JP2004076016A - Olefin polymerization catalyst, transition metal compound, method for polymerizing olefin and alpha-olefin-conjugated diene copolymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide olefin polymerization catalysts showing excellent polymerization activity, a method for polymerizing olefin using the catalyst, new transition metal compounds useful for olefin polymerization catalyst and α-olefin conjugated diene copolymers with specific physical properties. <P>SOLUTION: The olefin polymerization catalyst comprises (A) a transition metal compounds represented by formula (I) or (II) and (B) an organometallic compound, organic aluminumoxy compound or an ionizable compound which is ionized. The new transition metal compound is represented by formula (I) wherein M denotes a transition metal of group 4 or 5 of the Periodic Table; m denotes an integer of 1-3; R<SP>1</SP>denotes a hydrocarbon group or the like; R<SP>2</SP>-R<SP>5</SP>each denotes H, a halogen, a hydrocarbon group or the like; R<SP>6</SP>a denotes a halogen, a hydrocarbon group or the like; n denotes a number satisfying the valence of M; and X denotes a halogen, a hydrocarbon group or the like. <P>COPYRIGHT: (C)2004,JPO

Description

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

The 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.

カ As a catalyst for olefin polymerization, a so-called Kaminski catalyst is well known. This catalyst is characterized by a very high polymerization activity and a polymer having a narrow molecular weight distribution. Examples of the transition metal compound used in such a Kaminsky catalyst include bis (cyclopentadienyl) zirconium dichloride (see JP-A-58-19309, Patent Document 1) and ethylenebis (4,5,6). , 7-tetrahydroindenyl) zirconium dichloride (see Japanese Patent Application Laid-Open No. Sho 61-130314, Patent Document 2) and the like are known. It is also known that, when a transition metal compound used for 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 (see International Patent Publication No. WO9623010, Patent Document 3) has been proposed as a new catalyst for olefin polymerization.

By the way, polyolefins are generally used in various fields such as for various molded articles because of their excellent mechanical properties and the like.In recent years, however, demands for physical properties of polyolefins have been diversified, and polyolefins of various properties are desired. ing. It is also desired to improve productivity.

Under these circumstances, there has been a demand for an olefin polymerization catalyst that is excellent in olefin polymerization activity and can produce a polyolefin having excellent properties.

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

ジ Such a diene component includes conjugated dienes such as 1,3-butadiene and isoprene. These conjugated dienes are inexpensive and highly reactive compared to conventionally used non-conjugated dienes.However, when copolymerization is performed using a conventional Ziegler-Natta polymerization catalyst, the activity is significantly reduced, There has been a problem that only a heterogeneous copolymer having a wide composition distribution and molecular weight distribution can be obtained. Further, in a 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, research has been actively conducted, and copolymerization of ethylene and butadiene using a so-called metallocene catalyst which is known to exhibit high polymerization activity has been studied (Japanese Patent Laid-Open No. 1-501633, Patent Reference 4).

However, in this case, it is 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 unit. 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, the cyclopentane skeleton is an undesirable skeleton because it has an effect of increasing the glass transition temperature of the copolymer and impairs the low-temperature properties of the rubber.

Under such circumstances, the appearance of a copolymer of an α-olefin and a conjugated diene having a narrow molecular weight distribution, a uniform composition, and having almost no cyclopentane skeleton in the polymer chain has been strongly desired.
JP-A-58-19309 JP-A-61-130314 International Patent Publication No. WO9623010 Japanese Patent Publication No. Hei 1-501633

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.

The 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.

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

(Wherein, M represents a transition metal atom of 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 heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, A containing group, a 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,
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 satisfying the valence of M;
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, and a silicon-containing residue. A group, a germanium-containing group, or a tin-containing group, and when n is 2 or more, a plurality of groups represented by X may be the same or different from each other, and a plurality of groups represented by X bind to each other To form a ring. )
In the 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, a silicon-containing group. It is preferably a 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).

(Wherein, M represents a transition metal atom of 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 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. , 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 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),
n is a number satisfying the valence of M;
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, and a silicon-containing residue. A group, a germanium-containing group, or a tin-containing group, and when n is 2 or more, a plurality of groups represented by X may be the same or different from each other, and a plurality of groups represented by X bind to each other To form a ring. )
In the general formula (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, an 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 is preferable. .

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

(Wherein, M represents a transition metal atom of 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 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. Represents 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. Two or more of which may be connected 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),
n is a number satisfying the valence of M;
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 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 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, or 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.

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).

(Wherein, M represents a transition metal atom of 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, 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 nitrile group or a nitro group, two or more of these groups may be connected 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 connected (however, R ¹ is not bonded to each other). )
In the general 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, a sulfonamide group, a cyano group or a nitro group. Is preferred.

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 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) 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.

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

Further, the second olefin polymerization catalyst according to the present invention,
(A ′) a transition metal compound represented by the following general formula (II):
(B) (B-1) an organometallic compound,
(B-2) at least one compound selected from an organic aluminum oxy compound and (B-3) a compound which forms an ion pair by reacting with the transition metal compound (A ′).

(Wherein, M represents a transition metal atom of Groups 3 to 11 of the periodic table,
R ^{1 to} R ¹⁰ 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 containing group, a 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;
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, and a silicon-containing residue. A group, a germanium-containing group, or a tin-containing group, and when n is 2 or more, a plurality of groups represented by X may be the same or different from each other, and a plurality of groups represented by X bind to each other 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 when it is a hydrocarbon group, it is a group consisting of 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 group, a silicon-containing group, a germanium-containing group, or a tin-containing group.

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

(Wherein, M represents a transition metal atom of Groups 3 to 11 of the periodic table,
R ^{1 to} R ¹⁰ 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, and 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,
n is a number satisfying the valence of M;
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 bonding group 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, It is a group consisting of three or more carbon atoms. )
In the general 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 sulfonamide. It is preferably a 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 organic aluminum oxy compound, and (B-3) an ionized ionic compound. The carrier (C) may be contained in addition to at least one compound (B) selected from the compounds.

第 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.

新 規 The novel transition metal compound according to the present invention is represented by the following general formula (III).

(Wherein, M represents a transition metal atom of 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, 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, 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, an alkoxy group, an alkylthio group. , Aryloxy group, arylthio 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 Indicates that
R ⁶ is 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,
Two or more of R ^{1 to} R ⁶ 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),
n is a number satisfying the valence of M;
X represents 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, and germanium. 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 are bonded to each other to form a ring It may be formed. )
The transition metal compound is preferably represented by the following general formula (III-a).

(Wherein, M represents a transition metal atom of 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 represent 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;
Two or more of R ^{1 to} R ⁶ 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),
n is a number satisfying the valence of M;
X represents a halogen atom, a hydrocarbon group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a halogen-containing group or a silicon-containing group, and when n is 2 or more, a plurality of groups represented by X are the same as each other And a plurality of groups represented by X may be bonded to each other to form a ring. )
In the general formula (III-a), m is preferably 2.

The third olefin polymerization catalyst according to the present invention comprises the transition metal compound (A "), (B) an organometallic compound (B-1), (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 reacts with the 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 forming an ion pair.

第 A 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 content of the constituent unit derived from the conjugated diene is in the range of 50 to 99.9 mol%. It 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 preferably ethylene and / or propylene, and the conjugated diene is preferably butadiene and / or isoprene.

オ レ フ ィ ン The olefin polymerization catalyst according to the present invention 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 an α-olefin and a 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 an olefin polymerization catalyst, and provides an olefin (co) polymer having a high polymerization activity and a narrow molecular weight distribution.

Α The α-olefin / conjugated diene copolymer according to the present invention has a narrow molecular weight distribution and hardly contains a cyclopentane skeleton in a polymer chain.

Hereinafter, the olefin polymerization catalyst and the olefin polymerization method using the catalyst according to the present invention will be specifically described.

In the present specification, the term "polymerization" may be used to mean not only homopolymerization but also copolymerization, and the term "polymer" means not only homopolymer but also copolymer. It is sometimes used in a sense that also includes coalescence.

First olefin polymerization catalyst The first olefin polymerization catalyst according to the present invention is:
(A) a transition metal compound represented by the following general formula (I);
(B) (B-1) an organometallic compound,
And (B-3) at least one compound selected from the group consisting of an organic aluminum oxy compound and (B-3) a compound which reacts with a transition metal compound to form an ion pair.

First, each catalyst component forming the catalyst for olefin polymerization of the present invention will be described.

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

(Note that, here, N ... M generally indicates coordination, but in the present invention, coordination may or may not be performed.)
In the formula (I), M represents a transition metal atom of Groups 3 to 11 of the periodic table (Group 3 also includes lanthanoids), preferably Group 3 to Group 9 (Group 3 also includes lanthanoids). It is a metal atom, more preferably a metal atom of groups 3 to 5 and 9, and particularly preferably a metal atom of group 4 or 5. Specifically, scandium, titanium, zirconium, hafnium, vanadium, niobium, tantalum, cobalt, rhodium, yttrium, chromium, molybdenum, tungsten, manganese, rhenium, iron, ruthenium and the like, preferably scandium, titanium, zirconium, Hafnium, vanadium, niobium, tantalum, cobalt, rhodium, etc., more preferably titanium, zirconium, hafnium, cobalt, rhodium, vanadium, niobium, tantalum, etc., and particularly preferably titanium, zirconium, hafnium.

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 containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group, and two or more of these 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, n-hexyl, and the like. 1-20 linear or branched alkyl groups;
A linear or branched alkenyl group having 2 to 30, preferably 2 to 20 carbon atoms, such as vinyl, allyl and isopropenyl;
A linear or branched alkynyl group having 2 to 30 carbon atoms, preferably 2 to 20 carbon atoms, such as ethynyl and propargyl;
A cyclic saturated hydrocarbon group having 3 to 30, preferably 3 to 20 carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and adamantyl; and a cyclic unsaturated hydrocarbon group having 5 to 30 carbon atoms such as cyclopentadienyl, indenyl and fluorenyl. Saturated hydrocarbon groups;
Aryl groups having 6 to 30, preferably 6 to 20 carbon atoms, such as phenyl, benzyl, naphthyl, biphenyl, terphenyl, phenanthryl and anthracenyl;
Examples include alkyl-substituted aryl groups such as tolyl, iso-propylphenyl, t-butylphenyl, dimethylphenyl, di-t-butylphenyl, and the like.

In the hydrocarbon group, a hydrogen atom may be substituted with a halogen. For example, a halogenated hydrocarbon group having 1 to 30, preferably 1 to 20 carbon atoms such as trifluoromethyl, pentafluorophenyl, and chlorophenyl may be used. No.

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

Furthermore, the hydrocarbon group may be a heterocyclic compound residue; such as an alkoxy group, an aryloxy group, an ester group, an ether group, an acyl group, a carboxyl group, a carbonate group, a hydroxy group, a peroxy group, and a carboxylic anhydride group. Oxygen-containing group; amino group, imino group, amide group, imide group, hydrazino group, hydrazono group, nitro group, nitroso group, cyano group, isocyano group, cyanate ester group, amidino group, diazo group, and amino group are ammonium salts Nitrogen-containing groups such as those described below; boron-containing groups such as borandiyl, borantoriyl, and diboranyl groups; mercapto, thioester, dithioester, alkylthio, arylthio, thioacyl, thioether, and thiocyanate groups , Isothiocyanate group, sulfone ester group Sulfur-containing groups such as sulfonamide group, thiocarboxyl group, dithiocarboxyl group, sulfo group, sulfonyl group, sulfinyl group, and sulfphenyl group; phosphorus-containing groups such as phosphide group, phosphoryl group, thiophosphoryl group, phosphato group, and silicon-containing group Group, a germanium-containing group, or a tin-containing group.

Among them, in particular, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, neopentyl, n-hexyl and the like having 1 to 30, preferably 1 to 20 carbon atoms. A linear or branched alkyl group; an aryl group having 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms, such as phenyl, naphthyl, biphenyl, terphenyl, phenanthryl, and anthracenyl; A substituted aryl group in which 1 to 5 substituents such as an alkyl group or an alkoxy group having 1 to 30, preferably 1 to 20, an aryl group or an aryloxy group having 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms are substituted; Is preferred.

Examples of the oxygen-containing group, the nitrogen-containing group, the boron-containing group, the sulfur-containing group, and the phosphorus-containing group include the same as those exemplified above.

Examples of the heterocyclic compound residue include pyrrole, pyridine, pyrimidine, quinoline, triazine and other nitrogen-containing compounds, furan, pyran and other oxygen-containing compounds, thiophene and other sulfur-containing compounds, and the like. Examples thereof include groups in which a 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, a hydrocarbon-substituted siloxy group, and specifically, methylsilyl, dimethylsilyl, trimethylsilyl, ethylsilyl, diethylsilyl, triethylsilyl, diphenylmethylsilyl, triphenyl Examples include phenylsilyl, 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, ethylthio and the like.

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, 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.

Specific examples of the amide group include acetamido, N-methylacetamido, N-methylbenzamide, and the like.

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

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

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.

Preferably, R ⁶ is 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. Particularly, 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, 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 or a hydroxy group.

Preferred hydrocarbon groups as R ⁶ are those having 1 to 30 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, thiopentyl and n-hexyl. Is a linear or branched alkyl group having 1 to 20; a cyclic saturated hydrocarbon group having 3 to 30, preferably 3 to 20 carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and adamantyl; phenyl, benzyl , Naphthyl, biphenylyl, triphenylyl and the like having 6 to 30 carbon atoms, preferably 6 to 20 aryl groups; and these groups having 1 to 30 carbon atoms, preferably 1 to 20 alkyl groups or alkoxy groups. A halogenated alkyl group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms; The properly 6-20 aryl group or an aryloxy group, a halogen, a cyano group, a nitro group, a group having a substituted group is further substituted, such as hydroxy groups are preferably exemplified.

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

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

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

N is a number that satisfies the valence of M, and is specifically an integer of 0 to 5, preferably 1 to 4, and more preferably 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, a heterocyclic compound residue, and 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.

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

の う ち Among them, those having 1 to 20 carbon atoms are preferable.

Examples of the heterocyclic compound residue include the same as those exemplified above for R ^{1 to} R ⁶ .

Examples of the oxygen-containing group include the same groups as those exemplified above for R ^{1 to} R ^6. Specific examples include a hydroxy group; an alkoxy group such as methoxy, ethoxy, propoxy, and butoxy; phenoxy, methylphenoxy, and dimethyl. Examples include, but are not limited to, aryloxy groups such as phenoxy and naphthoxy; arylalkoxy groups such as phenylmethoxy and phenylethoxy; acetoxy groups; and carbonyl groups.

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, sulfonate groups such as p-toluenesulfonate, trimethylbenzenesulfonate, triisobutylbenzenesulfonate, p-chlorobenzenesulfonate, and pentafluorobenzenesulfonate; methylsulfinate, phenylsulfinate, benzyl Examples include, but are not limited to, sulfinate groups such as sulfinate, p-toluenesulfinate, trimethylbenzenesulfinate, and pentafluorobenzenesulfinate; alkylthio groups; and arylthio groups.

Specific examples of the nitrogen-containing group include the same groups as those exemplified above for R ^{1 to} R ⁶ , specifically, an amino group; methylamino, dimethylamino, diethylamino, dipropylamino, dibutylamino, Examples include, but are not limited to, alkylamino groups such as dicyclohexylamino; arylamino groups such as phenylamino, diphenylamino, ditolylamino, dinaphthylamino, and methylphenylamino, or alkylarylamino groups.

Specific examples of the boron-containing group include BR ₄ (R represents hydrogen, an alkyl group, an aryl group which may have a substituent, a halogen atom, or the like).

Specific examples of the phosphorus-containing group include trialkyl phosphine groups such as trimethyl phosphine, tributyl phosphine, and tricyclohexyl phosphine; triaryl phosphine groups such as triphenyl phosphine and tolyl phosphine; methyl phosphite, ethyl phosphite, and phenyl phosphite Phosphite groups (phosphide groups); phosphonic acid groups; phosphinic acid groups, and the like, but are not limited thereto.

Specific examples of the silicon-containing group include the same ones as those described above for R ^{1 to} R ⁶ , and specifically, phenylsilyl, diphenylsilyl, trimethylsilyl, triethylsilyl, tripropylsilyl, tricyclohexylsilyl Hydrocarbon-substituted silyl groups such as triphenylsilyl, methyldiphenylsilyl, tolylsilyl, and trinaphthylsilyl; hydrocarbon-substituted silyl ether groups such as trimethylsilyl ether; silicon-substituted alkyl groups such as trimethylsilylmethyl; And an aryl group.

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

Specific examples of the halogen-containing group include a fluorine-containing group such as PF ₆ and BF ₄ , a chlorine-containing group such as ClO ₄ and SbCl ₆ , and an iodine-containing group such as IO ₄ , but are not limited thereto. Absent.

Specific examples of the aluminum-containing group include AlR ₄ (R represents a hydrogen, an alkyl group, an aryl group which may have a substituent, a halogen atom, etc.), 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, and a plurality of groups represented by X 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.

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 heterocyclic compound residue, a hydrocarbon-substituted silyl group, a hydrocarbon-substituted siloxy group, an alkoxy group, an 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, 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 is specifically an integer of 0 to 5, preferably 1 to 4, and more preferably 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, a heterocyclic compound residue, and a silicon-containing residue. Group, germanium-containing group, or 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, and a plurality of groups represented by X may be bonded to each other to form a ring.と し て As such a transition metal compound, a compound represented by the following general formula (I-a-1) is particularly preferable.

In the formula (Ia-1), R ^{1 to} R ⁶ , M and X include the same as described above,
In particular, the following are 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 Group 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, 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, an alkoxy group, an alkylthio group. , An aryloxy group, an arylthio group, a thioester group, an ester group, an acyl 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, 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 having 3 to 20 carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and adamantyl; an aryl having 6 to 20 carbon atoms such as phenyl, benzyl, naphthyl, biphenylyl and triphenylyl A group having 5 to 20 carbon atoms such as cyclopentadienyl, indenyl, and fluorenyl A saturated hydrocarbon group; and 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, Examples thereof include an alkoxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, a group further substituted with a substituent such as a halogen, a cyano group, a nitro group or a hydroxy group. Among these, 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, hexyl, etc. 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. A substituted aryl group substituted with 1 to 5 substituents such as an alkoxy group having 1 to 20 and an aryloxy group having 6 to 20 carbon atoms is preferable.

Examples of the heterocyclic compound residue include pyrrole, pyridine, pyrimidine, quinoline, triazine and other nitrogen-containing compounds, furan, pyran and other oxygen-containing compounds, thiophene and other sulfur-containing compounds, and the like. Examples include groups in which a compound residue is further substituted with a substituent such as an alkyl group having 1 to 20 carbon atoms or an alkoxy group.

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

と し て 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, tert-butoxy and the like.

Specific examples of the alkylthio group include methylthio, ethylthio and the like. 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, 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.

Specific examples of the amide group include acetamido, N-methylacetamido, N-methylbenzamide, and the like.

Specific examples of the imido 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, and phenylimino.

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.

Preferably, R ⁶ is 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, 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.

Preferred hydrocarbon groups as R ⁶ include linear groups having 1 to 20 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl and hexyl. Or a branched alkyl 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 20 carbon atoms such as phenyl, benzyl, naphthyl, biphenylyl, and triphenylyl. 20 aryl groups; and 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. Groups which are further substituted by substituents such as a group, halogen, cyano group, nitro group and hydroxy group are preferred. Are listed.

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, as R ⁶ , particularly, a branched alkyl group having 3 to 20 carbon atoms such as isopropyl, isobutyl, sec-butyl, tert-butyl and the like, and a hydrogen atom of these groups having 6 to 6 carbon atoms. It is preferably a group selected from cyclic substituted hydrocarbon groups having 3 to 20 carbon atoms such as a group substituted with 20 aryl groups (such as a cumyl group), adamantyl, cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl, or It is also preferably a hydrocarbon-substituted silyl group.

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

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

N is a number that satisfies the valence of M, and is specifically an integer of 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, a silicon-containing group, and the like. In the case of two or more, they may be the same or different.

Examples of the halogen atom include 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, an aryl group and the like. More specifically, methyl, ethyl, propyl, butyl, 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; And aryl groups such as phenyl, tolyl, dimethylphenyl, trimethylphenyl, ethylphenyl, propylphenyl, biphenyl, naphthyl, methylnaphthyl, anthryl, and phenanthryl.

Examples of the halogenated hydrocarbon group having 1 to 20 carbon atoms include groups in which the above 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 the oxygen of the oxygen-containing group is substituted by sulfur, and methyl sulfonate, trifluoromethane sulfonate, phenyl sulfonate, benzyl sulfonate, p-toluene sulfonate, trimethyl Sulfonate groups such as benzenesulfonate, triisobutylbenzenesulfonate, p-chlorobenzenesulfonate, and pentafluorobenzenesulfonate; methylsulfinate, phenylsulfinate, benzylsulfinate, p-toluenes Examples include sulfinate groups such as ruffinate, 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, triphenylsilyl, Trihydrocarbon-substituted silyl groups such as dimethylphenylsilyl, methyldiphenylsilyl, tritolylsilyl and trinaphthylsilyl; silyl ether groups of hydrocarbon-substituted silyl such as trimethylsilyl ether; silicon-substituted alkyl groups such as trimethylsilylmethyl; And a silicon-substituted aryl group.

The group represented by 示 X 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 R ^{1 to} R ⁶
The compound in which two groups (excluding R ¹ ) among the groups represented by are linked is, for example, a compound represented by the following general formula (Ia-2).

In the formula (Ia-2), M, R ^{1 to} R ⁶ and X are the same as those in the general formula (I), and R ^{11 to} R ¹⁶ are 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 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, 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, and the like. shows the same atom or group as ¹ to R ^6. Two or more groups of R ^{1 to} R ¹⁶ , preferably adjacent groups, may be linked to each other to form an aliphatic ring, an aromatic ring, or a hydrocarbon ring containing a hetero atom such as a nitrogen atom. Good.

Y ′ bonds at least one or more groups selected from R ^{1 to} R ⁶ and at least one or more groups selected from R ^{11 to} R ¹⁶ (where R ¹ and R ¹¹ are 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. 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 A cyclic unsaturated hydrocarbon residue; a heterocyclic compound residue having 3 to 20 carbon atoms including a heteroatom such as pyridine, quinoline, thiophene and furan; -SiH _2- , -Si (CH ₃ ) _2- A silicon atom-containing group such as —SnH ₂ —
, -Sn (CH _{3) 2} - tin atom-containing groups such as; -BH -, - B (CH 3) -, - such as boron-containing group such as BF-, or a single bond.

Hereinafter, specific examples of the transition metal compound represented by the general formula (Ia-1) are shown, but the invention is not limited thereto.

In the following specific examples, M is a transition metal element, and Sc (III), Ti (III), Ti (IV), Zr (III), Zr (IV), Hf (IV), V ( IV), Nb (V), Ta (V), Co (II), Co (III), Rh (II), Rh (III), Rh (IV), but are not limited thereto. Of these, Ti (IV), Zr (IV) and Hf (IV) are particularly 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.

Δn is determined by the valence of the metal M. For example, when two monoanion species are bonded 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.

In the above examples, Me represents a methyl group, Et represents an ethyl group, iPr represents an i-propyl group, tBu represents a tert-butyl group, and Ph represents a phenyl group.

Further 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.

に お い て 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.

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

Δm is an integer of 1 to 6, preferably an integer of 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 or a nitro group.

の う ち Among these groups, 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, and a nitro group are particularly preferable.

Examples of the groups R ^{1 to} R ⁶ include those similar to those exemplified for the transition metal compounds represented by the general formulas (I) and (Ia).

When m is 2 or more, R ^{1 to} R ⁶ may form a ring by connecting two or more 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.

で は In the present invention, a transition metal compound in which cobalt metal is replaced with a metal such as titanium, zirconium, hafnium, iron, copper, rhodium or the like in the above-mentioned compounds can also be used.

遷移 The above transition metal compounds (A) are used alone or in combination of two or more. Further, it can be used in combination with a transition metal compound other than the 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 compound other than the 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)

In the formula, M represents a transition metal atom of 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, a halogenated hydrocarbon group having 1 to 50 carbon atoms, a hydrocarbon-substituted silyl group or nitrogen, oxygen, phosphorus, And a hydrocarbon group substituted with a substituent containing at least one element selected from sulfur and silicon.

Groups represented by R ²¹ to R ²⁴ is two or more of these, preferably may form a ring adjacent groups together.

Q represents an integer of 0 to 4.

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

In the formula, M represents a transition metal atom of Groups 3 to 6 of the periodic table, and is preferably titanium, zirconium, or hafnium.

R ′ and R ″ may be the same or different, 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 an integer of 1 to 5.

A represents an atom belonging to Groups 13 to 16 of the periodic table, and specifically includes boron, carbon, nitrogen, oxygen, silicon, phosphorus, sulfur, germanium, selenium, tin, and the like, and is carbon or silicon. Is preferred. 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, or may be linked to each other to form a ring.

P is an integer of 0 to 4.

X represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group, a sulfur-containing group, a silicon-containing group or a nitrogen-containing group. 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) Transition metal diphenoxy compound represented by the following formula (Ie)

In the formula, M represents a transition metal atom of Groups 3 to 11 of the periodic table, l and m are each an integer of 0 or 1, and A and A 'are a hydrocarbon group having 1 to 50 carbon atoms, 1 to 5 atoms
0 or a hydrocarbon group having a substituent containing oxygen, sulfur or silicon, or a halogenated hydrocarbon group having 1 to 50 carbon atoms, wherein A and A 'are the same or different. You may.

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

N is a number that satisfies the valence of M.

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. , 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-4) Transition metal compound containing a ligand having a cyclopentadienyl skeleton containing at least one hetero atom represented by the following formula (If)

ＭIn the formula, M represents a transition metal atom of Groups 3 to 11 of the periodic table.

X represents an atom belonging to Group 13, 14, or 15 of the periodic table, and at least one of X is an element other than carbon.

A represents 0 or 1.

R may be the same or different from each other, and at least one selected from a hydrogen atom, a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a hydrocarbon-substituted silyl group, or nitrogen, oxygen, phosphorus, sulfur, and silicon A hydrocarbon group substituted with a substituent containing a kind of element, and 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 even if Rs are cross-linked, Good.

C is a number that satisfies the valence of M.

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

When c is 2 or more, a plurality of groups represented by Y may be the same or different from each other, 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 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)

In the formula, Y ₁ and Y ₃ may be the same or different from each other, 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 include a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group, It represents a sulfur-containing group or a silicon-containing group, and two or more of these may be linked to each other to form a ring.
(a-7) a compound of the following formula (Ih) and a group VIII transition metal atom

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

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,
n is an integer of 0 or 1,
p is an integer of 1 to 3,
q is a number that satisfies the valence of M.

R ^{41 to} R ⁴⁸ 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, a silicon-containing group or a nitrogen-containing group, and two or more of these may be connected to each other to form a ring.

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

Y is a group that bridges the borata benzene ring, and represents carbon, silicon or germanium.

A represents an element belonging to Group 14, 15, or 16 of the periodic table.

(B-1) Organometallic compound As the (B-1) organometallic compound used in the present invention, specifically, organometallic compounds of Groups 1 and 2 and Groups 12 and 13 of the periodic table as shown below are used. Used.

(B-1a) formula _{^{R a m Al (OR b)}} n H p X q
(Wherein, R ^a and R ^b may be the same or different and each represent a hydrocarbon group having 1 to 15, preferably 1 to 4 carbon atoms, X represents a halogen atom, and m represents 0 <M ≦ 3, n is 0 ≦ n <3, p is 0 ≦ p <3, q is a number 0 ≦ q <3, and m + n + p + q = 3.)
An organoaluminum compound represented by the formula:

(B-1b) 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 a 1-4 hydrocarbon group.)
A complex alkylated product of a metal of Group 1 of the periodic table represented by the formula 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 represent a hydrocarbon group having 1 to 15, preferably 1 to 4 carbon atoms, and M ³ is Mg, Zn or Cd. .)
A dialkyl compound of a metal of Group 2 or 12 of the periodic table represented by the formula:

有機 Examples of the organoaluminum compound belonging to (B-1a) include the following compounds.

Formula _{^{R a m Al (OR b)}} 3-m
(Wherein, R ^a and R ^b may be the same or different from each other, and represent a hydrocarbon group having 1 to 15, preferably 1 to 4 carbon atoms, and m is preferably 1.5 ≦ m ≦ This is the number 3.)
An organoaluminum compound represented by
Formula R ^a _m AlX _3-m
(In the formula, Ra represents ^a hydrocarbon group having 1 to 15, preferably 1 to 4 carbon atoms, X represents a halogen atom, and m preferably represents 0 <m <3.) Organic aluminum compounds,
Formula R ^a _m AlH _3-m
(In the formula, Ra represents ^a hydrocarbon group having 1 to 15, preferably 1 to 4 carbon atoms, and m preferably satisfies 2 ≦ m <3.)
An organoaluminum compound represented by
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 and have 1 to 15 carbon atoms.
Preferably represents 1 to 4 hydrocarbon groups, X represents a halogen atom, m is a number of 0 <m ≦ 3, n is a number of 0 ≦ n <3, q is a number of 0 ≦ q <3, and m + n + q = 3. )
An organoaluminum compound represented by the formula:

More specifically, the organoaluminum compounds belonging to (B-1a) include trimethylaluminum, triethylaluminum, tri-n-butylaluminum, tripropylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum and the like. n-alkyl aluminum;
Triisopropylaluminum, triisobutylaluminum, trisec-butylaluminum, tritert-butylaluminum, tri2-methylbutylaluminum, tri3-methylbutylaluminum, tri2-methylpentylaluminum, tri3-methylpentylaluminum, tri4 Tri-branched alkyl aluminums such as -methylpentyl aluminum, tri 2-methylhexyl aluminum, tri 3-methylhexyl aluminum, tri 2-ethylhexyl aluminum;
Tricycloalkyl aluminums such as tricyclohexyl aluminum, tricyclooctyl aluminum;
Triaryl aluminums such as triphenyl aluminum and tolyl aluminum;
Dialkyl aluminum hydrides such as diisobutyl aluminum hydride;
_{(I-C 4 H 9)} x Al y (C 5 H 10) z ( wherein, x, y, z are each a positive number, and z ≧ 2x.) Tri isoprenylaluminum represented by like Trialkenyl aluminum such as;
Alkylaluminum alkoxides such as isobutylaluminum methoxide, isobutylaluminum ethoxide, isobutylaluminum isopropoxide;
Dialkylaluminum alkoxides such as dimethylaluminum methoxide, diethylaluminum ethoxide, dibutylaluminum butoxide;
Alkyl aluminum sesqui alkoxides such as ethyl aluminum sesqui ethoxide, butyl aluminum sesqui butoxide;
R ^a _2.5 Al (OR ^b) partially alkylaluminum which is alkoxylated with an average composition represented by like _0.5;
Diethyl aluminum phenoxide, diethyl aluminum (2,6-di-t-butyl-4-methylphenoxide), ethyl aluminum bis (2,6-di-t-butyl-4-methylphenoxide), diisobutyl aluminum (2,6- Dialkylaluminum aryloxides such as di-t-butyl-4-methylphenoxide) and isobutylaluminum bis (2,6-di-t-butyl-4-methylphenoxide);
Dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, dibutylaluminum chloride, diethylaluminum bromide and diisobutylaluminum chloride;
Alkyl aluminum sesquihalides such as ethylaluminum sesquichloride, butylaluminum sesquichloride and ethylaluminum sesquibromide; partially halogenated alkylaluminums such as alkylaluminum dihalides such as ethylaluminum dichloride, propylaluminum dichloride and butylaluminum dibromide ;
Dialkylaluminum hydrides such as diethylaluminum hydride, dibutylaluminum hydride;
Other partially hydrogenated alkylaluminums such as alkylaluminum dihydrides such as ethylaluminum dihydride, propylaluminum dihydride;
Partially alkoxylated and halogenated alkyl aluminums such as ethylaluminum ethoxycyclolide, butylaluminum butoxycyclolide, ethylaluminum ethoxybromide and the like can be mentioned.

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

As the compound belonging to (B-1b),
LiAl (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.

A compound that forms the above-mentioned organoaluminum compound in the polymerization system, for example, a combination of aluminum halide and alkyllithium, or a combination of aluminum halide and alkylmagnesium can also be used.

(B-1) Among the organometallic compounds, an organoaluminum compound is preferable.

は The above-mentioned (B-1) organometallic compounds are used alone or in combination of two or more.

(B-2) Organoaluminum oxy compound (B-2) The organoaluminum oxy compound used in the present invention may be a conventionally known aluminoxane, or as exemplified in JP-A-2-78687. It 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 cerous 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 water vapor 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 organometallic component. The solvent or the unreacted organoaluminum compound may be removed from the recovered solution of aluminoxane by distillation, and then redissolved in a solvent or suspended in a poor solvent for aluminoxane.

Specific examples of the organoaluminum compound used in preparing the aluminoxane include the same organoaluminum compounds as those exemplified as the organoaluminum compound belonging to the above (B-1a).

の う ち Of these, trialkylaluminum and tricycloalkylaluminum are preferable, and trimethylaluminum is particularly preferable.

有機 The above-mentioned organoaluminum compounds are used alone or in combination of two or more.

Solvents used in the preparation of aluminoxane include aromatic hydrocarbons such as benzene, toluene, xylene, cumene, cymene, aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane, octadecane, and cyclopentane , Cyclohexane, cyclooctane, alicyclic hydrocarbons such as methylcyclopentane, gasoline, kerosene, petroleum fractions such as light oil or the above aromatic hydrocarbons, aliphatic hydrocarbons, halides of alicyclic hydrocarbons, especially chlorine And hydrocarbon solvents such as bromides. Further, ethers such as ethyl ether and tetrahydrofuran can also be used. Among these solvents, aromatic hydrocarbons and aliphatic hydrocarbons are particularly preferred.

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

有機 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.

In the formula, R ¹⁷ represents a hydrocarbon group having 1 to 10 carbon atoms.

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

The organoaluminum oxy compound containing boron represented by the general formula (IV) includes an alkylboronic acid represented by the following general formula (V) and R ¹⁷ -B- (OH) ₂ ... (V)
(In the formula, R ¹⁷ represents the same group as described above.)
It can be produced by reacting an organoaluminum compound in an inert solvent under an inert gas atmosphere 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-hexylboron. Acid, cyclohexylboronic acid, phenylboronic acid, 3,5-difluoroboronic acid, pentafluorophenylboronic acid, 3,5-bis (trifluoromethyl) phenylboronic acid and the like. Among these, methylboronic acid, n-butylboronic acid, isobutylboronic acid, 3,5-difluorophenylboronic acid, and pentafluorophenylboronic acid are preferred. These may be used alone or in combination of two or more.

と し て Specific examples of the organoaluminum compound to be reacted with the alkylboronic acid include the same organoaluminum compounds as those exemplified as the organoaluminum compound belonging to (B-1a).

の う ち Among these, trialkylaluminum and tricycloalkylaluminum are preferable, and trimethylaluminum, triethylaluminum and triisobutylaluminum are particularly preferable. These may be used alone or in combination of two or more.

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

(B-3) A compound that forms an ion pair by reacting with a transition metal compound A compound that forms an ion pair by reacting with a transition metal compound used in the present invention (B-3) (hereinafter, referred to as an “ionized ionic compound” Is a compound which reacts with the transition metal compound (A) to form an ion pair. Examples of such a compound include JP-A-1-501950, JP-A-1-502036 and JP-A-1-502036. Lewis acids, ionic compounds, borane compounds, and carboranes described in JP-A-3-179005, JP-A-3-179006, JP-A-3-207703, JP-A-3-207704, and USP-5321106. And the like. Furthermore, heteropoly compounds and isopoly compounds can also be mentioned.

Specifically, as the Lewis acid, a compound represented by BR ₃ (R is a phenyl group or a fluorine which may have a substituent such as a fluorine, a methyl group, and a trifluoromethyl group) is exemplified. 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).

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

R ^{20 to} R ²³ may be the same or different from each other 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; N, N-dimethylanilinium cation; N, N-dialkylanilinium cations such as N, N-diethylanilinium cation and N, N-2,4,6-pentamethylanilinium cation; dialkylammonium cations such as di (isopropyl) ammonium cation and dicyclohexylammonium cation And the like.

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

R ¹⁹ is preferably a carbonium cation, an ammonium cation, or the like, and particularly preferably a triphenylcarbonium cation, an N, N-dimethylanilinium cation, or an N, N-diethylanilinium cation.

Also, examples of the ionic compound include a trialkyl-substituted ammonium salt, an N, N-dialkylanilinium salt, a dialkylammonium salt, and a triarylphosphonium salt.

Specific examples of the trialkyl-substituted ammonium salt include, for example, triethylammonium tetra (phenyl) boron, tripropylammonium tetra (phenyl) boron, tri (n-butyl) ammonium tetra (phenyl) boron, trimethylammonium tetra (p-tolyl) Boron, trimethylammonium tetra (o-tolyl) boron, tri (n-butyl) ammonium tetra (pentafluorophenyl) boron, tripropylammonium tetra (o, p-dimethylphenyl) boron, tri (n-butyl) ammonium tetra ( m, m-dimethylphenyl) boron, tri (n-butyl) ammonium tetra (p-trifluoromethylphenyl) boron, tri (n-butyl) ammonium tetra (3,5-ditrifluoromethylphenyl) boron, tri (n -Butyl) ammonium Umtetra (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 dialkylammonium salts include, for example, di (1-propyl) ammonium tetra (pentafluorophenyl) boron and dicyclohexylammonium tetra (phenyl) boron.

Further, as ionic compounds, triphenylcarbenium tetrakis (pentafluorophenyl) borate, N, N-dimethylaniliniumtetrakis (pentafluorophenyl) borate, ferrocenium tetra (pentafluorophenyl) borate, triphenylcarbenium pentaphenyl Examples thereof include a cyclopentadienyl complex, an N, N-diethylanilinium pentaphenylcyclopentadienyl complex, and a boron compound represented by the following formula (VII) or (VIII).

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

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 Salts of anions such as, bis [tri (n-butyl) ammonium] decachlorodecaborate, bis [tri (n-butyl) ammonium] dodecachlorododecaborate;
Of metal borane anions such as tri (n-butyl) ammonium bis (dodeca hydride dodecaborate) cobaltate (III) and bis [tri (n-butyl) ammonium] bis (dodeca hydride dodecaborate) nickelate (III) And the like.

Specific examples of the carborane compound include, for example, 4-carbanonaborane (14), 1,3-dicarbanonaborane (13), 6,9-dicarbadecaborane (14), dodecahydride-1-phenyl-1,3 -Dicarbanonaborane, dodecahydride-1-methyl-1,3-dicarbanonaborane, undecahydride-1,3-dimethyl-1,3-dicarbanonaborane, 7,8-dicarboundecaborane ( 13), 2,7-dicarboundecaborane (13), undecahydride-7,8-dimethyl-7,8-dicarboundecaborane, dodecahydride-11-methyl-2,7-dicarboundecaborane, Tri (n-butyl) ammonium 1-
Carbadecaborate, tri (n-butyl) ammonium 1-carboundecaborate, tri (n-butyl) ammonium 1-carbadodecaborate, tri (n-butyl) ammonium 1-trimethylsilyl-1-carbadecaborate, tri ( n-butyl) ammonium bromo-1-carbadedecaborate, tri (n-butyl) ammonium 6-carbadecaborate (14), tri (n-butyl) ammonium 6-carbadecaborate (12), tri (n-butyl) ) Ammonium 7-carboundecaborate (13), tri (n-butyl) ammonium 7,8-dicarboundecaborate (12), tri (n-butyl) ammonium 2,9-dicarboundecaborate (12), Tri (n-butyl) ammonium dodecahydride-8-methyl-7,9-dicarbaundecaborate, tri (n-butyl) ammonium unde Hydride-8-ethyl-7,9-dicarboundecaborate, tri (n-butyl) ammonium undecahydride -8-butyl-7,9-dicarboundecaborate, tri (n-butyl) ammonium undecahydride- 8-allyl-7,9-dicarboundecaborate, tri (n-butyl) ammonium undecahydride-9-trimethylsilyl-7,8-dicarboundecaborate, tri (n-butyl) ammonium undecahydride-4, Salts of anions such as 6-dibromo-7-carboundecaborate;
Tri (n-butyl) ammonium bis (nonahydride-1,3-dicarbanonaborate)
Cobaltate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-
Dicarboundecaborate) ferrate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarboundecaborate) cobaltate (III), tri (n-butyl) ammoniumbis ( Undecahydride-7,8-dicarboundecaborate) nickelate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarboundecaborate) cuprate (III), (N-butyl) ammonium bis (undecahydride-7,8-dicarboundecaborate) aurate (III), tri (n-butyl) ammonium bis (nonahydride-7,8-dimethyl-7,8- Dicarboundecaborate) ferrate (III), tri (n-butyl) ammonium bis (nonahydride-7,8-dimethyl-7,8-dicarboundecaborate) chromate (III), tri (n- Butyl) ammonium Mbis (tribromooctahydride-7,8-dicarboundecaborate) cobaltate (III), tris [tri (n-butyl) ammonium] bis (undecahydride-7-carboundecaborate) chromate ( III), bis [tri (n-butyl) ammonium] bis (undecahydride-7-
Carbaundecaborate) manganate (IV), bis [tri (n-butyl) ammonium] bis (undecahydride-7-carboundecaborate) cobaltate (III), bis [
Tri (n-butyl) ammonium] bis (undecahydride-7-carboundecaborate) nickelate (IV) and the like, and salts of metal carborane anions.

The heteropoly compound is composed of atoms composed of silicon, phosphorus, titanium, germanium, arsenic or tin, and one or more atoms selected from vanadium, niobium, molybdenum and tungsten. Specifically, phosphorus vanadic acid, germanovanadate, arsenic vanadate, phosphorus niobate, germanoniobate, siliconomolybdate, phosphomolybdate, titanium molybdate, germanomolybdate, arsenic molybdate, tin molybdate, phosphorus molybdate, phosphorus Tungstic acid, germanotoungstic acid, tin tungstic acid, phosphomolybdovanadic acid, phosphorus tungstovanadic acid, germanotangostovanadate acid, phosphomolybdo tongue vanadate acid, germano molybdo tungstovanadate 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 salt, and isopoly compound can be used but not limited thereto.

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.

は The (B-3) ionized ionic compound as described above is 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 used in combination with an organoaluminum oxy compound (B-2) such as methylaluminoxane as a co-catalyst component, it exhibits a very high polymerization activity for olefin compounds. 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.

Further, the catalyst for olefin polymerization according to the present invention comprises the above transition metal compound (A), (B-1) an organometallic compound, (B-2) an organoaluminum oxy compound, and (B-3) an ionized ionic compound. A carrier (C) as described below can be used together with at least one compound (B) selected, 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.

う ち 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 ₂
O ₃ , CaO, ZnO, BaO, ThO _2, etc., or composites or mixtures containing them, such as natural or synthetic zeolites, SiO ₂ —MgO, SiO ₂ —Al ₂ O ₃ , SiO ₂ —TiO ₂ , SiO _{2 -V 2 O 5, SiO 2} -Cr 2 O 3, etc. can be used SiO ₂ -TiO ₂ -MgO. Among them, those containing SiO ₂ and / or Al ₂ O ₃ as a main component are preferable.

In addition, the above inorganic oxide contains a small amount of Na ₂ CO ₃ , K ₂ CO ₃ , CaCO ₃ , MgCO ₃ , Na ₂ SO ₄ , Al ₂ (SO ₄ ) ₃ , BaSO ₄ , KNO ₃ , Mg (NO ₃ ) ₂ , carbonates such as Al (NO ₃ ) ₃ , Na ₂ O, K ₂ O and Li ₂ O, sulfates, nitrates and oxide components may be contained.

Such porous oxides have different properties depending on the kind and the production method, but the carrier preferably used in the present invention has a particle size of 10 to 300 μm, preferably 20 to 200 μm, and a specific surface area of 50 to 1000 m. ² / g, preferably in the range of 100 to 700 m ² / g, and the pore volume is desirably in the range of 0.3 to 3.0 cm ³ / g. Such a carrier is
If necessary, it is used by firing at 100 to 1000 ° C, preferably 150 to 700 ° C.

As the inorganic chloride, MgCl ₂ , MgBr 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 a fine particle with a precipitant can also be used.

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

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

Examples of such clays and clay minerals include kaolin, bentonite, kibushi clay, gairome clay, allophane, hysingelite, pyrophyllite, plum group, montmorillonite group, vermiculite, ryokudeite group, palygorskite, kaolinite, nacrite, dickite. , Halloysite, and the like, and examples of the ion-exchangeable layered compound include α-Zr (
HAsO ₄ ) ₂ .H ₂ O, α-Zr (HPO ₄ ) ₂ , α-Zr (KPO ₄ ) ₂ .3H ₂ O, α-Ti (HPO ₄ ) ₂ , α-Ti (HAsO ₄ ) ₂ .H ₂ O, α-Sn (HPO ₄ ) ₂ .H ₂ O, γ-Zr (HPO ₄ ) ₂ , γ-Ti (HPO ₄ ) ₂ , γ-Ti (NH ₄ PO ₄ ) ₂ .H ₂ O Crystalline acidic salts of polyvalent metals 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, preferably 0.3 to 5 cc / g, as measured by a mercury intrusion method. Is 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.

When a material having a pore volume of {radius 20} or more and smaller than 0.1 cc / g is used as a carrier, high polymerization activity tends to be hardly obtained.

粘土 It is also preferable to subject the clay or clay mineral used in the present invention to a chemical treatment. As the chemical treatment, any of a surface treatment for removing impurities adhering to the surface, a treatment that affects the crystal structure of clay, and the like can be used. Specific examples of the chemical treatment include an acid treatment, an alkali treatment, a salt treatment, and an organic substance treatment. The acid treatment removes impurities on the surface and increases the surface area by eluting cations such as Al, Fe, and Mg in the crystal structure. Alkali treatment destroys the crystal structure of the clay, causing 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 may be a layered compound in which the layers are expanded by utilizing ion-exchangeability and exchanging exchangeable ions between layers with another large bulky ion. . Such bulky ions play a pillar-like role for supporting the layered structure, and are usually called pillars. 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, and metal alkoxides such as Ti (OR) ₄ , Zr (OR) ₄ , PO (OR) ₃ and B (OR) ₃ ( R is a hydrocarbon group, etc.), metal hydroxide ions such as [Al ₁₃ O ₄ (OH) ₂₄ ] ⁷⁺ , [Zr ₄ (OH) ₁₄ ] ²⁺ , [Fe ₃ O (OCOCH ₃ ) ₆ ] ⁺ And the like. These compounds are used alone or in combination of two or more. When intercalating these compounds, they were obtained by hydrolyzing metal alkoxides (R is a hydrocarbon group, etc.) such as Si (OR) ₄ , Al (OR) ₃ , and Ge (OR) ₄ . Polymer, Si
A colloidal inorganic compound such as O ₂ can also coexist. Examples of the pillar include oxides formed by intercalating the metal hydroxide ions between layers and then heating and dehydrating the layers.

粘土 The clay, clay mineral, and ion-exchange layered compound used in the present invention may be used as they are, or may be used after performing a treatment such as ball milling or sieving. Further, it may be used after newly adding and adsorbing water or performing a heat dehydration treatment. Furthermore, they may be used alone or in combination of two or more.

Among them, preferred are clay or clay mineral, and particularly preferred are montmorillonite, vermiculite, pectolite, teniolite and synthetic mica.

Examples of the organic compound include a granular or particulate solid having a particle size in the range of 10 to 300 μm. Specifically, ethylene, propylene, 1-butene, 4-methyl-1-
(Co) polymers mainly composed of α-olefins having 2 to 14 carbon atoms such as pentene or (co) polymers mainly composed of vinylcyclohexane and styrene, and modified products thereof Can be exemplified.

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

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

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

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

The carboxylic acids, typically those represented by R ³² -COOH are used. R ³² represents a hydrocarbon group having 1 to 50 carbon atoms or a halogenated hydrocarbon group having 1 to 50 carbon atoms, particularly preferably a halogenated hydrocarbon group having 1 to 50 carbon atoms.

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.

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.

At the time of polymerization, the method of use and the order of addition of each component are arbitrarily selected, and the following methods are exemplified.
(1) Component (A) and at least one component (B) selected from the group consisting of (B-1) an organometallic compound, (B-2) an organoaluminum oxy compound, and (B-3) an ionized ionic compound Simply referred to as “component (B)”) in any order.
(2) A method in which the catalyst in which the component (A) and the component (B) are brought into contact in advance is added to the polymerization reactor. (3) A method in which the catalyst component in which the component (A) and the component (B) are brought into contact in advance and the component (B) are added to the polymerization reactor in an arbitrary order. In this case, the components (B) may be the same or different.
(4) A method in which the catalyst component in which the component (A) is supported on the carrier (C) and the component (B) are added to the polymerization reactor in any order.
(5) A method in which a catalyst in which the component (A) and the component (B) are supported on a carrier (C) is added to a polymerization reactor.
(6) A method in which the catalyst component in which the component (A) and the component (B) are supported on the carrier (C) and the component (B) are added to the polymerization reactor in an arbitrary order. In this case, the components (B) may be the same or different.
(7) A method in which the catalyst component in which the component (B) is supported on the carrier (C) and the component (A) are added to the polymerization reactor in any order.
(8) A method in which the catalyst component in which the component (B) is supported on the carrier (C), the component (A), and the component (B) are added to the polymerization reactor in any order. In this case, the components (B) may be the same or different.
(9) A method in which a component in which the component (A) is supported on the carrier (C) and a component in which the component (B) is supported on the carrier (C) are added to the polymerization reactor in any order.
(10) 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 a polymerization vessel in any order.
(12) A method in which the component (B) and the component (D) are brought into contact in advance, and the component (A) is added to the polymerization reactor in any order.
(13) A method in which the component (B) and the component (D) supported on the carrier (C) and the component (A) are added to the polymerization vessel in any order.
(14) A method in which the 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 vessel in any order.
(18) A method in which a component in which the component (A) is supported on the carrier (C) and a component in which the component (B) and the component (D) are brought into contact in advance are added to the polymerization reactor in an arbitrary order.
(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 component (A), the component (B), and the component (D) are supported on a carrier (C) is added to a polymerization reactor.
(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.

は 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.

で は 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.

で は 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 include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; cyclopentane, cyclohexane, and 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.

When olefin polymerization is carried out using the olefin polymerization catalyst as described above, the component (A) is used in an amount of usually 10 ^-12 to 10 ^-2 mol, preferably 10 ^-10 to 10 ^-3 , per liter of the reaction volume. It is used in a molar amount. 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.

Component (B-1) has a molar ratio [(B-1) / M] between component (B-1) and transition metal atom (M) in component (A) of usually 0.01 to 100,000, Preferably, it is used in an amount of 0.05 to 50,000. Component (B-2) has a molar ratio [(B-2) / M] of aluminum atom in component (B-2) to transition metal atom (M) in component (A) of usually 10 to 10. It is used in an amount of 500,000, preferably 20 to 100,000. Component (B-3) has a molar ratio [(B-3) / M] of component (B-3) to transition metal atom (M) in component (A) of usually 1 to 10, preferably 1 to 10. It is used in such an amount as to be 1 to 5.

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

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

(4) 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.

Examples of the olefin that can be polymerized by such an olefin polymerization catalyst include linear or branched α-olefins having 2 to 30 carbon atoms, preferably 2 to 20 carbon atoms, for example, 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;
Cyclic olefins having 3 to 30, preferably 3 to 20 carbon atoms, such as cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, 2-methyl 1,4,5,8-dimethano- 1,2,3,4,4a, 5,8,8a-octahydronaphthalene;
Polar monomers, for example, α, such as acrylic acid, methacrylic acid, fumaric acid, maleic anhydride, itaconic acid, itaconic anhydride, bicyclo (2,2,1) -5-heptene-2,3-dicarboxylic anhydride; β-unsaturated carboxylic acids and their sodium, potassium, lithium salts,
Metal salts such as zinc salt, magnesium salt and calcium salt; methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, acrylate 2 Α, β-unsaturated carboxylic esters such as -ethylhexyl, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate; vinyl acetate, vinyl propionate, caproon Vinyl esters such as vinyl acrylate, vinyl caprate, vinyl laurate, vinyl stearate and vinyl trifluoroacetate; and unsaturated glycidyl such as glycidyl acrylate, glycidyl methacrylate, and monoglycidyl itaconate. That. 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 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, for example styrene, o-methyl styrene, m-methyl styrene, p-methyl styrene, o, p-dimethyl styrene, o-ethyl styrene, m-ethyl styrene, mono- or poly-ethyl styrene Alkyl styrene;
Functional group-containing styrene derivatives such as methoxystyrene, ethoxystyrene, vinylbenzoic acid, methyl vinylbenzoate, vinylbenzyl acetate, hydroxystyrene, o-chlorostyrene, p-chlorostyrene, divinylbenzene; and 3-phenylpropylene, Examples include phenylpropylene and α-methylstyrene.

第 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.

オ レ フ ィ ン The olefin polymerization catalyst according to the present invention can also be used for copolymerizing an α-olefin and a conjugated diene.

Examples of the α-olefin used herein include the same linear or branched α-olefins having 2 to 30, preferably 2 to 20 carbon atoms as described above. 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, 1,3-hexadiene, Aliphatic conjugated dienes having 4 to 30, preferably 4 to 20 carbon atoms, such as octadiene, are mentioned. These conjugated dienes can be used alone or in combination of two or more.

In the present invention, when copolymerizing an α-olefin and a conjugated diene, a non-conjugated diene or polyene can be further used.As the non-conjugated diene or polyene, 1,4-pentadiene, 1,5-hexadiene, 1 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.

Second olefin polymerization catalyst Next, the second olefin polymerization catalyst according to the present invention will be described.

The second olefin polymerization catalyst according to the present invention,
(A ′) a transition metal compound represented by the following general formula (II):
(B) (B-1) an organometallic compound,
(B-2) an organic 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).

(Wherein, M represents a transition metal atom of Groups 3 to 11 of the periodic table;
R ^{1 to} R ¹⁰ 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 containing group, a 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;
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, and a silicon-containing residue. A group, a germanium-containing group, or a tin-containing group, and when n is 2 or more, a plurality of groups represented by X may be the same or different from each other, and a plurality of groups represented by X bind to each other 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 when it is a hydrocarbon group, it is a group consisting of 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, a boron-containing group, a sulfur-containing group, It is preferably 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 may 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.

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

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 particularly titanium. .

R ^{1 to} R ¹⁰ 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, and a sulfonamide group. , A nitrile group or a nitro group, two or more of which, preferably adjacent groups, may be connected to each other to form a ring.

N is a number satisfying the valence of M, and is generally an integer of 0 to 4, preferably 1 to 4, and 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 bonding group 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, It is a group consisting of three 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 or more and 20 or less, and particularly preferably 4 or more and 10 or less. In addition, these bonding groups may have a substituent.

In the general formula (II-a), at least one of R ^{6 and} R ¹⁰ , 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, It is preferably a sulfonamide group, a nitrile group or a nitro group.

In the general formula (II-a), specific examples of X and R ^{1 to} R ¹⁰ include the same groups as X and R ^{1 to} R ⁶ described in the general formulas (I) and (Ia). X is particularly preferably a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a sulfonate group. When n is 2 or more, the ring formed by connecting two or more Xs to each other may be an aromatic ring or an aliphatic ring.

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

Specific examples of the transition metal compound represented by the above general formula (II) are shown below, but it should not be construed that the invention is limited thereto.

In the above examples, Me represents a methyl group, and Ph represents a phenyl group.

で は 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 above-mentioned compounds can also be used.

In the second olefin polymerization catalyst according to the present invention, the transition metal compound (A ′) can be used in combination with another transition metal compound, as in the case of the transition metal compound (A). Specifically, the compounds (a-1) to (a-8) exemplified above are exemplified.

Further, the organometallic compound (B-1) used in the second olefin polymerization catalyst according to the present invention,
Examples of the compound (B-3) which reacts with the organoaluminum oxy compound (B-2) and the transition metal compound (A ') to form an ion pair include those described above.

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

２ 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.

に お い て 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 is represented by the following general formula (III).

In the formula (III), 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, 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, 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, an alkoxy group, an alkylthio group. , Aryloxy group, arylthio 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 Indicates that
R ⁶ is 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,
Two or more of R ^{1 to} R ⁶ 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),
n is a number satisfying the valence of M;
X represents 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, and germanium. 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 are bonded to each other to form a ring It may be formed.

の う ち Among the transition metal compounds of the general formula (III), those represented by the following general formula (III-a) are preferable.

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

m represents an integer of 1 to 3, preferably 2.
R ^{1 to} R ⁵ may be the same or different, and represent 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;
Two or more of R ^{1 to} R ⁶ 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),
n is a number satisfying the valence of M;
X represents a halogen atom, a hydrocarbon group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a halogen-containing group or a silicon-containing group, and when n is 2 or more, a plurality of groups represented by X are the same as each other And a 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).

Examples of the novel transition metal compound are as follows.

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.

First, the ligand constituting the transition metal compound according to the present invention may be a salicylaldehyde compound, a primary amine compound of the formula R ¹ —NH ₂ (R ¹ has the above-mentioned meaning), for example, an aniline compound It is obtained by reacting with a compound or an alkylamine compound. Specifically, both starting compounds are dissolved in a solvent. As the solvent, those commonly used for such a reaction 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, or toluenesulfonic acid may be used as a catalyst. Further, when molecular sieves, magnesium sulfate or sodium sulfate is used as a dehydrating agent, or when dehydration is performed by Dean-Stark, the reaction proceeds effectively.

Next, the ligand thus obtained is reacted with a transition metal M-containing compound, whereby 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. The mixture is stirred at -78 ° C to room temperature or under reflux for about 1 to 48 hours. As the solvent, those which are commonly used in such a reaction can be used, and among them, polar solvents such as ether and tetrahydrofuran (THF), and hydrocarbon solvents such as toluene are preferably used. Further, as a base used when preparing a phenoxide salt, a lithium salt such as n-butyllithium, a metal salt such as a sodium salt such as sodium hydride, and an organic base such as triethylamine and pyridine are preferable. Not as long.

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

新 規 The novel transition metal compound of the present invention represented by the general formula (III), preferably the general formula (III-a) can be suitably used, for example, as an olefin polymerization catalyst.

用 い る 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 has a constitutional unit derived from an α-olefin of 1 to 99.9 mol%, a constitutional unit derived from a conjugated diene. Is preferably from 99 to 0.1 mol%, more preferably from 50 to 99.9 mol% of the constituent unit derived from the α-olefin, and from 50 to 0.1 mol% of the constituent unit derived from the conjugated diene. .

In the polymer chain of the α-olefin / conjugated diene copolymer according to the present invention, the content of the 1,2-cyclopentane skeleton derived from the conjugated diene can be regarded as 1 mol% or less, preferably substantially not contained. Content (less than 0.1 mol%). 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.

Examples of the α-olefin used herein include the same linear or branched α-olefins having 2 to 30, preferably 2 to 20 carbon atoms as described above. 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, 1,3-hexadiene, Aliphatic conjugated dienes having 4 to 30, preferably 4 to 20 carbon atoms, such as octadiene, are mentioned. These conjugated dienes can be used alone or in combination of two or more.

In the present invention, when copolymerizing an α-olefin and a conjugated diene, a non-conjugated diene or polyene can be further used.As the non-conjugated diene or polyene, 1,4-pentadiene, 1,5-hexadiene, 1 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.

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. 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 can be measured by ¹³ C-NMR and ¹ H-NMR according to the method described in Die Makromolekulare 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 of 1,000 or more in weight average molecular weight (Mw). Preferably it is 5000 or more.

に お い て In the present invention, the α-olefin / conjugated diene copolymer can have various modifications by having a double bond in the main chain or side chain. For example, a double bond can be epoxidized by peroxide modification, and a highly reactive epoxy group can be introduced 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 all of the α-olefin / conjugated diene copolymer may be modified with an unsaturated carboxylic acid, a derivative thereof, or an aromatic vinyl compound, and the modification amount is 0.01 to 30% by weight. % Is preferable.

Examples of the monomer used for the modification (hereinafter, referred to as “graft monomer”) include an unsaturated carboxylic acid, a derivative thereof, and an aromatic vinyl compound. 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. Specific examples include 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, monomethyl itaconate 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-phenylmaleimide, sodium acrylate, sodium methacrylate, potassium acrylate, potassium methacrylate and the like can be mentioned. It is preferable to use maleic anhydride among these graft monomers.

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

Various known methods can be employed to produce a modified copolymer by graft copolymerizing a graft monomer with an α-olefin / conjugated diene copolymer. 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.

In order to produce a graft-modified α-olefin / conjugated diene copolymer having a graft ratio of 0.01 to 30% by weight partially or wholly modified, from the industrial viewpoint, a graft having a higher graft ratio is required. A modified α-olefin / conjugated diene copolymer is prepared, and then the unmodified α-olefin / conjugated diene copolymer is mixed with the graft-modified α-olefin / conjugated diene copolymer. The method of adjusting the ratio is a preferable method because the concentration of the graft monomer in the composition can be appropriately adjusted.However, from the beginning, the α-olefin / conjugated diene copolymer is graft-modified with a predetermined amount of the graft monomer. No problem.

The amount of modification 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 in the range of 0.01 to 30% by weight, particularly 0.05 to 10% by weight. Preferably, there is.

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

(i) Polyolefin resin The (a) 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. It may be a mixture of different polyolefin resins.

Examples of the crystalline polyolefin include a homopolymer or copolymer of an α-olefin or a cyclic olefin having 2 to 20 carbon atoms. Examples of the amorphous polyolefin include a copolymer of one or more α-olefins having 2 to 20 carbon atoms and one or more cyclic olefins.

Examples of the α-olefin having 2 to 20 carbon atoms include ethylene, propylene, 1-butene, 2-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene and 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 Examples thereof include 1-butene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene.

Cyclic olefins include cyclopentene, cycloheptene, cyclohexene, norbornene, 5-ethyl-2-norbornene, tetracyclododecene, 2-ethyl-1,4,5,8-dimetano
-1,2,3,4,4a, 5,8,8a-octahydronaphthalene and the like.

Specific examples of the crystalline polyolefin resin include the following (1) to (11) (co) polymers, and the following (3) and (5) are particularly preferable.
(1) Ethylene homopolymer (production method may be either low-pressure method or high-pressure method)
(2) Copolymer of ethylene and other α-olefin or vinyl monomer (eg, vinyl acetate, ethyl acrylate, etc.) or cyclic olefin of 20 mol% or less (3) Propylene homopolymer (4) Propylene and 20 (5) a random copolymer with not more than mol% of another α-olefin (5) a block copolymer of propylene and not more than 30 mol% of other α-olefin (6) 1-butene homopolymer (7) 1- (8) 4-methyl-1-pentene homopolymer (9) 4-methyl-1-pentene and 20% by mole or less of another α-butene and other α-olefin random copolymer (8) -Random copolymer with olefin (10) Cyclopentene homopolymer (11) Random copolymer of cyclopentene with 20% by mole or less of other α-olefin.

As the “other α-olefin” in the above (1) to (11), among the α-olefins exemplified above, preferably, ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-hexene , 1-octene is used. Further, as the cyclic olefin, preferably, cyclopentene, cyclohexene, norbornene, or tetracyclododecene is used.

Such a crystalline polyolefin resin has a melt flow rate (measured under the conditions of 230 ° C. and a load of 2.16 kg according to ASTM D1238-65T) of 0.01 to 100 g / 10 min, preferably 0.3 to 70 g / 10 min. Desirably within the range of minutes. The crystallinity determined by the X-ray diffraction method is usually in the range of 5 to 100%, preferably 20 to 80%.

Such a crystalline polyolefin resin can be produced 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 α-olefin / conjugated diene copolymer according to the present invention can be blended with the copolymer. (ii) As the filler, a commonly used filler can be used as needed without any particular limitation.

Specific examples of the inorganic filler include silicates such as fine powder talc, kaolinite, calcined clay, pyrophyllite, sericite, and wollastonite, and carbonates such as precipitated calcium carbonate, heavy calcium carbonate, and magnesium carbonate. Powders such as hydrated aluminum, hydroxides such as magnesium hydroxide, oxides such as zinc oxide, zinc white, and magnesium oxide; synthetic silica such as hydrous calcium silicate, hydrous aluminum silicate, hydrous silicic acid, and silicic anhydride; Fillers;
Flaky fillers such as mica;
Basic magnesium sulfate whisker, calcium titanate whisker, aluminum borate whisker, sepiolite, PMF (Processed Mineral Fiber), zonotolite,
Fibrous fillers such as potassium titanate and elestadite;
Balun-like fillers such as glass balun and 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 It is desirable that the olefin / conjugated diene copolymer is contained in an amount of 10 to 90 parts by weight, preferably 15 to 80 parts by weight, more preferably 20 to 75 parts by weight.

When the α-olefin / conjugated diene copolymer is used in an amount within the above range, a molded article having excellent impact resistance, weather resistance, and thermal stability, as well as excellent rigidity, strength, and heat resistance is provided. As a result, an α-olefin / conjugated diene copolymer composition having excellent moldability can be obtained.

(i) polyolefin resin, when the total amount of the resulting composition is 100 parts by weight, 1 to
It is desirable that it be contained in an amount of 99 parts by weight, preferably 10 to 85 parts by weight, more preferably 20 to 80 parts by weight.

(i) When the polyolefin resin is used in an amount in the above range, the α-olefin / conjugated diene polymer composition is excellent in impact resistance and cold resistance and excellent in rigidity, strength, heat resistance and moldability. Is obtained.

(Ii) The filler is preferably 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 having excellent rigidity, surface appearance, heat resistance and the like can be obtained.

Further, the α-olefin / conjugated diene copolymer according to the present invention includes a nucleating agent, an antioxidant, a hydrochloric acid absorber, a heat stabilizer, a light stabilizer, and an ultraviolet absorber as long as the object of the present invention is not impaired. Agents, lubricants, antistatic agents, flame retardants, pigments, dyes, dispersants, copper damage inhibitors, neutralizing agents, foaming agents, plasticizers, foam inhibitors, crosslinking agents, crosslinking aids, crosslinking accelerators, peroxides Additives such as flow improvers such as materials, weld strength improvers, processing aids, weathering stabilizers, and blooming inhibitors may be added. These optional additives may be used in combination of two or more.

[Example]
Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited to these examples.

The structure of the compound obtained in the synthesis example is 270 MHz ¹ H-NMR (JEOL GSH-270), FT-IR (SHIMAZU FTIR-8200D), FD-mass spectrometry (JEOL SX-102A), metal content It was determined by analysis (after dry incineration / dilute nitric acid dissolution, analysis by ICP method; SHIMAZU ICPS-8000), carbon, hydrogen, nitrogen content analysis (Heraus CHNO type) and the like.

構造 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 radiation using a Rigaku AFC7R four-axis diffractometer. Structural analysis was performed using the direct method (SIR92), and structural optimization was performed using a TeXan crystal structure analysis program.

In this example, the intrinsic viscosity [η] was measured in decalin at 135 ° C. The molecular weight distribution (Mw / Mn) was determined by measurement by gel permeation chromatography (GPC) at 140 ° C. using o-dichlorobenzene as a solvent.

具体 Specific examples of ligand synthesis are shown below.

[Ligand Synthesis Example 1]
Synthesis of Ligand (L1) 40 ml of ethanol, 0.71 g (7.62 mmol) of aniline and 1.35 g (7.58 mmol) of 3-t-butylsalicylaldehyde were charged into a 100 ml reactor which had been sufficiently purged with nitrogen. Stirring was continued for hours. The reaction solution was concentrated under reduced pressure to remove the solvent, 40 ml of ethanol 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.

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 Spec: 253
[Ligand Synthesis Example 2]
Synthesis of Ligand (L2) 30 ml of ethanol, 1.43 g (9.99 mmol) of α-naphthylamine and 1.40 g (7.86 mmol) of 3-t-butylsalicylaldehyde were charged into a 100 ml reactor which had been sufficiently purged with nitrogen. After adding 5 g of Sieves 3A, the mixture was stirred for 8 hours under reflux, and further stirred at room temperature for 12 hours. 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.

¹ H-NMR (CDCl ₃ ): 1.50 (s, 9H) 6.90-7.90 (m, 11H) 8.30-8.50 (m, 1H) 13.90 (s, 1H)
FD-Mass Spectrometry: 303
[Ligand Synthesis Example 3]
Synthesis of Ligand (L3) 30 ml of ethanol, 0.90 g (12.0 mmol) of t-butylamine and 1.78 g (10.0 mmol) of 3-t-butylsalicylaldehyde were charged into a 100 ml reactor which had been sufficiently purged with nitrogen. After adding 5 g of Sieves 3A, stirring was continued at room temperature for 12 hours. The reaction solution was concentrated under reduced pressure, and purified by a silica gel column to obtain 2.17 g (9.3 mmol, 93% yield) of a compound of a fluorescent yellow oil represented by L3.

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 Spec: 233
[Ligand Synthesis Examples 4 to 42]
The following ligands L4 to L42 were synthesized in the same manner as in the above ligand synthesis example.

The structure was identified by ¹ H-NMR and FD-mass spectrometry.

Specific synthesis examples of the transition metal compound according to the present invention are shown below.

[Synthesis Example 1]
Synthesis of Compound A-1 :
1.785 g (7.05 mmol) of compound L1 and 100 ml of diethyl ether were charged into a 300 ml reactor which was sufficiently dried and purged with argon, cooled to −78 ° C., and stirred. To this, 4.78 ml of n-butyllithium (1.55 mmol / 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. Prepared. This solution is -78 ° C
Was slowly added dropwise to 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.

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 obtained solid was dissolved and washed with 50 ml of methylene chloride to remove insolubles. The filtrate was concentrated under reduced pressure, the precipitated solid was dissolved in 10 ml of methylene chloride, and 70 ml of pentane was slowly added 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) of compound A-1 as red-brown crystals represented by the following formula.
Yield 61%).

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 Spec: 622 (M +)
Elemental analysis: Ti; 7.7% (7.7)
C; 65.8% (65.5) H; 6.0% (5.8) N; 4.5% (4.5) () is calculated value Melting point: 265 ℃
X-ray crystal structure analysis: The structure of the obtained compound A-1 is shown in FIG.

[Synthesis Example 2]
Synthesis of Compound B-1 :
Compound 200 (1.53 g, 6.04 mmol) and 60 ml of tetrahydrofuran were charged into a 200 ml reactor which was sufficiently dried and purged with argon, cooled to −78 ° C., and stirred. To this, 4.1 ml of n-butyllithium (1.55 mmol / ml n-hexane solution, 6.34 mmol) was added dropwise over 5 minutes, and then the temperature was slowly raised to room temperature, and further stirred at room temperature for 4 hours. A mixed solution obtained by adding 10 ml of tetrahydrofuran thereto was gradually added to a solution of 0.70 g of zirconium tetrachloride (purity: 99.9%, 3.02 mmol) in 30 ml of tetrahydrofuran cooled to -78 ° C. After the addition, the temperature was slowly raised to room temperature. After stirring at room temperature for 2 hours, stirring was continued under reflux for 4 hours.

The 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. for one day under nitrogen, whereby yellow crystals precipitated. The solid was filtered off, washed with hexane, and dried under reduced pressure to obtain 1.09 g (1.63 mmol, yield 54%) of compound B-1 as a fluorescent yellow crystal represented by the following formula.

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 Spec: 664 (M +)
Elemental analysis: Zr; 13.5% (13.7)
C; 61.0% (61.2) H; 5.5% (5.4) N; 4.2% (4.2) () is calculated value Melting point: 287 ℃
X-ray crystal analysis: FIG. 4 shows the structure of the obtained compound B-1.

[Synthesis Example 3]
Synthesis of Compound C-1 :
Compound L1; 0.66 g (2.60 mmol) and 8 ml of diethyl ether were charged into a 100 ml reactor which was sufficiently dried and purged with argon, cooled to −78 ° C., and stirred. To this, 1.81 ml of n-butyllithium (1.55 mmol / ml n-hexane solution, 2.80 mmol) was added dropwise over 5 minutes, and then the temperature was slowly raised to room temperature, followed by stirring at room temperature for 2 hours. A mixed solution obtained by adding 10 ml of tetrahydrofuran thereto was gradually added to a solution of 0.385 g of hafnium tetrachloride (purity: 99.9%, 3.02 mmol) cooled to −78 ° C. to a solution of 10 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 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 obtain 0.33 g (0.40 mmol, 33% yield) of compound C-1 as a fluorescent white crystal represented by the following formula.

¹ H-NMR (CDCl ₃ ): 1.30 (s, 18H) 6.70-7.50 (m, 16H) 8.18 (s, 2H)
FD-Mass Spec: 754 (M +)
Elemental analysis: Hf; 23.5% (23.7)
C; 54.4% (54.2) H; 4.8% (4.8) N; 3.6% (3.7) () is calculated value Melting point: 277 ℃
[Synthesis Example 4]
Synthesis of Compound D-1 :
In a 100 ml reactor that was sufficiently dried and purged with argon, 0.61 g (2.40 mmol) of compound L1 and 10 ml of diethyl ether were charged, cooled to −78 ° C., and stirred. 1.61 ml of n-butyllithium (1.55 mmol / ml n-hexane solution, 2.50 mmol) was added dropwise thereto over 5 minutes, and then the temperature was slowly raised to room temperature, followed by stirring at room temperature for 4 hours. The solution was gradually added to a solution of 0.385 g (purity: 99.9%, 3.02 mmol) of hafnium tetrachloride cooled to -78 ° C in 10 ml of anhydrous diethyl ether. After the addition, the temperature was slowly raised to room temperature, and stirring was 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. To this solution, 10 ml of hexane was slowly added while stirring, whereby a black-green solid precipitated. The solid was filtered off, washed with hexane for 1 hour at reslurry, and dried under reduced pressure to obtain 0.55 g (0.88 mmol, yield 73%) of a dark blue powdered compound D-1 represented by the following formula. Was.

¹ H-NMR (CDCl ₃ ): (cannot be measured due to paramagnetic metal complex)
FD-Mass Spec: 625 (M +)
Elemental analysis: V; 8.4% (8.1)
C; 65.3% (65.2) H; 5.5% (5.8) N; 4.5% (4.8) Values in parentheses are calculated values [Synthesis Example 5]
Synthesis of Compound E-1 :
In a 100 ml reactor that was sufficiently dried and purged with argon, 0.61 g (2.40 mmol) of compound L1 and 10 ml of diethyl ether were charged, cooled to −78 ° C., and stirred. To this, 1.60 ml of n-butyllithium (1.55 mmol / ml 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 thereto was gradually added to a solution of 0.34 g of niobium pentachloride (purity: 95%, 1.20 mmol) in 10 ml of tetrahydrofuran cooled to -78 ° C. 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 was deposited. 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. .

_{^{1 H-NMR (CDCl 3)}} : 1.46 (s, 18H) 7.20-7.50 (m, 16H) 8.65 (s, 2H)
FD-Mass Spec: 702 (M +)
Elemental analysis: Nb; 13.0% (13.2)
C; 58.4% (58.0) H; 5.0% (5.2) N; 3.9% (4.0) Figures in parentheses are calculated values [Synthesis Example 6]
Synthesis of Compound F-1 :
In a 100 ml reactor which was sufficiently dried and purged with argon, 0.61 g (2.40 mmol) of compound L1 and 10 ml of toluene were charged, cooled to −40 ° C. and stirred. To this, 0.43 g of tantalum pentachloride (purity 99.99%, 1.20 mmol) was gradually added 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.

30 ml of methylene chloride was added to the reaction solution, and insolubles were filtered. The filtrate was concentrated under reduced pressure, and 8 ml of hexane was added thereto, whereby an orange viscous oil was separated. The oil portion 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, reslurried in hexane at room temperature for 1 hour, and dried under reduced pressure to obtain 0.15 g (0.26 mmol) of a compound F-1 as a bright yellow powder represented by the following formula.
, Yield 22%).

¹ H-NMR (CDCl ₃ ): 1.50 (s, 9H) 6.80-7.75 (m, 8H) 8.23 (s, 1H)
FD-Mass Spec: 575 (M +)
Elemental analysis: Ta; 31.0% (31.5)
C; 58.4% (58.0) H; 3.3% (3.2) N; 4.5% (4.8) (): Calculated values [Synthesis Example 7]
Synthesis of compound A-2 :
In a 100 ml reactor which was sufficiently dried and purged with argon, 0.91 g (3.0 mmol) of compound L2 and 20 ml of diethyl ether were charged, cooled to −78 ° C., and stirred. Add 1.90 ml of n-butyl lithium (1
(5.44 mmol / ml n-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, 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 diethyl ether and hexane, and dried under reduced pressure to obtain 0.53 g (0.73 mmol yield 49%) of a brown crystal compound A-2 represented by the following formula. .

_{^{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 Spec: 722 (M +)
Elemental analysis: Ti; 6.6% (6.6)
C; 69.9% (69.7) H; 5.5% (5.6) N; 3.4% (3.9) Values in parentheses are calculated values [Synthesis Example 8]
Synthesis of compound B-2 :
In a 100 ml reactor which was sufficiently dried and purged with argon, 0.91 g (3.0 mmol) of compound L2 and 20 ml of diethyl ether were charged, cooled to −78 ° C., and stirred. To this, 1.94 ml of n-butyllithium (1.55 mmol / ml 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. Prepared. 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 obtain 0.21 g (yield: 0.73 mmol, 18%) of a yellow crystal compound B-2 represented by the following formula. .

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 Spec: 766 (M +)
Elemental analysis: Zr; 12.1% (11.9) Values in parentheses are calculated values [Synthesis Example 9]
Synthesis of compound A-3 :
In a 100 ml reactor sufficiently dried and purged with argon, 0.70 g (3.0 mmol) of compound L3 and 30 ml of diethyl ether were charged, cooled to -78 ° C, and stirred. To this, 1.90 ml of n-butyllithium (1.54 mmol / ml n-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. Prepared. 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. After further stirring at room temperature 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 yellowish brown compound A-3 represented by the following formula. Was.

_{^{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 Spec: 582 (M +)
Elemental analysis: Ti; 8.2% (8.2)
C; 62.1% (61.8) H; 7.1% (7.6) N; 4.7% (4.8) Figures in parentheses are calculated values [Synthesis Example 10]
Synthesis of compound B-3 :
In a 100 ml reactor that was sufficiently dried and purged with argon, 0.70 g (3.0 mmol) of compound L3; 30 ml of tetrahydrofuran was charged, cooled to -78 ° C, and stirred. To this, 1.90 ml of n-butyllithium (1.54 mmol / ml n-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. Prepared. 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 slowly raising the temperature to room temperature. After further stirring at room temperature for 15 hours, the reaction solution was evaporated, the resulting 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 methylene chloride and hexane, and dried under reduced pressure to obtain 0.31 g (0.50 mmol, 30% yield) of a yellow powder compound B-3 represented by the following formula. .

_{^{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 Spec: 626 (M +)
Elemental analysis: Zr; 15.0% (14.6)
C; 52.9 (57.5) H; 7.2 (7.1) N; 4.7 (4.8) Values in parentheses are calculated values [Synthesis Example 11]
Synthesis of compound A-4 :
In a 100 ml reactor which was sufficiently dried and purged with argon, compound L4; 0.50 g (2.02 mmol) and 30 ml of diethyl ether were charged, cooled to -78 ° C, and stirred. To this, 1.36 ml of n-butyllithium (1.54 mmol / ml 2.09 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. did. The solution was cooled to −78 ° C., and 2.00 ml of 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, 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.

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) Figures in parentheses are calculated values [Synthesis Example 12]
Synthesis of compound B-4 :
In a 100 ml reactor which was sufficiently dried and purged with argon, 0.46 g (1.86 mmol) of compound L4 and 30 ml of diethyl ether were charged, cooled to −78 ° C., and stirred. Add 1.30 ml of n-butyl lithium (1
.54 mmol / ml n-hexane solution, 2.00 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 zirconium tetrachloride (0.21 g, 0.91 mmol) was added as a solid. After completion of the addition, stirring was continued while slowly raising the temperature 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 yield 42%) )Obtained.

¹ H-NMR (CDCl ₃ ): 6.90-7.95 (m, 22H) 8.40-8.60 (m, 2H)
FD-Mass Spec: 652 (M +)
Elemental analysis: Zr; 14.3% (13.9). Values in parentheses are calculated values. [Synthesis Example 13]
Synthesis of compound A-5 :
In a 100 ml reactor that was sufficiently dried and purged with argon, 0.83 g (3.00 mmol) of compound L5 and 30 ml of diethyl ether were charged, cooled to −78 ° C., and stirred. To this, 2.00 ml of n-butyllithium (1.54 mmol / ml 3.08 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. did. This solution was gradually added dropwise to 3.00 ml (0.5 mmol / ml heptane solution, 1.50 mmol) of a titanium tetrachloride solution 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. 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 0.07 g (0.10 mmol, 7% yield) of ocher powdered compound A-5 represented by the following formula. .

FD-Mass Spec: 666 (M +)
Elemental analysis: Ti; 7.3% (7.2) Values in parentheses are calculated values [Synthesis Example 14]
Synthesis of compound B-5 :
In a 100 ml reactor sufficiently dried and purged with argon, 0.50 g (1.82 mmol) of compound L5 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. The solution was cooled to −78 ° C., and a solution of 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 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 0.04 g (0.05 mmol yield) of compound B-5 as a yellowish yellow powder represented by the following formula. Rate 5%).

FD-Mass spectrometry: 710 (M +)
Elemental analysis: Zr; 13.3% (12.8). Values in parentheses are calculated values. [Synthesis Example 15]
Synthesis of compound A-6 :
In a 100 ml reactor that was sufficiently dried and purged with argon, 0.93 g (3.01 mmol) of compound L6 and 30 ml of diethyl ether were charged, cooled to −78 ° C., and stirred. To this, 2.1 ml of n-butyllithium (1.54 mmol / ml n-hexane solution 3.23 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. did. 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. 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.
Recrystallized in hexane at ℃, dried under reduced pressure 0.41 g of compound A-6 of brown powder represented by the following formula
(0.56 mmol, 37% yield).

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 Spec: 734 (M +)
Elemental analysis: Ti; 6.6% (6.5)
C; 67.9% (68.6) H; 7.4% (7.1) N; 3.9% (3.8) Values in parentheses are calculated values [Synthesis Example 16]
Synthesis of compound B-6 :
In a 100 ml reactor that was sufficiently dried and purged with argon, 0.93 g (3.01 mmol) of compound L6 and 30 ml of diethyl ether were charged, cooled to −78 ° C., and stirred. To this, 2.1 ml of n-butyllithium (1.54 mmol / ml n-hexane solution, 3.23 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. Prepared. 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 slowly raising the temperature to room temperature. After further stirring at room temperature for 14 hours, 20 ml of methylene chloride was added, and insolubles were removed 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 0.55 g (0.71 mmol, 47% yield) of compound B-6 as a yellow powder represented by the following formula. Was.

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 Spec: 776 (M +)
Elemental analysis: Zr; 11.2% (11.7). Values in parentheses are calculated values. [Synthesis Example 17]
Synthesis of compound A-7 :
1.0 g (3.66 mmol) of compound L7 and 20 ml of diethyl ether were charged into a 100 ml reactor which had been sufficiently dried and purged with argon, cooled to −78 ° C., and stirred. To this, 2.48 ml of n-butyl lithium (1.55 mmol / ml 3.84 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. did. 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, washed by filtering hexane, and dried under reduced pressure to obtain 0.95 g of a brown powdered compound A-7 represented by the following formula.
(1.43 mmol, 78% yield).

¹ H-NMR (CDCl ₃ ): 6.90-7.90 (m, 26H) 8.00 (s, 2H)
FD-Mass Spec: 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 value [Synthesis Example 18]
Synthesis of compound B-7 :
1.0 g (3.66 mmol) of compound L7 and 20 ml of diethyl ether were charged into a 100 ml reactor which had been sufficiently dried and purged with argon, cooled to −78 ° C., and stirred. To this, 2.48 ml of n-butyllithium (1.55 mmol / ml n-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. Prepared. 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 insoluble materials were removed 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 0.94 g (1.33 g) of a yellow-green powdered compound B-7 represented by the following formula. mmol 73%).

¹ H-NMR (CDCl ₃ ): 7.00-7.90 (m, 26H) 8.20 (s, 2H)
FD-Mass Spec: 704 (M +)
Elemental analysis: Zr; 11.5% (11.7). Values in parentheses are calculated values. [Synthesis Example 19]
Synthesis of Compound A-8 :
In a 100 ml reactor which was sufficiently dried and purged with argon, 1.0 g (2.93 mmol) of compound L8 and 20 ml of diethyl ether were charged, cooled to −78 ° C. and stirred. To this, 2.0 ml of n-butyllithium (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 the mixture was stirred at room temperature for 4 hours to prepare a lithium salt solution. . This solution was cooled to −78 ° C. with 2.9 ml of titanium tetrachloride solution (0.5 mmol / ml heptane solution, 1.45 mmol) and 20 ml of diethyl ether.
Was gradually added dropwise to the mixed solution. After completion of the dropwise addition, stirring was continued while slowly raising the temperature to room temperature. After further stirring at room temperature for 15 hours, the reaction solution was filtered with a glass filter. The filtrate was concentrated under reduced pressure, and the precipitated solid was reslurried in hexane. The solid was washed by filtering off hexane and dried under reduced pressure to obtain 1.06 g (1.33 mmol yield) of brown powdered compound A-8 represented by the following formula. 91%).

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 Spec: 798 (M +)
Elemental analysis: Ti; 6.0% (6.0) Values in parentheses are calculated values [Synthesis Example 20]
Synthesis of Compound B-8 :
In a 100 ml reactor which was sufficiently dried and purged with argon, 1.0 g (2.93 mmol) of compound L8 and 20 ml of diethyl ether were charged, cooled to −78 ° C. and stirred. To this, 2.0 ml of n-butyllithium (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. Prepared. 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 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 1.02 g (1.21 g) of a yellow-green powdered compound B-8 represented by the following formula. mmol 83%).

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 Spec: 842 (M +)
Elemental analysis: Zr; 11.1% (10.8) Values in parentheses are calculated values [Synthesis Example 21]
Synthesis of compound A-9 :
In a 100 ml reactor which was sufficiently dried and purged with argon, 0.50 g (1.23 mmol) of compound L9 and 15 ml of diethyl ether were charged, cooled to −78 ° C. and stirred. To this, 0.84 ml of n-butyllithium (1.55 mmol / ml n-hexane solution 1.30 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. did. This solution was gradually dropped into a mixed solution of 1.2 ml of 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 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 0.33 g (0.36 mmol) of brown powdered compound A-9 represented by the following formula. Yield 58%).

¹ H-NMR (CDCl ₃ ): 1.70-1.90 (m, 18H) 6.60-7.80 (m, 34H)
FD-Mass Spec: 926 (M +)
Elemental analysis: Ti; 5.3% (5.2) (): Calculated value [Synthesis Example 22]
Synthesis of Compound B-9 :
In a 100 ml reactor which was sufficiently dried and purged with argon, 0.50 g (1.23 mmol) of compound L9 and 15 ml of diethyl ether were charged, cooled to −78 ° C. and stirred. To this, 0.84 ml of n-butyllithium (1.55 mmol / ml n-hexane solution, 1.30 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. Prepared. To this solution, a mixed solution of zirconium tetrachloride (0.14 g, 0.60 mmol) and 15 ml of diethyl ether cooled to -78 ° C 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 insoluble materials were removed with a glass filter. The filtrate was concentrated under reduced pressure, and the precipitated solid was reslurried in hexane. The solid was washed by filtration and dried under reduced pressure to obtain 0.19 g (0.20 g) of a pale yellow powder of the compound B-9 represented by the following formula. mmol yield 32%).

¹ H-NMR (CDCl ₃ ): 1.28-1.52 (m, 18H) 6.70-7.76 (m, 34H)
FD-Mass Spec: 970 (M +)
Elemental analysis: Zr; 9.6% (9.4) Values in parentheses are calculated values [Synthesis Example 23]
Synthesis of Compound A-10 :
A 100 ml reactor which was sufficiently dried and purged with argon was charged with 0.32 g (1.03 mmol) of compound L10 and 10 ml of diethyl ether, cooled to −78 ° C., and stirred. To this, 0.77 ml of n-butyllithium (1.59 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. did. This solution was gradually dropped into 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, 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 0.16 g (0.22 mmol, 43% yield) of a brown powdered compound A-10 represented by the following formula. .

¹ H-NMR (CDCl ₃ ): 0.40-0.90 (m, 30H) 6.60-7.80 (m, 18H)
FD-Mass Spec: 739 (M +)
Elemental analysis: Ti; 5.3% (5.2). Values in parentheses are calculated values. [Synthesis Example 24]
Synthesis of Compound A-11 :
In a 100 ml reactor which was sufficiently dried and purged with argon, 0.68 g (2.40 mmol) of compound L11 and 30 ml of diethyl ether were charged, cooled to −78 ° C. and stirred. To this, 1.49 ml of n-butyl lithium (1.61 mmol / ml 2.40 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. did. This solution was cooled to −78 ° C. and the titanium tetrachloride solution 2.4 ml (0.5 mmol / ml heptane solution, 1.20 mmol) diethyl ether 15 m
l The mixture was gradually dropped. 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, the precipitated solid was dissolved in 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 reprecipitated at 0 ° C. with methylene chloride and hexane, and dried under reduced pressure to obtain 0.37 g (0.54 mmol, 45% yield) of compound A-11 as a reddish brown powder.

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 Spec: 682 (M +)
Elemental analysis: Ti; 7.0% (7.0). Values in parentheses are calculated values. [Synthesis Example 25]
Synthesis of Compound B-11 :
In a 100 ml reactor which was sufficiently dried and purged with argon, 0.64 g (2.26 mmol) of compound L11 and 20 ml of diethyl ether were charged, cooled to −78 ° C. and stirred. To this, 1.40 ml of n-butyllithium (1.61 mmol / ml n-hexane solution, 2.26 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. Prepared. This solution was slowly dropped into a solution of zirconium tetrachloride.2THF (0.42 g, 1.10 mmol) in 20 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 50 ml of methylene chloride, and the insoluble matter was removed 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 0.25 g (0.34 mmol, 31%) of a yellow-green powdered compound B-11 represented by the following formula. Was.

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 Spec: 726 (M +)
Elemental analysis: Zr; 12.4% (12.6). Values in parentheses are calculated values. [Synthesis example 26]
Synthesis of Compound A-12 :
1.0 g (2.31 mmol) of compound L12 and 20 ml of diethyl ether were charged into a 100 ml reactor which had been sufficiently dried and purged with argon, cooled to −78 ° C., and stirred. To this, 1.56 ml of n-butyllithium (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. did. This solution was cooled to −78 ° C., 2.3 ml of titanium tetrachloride solution (0.5 mmol / ml heptane solution, 1.15 mmol), 20 ml of diethyl ether
The mixture 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 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.

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 Spec: 982 (M +)
Elemental analysis: Ti; 5.0% (4.9). Values in parentheses are calculated values. [Synthesis Example 27]
Synthesis of Compound B-12 :
1.0 g (2.31 mmol) of compound L12 and 20 ml of diethyl ether were charged into a 100 ml reactor which had been sufficiently dried and purged with argon, cooled to −78 ° C., and stirred. To this, 1.56 ml of n-butyllithium (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. Prepared. This solution was slowly added dropwise to a mixture of zirconium tetrachloride (0.27 g, 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, 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, hexane, heptane, and pentane, washed with reslurry, and dried under reduced pressure to obtain 0.02 g (0.02 g) of a yellow-green powdered compound B-12 represented by the following formula. mmol 1%).

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 Spec: 1026 (M +)
Elemental analysis: Zr; 9.1% (8.9). Values in parentheses are calculated values. [Synthesis Example 28]
Synthesis of Compound A-13 :
1.100 g (3.26 mmol) of compound L13 and 22 ml of diethyl ether were charged into a 100 ml reactor which was sufficiently dried and purged with argon, cooled to −78 ° C., and stirred. To this, 2.2 ml of n-butyllithium (1.55 mmol / ml 3.41 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. did. 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 matter 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.

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 Spec: 790 (M +)
Elemental analysis: Ti; 6.3% (6.1) Values in parentheses are calculated values [Synthesis Example 29]
Synthesis of Compound B-13 :
A 100 ml reactor which was sufficiently dried and purged with argon was charged with 1.03 g (3.02 mmol) of compound L13 and 20 ml of diethyl ether, cooled to −78 ° C., and stirred. To this, 2.0 ml of n-butyllithium (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. Prepared. 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%) of a yellow-green powdered compound B-13 represented by the following formula.

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 Spec: 834 (M +)
Elemental analysis: Zr; 10.9% (10.9) (): Calculated value [Synthesis Example 30]
Synthesis of Compound A-14 :
In a 100 ml reactor sufficiently dried and purged with argon, compound L14; 0.98 g (2.97 mmol) and 30 ml of diethyl ether were charged, cooled to -78 ° C and stirred. To this, 2.0 ml of n-butyllithium (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. did. This solution was gradually added dropwise to a mixture of 3.0 ml of a 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, the residue was dissolved in diethyl ether (30 ml) and methylene chloride (50 ml), and the insoluble material 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 (0.85 mmol, yield 57%) of compound A-14 as a black-brown powder.

¹ H-NMR (CDCl ₃ ): 1.41 (s, 18H) 6.70-7.90 (m, 24H) 8.18 (s, 2H)
FD-Mass Spec: 774 (M +)
Elemental analysis: Ti; 6.2% (6.2). Values in parentheses are calculated values. [Synthesis Example 31]
Synthesis of Compound B-14 :
A 100 ml reactor which was sufficiently dried and purged with argon was charged with 1.01 g (3.05 mmol) of compound L14 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, 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 slowly added dropwise to a solution of zirconium tetrachloride (0.36 g, 1.52 mmol) in 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 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 of a fluorescent yellow powdered compound B-14 represented by the following formula (0.74 mmol yield 49%). Obtained.

¹ H-NMR (CDCl ₃ ): 1.41 (s, 18H) 6.80-7.90 (m, 24H) 8.24 (s, 2H)
FD-Mass Spec: 818 (M +)
Elemental analysis: Zr; 11.0% (11.1). Values in parentheses are calculated values. [Synthesis Example 32]
Synthesis of Compound A-15 :
In a 100 ml reactor which was sufficiently dried and purged with argon, 0.40 g (1.01 mmol) of compound L15 and 10 ml of diethyl ether were charged, cooled to −78 ° C. and stirred. To this, 0.77 ml of n-butyllithium (1.59 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. did. This solution was gradually added dropwise to a mixture of 1.0 ml of a 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, and the precipitated solid was reprecipitated with diethyl ether and hexane, and dried under reduced pressure to obtain 0.19 g (0.21 mmol, 42% yield) of compound A-15 as a reddish brown powder.

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 Spec: 900 (M +)
Elemental analysis: Ti; 5.5% (5.3). Values in parentheses are calculated values. [Synthesis Example 33]
Synthesis of Compound B-15 :
In a 100 ml reactor that was sufficiently dried and purged with argon, 0.40 g (1.02 mmol) of compound L15 and 10 ml of tetrahydrofuran were charged, 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. After the solution was cooled to -78 ° C, zirconium tetrachloride (0.12 g, 0.50 mmol) was added as a solid. After completion of the addition, stirring was continued while slowly raising the temperature to room temperature. After further stirring at room temperature for 15 hours, the reaction solution was evaporated. The obtained solid was dissolved in 50 ml of methylene chloride, and 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 (0.21 mmol, 42% yield) of an off-white powder of the compound B-15 represented by the following formula. .

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 Spec: 944 (M +)
Elemental analysis: Zr; 9.4% (9.6) (): Calculated value [Synthesis Example 34]
Synthesis of compound A-16 :
1.0 g (4.73 mmol) of compound L16 and 20 ml of diethyl ether were charged into a 100 ml reactor which was sufficiently dried and purged with argon, cooled to −78 ° C., and stirred. To this, 3.2 ml of n-butyllithium (1.55 mmol / ml 4.96 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. did. 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 the insolubles in the solution, the solution was concentrated under reduced pressure to precipitate a solid, reprecipitated with methylene chloride and hexane, and dried under reduced pressure to obtain 0.96 g (1.78 g) of light brown powdered compound A-16. (yield: 75%).

¹ H-NMR (CDCl ₃ ): 1.90 (s, 6H) 6.50-7.30 (m, 16H) 7.90 (s, 2H)
FD-Mass Spec: 538 (M +)
Elemental analysis: Ti; 9.0% (8.9). Values in parentheses are calculated values. [Synthesis Example 35]
Synthesis of compound B-16 :
1.0 g (4.73 mmol) of compound L16 and 20 ml of diethyl ether were charged into a 100 ml reactor which was sufficiently dried and purged with argon, cooled to −78 ° C., and stirred. To this, 3.2 ml of n-butyllithium (1.55 mmol / ml 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. Prepared. 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 was distilled off from the filtrate to precipitate a solid, which was recrystallized from diethyl ether, methylene chloride and hexane, and dried under reduced pressure to obtain 0.49 g (0.84 g) of a yellow-green powdered compound B-16 represented by the following formula. mmol yield 36%).

¹ H-NMR (CDCl ₃ ): 2.00 (s, 6H) 6.40-7.40 (m, 16H) 8.10 (s, 2H)
FD-Mass Spec: 582 (M +)
Elemental analysis: Zr; 15.9% (15.7). Values in parentheses are calculated values. [Synthesis Example 36]
Synthesis of Compound A-17 :
1.0 g (2.77 mmol) of compound L17 and 20 ml of diethyl ether were charged into a 100 ml reactor which was sufficiently dried and purged with argon, cooled to −78 ° C., and stirred. To this, 1.87 ml of n-butyllithium (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. did. 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) 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, 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 0.15 g of compound A-17 as a brown powder (0.18 mmol, yield 13%). Obtained.

¹ H-NMR (CDCl ₃ ): 3.20-3.80 (m, 4H) 6.90-7.81 (m, 30H) 8.15 (s, 2H)
FD-Mass Spec: 838 (M +)
Elemental analysis: Ti; 5.9% (5.7). Values in parentheses are calculated values. [Synthesis Example 37]
Synthesis of Compound B-17 :
1.0 g (2.77 mmol) of compound L17 and 20 ml of diethyl ether were charged into a 100 ml reactor which was sufficiently dried and purged with argon, cooled to −78 ° C., and stirred. To this, 1.87 ml of n-butyllithium (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. Prepared. This solution was added dropwise to a mixture of zirconium tetrachloride (0.32 g, 1.37 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 with a glass filter to remove insolubles. 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 0.71 g (0.88 g) of a yellow-green powdered compound B-17 represented by the following formula. mmol yield 58%).

¹ H-NMR (CDCl ₃ ): 3.30-3.80 (m, 4H) 6.71-7.72 (m, 30H) 8.25 (s, 2H)
FD-Mass Spec: 882 (M +)
Elemental analysis: Zr; 10.6% (10.3). Values in parentheses are calculated values. [Synthesis Example 38]
Synthesis of Compound A-18 :
In a 100 ml reactor that was sufficiently dried and purged with argon, 0.59 g (2.20 mmol) of compound L18 and 10 ml of diethyl ether were charged, cooled to −78 ° C., and stirred. To this, 1.49 ml of n-butyllithium (1.55 mmol / ml 2.31 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. did. 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, the mixture was concentrated to dryness, and the obtained solid was dissolved in 20 ml of methylene chloride. The insoluble material was filtered through a glass filter, and the solution was concentrated under reduced pressure.
Then, the precipitate was reprecipitated with diethyl ether and hexane, and dried under reduced pressure to obtain 0.27 g (0.41 mmol, yield 37%) of compound A-18 as a brown powder.

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). Values in parentheses are calculated values. [Synthesis Example 39]
Synthesis of Compound B-18 :
In a 100 ml reactor which was sufficiently dried and purged with argon, 0.60 g (2.25 mmol) of compound L18 and 10 ml of diethyl ether were charged, cooled to −78 ° C. and stirred. To this, 1.52 ml of n-butyllithium (1.55 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. Prepared. 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, and the precipitated solid was reprecipitated with diethyl ether and hexane, and dried under reduced pressure to obtain 0.16 g of a compound B-18 as a yellow-green powder represented by the following formula.
(0.24 mmol, 21% yield).

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 Spec: 694 (M +)
Elemental analysis: Zr; 13.1% (13.1) Values in parentheses are calculated values [Synthesis Example 40]
Synthesis of Compound B-19 :
In a 100 ml reactor which was sufficiently dried and purged with argon, 0.70 g (2.25 mmol) of compound L19 and 10 ml of diethyl ether were charged, cooled to −78 ° C. and stirred. To this, 1.52 ml of n-butyllithium (1.55 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. Prepared. 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, the precipitated solid was reprecipitated with diethyl ether and hexane, and dried under reduced pressure to obtain 0.16 g (0.20 mmol, 18% yield) of a yellow-green powdered compound B-19 represented by the following formula. Was.

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). Values in parentheses are calculated values. [Synthesis Example 41]
Synthesis of Compound B-20 :
In a 100 ml reactor which was sufficiently dried and purged with argon, 0.63 g (2.25 mmol) of compound L20 and 10 ml of diethyl ether were charged, cooled to -78 ° C and stirred. To this, 1.52 ml of n-butyllithium (1.55 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. Prepared. 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, the precipitated solid was reprecipitated with diethyl ether and hexane, and dried under reduced pressure to obtain 0.35 g (0.48 mmol, 43% yield) of a yellow powdered compound B-20 represented by the following formula. .

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 Spec: 720 (M +)
Elemental analysis: Zr; 12.8% (12.6). Values in parentheses are calculated values. [Synthesis Example 42]
Synthesis of Compound A-21 :
In a 100 ml reactor that was sufficiently dried and purged with argon, 0.80 g (2.50 mmol) of compound L21 and 10 ml of diethyl ether were charged, cooled to −78 ° C., and stirred. 1.7 ml of n-butyllithium (1.55 mmol / ml 2.64 mmol of n-hexane solution) 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. Was prepared. This solution was cooled to −78 ° C. with 2.5 ml of titanium tetrachloride solution (0.5 mmol / ml heptane solution, 1.25 mmol) and 10 ml of diethyl ether.
The mixture 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 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.

¹ H-NMR (CDCl ₃ ): 1.34 (s, 18H) 6.75-7.75 (m, 14H) 8.10 (s, 2H)
FD-Mass Spec: 758 (M +)
Elemental analysis: Ti; 6.5% (6.3). Values in parentheses are calculated values. [Synthesis Example 43]
Synthesis of Compound B-21 :
A 100 ml reactor which was sufficiently dried and purged with argon was charged with 1.03 g (3.20 mmol) of compound L21 and 10 ml of diethyl ether, cooled to −78 ° C. and stirred. To this, 2.0 ml of n-butyllithium (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. A lithium salt solution was prepared. 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 under reflux conditions for 3 hours. 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, the precipitated solid was reprecipitated with diethyl ether and hexane, and dried under reduced pressure to obtain 0.33 g (0.41 mmol, 27% yield) of compound B-21 as an ocher powder represented by the following formula. Was.

¹ H-NMR (CDCl ₃ ): 1.24 (s, 18H) 6.80-7.78 (m, 14H) 8.15 (s, 2H)
FD-Mass Spec: 802 (M +)
Elemental analysis: Zr; 11.7% (11.4). Values in parentheses are calculated values. [Synthesis Example 44]
Synthesis of compound A-22 :
In a 100 ml reactor which was sufficiently dried and purged with argon, 0.50 g (1.77 mmol) of compound L22 and 40 ml of diethyl ether were charged, cooled to −78 ° C. and stirred. To this, 1.20 ml of n-butyllithium (1.56 mmol / ml 1.86 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. did. 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.

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 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 reprecipitated with diethyl ether and hexane at -78 ° C, and dried under reduced pressure to obtain 0.31 g of a brown powdered compound A-22. (0.45 mmol, 51% yield).

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 Spec: 682 (M +)
Elemental analysis: Ti; 7.3% (7.0). Values in parentheses are calculated values. [Synthesis Example 45]
Synthesis of Compound B-22 :
In a 100 ml reactor which was sufficiently dried and purged with argon, 0.50 g (1.77 mmol) of compound L22 and 25 ml of diethyl ether were charged, cooled to -78 ° C and stirred. To this, 1.20 ml of n-butyllithium (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. Prepared. The solution was added dropwise to a mixed solution of zirconium tetrachloride (0.21 g, 0.99 mmol) in diethyl ether (10 ml) and tetrahydrofuran (60 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 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. 100 ml of diethyl ether
After dissolving with 70 ml of hexane to remove insolubles in the solution, the solution is concentrated under reduced pressure. The precipitated solid was washed with hexane and dried under reduced pressure to obtain 0.08 g (0.11 mmol, 11% yield) of a yellow-green powdered compound B-22 represented by the following formula.

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 Spec: 726 (M +)
Elemental analysis: Zr; 12.3% (12.6). Values in parentheses are calculated values. [Synthesis Example 46]
Synthesis of Compound A-23 :
A 100 ml reactor which was sufficiently dried and purged with argon was charged with 1.01 g (4.33 mmol) of compound L23 and 22 ml of diethyl ether, cooled to −78 ° C. and stirred. To this, 2.9 ml of n-butyllithium (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. did. This solution was gradually added dropwise to a mixed solution 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 obtained solid was reprecipitated with methylene chloride, diethyl ether and hexane, and dried under reduced pressure to obtain 0.26 g (0.44 mmol, 21% yield) of a brown powdered compound A-23.

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 Spec: 594 (M +)
Elemental analysis: Ti; 8.0% (8.0). Values in parentheses are calculated values. [Synthesis Example 47]
Synthesis of Compound B-23 :
A 100 ml reactor which was sufficiently dried and purged with argon was charged with 1.02 g (4.25 mmol) of compound L23 and 20 ml of diethyl ether, cooled to −78 ° C. and stirred. To this, 3.43 ml of n-butyllithium (1.55 mmol / ml n-hexane solution, 5.32 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. Prepared. 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 0.61 g (0.96 mmol yield 45) of yellow-green powdered compound B-23 represented by the following formula. %)Obtained.

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 Spec: 638 (M +)
Elemental analysis: Zr; 14.0% (14.3). Values in parentheses are calculated values. [Synthesis Example 48]
Synthesis of Compound A-24 :
In a 100 ml reactor that was sufficiently dried and purged with argon, 0.52 g (2.05 mmol) of compound L24 and 40 ml of diethyl ether were charged, cooled to −78 ° C., and stirred. To this, 1.36 ml of n-butyllithium (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. did. This solution was gradually added dropwise to a mixture of 2.04 ml of titanium tetrachloride solution (0.5 mmol / ml heptane solution, 1.02 mmol), 40 ml of diethyl ether, and 20 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 100 ml of diethyl ether, the insoluble matter was separated with a glass filter, the residue was washed with diethyl ether, dissolved in methylene chloride, and the insoluble matter in the solution was removed. After concentration under reduced pressure, 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.

¹ H-NMR (CDCl ₃ ): 0.80-2.30 (m, 18H) 6.30-9.20 (m, 14H) 8.35 (brs, 2H)
FD-Mass Spec: 624 (M +)
Elemental analysis: Ti; 8.1% (7.7). Values in parentheses are calculated values. [Synthesis Example 49]
Synthesis of Compound B-24 :
In a 100 ml reactor that was sufficiently dried and purged with argon, 0.76 g (2.99 mmol) of compound L24 and 40 ml of diethyl ether were charged, cooled to −78 ° C., and stirred. To this, 1.91 ml of n-butyllithium (1.61 mmol / ml n-hexane solution, 3.08 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. Prepared. This solution was added dropwise to a mixed solution of zirconium tetrachloride / 2THF complex (0.563 g, 1.49 mmol) in 80 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, 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 with a glass filter. The residue is washed with diethyl ether, dissolved in methylene chloride, and the insolubles in the solution are removed. The solution 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.

¹ H-NMR (CDCl ₃ ): 0.60-2.30 (m, 18H) 6.30-9.40 (m, 14H) 8.35 (brs, 2H)
FD-Mass Spec: 668 (M +)
Elemental analysis: Zr; 13.2% (13.6) Values in parentheses are calculated values [Synthesis Example 50]
Synthesis of Compound A-25 :
A 100 ml reactor sufficiently dried and purged with argon was charged with 0.50 g (1.93 mmol) of compound L25 and 20 ml of diethyl ether, cooled to −78 ° C. and stirred. To this, 1.42 ml of n-butyllithium (1.55 mmol / ml 2.20 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. did. 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 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 0.11 g of compound A-25 as a reddish brown powder (0.17 mmol, 18% yield). )Obtained.

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 Spec: 634 (M +)
Elemental analysis: Ti; 7.6% (7.5). Values in parentheses are calculated values. [Synthesis Example 51]
Synthesis of Compound B-25 :
A 100 ml reactor sufficiently dried and purged with argon was charged with 0.50 g (1.93 mmol) of compound L25 and 20 ml of diethyl ether, cooled to −78 ° C. and stirred. To this, 1.42 ml of n-butyllithium (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. Prepared. 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. After further stirring at room temperature for 15 hours, the reaction solution was filtered with a glass filter, and 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) of compound B-25 as an ocher powder represented by the following formula.
Yield 43%).

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 Spec: 678 (M +)
Elemental analysis: Zr; 13.3% (13.4). Values in parentheses are calculated values. [Synthesis Example 52]
Synthesis of Compound A-26 :
In a 100 ml reactor which was sufficiently dried and purged with argon, 0.61 g (2.28 mmol) of compound L26 and 10 ml of diethyl ether were charged, cooled to −78 ° C. and stirred. 1.6 ml of n-butyllithium (1.55 mmol / ml 2.48 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. did. 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 12 hours, the insolubles in the reaction solution were filtered through a glass filter, the obtained filtrate was concentrated under reduced pressure, and the precipitated solid was reprecipitated at -78 ° C with diethyl ether and hexane, and dried under reduced pressure. This yielded 0.36 g (0.55 mmol, 51% yield) of compound A-26 as a brown powder.

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). Values in parentheses are calculated values. [Synthesis Example 53]
Synthesis of Compound B-26 :
In a 100 ml reactor which was sufficiently dried and purged with argon, 0.61 g (2.28 mmol) of compound L26 and 10 ml of diethyl ether were charged, cooled to −78 ° C. and stirred. To this, 1.6 ml of n-butyllithium (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. Prepared. 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. After further stirring at room temperature for 12 hours, 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 mmol, 18%) of a yellow-green powdered compound B-26 represented by the following formula. Was.

_{^{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 Spec: 694 (M +)
Elemental analysis: Zr; 13.1% (13.1). Values in parentheses are calculated values. [Synthesis Example 54]
Synthesis of Compound A-27 :
In a 100 ml reactor which was sufficiently dried and purged with argon, 0.30 g (1.00 mmol) of compound L27 and 10 ml of diethyl ether were charged, cooled to −78 ° C. and stirred. To this, 0.65 ml of n-butyl lithium (1.55 mmol / ml 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. did. This solution was gradually added dropwise to a mixture of 1.0 ml of a 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 stirring at room temperature for 12 hours and then under reflux for 1 hour, the 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.

¹ H-NMR (CDCl ₃ ): 1.13 (s, 18H) 1.25 (brd, 6H) 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 Spec: 706 (M +)
Elemental analysis: Ti; 6.8% (6.8) (): Calculated value [Synthesis Example 55]
Synthesis of Compound B-27 :
A 100 ml reactor sufficiently dried and purged with argon was charged with 0.95 g (3.20 mmol) of compound L27 and 10 ml of diethyl ether, cooled to −78 ° C., and stirred. To this, 2.08 ml of n-butyllithium (1.55 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. Prepared. 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 at 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 0.18 g (0.24 mmol, 15% yield) of a yellow powdered compound B-27 represented by the following formula.

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 Spec: 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 parentheses are calculated values [Synthesis Example 56]
Synthesis of Compound A-28 :
In a 100 ml reactor which was sufficiently dried and purged with argon, 0.50 g (1.37 mmol) of compound L28 and 40 ml of diethyl ether were charged, cooled to −78 ° C. and stirred. To this, 0.92 ml of n-butyllithium (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. did. 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.

¹ H-NMR (CDCl ₃ ): 0.70-1.40 (m, 54H) 6.65-7.75 (m, 12H) 8.35 (s, 2H)
FD-Mass Spec: 846 (M +)
Elemental analysis: Ti; 5.5% (5.7). Values in parentheses are calculated values. [Synthesis Example 57]
Synthesis of Compound B-28 :
In a 100 ml reactor which was sufficiently dried and purged with argon, 0.50 g (1.37 mmol) of compound L28 and 40 ml of diethyl ether were charged, cooled to −78 ° C. and stirred. To this, 0.92 ml of n-butyllithium (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. Prepared. This solution was added dropwise to a mixed solution of 20 ml of anhydrous diethyl ether and 50 ml of tetrahydrofuran of zirconium tetrachloride (0.16 g, 0.69 mmol) 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 0.26 g (0.29 mmol, 43% yield) of a yellow powdered compound B-28 represented by the following formula.

¹ H-NMR (CDCl ₃ ): 0.80-1.30 (m, 54H) 6.65 (m, 12H) 8.35 (s, 2H)
FD-Mass Spec: 890 (M +)
Elemental analysis: Zr; 9.9% (10.2) (): Calculated value [Synthesis Example 58]
Synthesis of Compound A-29 :
In a 100 ml reactor which was sufficiently dried and purged with argon, 0.60 g (1.79 mmol) of compound L29 and 40 ml of diethyl ether were charged, cooled to −78 ° C. and stirred. To this, 1.17 ml of n-butyllithium (1.55 mmol / ml 1.81 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. did. 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 diethyl ether 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 reaction solution was filtered through a glass filter to remove insolubles, the filtrate was concentrated under reduced pressure, the precipitated solid was washed with hexane, and dried under reduced pressure to obtain a compound of reddish brown powder. 0.10 g (0.13 mmol, 14% yield) of A-29 was obtained.

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 Spec: 786 (M +)
Elemental analysis: Ti; 6.4% (6.1). Values in parentheses are calculated values. [Synthesis Example 59]
Synthesis of Compound B-29 :
In a 100 ml reactor sufficiently dried and purged with argon, 0.50 g (1.48 mmol) of compound L29 and 40 ml of diethyl ether were charged, cooled to −78 ° C. and stirred. To this, 1.02 ml of n-butyllithium (1.61 mmol / ml n-hexane solution, 1.64 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. Prepared. This solution was added dropwise to a solution of zirconium tetrachloride.2THF complex (0.26 g, 0.69 mmol) in 40 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, 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 resulting solid was reslurried with 50 ml of diethyl ether, filtered through a glass filter to remove insolubles, and the filtrate was concentrated under reduced pressure to precipitate a solid again. The precipitated solid was reprecipitated with hexane at −78 ° C. and dried under reduced pressure to obtain 0.04 g (0.05 mmol, yield: 7%) of a yellow-white powdered compound B-29 represented by the following formula.

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 Spec: 830 (M +)
Elemental analysis: Zr; 11.3% (11.0) (): Calculated value [Synthesis Example 60]
Synthesis of Compound A-30 :
In a 100 ml reactor which was sufficiently dried and purged with argon, 0.51 g (1.86 mmol) of compound L30 and 50 ml of diethyl ether were charged, cooled to −78 ° C. and stirred. To this, 1.20 ml of n-butyllithium (1.61 mmol / ml 1.93 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. did. This solution was cooled to −78 ° C. 1.85 ml of titanium tetrachloride solution (0.5 mmol / ml heptane solution, 0.93 mmol) and tetrahydrofuran
It was slowly added dropwise to the 60 ml solution. After completion of the dropwise addition, stirring was continued while slowly raising the temperature to room temperature. After further stirring at room temperature for 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 removing the insoluble matter in the solution 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 of compound A-30 as a red-orange powder.
(0.21 mmol, 23% yield).

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 Spec: 662 (M +)
Elemental analysis: Ti; 7.1% (7.2) (): Calculated value [Synthesis Example 61]
Synthesis of Compound B-30 :
In a 100 ml reactor which was sufficiently dried and purged with argon, 0.51 g (1.86 mmol) of compound L30 and 50 ml of diethyl ether were charged, cooled to −78 ° C. and stirred. To this, 1.20 ml of n-butyllithium (1.61 mmol / ml n-hexane solution, 1.93 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. Prepared. 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.
After filtering through a glass filter to remove insolubles, the filtrate was concentrated under reduced pressure. The precipitated solid was washed with hexane and dried under reduced pressure to obtain 0.10 g (0.14 mmol, 15% yield) of compound B-30 as a milky white powder represented by the following formula.

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 Spec: 704 (M +)
Elemental analysis: Zr; 13.3% (12.9). Values in parentheses are calculated values. [Synthesis Example 62]
Synthesis of Compound A-31 :
A 100 ml reactor which was sufficiently dried and purged with argon was charged with 1.00 g (4.22 mmol) of compound L31 and 20 ml of diethyl ether, cooled to −78 ° C. and stirred. To this, 2.75 ml of n-butyllithium (1.61 mmol / ml 4.43 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. did. 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.

(4) 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. The filter cake was dissolved in 50 ml of methylene chloride to remove insolubles in the solution, the solution was evaporated to dryness under reduced pressure, and the resulting solid was reprecipitated with methylene chloride and diethyl ether, and dried under reduced pressure. 0.90 g (1.55 mmol, yield 72%) of compound A-31 as a brown powder was obtained.

¹ H-NMR (CDCl ₃ ): 6.70-7.40 (m, 16H) 7.90-8.20 (m, 2H)
FD-Mass Spec: 578 (M +)
Elemental analysis: Ti; 8.0% (8.3) (): Calculated value [Synthesis Example 63]
Synthesis of Compound B-31 :
A 100 ml reactor which was sufficiently dried and purged with argon was charged with 1.20 g (5.18 mmol) of compound L31 and 24 ml of diethyl ether, cooled to −78 ° C. and stirred. To this, 3.38 ml of n-butyllithium (1.61 mmol / ml n-hexane solution, 5.44 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. Prepared. This solution was added dropwise to a mixture of zirconium tetrachloride (0.60 g, 2.57 mmol) and 24 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 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. Thus, 0.20 g (0.32 mmol, 12% yield) of a green powdered compound B-31 was obtained.

¹ H-NMR (CDCl ₃ ): 6.70-7.45 (m, 16H) 7.90-8.25 (m, 2H)
FD-Mass Spec: 621 (M +)
Elemental analysis: Zr; 14.9% (14.6). Values in parentheses are calculated values. [Synthesis Example 64]
Synthesis of Compound A-32 :
A 100 ml reactor which was sufficiently dried and purged with argon was charged with 1.00 g (5.05 mmol) of compound L32 and 50 ml of diethyl ether, cooled to −78 ° C. and stirred. To this, 3.25 ml of n-butyl lithium (1.63 mmol / ml 5.30 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. did. 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. After further stirring at room temperature for 12 hours, the reaction solution was filtered through a glass filter, and the residue was washed with diethyl ether, dissolved in methylene chloride, the insolubles in the solution were removed, and the solution was concentrated under reduced pressure. The precipitated solid was washed with hexane and dried under reduced pressure to obtain 0.23 g (0.45 mmol, 18% yield) of compound A-32 as an orange powder.

FD-Mass Spectrometry: 512 (M +)
[Synthesis Example 65]
Synthesis of Compound A-33 :
In a 100 ml reactor which was sufficiently dried and purged with argon, 1.09 g (4.39 mmol) of compound L33 and 70 ml of diethyl ether were charged, cooled to −78 ° C. and stirred. To this, 2.80 ml of n-butyl lithium (1.66 mmol / ml 4.56 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. did. 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. After further stirring at room temperature for 12 hours, the reaction solution was filtered through a glass filter, and the residue was washed with diethyl ether, dissolved in methylene chloride, the insolubles in the solution were removed, and the solution was concentrated under reduced pressure. The precipitated solid was washed with diethyl ether and dried under reduced pressure to obtain 0.22 g (0.36 mmol, yield: 16%) of compound A-33 as a brown powder.

FD-Mass spectrometry: 612 (M +)
[Synthesis Example 66]
Synthesis of Compound A-34 :
In a 100 ml reactor which was sufficiently dried and purged with argon, 0.60 g (2.13 mmol) of compound L34 and 40 ml of diethyl ether were charged, cooled to −78 ° C. and stirred. To this, 2.75 ml of n-butyl lithium (1.63 mmol / ml n-hexane solution 4.48 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. did. The solution was cooled to -78 ° C, and 0.71 g (2.13 mmol) of titanium tetrachloride / tetrahydrofuran complex was gradually added. 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 0.19 g (0.48 mmol, 23% yield) of compound A-34 as a red powder. Was.

FD-Mass Spec: 398 (M +)
[Synthesis Example 67]
Synthesis of Compound A-35 :
0.19 g (60 wt% product, 4.75 mmol) of sodium hydride and 50 ml of tetrahydrofuran are charged into a 100 ml reactor which is sufficiently dried and purged with argon, and a solution of compound L35; 1.00 g (2.30 mmol) and 20 ml of tetrahydrofuran are stirred at room temperature while stirring. The mixture was added dropwise over 5 minutes, and 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 gradually added dropwise to a solution of titanium tetrachloride / tetrahydrofuran complex (0.77 g, 2.31 mmol) and tetrahydrofuran (50 ml) stirred at room temperature. 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 through a glass filter, and the cake 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.

FD-Mass Spec: 550 (M +)
[Synthesis Example 68]
Synthesis of Compound A-36 :
0.19 g (4.75 mmol of 60 wt% product) and 50 ml of tetrahydrofuran were charged into a 100 ml reactor which was sufficiently dried and purged with argon, and a solution of compound L36; 1.00 g (2.23 mmol) and 20 ml of tetrahydrofuran were stirred at room temperature while stirring. The solution was added dropwise over 5 minutes, and 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 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 0.55 g (0.97 mmol) of orange powdered compound A-36.
Yield 44%).

FD-Mass Spec: 564 (M +)
[Synthesis Example 69]
Synthesis of Compound B-37 :
In a 100 ml reactor sufficiently dried and purged with argon, 0.30 g of sodium hydride (7.50 mmol of a 60 wt% product) and 50 ml of tetrahydrofuran were charged, and while stirring at room temperature, a solution of compound L37; 1.00 g (3.16 mmol) and 20 ml of tetrahydrofuran was added. The mixture was added dropwise over 5 minutes, and 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. This solution was gradually added dropwise to a solution of 1.19 g (3.15 mmol) of a zirconium tetrachloride / 2THF complex and 50 ml of tetrahydrofuran stirred at room temperature. 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 filtrate was washed with tetrahydrofuran, and the insoluble matter was removed by filtration.The solvent of the filtrate was concentrated under reduced pressure about 1/3, The precipitated solid was filtered with a glass filter, and the precipitate was washed with cold tetrahydrofuran and dried under reduced pressure to obtain 1.00 g (2.10 mmol, 66% yield) of compound B-37 as a yellow powder.

FD-Mass Spec: 474 (M +)
[Synthesis Example 70]
Synthesis of Compound B-38 :
0.23 g (60 wt% product, 5.75 mmol) of sodium hydride and 50 ml of tetrahydrofuran are charged into a 100 ml reactor which is sufficiently dried and purged with argon, and while stirring at room temperature, a solution of compound L38; 1.00 g (2.73 mmol) and 20 ml of tetrahydrofuran is added. The mixture was added dropwise over 5 minutes, and 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 gradually added dropwise to a solution of 1.03 g (2.73 mmol) of zirconium tetrachloride / 2THF complex and 50 ml of tetrahydrofuran stirred at room temperature. 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 material was removed by filtration. 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 obtain 1.15 g (2.18 mmol, 80% yield) of compound B-38 as a yellow powder.

FD-Mass Spec: 524 (M +)
[Synthesis Example 71]
Synthesis of Compound A-39 :
A 100 ml reactor which was sufficiently dried and purged with argon was charged with 0.50 g (1.87 mmol) of compound L39 and 50 ml of diethyl ether, cooled to −78 ° C. and stirred. To this, 1.20 ml of n-butyllithium (1.61 mmol / ml 1.93 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. did. This solution was cooled to −78 ° C. and 1.87 ml of a titanium tetrachloride solution (0.5 mmol / ml heptane solution, 0.94 mmol) and diethyl ether 70
The mixture was gradually dropped into the ml mixture. 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 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 compound A-39 as a red powder (0.17 mmol, 18% yield). Obtained.

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). Values in parentheses are calculated values. [Synthesis Example 72]
Synthesis of Compound B-39 :
In a 100 ml reactor that was sufficiently dried and purged with argon, 0.50 g (1.87 mmol) of compound L39 and 40 ml of diethyl ether were charged, cooled to −78 ° C., and stirred. To this, 1.20 ml of n-butyllithium (1.61 mmol / ml n-hexane solution, 1.93 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. Prepared. This solution was cooled to -78 ° C and zirconium tetrachloride / 2THF complex (0.352 g, 0.93 mmol) in 50 ml of tetrahydrofuran
It was dropped into the mixed solution. After completion of the dropwise addition, stirring was continued while slowly raising the temperature to room temperature. After further stirring at room temperature for 8 hours, the reaction solution was heated and stirred at 60 ° C. for 3 hours, and then 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 (0.43 mmol, 46% yield) of a yellow-white powdered compound B-39 represented by the following formula.

¹ H-NMR (CDCl ₃ ): 1.60 (s, 18H) 4.65 (d, 2H) 4.95 (d, 2H) 6.70-7.70 (m, 16H) 7.85 (s, 2H)
FD-Mass Spec: 694 (M +)
Elemental analysis: Zr; 12.9% (13.1). Values in parentheses are calculated values. [Synthesis Example 73]
Synthesis of Compound A-40 :
In a 100 ml reactor that was sufficiently dried and purged with argon, 0.58 g (2.02 mmol) of compound L40 and 40 ml of diethyl ether were charged, cooled to −78 ° C., and stirred. To this, 1.50 ml of n-butyl lithium (1.61 mmol / ml 2.42 mmol of n-hexane solution) 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. did. 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. 0.19 g (0.28 mmol, 28% yield) of compound A-40 as a red-orange powder was obtained.

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 Spec: 692 (M +)
Elemental analysis: Ti; 7.0% (6.9). Values in parentheses are calculated values. [Synthesis Example 74]
Synthesis of Compound B-40 :
In a 100 ml reactor that was sufficiently dried and purged with argon, 0.58 g (2.02 mmol) of compound L40 and 40 ml of diethyl ether were charged, cooled to −78 ° C., and stirred. To this, 1.50 ml of n-butyllithium (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. Prepared. This solution was added dropwise to a mixed solution of zirconium tetrachloride / 2THF complex (0.38 g, 1.00 mmol) in 80 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 solvent was distilled off from the reaction solution. The obtained solid was reslurried with 150 ml of diethyl ether, 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 0.23 g (0.31 mmol, 31% yield) of a yellow powdered compound B-40 represented by the following formula.

¹ H-NMR (CDCl ₃ ): 0.80-1.70 (m, 18H) 6.50-7.90 (m, 14H) 8.20 (s, 2H)
FD-Mass Spec: 734 (M +)
Elemental analysis: Zr; 12.2% (12.4). Values in parentheses are calculated values. [Synthesis Example 75]
Synthesis of Compound A-41 :
In a 100 ml reactor sufficiently dried and purged with argon, compound L41; 0.50 g (1.15 mmol) and 10 ml of diethyl ether were charged, cooled to -78 ° C and stirred. To this, 1.47 ml of n-butyl lithium (1.61 mmol / ml 2.36 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. did. 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) 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 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 insoluble matter in the solution was filtered using 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 give compound A- as an orange powder. 0.49 g (0.93 mmol yield 76%) of 41 was obtained.

FD-Mass Spec: 525 (M +)
Elemental analysis: Ti; 8.9% (9.1) (): Calculated value [Synthesis Example 76]
Synthesis of Compound B-41 :
In a 100 ml reactor sufficiently dried and purged with argon, compound L41; 0.50 g (1.15 mmol) and 10 ml of diethyl ether were charged, cooled to -78 ° C and stirred. To this, 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. Prepared. This solution was added dropwise to a solution of zirconium tetrachloride · 2THF complex (0.43 g, 1.15 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 8 hours and then under reflux for 12 hours, the reaction solution was evaporated. The obtained solid was dissolved in 25 ml of methylene chloride, and insolubles were 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, dried under reduced pressure to obtain 0.36 g of a yellow powdered compound B-41 represented by the following formula (0.63 mmol, 51% yield). Obtained.

_{^{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 Spec: 568 (M +)
Elemental analysis: Zr; 16.2% (16.0). Values in parentheses are calculated values. [Synthesis Example 77]
Synthesis of Compound A-42 :
In a 100 ml reactor which was sufficiently dried and purged with argon, 0.500 g (1.22 mmol) of compound L42 and 10 ml of diethyl ether were charged, cooled to −78 ° C. and stirred. To this, 1.52 ml of n-butyllithium (1.61 mmol / ml 2.45 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. did. This solution 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) 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 reaction solution was evaporated, 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 red-brown powder of Compound A-42. 0.25 g (0.45 mmol, yield 40%) was obtained.

FD-Mass Spec: 552 (M +)
Elemental analysis: Ti; 9.0% (8.7). Values in parentheses are calculated values. [Synthesis Example 78]
Synthesis of Compound B-42 :
In a 100 ml reactor that was sufficiently dried and purged with argon, 0.50 g (1.22 mmol) of compound L42 and 10 ml of diethyl ether were charged, cooled to −78 ° C., and stirred. 1.52 ml of n-butyl lithium (1
(0.61 mmol / ml n-hexane solution, 2.45 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 solution of zirconium tetrachloride · 2THF complex (0.46 g, 1.22 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 8 hours and then under reflux for 6 hours, the solvent was distilled off from the reaction solution. The obtained solid was dissolved in 25 ml of methylene chloride, 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.

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

Specific examples of the polymerization method according to the present invention are shown below.

[Example 1]
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 ethylene at 100 liter / hr. Thereafter, methylaluminoxane (MAO) was added in an amount of 1.1875 mmol in terms of aluminum atom, and subsequently, 0.00475 mmol of the compound A-1 obtained in Synthesis Example 1 was added, and polymerization was started. 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 3,400 g / mmol-Ti · hr, and the intrinsic viscosity [η] of the obtained polyethylene was 8.44 dl / g.

[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 liter / hr of ethylene. Thereafter, 1.25 mmol of methylaluminoxane in terms of aluminum atom and 0.005 mmol of compound A-1 were 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 liter 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.

[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.

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

[Example 5]
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, 0.25 mmol of triisobutylaluminum (TIBA), 0.005 mmol of compound A-1 and 0.006 mmol of triphenylcarbenium tetrakis (pentafluorophenyl) borate (TrB) were added, and polymerization was started. 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.

[Example 6]
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 liter / hr of ethylene. Thereafter, 0.25 mmol of triisobutylaluminum, 0.005 mmol of compound A-1 and 0.006 mmol of triphenylcarbenium tetrakis (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.

(4) The obtained polymer suspension was added to 1.5 liter of methanol containing a small amount of hydrochloric acid to precipitate a polymer. After removing the solvent by filtration through a glass filter, the resultant was washed with methanol and dried under reduced pressure at 80 ° C. for 10 hours. 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.

[Example 7]
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 liter / hr of ethylene. Thereafter, 2.5 mmol of methylaluminoxane in terms of aluminum atom and subsequently 0.005 mmol of the zirconium compound B-1 obtained in Synthesis Example 2 were added, and polymerization was started. After a reaction at 25 ° C. for 5 minutes 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, 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.

[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.

[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 liter / hr of ethylene. Then, after adding 0.25 mmol of triisobutylaluminum, 0.05 mmol of triisobutylaluminum, 0.005 mmol of compound B-1 and 0.006 mmol of triphenylcarbeniumtetrakis (pentafluorophenyl) borate were mixed in advance. In addition, polymerization was started. After polymerization was carried out at 25 ° C. for 5 minutes in 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 obtained polyethylene was 0.99 g, the polymerization activity was 2380 g / mmol-Zr · hr, and the intrinsic viscosity [η] was 22.4 dl / g.

[Example 26]
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 liter / hr of ethylene. Thereafter, 0.25 mmol of triisobutylaluminum, 0.0005 mmol of compound B-1 and 0.001 mmol of triphenylcarbenium tetrakis (pentafluorophenyl) borate were added to initiate polymerization. The reaction was carried out at 25 ° C. for 10 minutes in an atmosphere of ethylene gas at normal pressure. 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.

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

[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.

[Examples 32-36]
Using the compounds shown in 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 Table 2. Table 2 shows the results.

[Examples 37 to 52]
When methylaluminoxane was used as a cocatalyst under the polymerization conditions shown in Table 3 using the compounds shown in Table 3, 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.

The results are shown in Table 3.

[Examples 53 to 78]
Using the compounds shown in Table 4 and under the polymerization conditions shown in Table 4, when methylaluminoxane was used as a cocatalyst, 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.

The results are shown in Table 4.

[Examples 79 to 111]
Using the compounds shown in Table 5 and under the polymerization conditions shown in Table 5, 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.

The results are shown in Table 5.

[Examples 112 to 121]
Using the compounds shown in Table 6 and 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.

The results are shown in Table 6.

[Examples 122 to 130]
Using the compounds shown in Table 7 and under the polymerization conditions shown in Table 7, 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.

The results are shown in Table 7.

[Example 131]
250 ml of toluene was charged into a glass autoclave having an inner volume of 500 ml which was sufficiently purged with nitrogen, and the liquid phase and the gas phase were saturated with a mixed gas of ethylene 50 liter / hr and propylene 150 liter / hr. 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 liter of methanol containing a small amount of hydrochloric acid to precipitate a polymer. After removing the solvent by filtration through a glass filter, the resultant was washed with methanol and dried under reduced pressure at 80 ° C. for 10 hours. The obtained ethylene-propylene copolymer was 0.95 g, the polymerization activity was 760 g / mmol-Ti · hr, the propylene content measured by IR was 4.67 mol%, and the intrinsic viscosity [η] was It was 2.21 dl / g.

[Example 132]
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 a mixed gas of 100 l / hr of ethylene and 100 l / hr of propylene. Then, after adding 0.25 mmol of triisobutylaluminum, 0.025 mmol of triisobutylaluminum, 0.0025 mmol of compound B-1 and 0.005 mmol of triphenylcarbenium tetrakis (pentafluorophenyl) borate (TrB) are previously mixed. The resulting solution was added to initiate copolymerization. After copolymerization at 50 ° C. for 5 minutes, the polymerization was stopped by adding a small amount of isobutanol.

(5) The obtained polymer solution was added to 1.5 liter 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.

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

The results are shown in Table 8.

[Examples 134 to 149]
Using the compounds shown in Table 8, copolymerization was carried out in the same manner as in Example 131.

The results are shown in Table 8.

[Example 150]
250 ml of toluene was charged into a 500 ml-volume glass autoclave sufficiently purged with nitrogen, 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 in terms of aluminum atom and then 0.01 mmol of titanium compound A-1 were 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, and then filtered through a glass filter. After drying under reduced pressure at 80 ° C. for 10 hours, 0.53 g of an ethylene / butadiene copolymer was obtained.

重合 The polymerization activity per 1 mmol of titanium was 149 g, and the intrinsic viscosity [η] of the obtained copolymer was 1.46 dl / g. According to NMR analysis, the content of all butadiene units in the copolymer was 0.9 mol% (0.8 mol% in total of 1,4-cis and 1,4-trans forms, and 0 mol 0.1 mol%, and the content of cyclopentane skeleton was less than 0.1 mol% (lower than the detection limit).

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

重合 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 mol% in total of 1,4-cis and 1,4-trans forms and 0.1 mol% in 1,2-vinyl form). 1 mol%, and the content of the cyclopentane skeleton was less than 0.1 mol% (lower than the detection limit).

[Example 152]
Polymerization was carried out in the same manner as in Example 151 except that the polymerization time was 20 minutes, 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.

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

[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 0.57 g.

重合 The polymerization activity per 1 mmol of zirconium was 342 g, and the intrinsic viscosity [η] of the obtained copolymer was 0.34 dl / g. According to NMR analysis, the content of butadiene units in the copolymer was 2.4 mol% (2.3 mol% of 1,4-cis-form and 1,4-trans-form 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).

[Example 154]
Polymerization was carried out in the same manner as in Example 153 except that the polymerization temperature was changed to 50 ° C. The yield of the obtained copolymer was 0.627 g.

The polymerization activity was 1488 g / mmol-Zr · hr, and the intrinsic viscosity [η] of the obtained copolymer was 0.1.
It was 16 dl / g. According to NMR analysis, the content of butadiene units in the copolymer was 3.3 mol% (3.2 mol% of 1,4-cis-form and 1,4-trans-form combined, and 0.1-mol of 1,2-vinyl-form). Mol%, the cyclopentane skeleton was less than 0.1 mol% (lower than the detection limit).

[Example 155]
Polymerization was carried out in the same manner as in Example 153 except that the polymerization temperature was 50 ° C., the flow rate of ethylene was 40 L / hr, and the flow rate of butadiene was 60 L / hr. 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 0.1
It was 7 dl / g. According to NMR analysis, the content of butadiene units 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% in the 1,2-vinyl form). Mol%, the cyclopentane skeleton was less than 0.1 mol% (lower than the detection limit).

[Example 156]
Polymerization was carried out in the same manner as in Example 153, except that the polymerization temperature was 60 ° C., the flow rate of ethylene was 40 L / hr, and the flow rate of butadiene was 60 L / hr. 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 0.1
It was 2 dl / g. According to NMR analysis, the content of butadiene units in the copolymer was 5.8 mol% (5.6 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 1.85.

[Example 157]
Polymerization was carried out in the same manner as in Example 153, except that the polymerization temperature was 50 ° C., the flow rate of ethylene was 30 L / hr, and the flow rate of butadiene was 70 L / hr. 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 0.1
It was 4 dl / g. According to NMR analysis, the content of butadiene units in the copolymer was found to be 6.6 mol% (6.3 mol% of 1,4-cis and 1,4-trans forms in total, 0.2% of 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.

[Example 158]
A 1-liter autoclave made of SUS sufficiently charged with nitrogen was charged with 500 ml of heptane, heated to 50 ° C., and the liquid phase and the gas phase were saturated with ethylene. Thereafter, 1.25 mmol of methylaluminoxane in terms of aluminum atoms and 0.001 mmol of compound A-1 were 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, which was filtered through a glass filter. After removing the solvent, the polymer was washed with methanol and then at 80 ° C. for 10 hours. It was dried under reduced pressure. 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.

[Examples 159 to 162]
Polymerization was carried out in the same manner as in Example 158 except that the compounds shown in Table 9 were used and the polymerization conditions were changed as shown in Table 9.

The results are shown in Table 9.

[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, 57.5 l of a methylaluminoxane solution (Al = 1.33 mol / l) was 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. Thereafter, the temperature was lowered to 60 ° C., and the supernatant was removed by a decantation method. The obtained solid catalyst component was washed twice with toluene and then resuspended in toluene to obtain a solid catalyst component (A) (total volume 200 liter).

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 a toluene solution of compound A-1 (Ti = 0.01 mmol / l) 4 And 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 sufficiently purged with nitrogen, and the temperature was raised to 50 ° C. to saturate the gas and liquid phases with ethylene. Thereafter, 1.0 mmol of triisobutylaluminum and 0.005 mmol of the solid catalyst component (B) in terms of the contained Ti atom were added, and polymerization was carried out at an ethylene pressure of 8 kg / cm ² -G for 90 minutes.

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

[Example 164]
To a 200 ml reactor sufficiently purged with nitrogen, 60 ml of heptane and 40 ml of 1-hexene were added and stirred at 25 ° C. Then, after adding 0.25 mmol of triisobutylaluminum, a solution of 0.1 mmol of premixed triisobutylaluminum, 0.01 mmol of compound A-1, and 0.012 mmol of triphenylcarbenium tetrakis (pentafluorophenyl) borate are added. Was added to initiate polymerization. After performing the reaction 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 obtained polyhexene was 3.15 g, the polymerization activity was 315 g / mmol-Ti · hr, and the molecular weights measured by GPC (polystyrene conversion) were Mw = 14.6 million and Mw / Mn = 2.06.

[Example 165]
250 ml of toluene was added to a 500 ml reactor sufficiently purged with nitrogen, and the liquid phase and the gas phase were saturated with ethylene at 25 ° C. Thereafter, 1.0 mmol of triisobutylaluminum, 0.01 mmol of titanium compound A-1 and 0.02 mmol of triphenylcarbenium tetrakis (pentafluorophenyl) borate were added while flowing 80 l / hr of butadiene, and polymerization was started. . 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.
It was 760,000 (in terms of polystyrene).

FIG. 1 shows a process for preparing a first olefin polymerization catalyst according to the present invention. FIG. 2 shows a process for preparing the 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 a structure of the transition metal compound B-1 produced in Synthesis Example 2 obtained by X-ray crystal structure analysis.

Claims (11)

(A ′) a transition metal compound represented by the following general formula (II):
(B) (B-1) an organometallic compound,
An olefin comprising: (B-2) an organic 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. Polymerization catalyst;

(Wherein, M represents a transition metal atom of Groups 3 to 11 of the periodic table,
R ^{1 to} R ¹⁰ 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 containing group, a 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;
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, and a silicon-containing residue. A group, a germanium-containing group, or a tin-containing group, and when n is 2 or more, a plurality of groups represented by X may be the same or different from each other, and a plurality of groups represented by X bind to each other 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 when it is a hydrocarbon group, it is a group consisting of 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. The catalyst for olefin polymerization according to claim 1, which is a group, a silicon-containing group, a germanium-containing group, or a tin-containing group. The catalyst for olefin polymerization according to claim 1, wherein the transition metal compound represented by the general formula (II) is a transition metal compound represented by the following general formula (II-a);

(Wherein, M represents a transition metal atom of Groups 3 to 11 of the periodic table,
R ^{1 to} R ¹⁰ 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, and 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,
n is a number satisfying the valence of M;
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 bonding group 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, It is a group consisting of three or more carbon atoms. ) In the general 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 sulfonamide. The catalyst for olefin polymerization according to claim 3, wherein the catalyst is a group, a cyano group or a nitro group. The olefin polymerization catalyst according to any one of claims 1 to 4, wherein in the transition metal compound (A '), M is a transition metal atom belonging to Group 4 or 5 of the periodic table. The transition metal compound (A ^′ ) according to any one of claims 1 to 5, and (B-1) an organometallic compound, (B-2) an organic aluminum oxy compound, and (B-3) an ionized ionic compound. A catalyst for olefin polymerization, comprising a carrier (C) in addition to at least one compound (B). A process 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 6. The value of the molecular weight distribution (Mw / Mn) is 3.5 or less, the content of the structural unit derived from the α-olefin is in the range of 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 mol% or less. Diene copolymer. The α-olefin / conjugated diene copolymer according to claim 8, wherein the 1,2-cyclopentane skeleton derived from the conjugated diene is not substantially contained in the polymer chain. 10. 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 in the range of 50 to 0.1 mol%. The α-olefin / conjugated diene copolymer according to the above. 11. The α-olefin / conjugated diene copolymer according to claim 8, wherein the α-olefin is ethylene and / or propylene, and the conjugated diene is butadiene and / or isoprene.

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