JP2002284789A - New organic metal complex compound having high metathesis activity, metathesis reaction catalyst containing the same, polymerization method using the catalyst and polymer produced by the polymerization method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new organic metal complex compound having excellent heat-resistance, oxygen resistance and reaction controllability and high metathesis activity, a metathesis reaction catalyst containing the complex compound, a polymerization method using the catalyst and a polymer produced by the polymerization method. SOLUTION: The organic metal complex compound is expressed by general formula I. A concrete example of the compound is expressed by formula (2).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel organometallic complex compound having stability against oxygen and hydrogen and excellent metathesis activity, a metathesis reaction catalyst containing the same, a polymerization method using the catalyst, and a method for producing the same. It relates to a polymer obtained by this polymerization method.

[0002]

2. Description of the Related Art A metathesis reaction is used to synthesize various types of monomers that can be used in pharmaceuticals and the like, or dicyclopentadiene (hereinafter sometimes abbreviated as DCPD), which is a typical monomer used for metathesis polymerization. By subjecting the first norbornene-based monomer to ring-opening polymerization in a mold by a reaction injection molding (hereinafter sometimes abbreviated as RIM) method or the like, mechanical strength, heat resistance,
It is used in a wide range of industrial fields, such as producing molded articles having excellent dimensional stability and the like. However, in the conventional metathesis reaction, for example, Japanese Patent No. 3038825
As described in the above publication, a catalyst system that exhibits a metathesis catalytic activity by reacting a catalyst precursor such as molybdenum or tungsten as an active catalyst with an alkyl metal in the system is known. Since the alkyl metal is a water-inhibiting reagent, there were many restrictions on the reaction environment and the like.

As a catalyst capable of solving the above problem, a ruthenium-based metathesis catalyst disclosed in Japanese Patent Application Laid-Open No. 11-510807 has been developed and has excellent metathesis catalyst activity without deactivation even in the presence of moisture or oxygen. It is clear that it has attracted attention. However, in this catalyst, since the ligand on the metal is limited to some extent, it has been an issue to diversify the variations. Furthermore, this catalyst is active in a single complex, rather than being activated in the system by an alkyl metal or the like, so that when the catalyst is added to the metathesis-reactive monomer, the reaction starts immediately, dispersing the catalyst. There was a problem that sex and the like were rate-limiting. This can be a fatal problem when polymerizing a crosslinkable monomer such as dicyclopentadiene, for example, which is extremely restricted in the process or leads to variation in the physical properties of the obtained polymer. A problem arose. In response to this, a method of delaying polymerization by adding triphenylphosphine or the like to the system is generally known. However, in this case, foreign substances such as phosphorus are mixed in the system, and thus the safety of the product is reduced. There was a problem.

[0004]

SUMMARY OF THE INVENTION In view of the above problems, an object of the present invention is to provide a novel organometallic complex compound having excellent stability to oxygen and hydrogen, excellent metathesis reactivity, and excellent reaction controllability. Another object of the present invention is to provide a metathesis reaction catalyst containing the novel organometallic complex compound, a polymerization method using the catalyst, and a polymer obtained by the polymerization method.

[0005]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the problems of the conventional metathesis reaction catalyst, and as a result, have found that an organometallic complex having a specific ruthenium or osmium and a counter anion. Has been found to be an organometallic complex compound that is stable to oxygen and hydrogen, has improved compatibility with strongly polar solvents, has excellent reaction controllability, and has high metathesis activity. 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):

[0007]

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(In the formula (1), M is ruthenium or osmium; R ₁ and R ₂ are the same or different and are each a hydrogen atom, an alkenyl group having 2 to 20 carbon atoms, 1 to 20 carbon atoms.
An alkyl group, an aryl group having 6 to 20 carbon atoms, and 2 carbon atoms
~ 20 carboxyl group, 2 ~ 20 carbon alkoxy group, 2 ~ 20 carbon alkenyloxy group, 6 ~ carbon
20 represents an aryloxy group, an alkoxycarbonyl group having 2 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, an alkylsilyl group having 1 to 20 carbon atoms, an arylsilyl group having 6 to 20 carbon atoms, and a ferrocene derivative; They are,
C1-C5 alkyl group, halogen atom, C1-C1
And may be optionally substituted by a phenyl group substituted by an alkoxy group of No. 5. X ₁ represents an anionic ligand, L ₁ and L ₂ are the same or different and represent a neutral electron donor, and in some cases, X ₁ , L ₁ and L ₂
And two or three of them may together form a multidentate chelating ligand. Y ₁ is a counter anion and is a compound having a monovalent negative charge. ) With ruthenium or osmium represented by
An organometallic complex compound having a counter anion is provided.

According to the second aspect of the present invention, L ₁
L ₂ and an organic metal complex compound according to the first invention is provided, characterized in that the same ligand with.

According to a third aspect of the present invention, the following general formula (2):

[0011]

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(In the formula (2), M is ruthenium or osmium; R ₃ and R ₄ are the same or different and each are a hydrogen atom, an alkenyl group having 2 to 20 carbon atoms, and 1 to 20 carbon atoms.
An alkyl group, an aryl group having 6 to 20 carbon atoms, and 2 carbon atoms
~ 20 carboxyl group, 2 ~ 20 carbon alkoxy group, 2 ~ 20 carbon alkenyloxy group, 6 ~ carbon
20 represents an aryloxy group, an alkoxycarbonyl group having 2 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, an alkylsilyl group having 1 to 20 carbon atoms, an arylsilyl group having 6 to 20 carbon atoms, and a ferrocene derivative; They are,
C1-C5 alkyl group, halogen atom, C1-C1
And may be optionally substituted by a phenyl group substituted by an alkoxy group of No. 5. X ₂ represents an anionic ligand, L ₃ and L ₄ are the same or different and represent a neutral electron donor, and in some cases, X ₂ , L ₃ and L ₄
And two or three of them may together form a multidentate chelating ligand. Y ₂ is a counter anion and is a compound having a monovalent negative charge. ) With ruthenium or osmium represented by
An organometallic complex compound having a counter anion is provided.

According to a fourth aspect of the present invention, L ₃
And L ₄ are the same ligands. The organometallic complex compound according to the third invention is provided.

According to a fifth aspect of the present invention, the following general formula (3):

[0015]

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(In the formula (3), M is ruthenium or osmium; R ₅ and R ₆ are the same or different and are each a hydrogen atom, an alkenyl group having 2 to 20 carbon atoms, 1 to 20 carbon atoms.
An alkyl group, an aryl group having 6 to 20 carbon atoms, and 2 carbon atoms
~ 20 carboxyl group, 2 ~ 20 carbon alkoxy group, 2 ~ 20 carbon alkenyloxy group, 6 ~ carbon
20 represents an aryloxy group, an alkoxycarbonyl group having 2 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, an alkylsilyl group having 1 to 20 carbon atoms, an arylsilyl group having 6 to 20 carbon atoms, and a ferrocene derivative; They are,
C1-C5 alkyl group, halogen atom, C1-C1
And may be optionally substituted by a phenyl group substituted by an alkoxy group of No. 5. X ₃ represents an anionic ligand; L ₅ , L _{6 and} L ₇ are the same or different and represent a neutral electron donor, and in some cases, X ₃ and L ₅ ,
Two or more of L ₆ and L ₇ may together form a polydentate chelating ligand. Y ₃ is a counter anion, which is a compound having a monovalent negative charge. The present invention provides an organometallic complex compound having ruthenium or osmium represented by the formula (1) and having a counter anion.

According to the sixth aspect of the present invention, L ₅
And L ₆ are the same ligand, provided is an organometallic complex compound according to the fifth invention.

According to a seventh aspect of the present invention, the following general formula (4):

[0019]

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(In the formula (4), M is ruthenium or male
Stands for M, X_FourRepresents an anionic ligand, and L₈, L
₉And L_TenRepresent the same or different neutral electron donors
Then Y _FourIs a counter anion and has a monovalent negative charge
Compounds. ) Represented by ruthenium or o
It is characterized by having smium and a counter anion.
An organometallic complex compound is provided.

According to the eighth aspect of the present invention, L ₈
And a L ₉ organometallic complex compound according to the seventh invention is provided, characterized in that the same ligand with.

According to a ninth aspect of the present invention, L ₁₀
Is an arene ligand, wherein the organometallic complex compound according to the seventh or eighth aspect is provided.

According to a tenth aspect of the present invention, there is provided a metathesis reaction catalyst comprising the organometallic complex compound according to any one of the first to ninth aspects.

According to an eleventh aspect of the present invention, there is provided a metathesis polymerization method comprising polymerizing a metathesis-reactive monomer in the presence of the metathesis reaction catalyst according to the tenth aspect.

According to a twelfth aspect of the present invention, acetylene is added as a co-catalyst.
The invention provides a method for metathesis polymerization.

According to a thirteenth aspect of the present invention, there is provided a polymer obtained by the polymerization method according to the eleventh or twelfth aspect.

[0027]

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 is an organometallic complex compound having ruthenium or osmium represented by the following general formula (1) and having a counter anion.

[0029]

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In the formula (1), M is ruthenium or osmium.

R ₁ and R ₂ , independently of one another, are the same or different and each represent a hydrogen atom, an alkenyl group having 2 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms. A carboxyl group having 2 to 20 carbon atoms, 2 carbon atoms
Alkoxy group having 20 to 20 carbon atoms, alkenyloxy group having 2 to 20 carbon atoms, aryloxy group having 6 to 20 carbon atoms, 2 carbon atoms
Represents an alkoxycarbonyl group having 1 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, an alkylsilyl group having 1 to 20 carbon atoms, an arylsilyl group having 6 to 20 carbon atoms, and a ferrocene derivative. It may be substituted by an alkyl group, a halogen atom, or a phenyl group substituted by an alkoxy group having 1 to 5 carbon atoms, if necessary. More preferred substituents include a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-
Butyl group, t-butyl group, phenyl group, ferrocenyl group, trimethylsilyl group, triisopropylsilyl group,
Examples thereof include a diphenylmethylsilyl group, a dimethylphenylsilyl group, and a triphenylsilyl group.

X ₁ represents an anionic ligand, preferably Cl or Br, and more preferably Cl.

L ₁ and L ₂ are the same or different and represent a neutral electron donor. In the case where they are independent from each other, it is possible to select a C ₁ -C ₂₀ alkyl group,
Phosphorus having three substituents selected from the group consisting of methyl, ethyl, isopropyl, t-butyl, cyclohexyl, phenyl and substituted phenyl groups more preferably from C _{6 to} C ₂₀ aryl groups. Preferred are compounds, nitrile compounds, carbon monoxide, imidazolium carbene derivatives, isocyanide derivatives, and arene ligands having a benzene skeleton.

When L ₁ and L ₂ are arene ligands, they mean those having a benzene skeleton in their molecular structure. Among those having a benzene skeleton, benzene or benzene substituted with an alkyl group is preferred. preferable. Specifically, benzene, toluene, isopropylbenzene, isopropyltoluene and the like are desirable.

When they are the same, the general formula (5)
Ligand compounds having the structures represented by (6) and (7) are preferred.

[0036]

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(In the formula (5), R ₇ , R ₈ , R ₉ and R
₁₀ represents a C ₁ -C ₂₀ alkyl group or a C ₆ -C ₂₀ aryl group, preferably a methyl group, an ethyl group, an isopropyl group, a t-butyl group, a cyclohexyl group , A phenyl group and a substituted phenyl group, and n is 1 to 4. )

Specific compounds of the formula (5) include bis (diphenylphosphino) methane, bis (dicyclohexylphosphino) methane, bis (di-tert-butylphosphino) methane, and 1,2-bis (diphenylphosphino) methane. Fino) ethane, 1,2-bis (di-tert-butylphosphino) ethane, 1,2-bis (dicyclohexylphosphino) ethane and the like.

[0039]

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(In the formula (6), R₁₁, R₁₂, R₁₃And R₁₄
Is C₁~ C₂₀An alkyl group of C₆~ C ₂₀The aryl group
Represent, and preferably allow duplicate selection,
Group, ethyl group, isopropyl group, t-butyl group,
From among rohexyl, phenyl and substituted phenyl groups
To be elected. )

Specific compounds of the formula (6) include 1,
1′-bis (diphenylphosphino) ferrocene, 1,
1'-bis (dicyclohexylphosphino) ferrocene, 1,1'-bis (di-tert-butylphosphino) ferrocene and the like can be mentioned.

[0042]

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(In the formula (7), R₁₅, R₁₆, R₁₇And R₁₈
Is C₁~ C₂₀An alkyl group of C₆~ C ₂₀The aryl group
Represent, and preferably allow duplicate selection,
Group, ethyl group, isopropyl group, t-butyl group,
From among rohexyl, phenyl and substituted phenyl groups
To be elected. )

Specific compounds of the formula (7) include 2,
2 '-(dicyclohexylphosphino) -1,1'-bisnaphthyl, 2,2'-(di-tert-butylphosphino)-
Examples thereof include 1,1′-bisnaphthyl and 2,2 ′-(diphenylphosphino) -1,1′-bisnaphthyl.

In the compound of the formula (7), a compound having an optically active structure may be used alone.

Further, two or three of X ₁ , L ₁ and L ₂ may together form a multidentate chelating ligand.

Y ₁ is a counter anion, a compound having a monovalent negative charge,
Substituted phosphates and organic acid anions are preferred, especially
Tetrafluoroborate, hexafluorophosphate, carboxylate anion and sulfonate anion are preferred.

When L ₁ and L ₂ are the same, two or more elements having an unshared electron pair may be contained in the same molecule, and at least two of them may be coordinated with ruthenium or osmium. Is a possible ligand. Here, examples of the element having an unshared electron pair include phosphorus, nitrogen, oxygen, and sulfur. Preferred ligands include structures represented by general formulas (8), (9), and (10). And a bisphosphine ligand having the formula:

[0049]

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(In the formula (8), R₁₉, R₂₀, R_{twenty one}And R_{twenty two}
Is C₁~ C₂₀An alkyl group of C₆~ C ₂₀The aryl group
Represent, and preferably allow duplicate selection,
Group, ethyl group, isopropyl group, t-butyl group,
From among rohexyl, phenyl and substituted phenyl groups
And n is 1 to 4. )

Specific examples of the compound represented by the formula (8) include bis (diphenylphosphino) methane, bis (dicyclohexylphosphino) methane, bis (di-tert-butylphosphino) methane, and 1,2-bis (diphenylphosphino) methane. Fino) ethane, 1,2-bis (di-tert-butylphosphino) ethane, 1,2-bis (dicyclohexylphosphino) ethane and the like.

[0052]

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(In the formula (9), R_{twenty three}, R_{twenty four}, R_{twenty five}And R₂₆
Is C₁~ C₂₀An alkyl group of C₆~ C ₂₀The aryl group
Represent, and preferably allow duplicate selection,
Group, ethyl group, isopropyl group, t-butyl group,
From among rohexyl, phenyl and substituted phenyl groups
To be elected. )

Specific compounds of the formula (9) include 1,
1′-bis (diphenylphosphino) ferrocene, 1,
1'-bis (dicyclohexylphosphino) ferrocene, 1,1'-bis (di-tert-butylphosphino) ferrocene and the like can be mentioned.

[0055]

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(In the formula (10), R ₂₇ , R ₂₈ , R ₂₉ and R
₃₀ represents a C ₁ -C ₂₀ alkyl group or a C ₆ -C ₂₀ aryl group, preferably a methyl group, an ethyl group, an isopropyl group, a t-butyl group, a cyclohexyl group , A phenyl group and a substituted phenyl group. )

Specific compounds of the formula (10) include:
2,2 ′-(dicyclohexylphosphino) -1,1 ′
-Bisnaphthyl, 2,2 '-(di-t-butylphosphino) -1,1'-bisnaphthyl, 2,2'-(diphenylphosphino) -1,1'-bisnaphthyl, and the like.

In the ligand compound of the formula (10), a compound having an optically active structure may be used alone.

The organometallic complex compound according to the first invention of the present invention can be produced by various methods. For example, first, a ruthenium or osmium complex precursor, one of the raw materials, is known. The other raw material, a neutral electron donor ligand compound, is synthesized according to a known production method, and both raw materials are mixed to perform a ligand exchange reaction. General formula (1), which is the target product by reacting
Is obtained.

The organometallic complex compound according to the third aspect of the present invention is an organometallic complex compound having ruthenium or osmium represented by the following general formula (2) and having a counter anion.

[0061]

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In the formula (2), M is ruthenium or osmium.

R ₃ and R ₄ are independently the same or different and each independently represent a hydrogen atom, an alkenyl group having 2 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms. A carboxyl group having 2 to 20 carbon atoms, 2 carbon atoms
Alkoxy group having 20 to 20 carbon atoms, alkenyloxy group having 2 to 20 carbon atoms, aryloxy group having 6 to 20 carbon atoms, 2 carbon atoms
Represents an alkoxycarbonyl group having 1 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, an alkylsilyl group having 1 to 20 carbon atoms, an arylsilyl group having 6 to 20 carbon atoms, and a ferrocene derivative. It may be substituted by an alkyl group, a halogen atom, or a phenyl group substituted by an alkoxy group having 1 to 5 carbon atoms, if necessary. More preferred substituents include a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-
Butyl group, t-butyl group, phenyl group, ferrocenyl group, trimethylsilyl group, triisopropylsilyl group,
Examples thereof include a diphenylmethylsilyl group, a dimethylphenylsilyl group, and a triphenylsilyl group.

X ₂ represents an anionic ligand, preferably Cl and Br, and more preferably Cl.

L_ThreeAnd L_FourAre the same or different
Represents children giving. Overlap on phosphorus if independent of each other
C to choose₁~ C₂₀An alkyl group of C₆
~ C ₂₀Among the aryl groups of the above, more preferably methyl
Group, ethyl group, isopropyl group, t-butyl group, cyclo
Select from hexyl, phenyl and substituted phenyl groups
Phosphorus compound having three substituents, nitrile compound
Substances, carbon monoxide, imidazolium carbene derivatives, iso
Cyanide derivatives, arene ligands having a benzene skeleton
Is preferred.

When the compound is an arene ligand, it means one having a benzene skeleton in its molecular structure, and among those having a benzene skeleton, benzene or alkyl-substituted benzene is preferable. Specifically, benzene, toluene, isopropylbenzene, isopropyltoluene and the like are desirable.

When they are the same, a ligand compound having a structure represented by the general formula (5), (6) or (7) is preferable as in the case of the organometallic complex compound of the first invention. Specific preferred compounds can also be the same.

Further, two or three of X ₂ , L ₃ and L ₄ may together form a polydentate chelating ligand.

Y ₂ is a counter anion, a compound having a monovalent negative charge,
Substituted phosphates and organic acid anions are preferred, especially
Tetrafluoroborate, hexafluorophosphate, carboxylate anion and sulfonate anion are preferred.

When L ₃ and L ₄ are the same, two or more elements having an lone pair in the same molecule may be contained, and at least two of them may be coordinated to ruthenium or osmium. Is a possible ligand. Here, examples of the element having an unshared electron pair include phosphorus, nitrogen, oxygen, sulfur, and the like. Preferred ligands are the same as those in the case of the organometallic complex compound of the first invention, represented by the general formula (8) ),
Bisphosphine ligands having the structures represented by (9) and (10) are mentioned, and preferred specific compounds are also the same.

The organometallic complex compound according to the third aspect of the present invention can be produced by various methods, and is mainly obtained by dimerizing the organometallic complex compound of the general formula (1). As another example, first, a ruthenium or osmium complex precursor, one of the raw materials, is synthesized according to a known method, and a neutral electron donor ligand compound, another raw material, is synthesized according to a known method. Then, both raw materials are mixed, a ligand exchange reaction is performed, and a cationizing reagent is further reacted to obtain an organometallic complex compound of the general formula (2) as a target product.

The organometallic complex compound according to the fifth aspect of the present invention is an organometallic complex compound having ruthenium or osmium and a counter anion represented by the following general formula (3).

[0073]

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In the formula (3), M is ruthenium or osmium.

R ₅ and R ₆ are the same or different and are each independently a hydrogen atom, an alkenyl group having 2 to 20 carbon atoms,
C1-C20 alkyl group, C6-C20 aryl group, C2-C20 carboxyl group, C2-C2
0 alkoxy group, alkenyloxy group having 2 to 20 carbon atoms, aryloxy group having 6 to 20 carbon atoms, 2 to 2 carbon atoms
0 represents an alkoxycarbonyl group having 1 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, an alkylsilyl group having 1 to 20 carbon atoms, an arylsilyl group having 6 to 20 carbon atoms, and a ferrocene derivative. It may be optionally substituted by a phenyl group substituted by a group, a halogen atom or an alkoxy group having 1 to 5 carbon atoms.
More preferred substituents include a hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, phenyl group, ferrocenyl group, trimethylsilyl group, triisopropylsilyl group, diphenylmethyl Examples thereof include a silyl group, a dimethylphenylsilyl group, and a triphenylsilyl group.

X ₃ represents an anionic ligand, preferably Cl and Br, and more preferably Cl.

L _{5 to} L ₇ are the same or different and represent a neutral electron donor. In the case where they are independent from each other, it is possible to select a C ₁ -C ₂₀ alkyl group,
Phosphorus having three substituents selected from the group consisting of methyl, ethyl, isopropyl, t-butyl, cyclohexyl, phenyl and substituted phenyl groups more preferably from C _{6 to} C ₂₀ aryl groups. Preferred are compounds, nitrile compounds, carbon monoxide, imidazolium carbene derivatives, isocyanide derivatives, and arene ligands having a benzene skeleton.

When the compound is an arene ligand, it means one having a benzene skeleton in its molecular structure, and among those having a benzene skeleton, benzene or alkyl-substituted benzene is preferable. Specifically, benzene, toluene, isopropylbenzene, isopropyltoluene and the like are desirable.

When they are the same, a ligand compound having a structure represented by the general formulas (5), (6) and (7) is preferable as in the case of the organometallic complex compound of the first invention. Specific preferred compounds can also be the same.

In some cases, X ₃ and L ₅ , L ₆ ,
Two or more of L ₇ may together form a multidentate chelating ligand.

Y ₃ is a counter anion and is a compound having a monovalent negative charge, and is preferably a 4-substituted borate, a 6-substituted phosphate, or an organic acid anion, particularly, tetrafluoroborate, hexafluorophosphate,
Carboxylates and sulfonates are preferred.
Among them, tetrafluoroborate and hexafluorophosphate are preferable.

When L ₅ and L ₆ are the same, two or more elements having an unshared electron pair in the same molecule may be contained, and at least two of them may be coordinated with ruthenium or osmium. Is a possible ligand. Here, examples of the element having an unshared electron pair include phosphorus, nitrogen, oxygen, sulfur, and the like. Preferred ligands are the same as those in the case of the organometallic complex compound of the first invention, represented by the general formula (8) ),
Bisphosphine ligands having the structures represented by (9) and (10) are mentioned, and preferred specific compounds are also the same.

The organometallic complex compound according to the fifth aspect of the present invention can be produced by various methods. For example, first, one of the raw materials, a ruthenium or osmium complex precursor, is known. The other raw material, a neutral electron donor ligand compound, is synthesized according to a known production method, and both raw materials are mixed to perform a ligand exchange reaction. General formula (3), which is the target product by reacting
Is obtained.

The organometallic complex compound according to the seventh aspect of the present invention is an organometallic complex compound having ruthenium or osmium and a counter anion represented by the following general formula (4).

[0085]

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In the formula (4), M is ruthenium or osmium.

X ₄ represents an anionic ligand, preferably Cl or Br, and more preferably Cl.

L ₈ , L ₉ and L ₁₀ are the same or different and represent neutral electron donors. When independent of each other, L ₈ , L ₉ and L ₁₀ can be selected on C _{1 to} C ₂₀ by overlapping on phosphorus. Among the alkyl groups and C ₆ -C ₂₀ aryl groups, more preferably three substituents selected from a methyl group, an ethyl group, an isopropyl group, a t-butyl group, a cyclohexyl group, a phenyl group and a substituted phenyl group A phosphorus compound having an arene ligand having a benzene skeleton, a nitrile compound,
Carbon monoxide, imidazolium carbene derivatives, isocyanide derivatives and the like are preferred.

In the case of an arene ligand, it means a compound having a benzene skeleton in its molecular structure, and among those having a benzene skeleton, benzene or alkyl-substituted benzene is preferable. Specifically, benzene, toluene, isopropylbenzene, isopropyltoluene and the like are desirable.

When they are the same, a ligand compound having a structure represented by the general formula (5), (6) or (7) is preferable as in the case of the organometallic complex compound of the first invention. Specific preferred compounds can also be the same.

Y ₄ is a counter anion and is a compound having a monovalent negative charge.
Substituted phosphates and organic acid anions are preferred, especially
Tetrafluoroborate, hexafluorophosphate, carboxylate anion and sulfonate anion are preferred. Among them, tetrafluoroborate and hexafluorophosphate are preferable.

When L ₈ and L ₉ are the same, two or more elements having an unshared electron pair in the same molecule may be contained, and at least two of them may be coordinated with ruthenium or osmium. Is a possible ligand. Here, examples of the element having an unshared electron pair include phosphorus, nitrogen, oxygen, sulfur, and the like. Preferred ligands are the same as those in the case of the organometallic complex compound of the first invention, represented by the general formula (8) ),
Bisphosphine ligands having the structures represented by (9) and (10) are mentioned, and preferred specific compounds are also the same.

When L ₁₀ is an arene ligand, it means one having a benzene skeleton in its molecular structure, and among those having a benzene skeleton, benzene or benzene substituted with an alkyl group is preferable. Specifically, benzene, toluene, isopropylbenzene and the like are desirable.

The organometallic complex compound according to the seventh aspect of the present invention can be produced by various methods. For example, first, a ruthenium or osmium complex precursor, which is one of the raw materials, is known. And a neutral electron donor ligand compound, which is another raw material, is synthesized according to a known manufacturing method, and both raw materials are mixed to carry out a ligand exchange reaction. General formula (4), which is the target product by reacting
Is obtained.

The organometallic complex compounds according to the first to ninth 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. Examples of the metathesis reaction include a structural change in the same monomer having an unsaturated bond, a cross metathesis reaction between monomers having an unsaturated bond, and metathesis polymerization.

The compound used in the metathesis reaction may be any compound that exhibits metathesis reaction activity. If the compound having metathesis activity is an acyclic olefin compound, a new carbon-carbon bond is formed by an olefin exchange reaction, which is a useful reaction for the synthesis of a novel compound. In a metathesis reaction of a compound having two or more unsaturated bonds, a structural change occurs due to an intramolecular reaction. For example, a cyclic compound can be obtained with a diene or the like. When the compound having metathesis activity is a cyclic olefin compound, the reaction is a polymerization reaction, and a polymer is obtained.

As the metathesis polymerization reaction, the polymerization reaction form may be ring-opening metathesis polymerization or acyclic metathesis polymerization. When an acyclic monomer is used, the polymerization reaction can proceed with the elimination of ethylene gas, and two or more monomers can be copolymerized.

The organometallic complex compound of the present invention is excellent in stability in the air, stability to functional groups and polar groups, and heat resistance as compared with conventional metathesis reaction catalysts. In this case, this property can be used to significantly reduce the amount of monomers remaining after polymerization.

When a metathesis reaction is carried out using the organometallic complex compound of the present invention, a solvent may be used for the reaction. When the reaction is performed in a homogeneous system, an organic solvent in which the metathesis reactive monomer is dissolved is preferable, for example, toluene,
Benzene, chloroform, hexane, xylene and the like can be mentioned. In particular, since the organometallic complex compound of the present invention is an ionic compound, the metathesis reaction can be performed even in a polar solvent system.

Further, the reaction can be carried out in a heterogeneous system. For example, since the organometallic complex compound of the present invention is stable against hydrogen and oxygen, it can be polymerized using a solvent in which the metathesis reactive monomer is not dissolved, such as water. Furthermore, suspension polymerization or dispersion polymerization can also be performed by adding a dispersion stabilizer or the like and performing polymerization.

The specific reaction conditions when the organometallic complex compound of the present invention is used for the metathesis reaction will be described. The amount of the organometallic complex compound used is from 1/5 to 1/50 of the total amount of the metathesis-reactive monomer. It is preferably 10,000 molar equivalents. When the proportion exceeds 1/5 molar equivalent, the molecular weight of the obtained polymer is difficult to increase when used at the time of polymerization. On the other hand, when the proportion is less than 1 / 500,000 molar equivalent, the reaction rate decreases, which is not preferable. More preferably 1/30 to
It is 1/200000 mole equivalent.

The reaction temperature in the metathesis reaction using the organometallic complex compound catalyst of the present invention varies depending on the melting point and boiling point of the solvent and the reaction modifier used.
It is preferably in the range of 70 ° C., more preferably −
30-150 ° C.

When the organometallic complex compound of the present invention is used in ring-opening metathesis polymerization, the monomer to be used is not particularly limited. Examples of the cyclic unsaturated compound include norbornene and derivatives thereof, and dicyclopentadiene and derivatives thereof. Examples include polycyclic unsaturated compounds, cyclobutene, cyclohexene, cyclooctene, cyclooctadiene and the like.

As the norbornene and derivatives thereof, polycyclic norbornene monomers having two or more rings are preferred. By using a monomer having two or more rings, a norbornene-based polymer having a high heat distortion temperature can be obtained.

The bicyclic norbornene-based monomer is not particularly restricted but includes, for example, 2-norbornene,
-Methyl-2-norbornene, 5-ethylidene-2-norbornene, 5-phenylnorbornene and the like.

The norbornene-based monomer having three or more rings is not particularly restricted but includes, for example, three rings such as dicyclopentadiene and dihydroxypentadiene, four rings such as tetracyclododecene, and tricyclopentadiene. 5-rings, 7-rings such as tetracyclopentadiene, and alkyl-substituted (eg, methyl, ethyl, propyl, butyl-substituted), alkylidene-substituted (eg, ethylidene-substituted) and aryl-substituted polycyclics thereof (Eg, phenyl, tolyl, naphthyl-substituted products) and the like. These norbornene monomers may be used alone or in combination of two or more. Among these, from the viewpoints of availability, reactivity, heat resistance, etc., dicyclopentadiene, which is a crosslinkable monomer, is excellent in reaction rate controllability, and is also preferable because it has high reactivity. A resin with excellent impact resistance can be obtained.
Further, if norbornene is used as a monomer, a transparent resin having a small haze can be obtained, so that application to optical materials and the like is expected.

In the case of polymerization of norbornene-based monomers, if a conventional polymerization catalyst is used, the heat generated in the reaction process is severe unless the system is a dilute solution system, and 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.

In the metathesis polymerization reaction using the organometallic complex compound of the present invention as a catalyst, the reaction can be promoted by the presence of an acetylene compound represented by the general formula (11) as a co-catalyst in the reaction system.

[0109]

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(In the formula (11), R ₃₁ and R ₃₂ each independently represent hydrogen, an alkyl group, an aryl group, a substituted aryl group, an alkylsilyl group, an arylsilyl group, an alkylarylsilyl group, a ferrocenyl group or a substituted ferrocenyl. Represents a group.)

R _{31 in the} general formula (11) is preferably hydrogen or a trialkylsilyl group, and R ₃₂ is a tertiary alkyl group, a secondary alkyl group, a primary alkyl group, a methyl group, a ferrocenyl group, An electron-emitting group such as a trialkylsilyl group is desirable.

Specific compounds represented by the general formula (11) include phenylacetylene, t-butylacetylene, trimethylsilylacetylene, 1-trimethylsilylhexyne, 1-trimethylsilylpentine, 1,2-
Bistrimethylsilylacetylene, ferrocenylacetylene and the like can be mentioned.

Further, in the polymerization reaction using the organometallic complex compound of the present invention as a catalyst, the reaction rate can be controlled by adding an additive such as phosphine.

Further, the polymer obtained by the metathesis reaction may be deteriorated by oxygen in the air due to having a double bond, but an antioxidant may be added to the polymerization system to inhibit the deterioration. It is.

The antioxidant which can be added is not particularly limited as long as it does not participate in the metathesis polymerization reaction. For example, pentaerythritol-tetrakis [3-
(3-di-t-butyl-4-hydroxyphenyl) propionate], 1,3,5-trimethyl-2,4,6-
Tris (3,5-tert-butyl-4-hydroxybenzyl) benzene, 2,6-di-tert-butyl-4-methylphenol, tris- (3,5-di-tert-butyl-4-hydroxybenzyl) isocyan Nurate and 1,3,5-tris (4-t-butyl-3-hydroxy-2,6-dimethyldibenzyl) isocyanurate are preferred.

In the metathesis reaction using the organometallic complex compound of the present invention as a catalyst, the design of the ligand is different from that of the conventional metathesis catalyst, so that the structure and physical properties of the product can be characterized. In particular, a polymer or a resin composition obtained by polymerizing a metathesis-reactive monomer such as a norbornene under the organometallic complex compound catalyst of the present invention,
It excels in adhesiveness, heat resistance, chemical resistance, etc., and can be used for various applications such as electric and electronic parts, bathtubs, and combined septic tanks that require these properties.

[0117]

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

Example 1 In a 100 ml flask, under a nitrogen stream, 1.0 mmol of (p-cymene) dichlororuthenium dimer was dissolved in 10 ml of toluene, and 2.0 mmol of tricyclohexylphosphine was added. Stirred. Further, 2.0 mmol of NH ₄ PF ₆ was added, and 10 mmol of t-butylacetylene was added to react. The obtained reaction product was filtered to remove ammonium salts, washed with hexane and recrystallized. The obtained reaction product has the formula (12)
A ruthenium complex compound represented by The yield is 79
%Met.

[0119]

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Example 2 In a 100 ml flask, under a nitrogen stream, 1.0 mmol of (p-cymene) dichlororuthenium dimer was dissolved in 10 ml of toluene, and 2.0 mmol of tricyclohexylphosphine was added. Stirred. Further, 2.0 mmol of NH ₄ PF ₆ was added, and 10 mmol of triisopropylsilylacetylene was added to react. The obtained reaction product was filtered to remove ammonium salts, washed with hexane and recrystallized. The obtained reaction product was a ruthenium complex compound represented by the formula (13). The yield was 68%.

[0121]

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Example 3 In a 100 ml flask, 1.0 mmol of (p-cymene) dichlororuthenium dimer was dissolved in 10 ml of toluene under a nitrogen stream, and 4.0 mmol of tricyclohexylphosphine and 10 mmol of t-butylacetylene were dissolved in 10 ml of toluene. In addition, the mixture was heated and stirred at 80 ° C. for 12 hours. Ag there
The BF ₄ was reacted by adding 2.0 mmol. The obtained reaction product was filtered to remove the silver salt, and the solid obtained after removing the solvent was washed with hexane and recrystallized. The obtained reaction product was a ruthenium complex compound represented by the formula (14). The yield was 88%.

[0123]

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Example 4 In a 100 ml flask, under a nitrogen stream, 1.0 mmol of (p-cymene) dichlororuthenium dimer was dissolved in 10 ml of toluene, and 6.0 mmol of dimethylphenylphosphine and 10 mmol of t-butylacetylene were dissolved in 10 ml of toluene. In addition, the mixture was heated and stirred at 80 ° C. for 12 hours. There, N
2.0 mmol of H ₄ PF ₆ was added and reacted. The obtained reaction product was filtered to remove ammonium salts, and the solid obtained after removing the solvent was washed with hexane and recrystallized. The obtained reaction product was a ruthenium complex compound represented by the formula (15). Yield was 63%.

[0125]

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Example 5 In a 100 ml flask, under a nitrogen stream, 1.0 mmol of (p-cymene) dichlororuthenium dimer was dissolved in 10 ml of toluene, and 2.0 mmol of dimethylphenylphosphine and 1,2-bisdimethylphosphonate were dissolved. Finoethane 2.0 mmol and t-butylacetylene 10 mmol
Was added and the mixture was heated and stirred at 80 ° C. for 12 hours. there,
2.0 mmol of NH ₄ PF ₆ was added and reacted. The obtained reaction product was filtered to remove ammonium salts, and the solid obtained after removing the solvent was washed with hexane and recrystallized. The obtained reaction product was a ruthenium complex compound represented by the formula (16). The yield was 21%.

[0127]

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Example 6 [Ru was placed in a dried 200 ml Schlenk flask.
Cl ₂ (p-cymene)] complex, 156 mg,
The atmosphere was replaced with nitrogen. 25 ml of distilled methylene chloride as a solvent
And 75 ml of distilled ethanol, and the Ru complex concentration was 5 m.
M and stirred. An equal amount of 1,2-bisdicyclohexylphosphinoethane (DCPE) was added thereto, and an equal amount of NaPF ₆ was further added thereto, followed by reacting at room temperature overnight. After completion of the reaction, the solvent was removed by evaporation, dissolved again in methylene chloride, the precipitate was removed by filtration, concentrated again, recrystallized, and [RuCl (dcpe) (p
-Cymene)] to obtain a PF ₆ complex. Yield 163m
g, the yield was 50%.

Example 7 [Ru was placed in a dried 200 ml Schlenk flask.
Cl ₂ (benzen)] complex, 50.0 mg,
The atmosphere was replaced with nitrogen. 25 ml of distilled methylene chloride as a solvent
And 75 ml of distilled ethanol, and the Ru complex concentration was 5 m.
M and stirred. An equal amount of 1,2-bisdicyclohexylphosphinoethane (DCPE) was added thereto, and an equal amount of NaPF ₆ was further added thereto, followed by reacting at room temperature overnight. After completion of the reaction, the solvent was removed by evaporation, dissolved again in methylene chloride, the precipitate was removed by filtration, concentrated again, recrystallized, and [RuCl (dcpe) (b
enzene)] to obtain a PF ₆ complex. The yield is 84.4m
g, the yield was 54%.

Example 8 [Ru was placed in a dried 200 ml Schlenk flask.
[Cl ₂ (p-cymene)] complex (62.3 mg) was taken and replaced with nitrogen. Distilled methylene chloride 25 as solvent
ml and 75 ml of distilled ethanol were added to adjust the Ru complex concentration to 5 mM, followed by stirring. An equal amount of bisdicyclohexylphosphinomethane (DCPM) was added thereto, and
APF ₆ was added an equal amount, and reacted overnight at room temperature. After completion of the reaction, the solvent was removed by evaporation, dissolved again in methylene chloride, the precipitate was removed by filtration, concentrated again, recrystallized, and [RuCl (dcpm) (p-c
ymene)] to obtain a PF ₆ complex. Yield 157mg
And the yield was 94%.

Example 9 20 mmol of norbornene and 10 ml of toluene were dissolved in a 50 ml Schlenk tube, and 0.002 mmol of the complex (formula (14)) synthesized in Example 3 was added thereto.
The reaction was carried out at 80 ° C. with stirring for 2 hours. After the reaction,
The reaction solution was dropped into methanol to recover the polymer. The yield of the polymer was 1.5 g, and the yield was 80%.

Example 10 A 200 ml beaker was charged with 1.0 parts of dicyclopentadiene.
Then, after dissolving by heating at 40 ° C., 0.1 mmol of the complex (formula (14)) synthesized in Example 3 was added and stirred. After 1 hour, it was confirmed that a hard polymer was obtained. 1 g of the obtained polymer is immersed in 10 ml of xylene,
After heating for 24 hours and collecting and drying the solid content, the weight was measured to be 0.98 g.

Example 11 20 mmol of norbornene and 10 ml of toluene were dissolved in a 50 ml Schlenk tube, and 0.002 mmol of the complex (formula (16)) synthesized in Example 5 was added thereto.
The reaction was carried out at 80 ° C. with stirring for 2 hours. After the reaction,
The reaction solution was dropped into methanol to recover the polymer. The yield of the polymer was 1.5 g, and the yield was 80%.

Example 12 A 200 ml beaker was charged with 1.0 parts of dicyclopentadiene.
After the mixture was dissolved by heating to 40 ° C., 0.1 mmol of the complex (formula (16)) synthesized in Example 5 was added and stirred. After 1 hour, it was confirmed that a hard polymer was obtained. 1 g of the obtained polymer is immersed in 10 ml of xylene,
After heating for 24 hours and collecting and drying the solid content, the weight was measured to be 0.97 g.

Example 13 In a 10 ml Schlenk tube, 173 mg of norbornene and T
2 ml of HF was taken and dissolved, and 2.1 mg of phenylacetylene and [RuCl (dcp) synthesized in Example 6 were added thereto.
e) (p-cymene)] 15.3 mg of PF ₆ complex was added, and the mixture was reacted by irradiation with a UV lamp while stirring at room temperature for 2 hours. After completion of the reaction, the reaction solution was dropped into methanol to recover a polymer. 117m polymer yield
g, and the yield was 68%.

Example 14 In a 10 ml Schlenk tube, 194 mg of norbornene and 2 ml of dichloroethane were taken and dissolved, and 10 mg of phenylacetylene and [RuCl (d
cpe) (p-cymene)] PF 6 complex 17.3m
g was added and reacted at 80 ° C. for 2 hours with stirring. After completion of the reaction, the reaction solution was dropped into methanol to recover a polymer. The yield of the polymer was 20 mg, and the yield was 10%.

[0137]

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.

Continuation of front page (72) Inventor Hiroyuki Katayama 3-3-138 Sugimoto, Sumiyoshi-ku, Osaka-shi, Osaka F-term in Osaka City University (reference) 4H050 AA01 AA03 AB40 WB11 WB16 WB17 WB21 4J032 CA22 CA23 CA25 CA28 CA34 CA38 CC02 CC03 CD02 CE03 CG07

Claims (13)

[Claims] 1. The following general formula (1): (In the formula (1), M is ruthenium or osmium; R ₁ and R ₂ are the same or different and are a hydrogen atom, an alkenyl group having 2 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, 6-20 aryl group, C2-C20 carboxyl group, C2-C20 alkoxy group, C2-C20 alkenyloxy group, C6-C20 aryloxy group, C2-C20 An alkoxycarbonyl group, an alkylthio group having 1 to 20 carbon atoms, and 1 to 20 carbon atoms
Represents an alkylsilyl group, an arylsilyl group having 6 to 20 carbon atoms and a ferrocene derivative, X ₁ represents an anionic ligand, and L ₁ and L ₂ represent the same or different neutral electron donor. , Y ₁ is a counter anion and is a compound having a monovalent negative charge. An organometallic complex compound having ruthenium or osmium represented by the formula (1) and having a counter anion. 2. The organometallic complex compound according to claim 1, wherein L ₁ and L ₂ are the same ligand. 3. The following general formula (2): (In the formula (2), M is ruthenium or osmium; R ₃ and R ₄ are the same or different and are a hydrogen atom, an alkenyl group having 2 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, 6-20 aryl group, C2-C20 carboxyl group, C2-C20 alkoxy group, C2-C20 alkenyloxy group, C6-C20 aryloxy group, C2-C20 An alkoxycarbonyl group, an alkylthio group having 1 to 20 carbon atoms, and 1 to 20 carbon atoms
Represents an alkylsilyl group, an arylsilyl group having 6 to 20 carbon atoms and a ferrocene derivative, X ₂ represents an anionic ligand, and L ₃ and L ₄ represent the same or different neutral electron donors , Y ₂ are counter anions and are compounds having a monovalent negative charge. An organometallic complex compound having ruthenium or osmium represented by the formula (1) and having a counter anion. 4. The organometallic complex compound according to claim 3, wherein L ₃ and L ₄ are the same ligand. 5. The following general formula (3): (In the formula (3), M is ruthenium or osmium; R ₅ and R ₆ are the same or different and are a hydrogen atom, an alkenyl group having 2 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, 6-20 aryl group, C2-C20 carboxyl group, C2-C20 alkoxy group, C2-C20 alkenyloxy group, C6-C20 aryloxy group, C2-C20 An alkoxycarbonyl group, an alkylthio group having 1 to 20 carbon atoms, and 1 to 20 carbon atoms
, An arylsilyl group having 6 to 20 carbon atoms and a ferrocene derivative, X ₃ represents an anionic ligand, and L ₅ , L ₆ and L ₇ are the same or different neutral electron donors. Wherein Y ₃ is a counter anion and is a compound having a monovalent negative charge. An organometallic complex compound having ruthenium or osmium represented by the formula (1) and having a counter anion. 6. The organometallic complex compound according to claim 5, wherein L ₅ and L ₆ are the same ligand. 7. The following general formula (4):(In the formula (4), M represents ruthenium or osmium.
Then X_FourRepresents an anionic ligand, and L₈, L₉And L_Ten
Represents the same or different neutral electron donors, _FourIs
A compound that is a counter anion and has a monovalent negative charge
Things. Ruthenium or osmium
Characterized by having a counter anion
Metal complex compounds. 8. The organometallic complex compound according to claim 7, wherein L ₈ and L ₉ are the same ligand. 9. The organometallic complex compound according to claim 7, wherein L ₁₀ is an arene ligand. 10. A metathesis reaction catalyst comprising the organometallic complex compound according to claim 1. Description: 11. A metathesis polymerization method comprising polymerizing a metathesis reactive monomer in the presence of the metathesis reaction catalyst according to claim 10. 12. The metathesis polymerization method according to claim 11, wherein acetylene is added as a co-catalyst. 13. A polymer obtained by the polymerization method according to claim 11. Description: