reaction solution was evaporated. The resulting solid is methylene chloride 25
The resulting solution was dissolved in an aliquot and the insoluble material was removed from the solution using a glass filter. The solution was concentrated under reduced pressure, and the precipitated solid was reprecipitated with methylene chloride, diethyl ether and hexane, and dried under reduced pressure to obtain a yellow powdered compound B-41 represented by the following formula.
36 g (0.63 mmol, 51% yield) were obtained.

[0621]

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¹ H-NMR (CDCl ₃ ): 1.41 (s, 18H) 2.10 (s, 2H)
3.70 (s, 2H) 6.94 (t, 2H) 7.30 (dd, 2H) 7.50 (dd, 2H) 8.39
(s, 2H) FD-Mass spectrometry: 568 (M +) Elemental analysis: Zr; 16.2% (16.0)
Figures in parentheses are calculated values

[0623]

[Synthesis Example 77] Synthesis of compound A-42 : In a 100 ml reactor sufficiently dried and purged with argon, compound L42; 0.500 g
(1.22 mmol) and 10 ml of diethyl ether were charged, cooled to -78 ° C and stirred. 1.52 ml of n-butyl lithium (1.61
mmol / ml n-hexane solution 2.45 mmol) was added dropwise over 5 minutes, then the temperature was slowly raised to room temperature, and stirring was continued at room temperature for 4 hours to prepare a lithium salt solution. Add this solution to -7
The mixture was gradually added dropwise to a mixture of 2.45 ml of a titanium tetrachloride solution (0.5 mmol / ml heptane solution, 1.23 mmol) and 10 ml of diethyl ether cooled to 8 ° C. After completion of the dropwise addition, stirring was continued while slowly raising the temperature to room temperature. After stirring at room temperature for 8 hours, the solvent of the reaction solution was distilled off, and the obtained solid was dissolved in 25 ml of methylene chloride. After filtering the insoluble matter from the solution with a glass filter, the solution was concentrated under reduced pressure, and the precipitated solid was reprecipitated with diethyl ether, methylene chloride and hexane, and dried under reduced pressure to obtain a compound A-42 as a red-brown powder. 0.25g
(0.45 mmol yield: 40%) was obtained.

[0624]

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FD-mass spectrometry: 552 (M +) Elemental analysis: Ti; 9.0% (8.7)

[0626]

Synthesis Example 78 Synthesis of Compound B-42 : In a 100 ml reactor which was thoroughly dried and purged with argon, 0.50 g of Compound L42 (1.
22 mmol) and 10 ml of diethyl ether were charged, cooled to -78 ° C and stirred. 1.52 ml of n-butyl lithium (1.61 mmol
/ ml n-hexane solution, 2.45 mmol) was added dropwise over 5 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. This solution was cooled to −78 ° C. and zirconium tetrachloride · 2THF complex (0.46 g, 1.
(22 mmol) in 10 ml of tetrahydrofuran. After completion of the dropwise addition, stirring was continued while slowly raising the temperature to room temperature. After stirring at room temperature for 8 hours and then under reflux for 6 hours, the solvent was distilled off from the reaction solution. The resulting solid is methylene chloride
The solution was dissolved in 25 ml, and the insolubles in the solution were removed with a glass filter. The solution was concentrated under reduced pressure, and the precipitated solid was reprecipitated with methylene chloride, diethyl ether and hexane, and dried under reduced pressure to obtain 0.22 g of a yellow powdered compound B-42 represented by the following formula (0.37 mmol yield 32%). )Obtained.

[0627]

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FD-Mass spectrometry: 596 (M +) Elemental analysis: Zr; 15.5% (15.3)
Values in parentheses are calculated values. All the above operations in the synthesis of transition metal compounds were performed under an argon or nitrogen atmosphere, and a commercially available anhydrous solvent was used as a solvent.

The following are specific examples of the polymerization method according to the present invention.

[0630]

Example 1 250 ml of toluene was charged into a 500 ml-volume glass autoclave sufficiently purged with nitrogen.
The liquid and gas phases were saturated with ethylene at 100 liters / hr of ethylene. Then, methylaluminoxane (MA
O) was converted to 1.1875 mmol in terms of aluminum atom, and then the compound A-1 obtained in Synthesis Example 1 was treated with 0.0
0475 mmol was added to initiate polymerization. After reacting at 25 ° C. for 30 minutes under an atmosphere of ethylene gas at normal pressure, the polymerization was stopped by adding a small amount of isobutanol. After completion of the polymerization, the reaction product was poured into a large amount of methanol to precipitate the entire amount of the polymer, and hydrochloric acid was added, followed by filtration through a glass filter. After drying the polymer under reduced pressure at 80 ° C. for 10 hours, 8.02 g of polyethylene (PE) was obtained.

The polymerization activity was 3400 g / mmol-Ti · hr,
The intrinsic viscosity [η] of the obtained polyethylene is 8.44 dl.
/ G.

[0632]

Example 2 250 ml of toluene was charged into a 500 ml-volume glass autoclave sufficiently purged with nitrogen, and the liquid phase and the gas phase were saturated with 100 l / hr of ethylene. Thereafter, 1.25 mmol of methylaluminoxane was converted to aluminum atom, and 0.001 of compound A-1 was added.
5 mmol was added to initiate polymerization. After polymerization at 50 ° C. for 10 minutes, the polymerization was stopped by adding a small amount of isobutanol.

The obtained polymer suspension was added to 1.5 liters of methanol containing a small amount of hydrochloric acid to precipitate a polymer. After filtering through a glass filter to remove the solvent, the resultant was washed with methanol and dried under reduced pressure at 80 ° C. for 10 hours. The obtained polyethylene was 3.30 g, the polymerization activity was 3960 g / mmol-Ti · hr, and the intrinsic viscosity [η]
Was 6.37 dl / g.

[0634]

Example 3 Polymerization was carried out in the same manner as in Example 2 except that the polymerization temperature was 75 ° C. Table 1 shows the results.

[0635]

Example 4 Example 2 was repeated except that the polymerization temperature was 25 ° C. and hydrogen was supplied at 2 liter / hr together with ethylene.
Polymerization was carried out in the same manner as described above. Table 1 shows the results.

[0636]

Example 5 250 ml of toluene was charged into a 500 ml-volume glass autoclave sufficiently purged with nitrogen.
The liquid and gas phases were saturated with 100 l / hr of ethylene. Then, triisobutyl aluminum (TIB)
A) was added in an amount of 0.25 mmol.
0.05 mmol of triphenylcarbenium tetrakis (pentafluorophenyl) borate (TrB) in 0.1%.
006 mmol was added to initiate polymerization. After reacting at 25 ° C. for 1 hour in an atmosphere of ethylene gas at normal pressure, the polymerization was stopped by adding a small amount of isobutanol. After completion of the polymerization, the reaction product was poured into a large amount of methanol to precipitate the entire amount of the polymer, and hydrochloric acid was added, followed by filtration through a glass filter. After drying the polymer under reduced pressure at 80 ° C. for 10 hours, 0.50 g of polyethylene (PE) was obtained.

The polymerization activity was 100 g / mmol-Ti · hr, and the intrinsic viscosity [η] was 10.6 dl / g.

[0638]

Example 6 250 ml of toluene was charged into a 500 ml glass autoclave having an internal volume of 500 ml which had been sufficiently purged with nitrogen, and the liquid phase and the gas phase were saturated with 100 liter / hr of ethylene. Then, triisobutyl aluminum 0.25
Then, 0.005 mmol of compound A-1 and 0.006 mmol of triphenylcarbeniumtetrakis (pentafluorophenyl) borate were added to initiate polymerization. After conducting the polymerization at 75 ° C. for 30 minutes, the polymerization was stopped by adding a small amount of isobutanol.

The obtained polymer suspension was added to 1.5 liters of methanol containing a small amount of hydrochloric acid to precipitate a polymer. After removing the solvent by filtration with a glass filter, the resultant was washed with methanol and dried at 80 ° C. for 10 hours under reduced pressure. The obtained polyethylene was 0.71 g, the polymerization activity was 280 g / mmol-Ti · hr, and the intrinsic viscosity [η] was 7.22 dl / g.

[0640]

Example 7 250 ml of toluene was charged into a glass autoclave having an internal volume of 500 ml sufficiently purged with nitrogen, and a liquid phase and a gas phase were saturated with 100 liter / hr of ethylene. Thereafter, 2.5 mmol of methylaluminoxane was calculated in terms of aluminum atom.
The polymerization was initiated by adding 0.005 mmol of the zirconium compound B-1 obtained in the above. Under normal pressure ethylene gas atmosphere, 25
After reacting at 5 ° C. for 5 minutes, the polymerization was stopped by adding a small amount of isobutanol. After completion of the polymerization, the reaction product was poured into a large amount of methanol to precipitate the entire amount of the polymer, and hydrochloric acid was added, followed by filtration through a glass filter. After drying the polymer under reduced pressure at 80 ° C. for 10 hours, 6.10 g of polyethylene was obtained.

The polymerization activity was 14,600 g / mmol-Zr · hr, and the intrinsic viscosity [η] was 0.30 dl / g.

[0642]

Examples 8 to 24 The polymerization of ethylene was carried out in the same manner as in Example 7 except that the polymerization conditions were changed as shown in Table 1. Table 1 shows the results.

[0643]

Example 25 250 ml of toluene was charged into a 500 ml-volume glass autoclave sufficiently purged with nitrogen, and the liquid phase and the gas phase were saturated with 100 l / hr of ethylene. Then, triisobutylaluminum was added for 0.2
After the addition of 5 mmol, a solution in which 0.05 mmol of triisobutylaluminum, 0.005 mmol of compound B-1 and 0.006 mmol of triphenylcarbenium tetrakis (pentafluorophenyl) borate were previously mixed was added, and polymerization was started. After polymerization was performed at 25 ° C. for 5 minutes under an atmosphere of ethylene gas at normal pressure, the polymerization was stopped by adding a small amount of isobutanol. The obtained polymer solution was added to 1.5 liter of methanol containing a small amount of hydrochloric acid to precipitate a polymer. After washing with methanol, it was dried under reduced pressure at 80 ° C. for 10 hours. The resulting polyethylene weighed 0.99 g and had a polymerization activity of 238.
0 g / mmol-Zr · hr, and the intrinsic viscosity [η] is 22.4 dl.
/ G.

[0644]

Example 26 250 ml of toluene was charged into a glass autoclave having an internal volume of 500 ml sufficiently purged with nitrogen, and the liquid phase and the gas phase were saturated with 100 liter / hr of ethylene. Then, triisobutylaluminum was added for 0.2
5 mmol, then 0.0005 mmol of compound B-1
1, 0.001 mmol of triphenylcarbenium tetrakis (pentafluorophenyl) borate was added to initiate polymerization. 1 at 25 ° C under normal pressure ethylene gas atmosphere
The reaction was performed for 0 minutes. After completion of the polymerization, the reaction product was poured into a large amount of methanol to precipitate the entire amount of the polymer, and hydrochloric acid was added, followed by filtration through a glass filter. After drying the polymer under reduced pressure at 80 ° C. for 10 hours, 0.34 g of polyethylene was obtained.
Obtained.

The polymerization activity was 4080 g / mmol-Zr · hr,
The intrinsic viscosity [η] was 12.6 dl / g.

[0646]

Examples 27 to 31 The polymerization of ethylene was carried out in the same manner as in Example 26 except that the polymerization conditions were changed as shown in Table 1. Table 1 shows the results.

[0647]

[Table 1]

[0648]

Examples 32 to 36 Using the compounds shown in Table 2, Table 2
The polymerization of ethylene was carried out in the same manner as in Example 7, except that the polymerization conditions were changed as shown in (1). Table 2 shows the results.

[0649]

[Table 2]

[0650]

Examples 37 to 52 Using the compounds shown in Table 3, Table 3
When methylaluminoxane was used as a co-catalyst under the polymerization conditions shown in (1), ethylene was polymerized in the same manner as in Example 7. When triisobutylaluminum and triphenylcarbeniumtetrakis (pentafluorophenyl) borate were used as the cocatalyst, ethylene was polymerized in the same manner as in Example 26.

Table 3 shows the results.

[0652]

[Table 3]

[0653]

Examples 53 to 78 Using the compounds shown in Table 4, Table 4
In the case where methylaluminoxane was used as a co-catalyst under the polymerization conditions shown in (1), polymerization of ethylene was carried out in the same manner as in Example 7. When triisobutylaluminum and triphenylcarbeniumtetrakis (pentafluorophenyl) borate were used as the cocatalyst, ethylene was polymerized in the same manner as in Example 26.

Table 4 shows the results.

[0655]

[Table 4]

[0656]

Examples 79 to 111 Using the compounds shown in Table 5, under the polymerization conditions shown in Table 5, when methylaluminoxane was used as a cocatalyst, ethylene was polymerized in the same manner as in Example 7. . When triisobutylaluminum and triphenylcarbeniumtetrakis (pentafluorophenyl) borate were used as the cocatalyst, ethylene was polymerized in the same manner as in Example 26.

[0657] The results are shown in Table 5.

[0658]

[Table 5]

[0659]

Examples 112 to 121 Using the compounds shown in Table 6,
Under the polymerization conditions shown in Table 6, when methylaluminoxane was used as the cocatalyst, the polymerization of ethylene was carried out in the same manner as in Example 7. When triisobutylaluminum and triphenylcarbeniumtetrakis (pentafluorophenyl) borate were used as the cocatalyst, ethylene was polymerized in the same manner as in Example 26.

Table 6 shows the results.

[0661]

[Table 6]

[0662]

Examples 122 to 130 Using the compounds shown in Table 7,
Under the polymerization conditions shown in Table 7, when methylaluminoxane was used as a cocatalyst, the polymerization of ethylene was carried out in the same manner as in Example 7. When triisobutylaluminum and triphenylcarbeniumtetrakis (pentafluorophenyl) borate were used as the cocatalyst, ethylene was polymerized in the same manner as in Example 26.

Table 7 shows the results.

[0664]

[Table 7]

[0665]

Example 131 500 ml of internal volume sufficiently purged with nitrogen
Was charged with 250 ml of toluene, and the liquid phase and the gas phase were saturated with a mixed gas of 50 l / hr of ethylene and 150 l / hr of propylene.
Thereafter, 1.25 mmol of methylaluminoxane in terms of aluminum atom and 0.005 mmol of compound A-1 were added, and copolymerization was started. After copolymerization at 25 ° C for 15 minutes,
The polymerization was stopped by adding a small amount of isobutanol.

The obtained polymer suspension was added to 1.5 liters of methanol containing a small amount of hydrochloric acid to precipitate a polymer. After removing the solvent by filtration with a glass filter, the resultant was washed with methanol and dried at 80 ° C. for 10 hours under reduced pressure. The obtained ethylene / propylene copolymer is 0.1%.
95 g, the polymerization activity is 760 g / mmol-Ti · hr,
The propylene content measured by IR was 4.67 mol%, and the intrinsic viscosity [η] was 2.21 dl / g.

[0667]

Example 132 Internal volume 500 ml sufficiently purged with nitrogen
Was charged with 250 ml of toluene, and 100 liters / hr of ethylene and 100 parts of propylene
The liquid phase and the gas phase were saturated with a mixed gas of liter / hr. Then, triisobutylaluminum was 0.25 m
mol, then add triisobutylaluminum to 0.0
25 mmol, 0.0025 mmol of compound B-1 and 0.005 mmol of triphenylcarbenium tetrakis (pentafluorophenyl) borate (TrB)
The previously mixed solution was added to initiate copolymerization. 5
After copolymerization at 0 ° C. for 5 minutes, the polymerization was stopped by adding a small amount of isobutanol.

The obtained polymer solution was added to 1.5 liters of methanol containing a small amount of hydrochloric acid to precipitate a polymer. The precipitated polymer was washed with methanol and dried under reduced pressure at 130 ° C. for 10 hours. The obtained ethylene / propylene copolymer was 1.63 g, the polymerization activity was 7820 g / mmol-Zr · hr, the propylene content measured by IR was 20.7 mol%, and the intrinsic viscosity [η] was It was 13.4 dl / g.

[0669]

Example 133 Using compound B-1, except that the monomer flow rate was changed to 50 l / hr of ethylene and 150 l / hr of propylene, and the polymerization temperature and the amount of catalyst were changed as shown in Table 8, the procedure was as follows. Copolymerization was carried out as in Example 132.

[0670] The results are shown in Table 8.

[0671]

Examples 134 to 149 Using the compounds shown in Table 8,
The copolymerization was carried out in the same manner as in Example 131. Table 8 shows the results.
Shown in

[0672]

[Table 8]

[0673]

Example 150: 500 ml of internal volume sufficiently purged with nitrogen
Was charged with 250 ml of toluene, and 100 l / h of ethylene and 20 l / h of butadiene were passed through the system. After 10 minutes, 5.0 mmol of methylaluminoxane was converted to aluminum atoms.
1) Then, 0.01 mmol of titanium compound A-1 was added to initiate polymerization. After reacting at 25 ° C. for 20 minutes while flowing a mixed gas of ethylene and butadiene at normal pressure, a small amount of methanol was added to terminate the polymerization. The reaction product was poured into a large amount of hydrochloric acid-methanol to precipitate the entire amount of the polymer, followed by filtration with a glass filter. After drying under reduced pressure at 80 ° C. for 10 hours, an ethylene / butadiene copolymer 0.53 was obtained.
g was obtained.

The polymerization activity per 1 mmol of titanium is 14
9 g, and the intrinsic viscosity [η] of the obtained copolymer was 1.
It was 46 dl / g. According to NMR analysis, the content of all butadiene units in the copolymer was 0.9 mol% (a total of 0.8 mol% of 1,4-cis-form and 1,4-trans-form was 1,2-viny
The l-isomer was 0.1 mol%, and the cyclopentane skeleton was less than 0.1 mol% (lower than the detection limit).

[0675]

EXAMPLE 151 The same procedure as in Example 150 was repeated, except that titanium compound A-
Polymerization was carried out in the same manner as in Example 1, except that the zirconium compound B-1 was used and the polymerization time was changed to 5 minutes. The yield of the obtained copolymer was 2.65 g.

The polymerization activity per 1 mmol of zirconium was 3,180 g, and the intrinsic viscosity [η] of the obtained copolymer was 0.70 dl / g. According to NMR analysis, the content of all butadiene units in the copolymer was 1.2 mol.
1% (1.1 mol% of 1,4-cis and 1,4-trans forms in total, 0.1 mol% of 1,2-vinyl form, less than 0.1 mol% of cyclopentane skeleton (detection Below the limit)).

[0677]

EXAMPLE 152 The polymerization time of Example 151 was changed to 20 minutes.
Polymerization was carried out by the same operation except that the flow rate of ethylene was 20 l / h and the flow rate of butadiene was 80 l / h. The yield of the obtained copolymer was 0.74 g.

The polymerization activity per 1 mmol of zirconium was 446 g, and the intrinsic viscosity [η] of the obtained copolymer was
Was 0.87 dl / g. According to NMR analysis, the content of the butadiene unit in the copolymer was 5.3 mol% (1,1 mol%).
4.7 mol% of the 4-cis form and the 1,4-trans form in total,
0.6 mol% of 2-vinyl form, 0.1% of cyclopentane skeleton.
It was less than 1 mol% (lower than the detection limit).

[0679]

Example 153 Polymerization was carried out in the same manner as in Example 151, except that the polymerization time was 5 minutes, the flow rate of ethylene was 50 l / h, and the flow rate of butadiene was 50 l / h. The yield of the obtained copolymer was 0.1.
57 g.

The polymerization activity per 1 mmol of zirconium was 342 g, and the intrinsic viscosity [η] of the obtained copolymer was
Was 0.34 dl / g. According to NMR analysis, the content of butadiene units in the copolymer was 2.4 mol% (1,1 mol%).
2.3 mol% of 4-cis form and 1,4-trans form in total,
0.1 mol% 2-vinyl, 0.1% cyclopentane skeleton.
It was less than 1 mol% (lower than the detection limit).

[0681]

Example 154 The procedure of Example 153 was repeated, except that the polymerization temperature was changed to 5.
Polymerization was carried out in the same manner as in Example 153 except that the temperature was changed to 0 ° C. The yield of the obtained copolymer was 0.627 g.

The polymerization activity is 1488 g / mmol-Zr · hr,
The intrinsic viscosity [η] of the obtained copolymer is 0.16 dl / g.
Met. According to NMR analysis, the content of the butadiene unit in the copolymer was 3.3 mol% (3.2 mol% of 1,4-cis and 1,4-trans forms in total and 0.1 mol of 1,2-vinyl form).
Mol%, the cyclopentane skeleton was less than 0.1 mol% (lower than the detection limit).

[0683]

EXAMPLE 155 The procedure of Example 153 was repeated, except that the polymerization temperature was changed to 5.
Example 153 except that the flow rate of ethylene was 40 l / hr and the flow rate of butadiene was 60 l / hr at 0 ° C.
Polymerization was carried out in the same manner as described above. The yield of the obtained copolymer was 0.37 g.

The polymerization activity was 888 g / mmol-Zr · hr, and the intrinsic viscosity [η] of the obtained copolymer was 0.17 dl / g. According to NMR analysis, the content of the butadiene unit in the copolymer was 4.8 mol% (4.6 mol% in total of the 1,4-cis and 1,4-trans forms and 0.2 mol in the 1,2-vinyl form). Mol%, the cyclopentane skeleton was less than 0.1 mol% (lower than the detection limit).

[0685]

Example 156 The procedure of Example 153 was repeated except that the polymerization temperature was changed to 6.
Example 153 except that the flow rate of ethylene was 40 l / hr and the flow rate of butadiene was 60 l / hr at 0 ° C.
Polymerization was carried out in the same manner as described above. The yield of the obtained copolymer was 0.417 g.

The polymerization activity was 984 g / mmol-Zr · hr, and the intrinsic viscosity [η] of the obtained copolymer was 0.12 dl / g. According to NMR analysis, the content of the butadiene unit in the copolymer was 5.8 mol% (5.6 mol% in total of the 1,4-cis-form and 1,4-trans-form and 0.2% in the 1,2-vinyl-form). Mol%, the cyclopentane skeleton was less than 0.1 mol% (lower than the detection limit). The molecular weight distribution (Mw / Mn) measured by GPC was 1.85.

[0687]

EXAMPLE 157 The procedure of Example 153 was repeated except that the polymerization temperature was changed to 5.
Example 153 except that the flow rate of ethylene was 30 l / hr and the flow rate of butadiene was 70 l / hr at 0 ° C.
Polymerization was carried out in the same manner as described above. The yield of the obtained copolymer was 0.24 g.

The polymerization activity was 576 g / mmol-Zr · hr, and the intrinsic viscosity [η] of the obtained copolymer was 0.14 dl / g. According to NMR analysis, the content of butadiene units in the copolymer was found to be 6.6 mol% (6.3 mol% in total of 1,4-cis and 1,4-trans forms, 0.2% in 1,2-vinyl form). Mol%, the cyclopentane skeleton was less than 0.1 mol% (lower than the detection limit). The molecular weight distribution (Mw / Mn) measured by GPC was 2.05.

[0689]

EXAMPLE 158 500 ml of heptane was charged into a 1-liter autoclave made of SUS which had been sufficiently purged with nitrogen.
At 0 ° C., the liquid and gas phases were saturated with ethylene. Then, 1.25 mmol of methylaluminoxane in terms of aluminum atom and compound A-1 of 0.001 mm
was added and polymerization was carried out at an ethylene pressure of 8 kg / cm ² -G for 15 minutes.

To the obtained polymer suspension, 1.5 liters of methanol containing a small amount of hydrochloric acid was added to precipitate a polymer. The polymer was filtered through a glass filter, the solvent was removed, and the polymer was washed with methanol and heated to 80 ° C. And dried under reduced pressure for 10 hours.
The obtained polyethylene was 11.22 g, the polymerization activity was 44.9 kg / mmol-Ti · hr, and the intrinsic viscosity [η] was 7.91 dl / g.

[0691]

Embodiments 159 to 162 In Embodiment 158, Table 9
The polymerization was carried out in the same manner as in Example 158, except that the polymerization conditions were changed as shown in Table 9 using the compound shown in Table 9.

[0691] The results are shown in Table 9.

[0693]

[Table 9]

[0694]

Example 163 Preparation of solid catalyst component 10 kg of silica dried at 250 ° C. for 10 hours was suspended in 154 liters of toluene, and then cooled to 0 ° C. Thereafter, a methylaluminoxane solution (Al = 1.33)
(Mol / liter) 57.5 liters were added dropwise over 1 hour. At this time, the temperature in the system was kept at 0 ° C. Subsequently, the reaction was carried out at 0 ° C. for 30 minutes, then the temperature was raised to 95 ° C. over 1.5 hours, and the reaction was carried out at that temperature for 20 hours. Then 60 ° C
The temperature was lowered until the supernatant was removed by a decantation method. The obtained solid catalyst component was washed twice with toluene and then resuspended with toluene to obtain a solid catalyst component (A) (total volume 200 liter).

[0695] 22.4 ml of the suspension of the solid catalyst component (A) thus obtained was transferred to a 200 ml glass flask, and 175 ml of toluene and compound A-1 were further added.
Solution in toluene (Ti = 0.01mmol / L)
4.8 ml was added, and the mixture was stirred at room temperature for 2 hours. This suspension was washed three times with 200 ml of hexane, and hexane was added to obtain a solid catalyst component (B) as a 200 ml suspension.

Polymerization 1 liter of heptane was charged into a 2 liter autoclave made of SUS which had been sufficiently purged with nitrogen, and the temperature was raised to 50 ° C. to saturate the gas phase and the liquid phase with ethylene. Thereafter, 1.0 mmol of triisobutylaluminum and the solid catalyst component (B) were
0.005 mmol added in terms of the contained Ti atom,
Polymerization was carried out at an ethylene pressure of 8 kg / cm ² -G for 90 minutes.

The obtained polymer suspension was filtered through a glass filter, washed twice with 500 ml of hexane, and washed at 80 ° C.
And dried under reduced pressure for 10 hours. The obtained polyethylene was 8.96 g, and the polymerization activity was 1790 g / mmol-Ti · h.
r, intrinsic viscosity [η] was 11.7 dl / g.

[0698]

EXAMPLE 164 To a 200 ml reactor sufficiently purged with nitrogen, 60 ml of heptane and 40 ml of 1-hexene were added, and 2
Stirred at 5 ° C. Then, after adding 0.25 mmol of triisobutylaluminum, 0.1 mmol of triisobutylaluminum previously mixed, 0.01 mmol of compound A-1, and 0.0 mmol of triphenylcarbenium tetrakis (pentafluorophenyl) borate were added.
A 12 mmol solution was added to initiate the polymerization. After reacting at 25 ° C. for 1 hour, the polymerization was stopped by adding a small amount of isobutanol.

The obtained polymer suspension was added little by little to 1 liter of acetone to precipitate a polymer, separated from a solvent, and dried under reduced pressure at 130 ° C. for 10 hours. The amount of the obtained polyhexene was 3.15 g, and the polymerization activity was 31.
The molecular weight measured by GPC (polystyrene conversion) at 5 g / mmol-Ti · hr was Mw = 1.46 million and Mw / Mn = 2.06.

[0700]

Example 165 To a 500 ml reactor sufficiently purged with nitrogen, 250 ml of toluene was added, and the liquid phase and the gas phase were saturated with ethylene at 25 ° C. Thereafter, 1.0 mmol of triisobutylaluminum and then 0.1 mol of titanium compound A-1 were added while flowing 80 l / hr of butadiene.
01 mmol, triphenylcarbenium tetrakis (pentafluorophenyl) borate in 0.02 mmol
1 to start polymerization. After reacting at 25 ° C. for 20 minutes, the polymerization was stopped by adding a small amount of isobutanol. After completion of the polymerization, the reaction product was poured into a large amount of methanol to precipitate the entire amount of the polymer, and hydrochloric acid was added, followed by filtration through a glass filter. After drying the polymer under reduced pressure at 80 ° C. for 10 hours, 1.481 g of polybutadiene was obtained.

The polymerization activity was 444 g / mmol-Ti · hr, and the molecular weight of the obtained polybutadiene was Mw = 1.76 million (in terms of polystyrene).

[Brief description of the drawings]

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

FIG. 2 shows a process for preparing a second olefin polymerization catalyst according to the present invention.

FIG. 3 shows a structure of the transition metal compound A-1 produced in Synthesis Example 1 obtained by X-ray crystal structure analysis.

FIG. 4 shows the structure of transition metal compound B-1 produced in Synthesis Example 2 obtained by X-ray crystal structure analysis.

 ──────────────────────────────────────────────────続 き Continued on the front page (31) Priority claim number Japanese Patent Application No. 10-50541 (32) Priority date Hei 10 (1998) March 3 (33) Priority claim country Japan (JP) (72) Inventor Nariwa Matsui, 1-2-1, Waki, Waki-machi, Kuga-gun, Yamaguchi Prefecture Inside Mitsui Chemicals, Inc. (72) Inventor Junji Saito 6-1, 1-2, Waki, Waki-cho, Kuga, Yamaguchi Prefecture Mitsui Chemicals, Inc. (72) Inventor Masatoshi Nitahara 1-2-1, Waki, Waki-machi, Kuga-gun, Yamaguchi Prefecture Inside Mitsui Chemicals, Inc. (72) Kiyoshiaki Sugi 1-2-1-2, Waki, Waki-cho, Kuga-gun, Yamaguchi Prefecture No. Mitsui Chemicals Co., Ltd. (72) Inventor Haruyuki Makio 1-2-1, Waki, Waki-cho, Kuga-gun, Yamaguchi Prefecture Inside Mitsui Chemicals Co., Ltd. 6-1-2 Ki, Mitsui Chemicals, Inc.

Claims (28)

[Claims] (1) (A) a transition metal compound represented by the following general formula (I), (B) (B-1) an organometallic compound, (B-2) an organoaluminum oxy compound, and (B-3) ) An olefin polymerization catalyst comprising at least one compound selected from compounds which form an ion pair by reacting with the transition metal compound (A); (Wherein, M represents a transition metal atom belonging to Groups 3 to 11 of the periodic table, m represents an integer of ^{1 to 6} , R ^{1 to} R ⁶ may be the same or different from each other, and represent a hydrogen atom. Represents a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group, Two or more of these may be connected to each other to form a ring, and when m is 2 or more, two of the groups represented by R ^{1 to} R ⁶ are connected. (However, R ¹ is not bonded to each other), n is a number that satisfies the valence of M, and X is a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, and a sulfur-containing group. Group, nitrogen-containing group, boron-containing group, aluminum-containing group, phosphorus-containing group, halogen-containing group Group, a heterocyclic compound residue, a silicon-containing group, a germanium-containing group, or a tin-containing group, and when n is 2 or more, a plurality of groups represented by X may be the same or different from each other; A plurality of groups represented by X may combine with each other to form a ring.) 2. In the general formula (I), R ⁶ represents a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, The olefin polymerization catalyst according to claim 1, which is a silicon-containing group, a germanium-containing group, or a tin-containing group. 3. The olefin polymerization catalyst according to claim 1, wherein the transition metal compound represented by the general formula (I) is a transition metal compound represented by the following general formula (Ia): Embedded image (Wherein, M represents a transition metal atom belonging to Groups 3 to 11 of the periodic table, m represents an integer of 1 to 3, R ^{1 to} R ⁶ may be the same or different, and each represents a hydrogen atom. A, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, a hydrocarbon-substituted silyl group, a hydrocarbon-substituted siloxy group, an alkoxy group, an alkylthio group, an aryloxy group,
Arylthio group, acyl group, ester group, thioester group, amide group, imide group, amino group, imino group, sulfone ester group, sulfonamide group, cyano group, nitro group, carboxyl group, sulfo group, mercapto group or hydroxy group And two or more of these groups may be linked to each other to form a ring. When m is 2 or more, two of the groups represented by R ^{1 to} R ⁶ are linked to each other. (However, R ¹ is not bonded to each other), n is a number satisfying the valence of M, X is a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, N represents a sulfur-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, a halogen-containing group, a heterocyclic compound residue, a silicon-containing group, a germanium-containing group, or a tin-containing group; In the above case, the groups represented by X may be the same or different from each other, and the groups represented by X may be bonded to each other to form a ring. ) 4. In the general formula (Ia), R ⁶ is a halogen atom, a hydrocarbon group, a heterocyclic compound residue, a hydrocarbon-substituted silyl group, a hydrocarbon-substituted siloxy group, an alkoxy group, an alkylthio group, an aryloxy group. , Arylthio, acyl, ester, thioester, amide, imide, amino, imino, sulfone ester, sulfonamide, cyano, nitro, carboxyl, sulfo, mercapto or hydroxy group The catalyst for olefin polymerization according to claim 3, which is 5. The olefin polymerization according to claim 1, wherein the transition metal compound represented by the general formula (I) is a transition metal compound represented by the following general formula (Ia-1). Catalyst; (Wherein, M represents a transition metal atom belonging to Groups 3 to 11 of the periodic table, m represents an integer of 1 to 3, R ^{1 to} R ⁶ may be the same or different, and each represents a hydrogen atom. A, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, a hydrocarbon-substituted silyl group, a hydrocarbon-substituted siloxy group, an alkoxy group, an alkylthio group, an aryloxy group,
An arylthio group, an acyl group, an ester group, a thioester group, an amide group, an imide group, an amino group, an imino group, a sulfone ester group, a sulfonamide group, a cyano group, a nitro group, or a hydroxy group; May be connected to each other to form a ring, and when m is 2 or more, two of the groups represented by R ^{1 to} R ⁶ may be connected (provided that R is ¹ is not bonded to each other), n is a number satisfying the valence of M, X is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, 1 to 20 carbon atoms. Represents a halogenated hydrocarbon group, an oxygen-containing group, a sulfur-containing group or a silicon-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; Groups are bonded to each other A ring may be formed. ) 6. In the above formula (Ia-1), R ⁶ represents a halogen atom, a hydrocarbon group, a heterocyclic compound residue, a hydrocarbon-substituted silyl group, a hydrocarbon-substituted siloxy group, an alkoxy group, an alkylthio group, 6. An aryloxy group, an arylthio group, an acyl group, an ester group, a thioester group, an amide group, an imide group, an amino group, an imino group, a sulfone ester group, a sulfonamide group, a cyano group, a nitro group or a hydroxy group. Olefin polymerization catalyst. 7. The catalyst for olefin polymerization according to claim 1, wherein the transition metal compound represented by the general formula (I) is a transition metal compound represented by the following general formula (Ib). Embedded image (Wherein, M represents a transition metal atom belonging to Groups 3 to 11 of the periodic table, m represents an integer of ^{1 to 6} , R ^{1 to} R ⁶ may be the same or different from each other, and represent a hydrogen atom. , A halogen atom, a hydrocarbon group, a hydrocarbon-substituted silyl group, an alkoxy group, an aryloxy group, an ester group, an amide group, an amino group, a sulfonamide group, a nitrile group or a nitro group, and two or more of these groups May be connected to each other to form a ring, and when m is 2 or more, two of the groups represented by R ^{1 to} R ⁶ may be connected (provided that R is ¹ is not combined).) 8. In the general formula (Ib), R ⁶ represents a halogen atom, a hydrocarbon group, a hydrocarbon-substituted silyl group, an alkoxy group, an aryloxy group, an ester group, an amide group, an amino group, a sulfonamide group, a cyano group. Or the catalyst for olefin polymerization according to claim 7, wherein the catalyst is a nitro group. 9. In the transition metal compound (A), M is at least one selected from Groups 3 to 5 and Group 9 of the periodic table.
9. A transition metal atom of any kind.
The olefin polymerization catalyst according to any one of the above. 10. The transition metal compound (A) according to any one of claims 1 to 9, and (B-1) an organometallic compound, (B-2)
An olefin polymerization catalyst comprising a carrier (C) in addition to at least one compound (B) selected from an organic aluminum oxy compound and (B-3) an ionized ionic compound. 11. A method for polymerizing olefins, comprising polymerizing or copolymerizing olefins in the presence of the catalyst for olefin polymerization according to any one of claims 1 to 10. (A ') a transition metal compound represented by the following general formula (II), (B) an organometallic compound (B-1), and (B-2)
An olefin polymerization catalyst comprising: an organoaluminum oxy compound; and (B-3) at least one compound selected from compounds which form an ion pair by reacting with the transition metal compound (A '); Formula 5 (Wherein, M represents a transition metal atom belonging to Groups 3 to 11 of the periodic table, and R ^{1 to} R ¹⁰ may be the same or different from each other, and represent a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic group, A compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group, two or more of which are linked to each other N is a number that satisfies the valence of M; X is a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, and a boron-containing group. A group, an aluminum-containing group, a phosphorus-containing group, a halogen-containing group, a heterocyclic compound residue, a silicon-containing group, a germanium-containing group, or a tin-containing group, and when n is 2 or more, a plurality of groups represented by X The radicals may be identical or different And a plurality of groups represented by X may be bonded to each other to form a ring; and Y is selected from the group consisting of oxygen, sulfur, carbon, nitrogen, phosphorus, silicon, selenium, tin and boron. And a divalent linking group containing at least one element, and a hydrocarbon group if it is a hydrocarbon group.) 13. In the general formula (II), at least one of R ^{6 and} R ¹⁰ is a halogen atom, a hydrocarbon group,
Heterocyclic compound residue, oxygen-containing group, nitrogen-containing group, boron-containing group, sulfur-containing group, phosphorus-containing group, silicon-containing group,
The olefin polymerization catalyst according to claim 12, which is a germanium-containing group or a tin-containing group. 14. The olefin polymerization according to claim 12, wherein the transition metal compound represented by the general formula (II) is a transition metal compound represented by the following general formula (II-a). Catalyst for use; (Wherein, M represents a transition metal atom of Groups 3 to 11 of the periodic table, and R ^{1 to} R ¹⁰ may be the same or different from each other, and may be a hydrogen atom, a halogen atom, a hydrocarbon group, or a hydrocarbon substitution. A silyl group, an alkoxy group, an aryloxy group, an ester group, an amide group, an amino group, a sulfonamide group, a nitrile group or a nitro group, two or more of which may be linked to each other to form a ring And n is a number that satisfies the valence of M; X is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, and an oxygen-containing group. , A sulfur-containing group, or a silicon-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;
May be linked to each other to form a ring, and Y is a divalent containing at least one element selected from the group consisting of oxygen, sulfur, carbon, nitrogen, phosphorus, silicon, selenium, tin and boron. And, when it is a hydrocarbon group, a group consisting of 3 or more carbon atoms. ) 15. In the formula (II-a), at least one of R ^{6 and} R ¹⁰ is a halogen atom, a hydrocarbon group, a hydrocarbon-substituted silyl group, an alkoxy group, an aryloxy group, an ester group, an amide group, The catalyst for olefin polymerization according to claim 14, wherein the catalyst is an amino group, a sulfonamide group, a cyano group or a nitro group. 16. The catalyst for olefin polymerization according to claim 12, wherein in the transition metal compound (A ′), M is a transition metal atom belonging to Group 4 or 5 of the periodic table. . 17. The transition metal compound (A ^′ ) according to any one of claims 12 to 16, and (B-1) an organometallic compound,
-2) An olefin polymerization catalyst comprising a carrier (C) in addition to at least one compound (B) selected from an organic aluminum oxy compound and (B-3) an ionized ionic compound. 18. A method for polymerizing olefins, comprising polymerizing or copolymerizing olefins in the presence of the catalyst for olefin polymerization according to claim 12. 19. A transition metal compound represented by the following general formula (III): (Wherein, M represents a transition metal atom belonging to Group 4 or 5 of the periodic table, m represents an integer of 1 to 3, R ¹ represents a hydrocarbon group, a hydrocarbon-substituted silyl group, or a hydrocarbon-substituted siloxy group) A group, an alkoxy group, an alkylthio group, an aryloxy group, an arylthio group, an ester group, a thioester group, a sulfone ester group or a hydroxy group; R ^{2 to} R ⁵ may be the same or different; A hydrocarbon group, a heterocyclic compound residue, a hydrocarbon-substituted silyl group, a hydrocarbon-substituted siloxy group,
Alkoxy group, alkylthio group, aryloxy group, arylthio group, ester group, thioester group, amide group,
Imide group, amino group, imino group, sulfone ester group,
A sulfonamide group, a cyano group, a nitro group, a carboxyl group, a sulfo group, a mercapto group or a hydroxy group; R ⁶ represents a halogen atom, a hydrocarbon group, a hydrocarbon-substituted silyl group, a hydrocarbon-substituted siloxy group, an alkoxy group, Alkylthio group, aryloxy group, arylthio group, ester group, thioester group, amide group, imide group, imino group,
A sulfone ester group, a sulfonamide group or a cyano group, two or more of R ^{1 to} R ⁶ may be connected to each other to form a ring, and when m is 2 or more, R ¹ Two of the groups represented by R ⁶ to R ⁶ may be linked (however, R ¹ is not bonded to each other), n is a number satisfying the valence of M, and X is , 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, when n is 2 or more, a plurality of groups represented by X may be the same or different from each other, and a plurality of groups represented by X are bonded to each other to form a ring. You may. ) 20. The transition metal compound according to claim 19, which is represented by the following general formula (III-a): (Wherein, M represents a transition metal atom belonging to Group 4 or 5 of the periodic table, m represents an integer of 1 to 3, R ^{1 to} R ⁵ may be the same or different, and may be a hydrocarbon. R ⁶ represents a halogen atom, a hydrocarbon group, a hydrocarbon-substituted silyl group, an alkoxy group, an alkylthio group or a cyano group; and 2 of R ^{1 to} R ⁶ Or more may be connected to each other to form a ring, and when m is 2 or more, two of the groups represented by R ^{1 to} R ⁶ may be connected (provided that , R ¹ are not bonded to each other), n is a number that satisfies the valence of M, X is a halogen atom, a hydrocarbon group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a halogen-containing group. A group or a silicon-containing group, and when n is 2 or more, a plurality of groups represented by X Groups may be the same or different from each other, and a plurality of groups represented by X may be bonded to each other to form a ring.) 21. The method according to claim 2, wherein m is 2.
0. The transition metal compound according to 0. 22. The transition metal compound (A ") according to any one of claims 19 to 21, (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 the transition metal compound (A). 23. The transition metal compound (A ") according to claim 22, and (B-1) an organometallic compound, (B-2) an organoaluminum oxy compound and (B-3) a transition metal compound (A"). ). A catalyst for olefin polymerization, which comprises a carrier (C) in addition to at least one compound (B) selected from compounds that form an ion pair by reacting with (a). 24. A method for polymerizing olefins, comprising polymerizing or copolymerizing olefins in the presence of the catalyst for olefin polymerization according to claim 22 or 23. 25. The molecular weight distribution (Mw / Mn) is 3.5.
Wherein the content of the structural unit derived from the α-olefin is in the range of 1 to 99.9 mol%, the content of the structural unit derived from the conjugated diene is in the range of 99 to 0.1 mol%, And 1, derived from a conjugated diene in the polymer chain
An α-olefin / conjugated diene copolymer having a 2-cyclopentane skeleton content of 1 mol% or less. 26. A polymer chain comprising 1,1 derived from a conjugated diene.
The α-olefin / conjugated diene copolymer according to claim 25, which does not substantially contain a 2-cyclopentane skeleton. 27. The content of the structural unit derived from the α-olefin is in the range of 50 to 99.9 mol%, and the content of the structural unit derived from the conjugated diene is 50 to 0.1 mol%.
The α-olefin / conjugated diene copolymer according to claim 25 or 26, wherein 28. The α-olefin is ethylene and / or propylene, and the conjugated diene is butadiene and / or propylene.
28. The α-olefin / conjugated diene copolymer according to claim 25, which is isoprene.