JP2002020395A - New organometallic complex having high metathesis activity, metathesis reaction catalyst containing the same, polymerization method by using the catalyst, and resin composition obtained by the polymerization method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new organometal complex excellent in heat resistance, oxygen resistance and reaction controllability and having a high metathesis activity, and to provide a metathesis reaction catalyst containing the complex, a polymerization method by using the catalyst and a resin composition obtained by the polymerization method. SOLUTION: This organometal complex compound is represented by general formulas 1, 5 or 6 (wherein, M is a metal such as Ru; R1 and R2 are each hydrogen or a hydrocarbon group; and L1 and L2 are each a ligand and at least one thereof is a group represented by general formulas 2 to 4).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel organometallic complex compound having excellent heat resistance, oxygen resistance and reaction controllability and having high metathesis activity, a metathesis reaction catalyst containing the same, and the use of this catalyst. And a resin composition obtained by the polymerization method.

[0002]

2. Description of the Related Art It has long been known that ring-opening polymerization of cyclic olefins is carried out in the presence of a transition metal catalyst such as tungsten or molybdenum. Generally, this type of polymerization reaction is referred to as a metathesis reaction or a metathesis polymerization. I say. Norbornene monomers such as dicyclopentadiene (hereinafter sometimes abbreviated as DCPD) are:
It is a typical monomer used for metathesis polymerization. From these monomers, ring-opening polymerization is performed in a mold by a reaction injection molding (hereinafter, sometimes abbreviated as RIM) method or the like to obtain a mechanical strength. Since a molded article having excellent heat resistance, dimensional stability, and the like can be obtained, a molding method utilizing such metathesis polymerization has been frequently used because of the convenience that polymerization and molding can be performed simultaneously.

However, the molding method utilizing such metathesis polymerization has the following serious problems. (1) The metathesis reaction catalyst conventionally used is
There is a drawback that the catalyst is deactivated when exposed to the atmosphere. Therefore, at the time of RIM molding, a molding process in an expensive hermetic mold is required, and there is a limitation in terms of process. (2) Furthermore, DCPD obtained by metathesis polymerization
The crosslinked product has a residual monomer, and the residual odor has a limitation in use.

[0004] Therefore, research and development have been conducted on a novel metathesis reaction catalyst which does not have such problems, and various metathesis reaction catalysts have been proposed so far, but all of them are still in view of the active surface and handleability. It was not satisfactory enough. For example, U.S. Pat. No. 5,831,1
No. 08 discloses a ruthenium alkylidene complex as a metathesis reaction catalyst. Although this complex has a very high reactivity at room temperature in air, it is difficult to control the reaction and has low heat resistance. There was a problem.

[0005]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a novel organometallic complex compound which is excellent in heat resistance, oxygen resistance and reaction controllability and has a high metathesis activity. An object of the present invention is to provide a metathesis reaction catalyst containing an organometallic complex compound, a polymerization method using the catalyst, and a resin composition obtained by the polymerization method.

[0006]

Means for Solving the Problems The present inventors have conducted intensive studies in order to solve the problems of the conventional metathesis reaction catalyst, and as a result, have found that a specific organometallic complex and a specific N-based ligand have been obtained. It has been found that an organic metal complex compound having excellent heat resistance, oxygen resistance, and reaction controllability and having high metathesis activity can be obtained by combining and combining. The present invention has been completed based on these findings.

That is, according to the first aspect of the present invention,
The following general formula (1):

Embedded image (Wherein M is a metal selected from ruthenium, osmium, iron or tungsten; R ₁ and R ₂ are the same or different and are a hydrogen atom, an alkenyl group having 2 to 20 carbon atoms,
Optionally substituted by an alkyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkyl group having 1 to 5 carbon atoms, a halogen atom, and a phenyl group substituted by an alkoxyl group having 1 to 5 carbon atoms. Carbon number 2 which may be
-20 carboxylate, C2-C20 alkoxyl group, C2-C20 alkenyloxy group, aryloxy group, C2-C20 alkoxycarbonyl group, C2-C20 alkylthio group or ferrocene derivative Wherein R ₁ and R ₂ may together form a cyclic structure; X and X ₁ are independently selected from anionic ligands; L and L ₁ are independent A ligand, at least one of which is represented by the following formula (2)
Any of the ligands represented by (4), but in some cases, two or three of X, X ₁ , L and L ₁ may together form a multidentate chelating ligand good. ) Is provided.

Embedded image

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Embedded image However, in the above formulas (2) to (4), R _{3 to} R ₁₇ each represent an independent substituent, but in some cases, a part thereof may be integrally formed to form a ring.

According to the second aspect of the present invention, the following general formula (5):

Embedded image(Wherein Y is a hetero atom selected from sulfur, oxygen or selenium)
An atom; R₁₈And R ₁₉Are the same or different, and
Alkenyl group having 2 to 20 carbon atoms, 2 to 20 carbon atoms
Alkyl group, aryl group having 6 to 20 carbon atoms, 1 to 1 carbon atom
5 alkyl groups, halogen atoms, alcohols having 1 to 5 carbon atoms
Required by phenyl group substituted by xyl group
Optionally substituted carboxy having 2 to 20 carbon atoms
Silate, alkoxy group having 2 to 20 carbon atoms, 2 carbon atoms
-20 alkenyloxy, aryloxy, carbon
An alkoxycarbonyl group having 2 to 20 carbon atoms, 2 to 20 carbon atoms
Represents an alkylthio group or a ferrocene derivative,
Depending on R₁And R_TwoUnite to form an annular structure
May be; M, X, X₁, L and L₁Is the general formula
This is the same as the case of (1). Organometallic complex represented by)
Compounds are provided.

Further, according to the third aspect of the present invention, the following general formula (6):

Embedded image (Wherein, R ₂₀ , R ₂₁ and R ₂₂ are the same or different and each represent a hydrogen atom, an alkenyl group having 2 to 20 carbon atoms,
An alkyl group, an aryl group having 6 to 20 carbon atoms, and 1 carbon atom
C5 to C20 carboxylate, C2 to C20 alkoxyl optionally substituted by a phenyl group substituted by an alkyl group having 5 to 5 halogen atoms, and a C1 to C5 alkoxyl group Group, alkenyloxy group having 2 to 20 carbon atoms, aryloxy group, alkoxycarbonyl group having 2 to 20 carbon atoms, 2 to 2 carbon atoms
0 represents an alkylthio group or a ferrocene derivative, and in some cases, a part of R ₂₀ , R ₂₁ and R ₂₂ may be combined to form a cyclic structure; M, X, X ₁ , L and L ₁ has the same meaning as in formula (1). ) Is provided.

According to the fourth aspect of the present invention, the first aspect is provided.
In any one of the third to third inventions, there is provided an organometallic complex compound, wherein M in the formula is ruthenium or osmium.

Further, according to a fifth aspect of the present invention, in any one of the first to third aspects, L in the formula
And at least one of L ₁ is a ligand represented by the above formula (3) or (4).

Further, according to a sixth aspect of the present invention, in the fifth aspect, the ligand represented by the formula (3) is represented by the following formula (7):

Embedded image An organometallic complex compound having a structure represented by the following formula: is provided.

According to the seventh aspect of the present invention, the fifth aspect is provided.
In the invention of the above, the ligand represented by the formula (4) is represented by the following formula (8):

Embedded image An organometallic complex compound having a structure represented by the following formula: is provided.

According to an eighth aspect of the present invention, in any one of the first to seventh aspects, the decomposition rate after one hour in an organic solvent at 100 ° C. is 3%.
Provided is an organometallic complex compound, which is 0% or less and has high metathesis activity.

On the other hand, according to the ninth aspect of the present invention, the first aspect
To a metathesis reaction catalyst comprising the organometallic complex compound obtained by any one of the inventions according to the eighth to eighth aspects.

On the other hand, according to a tenth aspect of the present invention, there is provided a polymerization method comprising polymerizing a metathesis reactive monomer in the presence of the metathesis reaction catalyst obtained according to the ninth aspect.

Further, according to an eleventh aspect of the present invention,
In the tenth invention, the metathesis reactive monomer is
A polymerization method characterized by being a bicyclic or tricyclic or higher norbornene-based monomer is provided.

According to a twelfth aspect of the present invention, there is provided the polymerization method according to the eleventh aspect, wherein the norbornene-based monomer is dicyclopentadiene.

According to a thirteenth aspect of the present invention, there is provided a resin composition obtained by the polymerization method according to any one of the ninth to twelfth aspects.

[0020]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.

The organometallic complex compound according to the first invention of the present invention has the following general formula (1):

[0022]

Embedded image It is represented by Where M is ruthenium, osmium,
R ₁ and R ₂ are the same or different and are each a hydrogen atom, having 2 to 2 carbon atoms.
An alkenyl group having 0, an alkyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkyl group having 1 to 5 carbon atoms,
A halogen atom, a carboxylate having 2 to 20 carbon atoms which may be optionally substituted by a phenyl group substituted by an alkoxyl group having 1 to 5 carbon atoms, an alkoxyl group having 2 to 20 carbon atoms, 20 alkenyloxy group, an aryloxy group, an alkoxycarbonyl group having 2 to 20 carbon atoms, represents an alkylthio group or a ferrocene derivative having 2 to 20 carbon atoms, optionally, R ₁
And R ₂ may together form a cyclic structure; X
And X ₁ are independently selected from anionic ligands; L and L ₁ are independent ligands, at least one of which is a ligand represented by the following formulas (2) to (4): In some cases, two or three of X, X ₁ , L, and L ₁ may form a polydentate chelating ligand.

[0023]

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[0024]

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[0025]

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However, in the above formulas (2) to (4), R
_{3 to} R ₁₇ each represent an independent substituent, but in some cases, a part thereof may be integrally formed to form a ring. And these independent substituents are not particularly limited as long as they do not impair the metathesis reactivity of the complex.Stability in the air, stability to functional groups and polar groups, which are characteristic of the present invention, In order to obtain an organometallic complex compound having excellent heat resistance, the substituent is preferably a bulky substituent, and more preferably a substituent having a ring structure. Among these, a particularly preferable structure includes, for example, an aromatic ring structure having the structure of the following formula (7) or (8). From the viewpoint of the stability and heat resistance of the organometallic complex compound itself, The former ligand having the structure of the formula (7) is particularly preferred.

[0027]

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[0028]

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As described above, L and L ₁ are independent ligands, at least one of which is represented by the above formula (2).
Must be one of the ligands represented by
When either one is other than formulas 1 to 4, it is preferably a phosphorus-based ligand. Preferred phosphorus ligands include the following formula (11): PR ₂₆ R ₂₇ R ₂₈ Formula (11) wherein R ₂₆ is a secondary alkyl or cycloalkyl, and R ₂₇ and R ₂₈ are , aryl, C ₁ -C ₁₀ primary alkyl, secondary alkyl, or phosphine and the like represented by cycloalkyl is). Where R
₂₇ and R ₂₈ may be the same or different. Then, L and L ₁ are most preferably the same, specifically, -P (cyclohexyl) _3, -P (cyclopentyl) _3, -P (isopropyl) _3.

The metal in the formula (1) is ruthenium,
Osmium, iron, or tungsten is selected, but among these metals, preferred are ruthenium or osmium in terms of stability of the organometallic complex compound itself.
Particularly preferred is ruthenium.

Further, X and X ₁ in the formula (1) can be selected from any anionic ligand, but are preferably Cl or Br, and more preferably Cl.

The organometallic complex compound according to the first invention of the present invention can be produced by various methods. To give an example, first, one of the raw materials represented by the general formulas (A ₁ ) to (A ₁ ) The ligand precursor represented by A ₃ ) is synthesized according to a known production method, and another raw material, an organometallic complex precursor represented by the general formula (B), is synthesized according to a known production method. Finally, when both raw materials are mixed, a ligand exchange reaction as shown below occurs, and an organometallic complex compound of the general formula (1) as a target product is obtained.

[0033]

Embedded image

The organometallic complex compound according to the second invention of the present invention has the following general formula (5):

[0035]

Embedded image It is represented by

Wherein Y is a heteroatom selected from sulfur, oxygen or selenium; R ₁₈ and R ₁₉ are the same or different and are a hydrogen atom, an alkenyl group having 2 to 20 carbon atoms,
Optionally substituted by an alkyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkyl group having 1 to 5 carbon atoms, a halogen atom, and a phenyl group substituted by an alkoxyl group having 1 to 5 carbon atoms. Carbon number 2 which may be
-20 carboxylate, C2-C20 alkoxyl group, C2-C20 alkenyloxy group, aryloxy group, C2-C20 alkoxycarbonyl group, C2-C20 alkylthio group or ferrocene derivative In some cases, R ₁₈ and R ₁₉ may be combined to form a ring structure. Further, M, X, X ₁ , L and L ₁ in the formula (5) have the same meaning as in the case of the general formula (1).

In the organometallic complex compound according to the second aspect of the present invention, one of the major features is that a hetero atom selected from sulfur, oxygen and selenium is present in the complex. The stability of the complex is further improved, resulting in an organometallic complex compound having excellent heat resistance.

Further, the organometallic complex compound according to the third invention of the present invention has the following general formula (6):

[0039]

Embedded image It is represented by Here, R ₂₀ , R ₂₁ and R ₂₂ are the same or different and are a hydrogen atom, an alkenyl group having 2 to 20 carbon atoms,
Optionally substituted by an alkyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkyl group having 1 to 5 carbon atoms, a halogen atom, and a phenyl group substituted by an alkoxyl group having 1 to 5 carbon atoms. Carbon number 2 which may be
-20 carboxylate, C2-C20 alkoxyl group, C2-C20 alkenyloxy group, aryloxy group, C2-C20 alkoxycarbonyl group, C2-C20 alkylthio group or ferrocene derivative In some cases, some of R ₂₀ , R _21, and R ₂₂ may be integrated to form a ring structure. Further, M, X, X ₁ , L and L ₁ in the formula (6) have the same meaning as in the case of the general formula (1).

One of the major features of the organometallic complex compound according to the third aspect of the present invention is that a heteroatom consisting of nitrogen is present in the complex, and the heteroatom reduces the stability of the complex. It is further improved, and as a result, an organometallic complex compound having excellent heat resistance is obtained.

The organometallic complex compounds according to the second and third inventions of the present invention can be produced by various methods. To give an example, first, one of the raw materials represented by the general formula (1) (The organometallic complex compound according to the first invention of the present invention) or the metal complex compound described in U.S. Pat. No. 5,831,108 is synthesized according to a known production method, and on the other hand, it is another raw material. A ligand precursor containing an unsaturated bond with a sulfur, oxygen, selenium or nitrogen atom is also synthesized according to a known method, and finally the former metal complex is mixed with an equal or excess amount of the latter compound to form a ligand. A child exchange reaction occurs, and the desired organometallic complex compound of the formula (5) or (6) is obtained. At that time, the above sulfur,
Examples of the compound (ligand precursor) containing an oxygen, selenium, or nitrogen atom and an unsaturated bond include compounds having structures represented by the following formulas (9) and (10).

[0042]

Embedded image

[0043]

Embedded image Here, in the formula (9) or the formula (10), Y is a hetero atom selected from sulfur, oxygen or selenium, and R _{23 to} R _23
25, halogen, C ₂ -C ₂₀ alkenyl, C ₂ -C ₂₀ alkynyl, C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ aryl, C ₁ -
C ₂₀ carboxylate, C ₁ -C ₂₀ alkoxy, C ₂ -C
₂₀ alkenyloxy, C ₂ -C ₂₀ aryloxy, C ₁ -C ₂₀ alkoxycarbonyl, C ₁ - ₂₀ alkylthio, C ₁ -C ₂₀
Selected from the group consisting of alkoxysulfonyl and C ₁ -C ₂₀ alkylsulfonyl;
₂₄ and R ₂₅ may form a polydentate chelating ligand with a plurality of substituents.

The organometallic complex compounds according to the first, second and third aspects of the present invention (hereinafter sometimes collectively referred to as the organometallic complex compounds of the present invention) are suitably used for metathesis reactions. And, since the organometallic complex compound of the present invention is superior in stability in the air, stability to functional groups and polar groups, and heat resistance as compared with the conventional metathesis reaction catalyst, when used in metathesis polymerization, Taking advantage of this property, the amount of monomers remaining after polymerization can be significantly reduced.

Hereinafter, the case where the organometallic complex compound of the present invention is used for metathesis polymerization will be specifically described.
The amount of the organometallic complex compound used is preferably 1/100000 to 1/50 mol per 1 mol of the metathesis reactive monomer. If the proportion is less than 1 / 100,000, the catalytic activity is insufficient, and the physical properties of the obtained polymer are reduced. On the other hand, if it exceeds 1/50 mol, it is disadvantageous in terms of cost, which is not preferable.

The organometallic complex compound of the present invention is not only excellent in metathesis reactivity in terms of properties, but also has a decomposition rate of 30% or less after 1 hour when left at 100 ° C. in an organic solvent. It has excellent heat resistance. These properties are well utilized in the actual metathesis polymerization reaction, and the decomposition of the organometallic complex catalyst due to the heat generated during the metathesis reaction, which has occurred with conventional metathesis reaction catalysts, is suppressed, resulting in an increase in yield. It is thought that it led to the reduction of the residual monomer. A preferable property of heat resistance of the organometallic complex compound of the present invention is that when left at 120 ° C. in an organic solvent, the decomposition rate after one hour is 30% or less.

The organometallic complex compound of the present invention can be used for subjecting a functional group-containing monomer to metathesis polymerization. Examples of the functional group-containing monomer include a hydroxyl group, a carboxyl group, an amino group, an ester group, an acetoxy group, an alkoxy group, a halogen group, a carbonyl group, a mercapto group, an epoxy group, a silyl group, an oxazoline group, a sulfonic acid group, a maleimide group, and azlactone. And monomers having a wide range of functional groups, whether polar or non-polar, including vinyl groups.

In the case where the organometallic complex compound of the present invention is used for metathesis polymerization, examples of applications in which the feature of high heat resistance is utilized include polymerization of norbornene monomers. In the case of polymerization of such norbornene monomers,
When a conventional polymerization catalyst is used, a large amount of heat is generated in the reaction process unless a dilute solution system is used, so that some catalysts are deactivated. On the other hand, when the organometallic complex compound of the present invention is used, the deactivation of the catalyst is small, and the residual monomer after the polymerization is completed is small. In particular, when dicyclopentadiene is used as a monomer, such effects are more remarkably exhibited.

When a norbornene monomer is used as the metathesis reactive monomer, the polymerization temperature is from -20 ° C.
A range of 220 ° C. is preferred. When the polymerization temperature is lower than −20 ° C., the fluidity of the norbornene-based monomer is low, which is not preferable in blending the organometallic compound of the present invention. On the other hand, a temperature higher than 220 ° C. is not preferable because the metathesis catalyst is deactivated. More preferably, 10 to 20
0 ° C, and even more preferably in the range of 20 ° C to 180 ° C. Most preferably, it is in the range of 60 to 180 ° C.

The above norbornene-based monomers include:
There are bicyclic or tricyclic or higher polycyclic norbornene monomers. In the case of having three or more rings, a polymer having a high heat distortion temperature can be obtained, and the heat resistance required as a composite material can be satisfied. In the present invention, the resulting polymer may be of a thermosetting type. For this purpose, at least 10% by weight, preferably 30% by weight, of all the monomers is used.
It is preferable to use the above crosslinking monomers.

Examples of the bicyclic norbornene-based monomer include 2-norbornene, 5-methyl-2-norbornene, 5-ethylidene-2-norbornene, and 5-phenylnorbornene.

Examples of tricyclic or higher norbornene monomers include tricyclics such as dicyclopentadiene and dihydrodicyclopentadiene; tetracyclics such as tetracyclododecene; pentacyclics such as tricyclopentadiene; Hexacycles such as cyclopentadiene, and alkyl-substituted products thereof (eg, methyl, ethyl, propyl, butyl-substituted products), alkylidene-substituted products (eg, ethylidene-substituted products), aryl-substituted products (eg, phenyl,
Tolyl, naphthyl-substituted products, etc.). Among these, a tricyclic or pentacyclic norbornene-based monomer is preferable from the viewpoints of availability, reactivity, heat resistance and the like.

The crosslinking monomer is a polycyclic norbornene monomer having two or more reactive double bonds, and specific examples thereof include dicyclopentadiene, tricyclopentadiene, and tetracyclopentadiene. . Therefore, when the norbornene-based monomer and the crosslinkable monomer are the same substance, it is not necessary to use any other monomer. These norbornene-based monomers may be used alone or in combination of two or more. The tricyclic or higher norbornene-based monomer can also be obtained by heat-treating dicyclopentadiene.

The norbornene-based oligomer can be obtained by metathesis polymerization or another polymerization method using the norbornene-based monomer as a raw material. When synthesizing an oligomer, the starting material may be a plurality of monomers. Further, by allowing the monomer to coexist with the oligomer, the polymerization rate can be increased. The metathesis reaction of the present invention is preferably performed in an inert gas atmosphere, but when a stable catalyst is used, polymerization can be performed in air.

The resin composition obtained by polymerizing a metathesis-reactive monomer such as a norbornene compound under the catalyst of the organometallic complex compound of the present invention is excellent in adhesiveness, heat resistance, chemical resistance and the like, and needs these characteristics. It can be used for various applications such as electrical and electronic parts, bathtubs, combined septic tanks, etc.

[0056]

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

[Evaluation of heat resistance of organometallic complex compound]Example 1  [The ligand precursor of the formula (12) (1,3-dimesit
yl-4,5-dihydroimidazolium
 Synthesis of tetrafluoroborate)
(a) Angew. Chem. 1
961, 37, 493, (b) Angew. Che
m. , Int. Ed. Engl. 1962, 1,75-
80, (c) Chem. Ber. 1961, 94, 23
89-2393, (d) Chem. Ber. 1963,
96, 1208-1212, or by Soba et al.
(E) Tetrahedron Lett. 1991,
32, 5031-5034, the following formula:
Compound (12) was synthesized.

[0058]

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[Synthesis of Ruthenium Complex Precursor of Formula (13) (Ruthenium Vinylidene Complex)] 5.57 g (9.1)
(mmol) of Ru (p-cymene) Cl ₂ with 18.2 mmol of PCy ₃ and 9.1 mmol of t-butylacetylene together with 150 ml of toluene in a 300 ml flask under a nitrogen stream at 80 ° C. for 7 hours. I let it. After the completion of the reaction, toluene was removed under reduced pressure, and TH was removed.
The compound of the following formula (13) was synthesized by recrystallization in an F / ethanol system.

[0060]

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[Synthesis of Ruthenium Complex of the Formula (14)] First, 5.3 g (13.61 mmol) of the compound of the formula (12) and 150 mL of dry tetrahydrofuran were placed in a 2 L flask, and 1 mL of the mixture was added to the mixture. 0.52 g (13.6
200 mmol of a dry tetragidrofuran solution containing 1 mmol) of KOt-Bu was slowly added, and the mixture was stirred under a nitrogen stream for 1 hour. Subsequently, 600 mL of a benzene solution containing 8.150 g (10 mmol) of the compound of formula (13) (ruthenium vinylidene complex) was added by Cannula.
The reaction was further carried out at 0 ° C. for 18 hours. After the reaction, the solvent was removed under reduced pressure, and the residue was washed with methanol to obtain a crystal of a ruthenium complex represented by the following formula (14).

[0062]

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[Evaluation of heat resistance of ruthenium complex] A toluene solution containing 30 mM of the ruthenium complex of the formula (14) was treated with NM.
After sealing in R tube and leaving at 100 ° C for 30 minutes, 31P
As a result of analysis by -NMR measurement, the decomposition rate of the ruthenium complex of the formula (14) was 1% or less. Further, when the same heat resistance evaluation was performed at 120 ° C., the decomposition rate of the complex of the formula (14) was also 1% or less.

[0064]Example 2  [The ligand precursor of the formula (15) (1,3-dimesit
yl imidazolium tetrafluor
Oberate]] by Hermann et al.
Organomet. Chem. 1997, 547, 3
The following formula (15) is converted according to the method described in JP-A-57-366.
The compound was synthesized.

[0065]

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[Synthesis of Ruthenium Complex Precursor of Formula (17)] 8.23 g (1) of a compound of the following formula (16) synthesized according to the method described in US Pat. No. 5,831,108.
0 mmol) in 70 mL of toluene,
1.1 equivalent of phenylvinyl sulfide
The reaction was performed for 5 hours. Then, it was dried under reduced pressure and recrystallized in a THF / ethanol system to obtain a ruthenium complex precursor of the following formula (17).

[0067]

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[0068]

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[Synthesis of Ruthenium Complex of the Formula (18)] First, 5.3 g (13.61 mmol) of the compound of the formula (15) and 150 mL of dry tetrahydrofuran were put into a 2 L flask, and 1 mL of the mixture was added to the mixture. 0.52 g (13.6
200 mmol of a dry tetragidrofuran solution containing 1 mmol) of KOt-Bu was slowly added, and the mixture was stirred under a nitrogen stream for 1 hour. Subsequently, 600 mL of a benzene solution containing 8.450 g (10 mmol) of the ruthenium complex precursor of the formula (17) was added by Cannula.
The reaction was performed for 8 hours. After the reaction, the solvent was removed under reduced pressure, and the residue was washed with methanol to obtain a crystal of a ruthenium complex represented by the following formula (18).

[0070]

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[Evaluation of heat resistance of ruthenium complex] A 30 mM toluene solution of a ruthenium complex of the formula (18) was sealed in an NMR tube, left at 100 ° C for 30 minutes, and then subjected to 31P-N
When analyzed by MR measurement, the decomposition rate of the ruthenium complex of the formula (18) was 1% or less. Further, when the same heat resistance evaluation was performed at 120 ° C., the decomposition rate of the complex of the formula (18) was 5%.

[0072]Comparative Example 1  Synthesis according to the method described in U.S. Pat. No. 5,831,108.
30 mM toluene of the formed ruthenium complex of formula (16)
The en solution is sealed in an NMR tube and left at 100 ° C for 30 minutes.
After analyzing by 31 P-NMR measurement, the formula
The decomposition rate of the complex of (16) was 85%. Further similar
The evaluation of the heat resistance at 120 ° C. showed that the formula (16)
The decomposition rate of the complex was 95% or more.

[Evaluation of Performance as Metathesis Polymerization Catalyst]Example 3  Formula of 42 mg (1/20000 molar equivalent of DCPD)
The ruthenium complex of (14) was dissolved in 1 mL of toluene.
And then 132 g (1 mol) of dicyclopentadiene
(DCPD). Exothermic reaction after adding ruthenium complex
Response has started. Viscous resin with 4mm thick spacer
And maintain at 80 ° C for 1 hour
An evaluation sample was prepared. Dynamic viscoelasticity for the obtained sample
Measurement (based on JIS K 7198, viscoelastic spectrum)
Tensile method (n = 1) using a
Measure the temperature of the δ peak and use that temperature as the glass transition of the resin.
Temperature.

Next, a 0.5 g sample piece was taken from the obtained cured product and weighed in a 10 mL measuring flask.
It was made up with toluene. After leaving at room temperature for 20 hours to extract residual monomers, the solution was filtered through a 0.2 μm filter,
It was used as a measurement sample. The measurement of the residual monomer amount was performed as follows. Quantitative method: Calibration solution (DCPD) 0.01%, 0.1% and 0.5% (wt / vol%) Each sample was diluted with toluene and quantified by the absolute calibration curve method (least square method). The above calibration liquid was measured under the following GC conditions. The residual monomer amount was calculated by the following equation. Residual monomer amount (wt%) = (GC detection amount (wt / vol)
%) × 10 ml) / sample weight (g) Tester: Shimadzu Gas Chromatograph GC14A (DCPD measurement column and temperature) Column: THERMON-3000 5% SHINCA
RBON60 / 80mesh 2.1M I. D. 3.
2 mm temperature: column 100 (1 minute) to (10 ° C./min) to 150
° C (1 minute) Inlet 200 ° C, detector 200 ° C Carrier gas: He 60 kPa, Combustion gas: AIR 6
0 kPa, H ₂ 60 kPa Carrier flow rate: He 55 cm ³ / min

Tan δ measured based on the above measuring method
Table 1 shows the measurement results of the peak temperature and the residual monomer amount.

[0076]Example 4  84 mg (1/10000 molar equivalent of DCPD) Formula
Dissolve the ruthenium complex of (18) in 1 mL of toluene
After that, it was added to 132 g (1 mol) of DCPD. Le
After the addition of the ruthenium complex, an exothermic reaction started. Viscous resin
At a temperature of 80 ° C. with a 4 mm thick spacer.
A sample for physical property evaluation was prepared by holding for a time. Profit
Dynamic viscoelasticity measurement (JIS K71)
98, tensile method using a viscoelastic spectrometer
(N = 1)) to measure the temperature of the tan δ peak.
The temperature was taken as the glass transition temperature of the resin.

Next, a 0.5 g sample piece was taken from the obtained cured product and weighed in a 10 mL measuring flask.
It was made up with toluene. After leaving at room temperature for 20 hours to extract residual monomers, the solution was filtered through a 0.2 μm filter,
It was used as a measurement sample. The measurement of the residual monomer amount was performed as follows. Quantitative method: Calibration solution (DCPD) 0.01%, 0.1% and 0.5% (wt / vol%) Each sample was diluted with toluene and quantified by the absolute calibration curve method (least square method). The above calibration liquid was measured under the following GC conditions. The residual monomer amount was calculated by the following equation. Residual monomer amount (wt%) = (GC detection amount (wt / vol)
%) × 10 ml) / sample weight (g) Test machine: Shimadzu gas chromatograph GC14A (DCPD measurement column and temperature) Column: THERMON-3000 5% SHINC
ARBON 60 / 80mesh 2.1M I. D.
3.2 mm temperature: column 100 (1 minute) to (10 ° C./min) to 150
℃ (1 minute) Inlet 200 ° C, Detector 200 ° C Carrier gas: He 60 kPa, Combustion gas: AIR
60 kPa, H ₂ 60 kPa Carrier flow rate: He 55 cm ³ / min

Tan δ measured based on the above measuring method
Table 1 shows the measurement results of the peak temperature and the residual monomer amount.

[0079]Comparative Example 2  Synthesis according to the method described in U.S. Pat. No. 5,831,108.
41 mg of the formed ruthenium complex of the formula (16) (DCP
D) in 1 mL of toluene
After dissolving, it was added to 132 g (1 mol) of DCPD.
Was. After the addition of the ruthenium complex, an exothermic reaction started. viscous
Resin is provided with a 4 mm thick spacer and poured.
A sample for physical property evaluation was prepared by holding at
Was. Dynamic viscoelasticity measurement (JIS K
 7198, viscoelastic spectrometer
The temperature of the tan δ peak was measured by the Zhang method (n = 1).
The temperature was defined as the glass transition temperature of the resin.

Next, a 0.5 g sample piece was taken from the obtained cured product and weighed in a 10 mL measuring flask.
It was made up with toluene. After leaving at room temperature for 20 hours to extract residual monomers, the solution was filtered through a 0.2 μm filter,
It was used as a measurement sample. The measurement of the residual monomer amount was performed as follows. Quantitative method: Calibration solution (DCPD) 0.01%, 0.1% and 0.5% (wt / vol%) Each sample was diluted with toluene and quantified by the absolute calibration curve method (least square method). The above calibration liquid was measured under the following GC conditions. The residual monomer amount was calculated by the following equation. Residual monomer amount (wt%) = (GC detection amount (wt / vo
1%) × 10 ml) / sample weight (g) Tester: Shimadzu GC14 GC (DCPD measurement column and temperature) Column: THERMON-3000 5% SHINC
ARBON 60 / 80mesh 2.1M I. D.
3.2 mm temperature: column 100 (1 minute) to (10 ° C./min) to 150
℃ (1 minute) Inlet 200 ° C, Detector 200 ° C Carrier gas: He 60 kPa, Combustion gas: AIR
60 kPa, H ₂ 60 kPa Carrier flow rate: He 55 cm ³ · min

Tan δ measured based on the above measuring method
Table 1 shows the measurement results of the peak temperature and the residual monomer amount.

[0082]

[Table 1]

As is evident from Table 1, when the metathesis reaction was carried out using the organometallic complex compound of the present invention, compared with the case where a conventional metathesis reaction catalyst was used,
It was confirmed that the tan δ peak temperature was high and the amount of residual monomer was extremely small.

[0084]

As described above, since the organometallic complex compound of the present invention is excellent in heat resistance, oxygen resistance and reaction controllability and has high metathesis activity, it can be used as a metathesis reaction catalyst. The resin obtained has a higher glass transition temperature and a lower residual amount of monomer compared to the case of using a conventional metathesis reaction catalyst, so there is no residual odor, and there is no adhesion, heat resistance, chemical resistance, etc. It can be used for various applications such as electric and electronic parts, bathtubs, combined septic tanks, etc., which require the above characteristics.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Masafumi Nakatani 2-2, Kamitobakamichocho-cho, Minami-ku, Kyoto-shi, Kyoto Sekisui Chemical Co., Ltd. (72) Inventor Fumiyuki Ozawa 3-, Sugimoto, Sumiyoshi-ku, Osaka, Osaka 3-138 Osaka City University (72) Inventor Hiroyuki Katayama 3-3-138 Sugimoto, Sumiyoshi-ku, Osaka-shi, Osaka F-term (reference) 4H050 AA01 AB40 WB11 WB17 WB21 4J032 CA34 CA38 CA43 CA45 CB01 CB03 CD02 CD03 CE05 CE22 CG07

Claims (13)

[Claims] 1. The following general formula (1): (Wherein M is a metal selected from ruthenium, osmium, iron or tungsten; R ₁ and R ₂ are the same or different and are a hydrogen atom, an alkenyl group having 2 to 20 carbon atoms,
Optionally substituted by an alkyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkyl group having 1 to 5 carbon atoms, a halogen atom, and a phenyl group substituted by an alkoxyl group having 1 to 5 carbon atoms. Carbon number 2 which may be
-20 carboxylate, C2-C20 alkoxyl group, C2-C20 alkenyloxy group, aryloxy group, C2-C20 alkoxycarbonyl group, C2-C20 alkylthio group or ferrocene derivative Wherein R ₁ and R ₂ may together form a cyclic structure; X and X ₁ are independently selected from anionic ligands; L and L ₁ are independent A ligand, at least one of which is represented by the following formula (2)
Any of the ligands represented by (4), but in some cases, two or three of X, X ₁ , L and L ₁ may together form a multidentate chelating ligand good. An organometallic complex compound represented by the formula: Embedded image Embedded image Embedded image However, in the above formulas (2) to (4), R _{3 to} R ₁₇ each represent an independent substituent, but in some cases, a part thereof may be integrally formed to form a ring. 2. The following general formula (5):(Where M is ruthenium, osmium, iron, or tongue
Y is sulfur, oxygen or sulfur.
A heteroatom selected from ene; R₁₈And R ₁₉Is the same
One or different hydrogen atom, alkenyl having 2 to 20 carbon atoms
, A C2-20 alkyl group, a C6-20
Aryl group, alkyl group having 1 to 5 carbon atoms, halogen atom
Substituted by an alkoxyl group having 1 to 5 carbon atoms
Optionally substituted by a phenyl group
C2-C20 carboxylate, C2-C20 carboxylate
Alkoxyl group, alkenyloxy having 2 to 20 carbon atoms
Group, aryloxy group, alkoxy group having 2 to 20 carbon atoms
Rubonyl group, alkylthio group having 2 to 20 carbon atoms or
Represents a rocene derivative, but optionally R₁And R_TwoBut
X and X may be united to form an annular structure;₁Is
Independently selected from anionic ligands; L and L₁Is independent
Wherein at least one of the ligands is represented by the following formula:
Any of the ligands represented by (2) to (4),
In some cases, X, X ₁, L, L₁Two or three of
A polydentate chelating ligand may be formed together. )
Organometallic complex compounds. Embedded imageEmbedded imageEmbedded imageHowever, in the above formulas (2) to (4), R_Three~ R₁₇Is it
Each represents an independent substituent, but in some cases,
May be integrally formed in an annular shape. 3. The following general formula (6): (Wherein M is a metal selected from ruthenium, osmium, iron or tungsten; R ₂₀ , R ₂₁ and R ₂₂ are the same or different and are a hydrogen atom, an alkenyl group having 2 to 20 carbon atoms, 2 carbon atoms) To 20 alkyl groups, 6 to 20 carbon atoms
An aryl group, an alkyl group having 1 to 5 carbon atoms, a halogen atom, a carboxylate having 2 to 20 carbon atoms which may be optionally substituted by a phenyl group substituted by an alkoxyl group having 1 to 5 carbon atoms, Represents an alkoxyl group having 2 to 20 carbon atoms, an alkenyloxy group having 2 to 20 carbon atoms, an aryloxy group, an alkoxycarbonyl group having 2 to 20 carbon atoms, an alkylthio group having 2 to 20 carbon atoms, or a ferrocene derivative; May form a ring structure in which some of R ₂₀ , R ₂₁ and R ₂₂ are united; X and X ₁ are independently selected from anionic ligands;
L and L ₁ is a independent ligand, the at least one is either ligand represented by the following formula (2) to (4), optionally, X, X ₁ , L, L ₁ may together form a polydentate chelating ligand. An organometallic complex compound represented by the formula: Embedded image Embedded image Embedded image However, in the above formulas (2) to (4), R _{3 to} R ₁₇ each represent an independent substituent, but in some cases, a part thereof may be integrally formed to form a ring. 4. The organometallic complex compound according to claim 1, wherein M in the formula is ruthenium or osmium. 5. At least one of L and L _{1 in} the formula is:
The organometallic complex compound according to any one of claims 1 to 3, wherein the ligand is a ligand represented by the formula (3) or (4). 6. The ligand represented by the formula (3) is represented by the following formula (7): The organometallic complex compound according to claim 5, having a structure represented by the following formula: 7. The ligand represented by the formula (4) is represented by the following formula (8): The organometallic complex compound according to claim 5, having a structure represented by the following formula: 8. The method according to claim 1, wherein a decomposition rate after one hour when left at 100 ° C. in an organic solvent is 30% or less, and the composition has a high metathesis activity. Organometallic complex compounds. 9. A metathesis reaction catalyst comprising the organometallic complex compound according to claim 1. Description: 10. A polymerization method comprising polymerizing a metathesis reactive monomer in the presence of the metathesis reaction catalyst according to claim 9. 11. The polymerization method according to claim 10, wherein the metathesis reactive monomer is a bicyclic or tricyclic or higher norbornene-based monomer. 12. The polymerization method according to claim 11, wherein the norbornene-based monomer is dicyclopentadiene. 13. A resin composition obtained by the polymerization method according to claim 9.