JP2001059018A - Hardenable composition and hardened product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition stable to oxygen and water in air, and capable of being readily treated in a polymerization reaction by including a mixture of a specific metathesis polymerization catalyst with a specified coordination compound in a specific proportion, and a metathetically polymerizable monomer as essential components. SOLUTION: This hardenable composition consists essentially of a mixture of (A) a metathesis polymerization catalyst of formulas I and/or II [M is ruthenium or osmium; X1 to X4 are each an anionic ligand; L1 to L4 are each a neutral electron donor group; R1 to R4 are each H, a 1-20C alkyl (substituted with a halogen or the like) or the like], with (B) 1-1000 mol eq. coordinating compound having a nitrogen atom (preferably 4-vinylpyridine) based on the component A, and (C) a metathetically polymerizable monomer such as dicyclopentadiene.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a curable composition using a metathesis polymerizable monomer and a cured product obtained therefrom.

[0002]

2. Description of the Related Art Ring-opened polymers of cycloolefins such as norbornene and dicyclopentadiene are used in electrical insulation and optical fields due to their low water absorption, low dielectric properties, transparency and good mechanical properties. Is expected. It is known that cycloolefins undergo ring-opening polymerization with a metathesis polymerization catalyst, and as such a metathesis polymerization catalyst, for example, a tungsten or molybdenum catalyst is known. However, since many of these tungsten and molybdenum catalysts do not have sufficient activity, an activator (co-catalyst) such as alkyl aluminum is required, and alkyl aluminum is unstable to oxygen and moisture in the air. The polymerization of cycloolefins had to be carried out in a closed system. Therefore, these catalysts cannot be applied to the process of molding in an open system such as hand lay-up or open mold. Further, when a filler is used, if the filler used is stored at room temperature, usually 0.01 to 0.3% by weight of water is attached, so that ring-opening polymerization of cycloolefins with the above catalyst is carried out. If so, there is a problem that the catalyst is deactivated due to the effect of the attached water, and curing is inhibited. Ring-opening polymerization of norbornene by metathesis polymerization using a ruthenium or osmium complex as a catalyst, which is more stable to oxygen and moisture in the air than a conventional catalyst and is easy to handle as a reagent, is disclosed in US Pat.
No. 909. For the metathesis polymerization catalyst of ruthenium and osmium complexes, see US Pat. No. 5,341,404 and Organometallics (Orga Metals).
nometallics), Vol. 16, p. 3867 (1997).

[0003]

The metathesis polymerization catalysts of ruthenium and osmium complexes are more stable to oxygen and moisture in the air than conventional catalysts and are easier to handle as reagents, but they are easier to handle as metathesis catalysts. It has high catalytic activity for polymerizable monomers, and has a problem in handling in the polymerization reaction. These catalysts are in a powder form, and are difficult to uniformly mix with the metathesis polymerizable monomer. If the dispersion is insufficient, local polymerization proceeds. In addition, a molding method in which a metathesis catalyst and a metathesis polymerizable monomer are mixed in advance and molded in a predetermined mold cannot be applied because polymerization proceeds in a mixed solution. The present invention is also stable to oxygen and moisture in the air, and is easy to handle in a polymerization reaction, and is also applicable to a molding method in which a metathesis catalyst and a metathesis polymerizable monomer are previously mixed and molded in a predetermined mold. It is intended to provide a curable composition and a cured product that can be applied.

[0004]

Means for Solving the Problems The inventors of the present invention have made intensive studies to solve the above-mentioned problems, and as a result, by adding a coordinating compound having a nitrogen atom, the catalytic activity of the metathesis polymerization catalyst was temporarily reduced. The present inventors have found that the present invention can be suppressed, and completed the present invention.

That is, the present invention relates to (1) (A) a metathesis polymerization catalyst represented by the following general formula (I) and / or a metathesis polymerization catalyst represented by the following general formula (II):
A mixture with a coordinating compound having a nitrogen atom in an amount of 1 to 1000 molar equivalents based on the metathesis polymerization catalyst (A),
(C) a curable composition containing a metathesis polymerizable monomer as an essential component,

Embedded image (Where M is ruthenium or osmium, X ^{1 to} X ⁴ are anionic ligands, L ^{1 to} L ⁴ are neutral electron donating groups, and R ^{1 to} R ⁴ are each independently hydrogen, carbon, Numbers 1-20
An alkyl group, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an aryl group having 2 to 20 carbon atoms, a carboxylate group having 1 to 20 carbon atoms,
20 alkoxy groups, alkenyloxy group having 2 to 20 carbon atoms, aryloxy group having 1 to 20 carbon atoms, 2 to 2 carbon atoms
20 alkoxycarbonyl group, C1-20 alkylthio group, C1-20 alkylsulfonyl group, C1-20 alkylsulfinyl group, C1-20 alkylseleno group, C1-20 Selected from an alkyl seleninyl group having 1 to 20 carbon atoms, and an alkyl group having 1 to 5 carbon atoms, a halogen, an alkoxy group having 1 to 5 carbon atoms or an aryl having 2 to 20 carbon atoms. The aryl group may be substituted with a halogen, an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms. (2) 0.1 to 300 parts by weight of the filler (D) based on 100 parts by weight of the metathesis polymerizable monomer (C).
The curable composition according to the above (1), which further contains (3) a coordinating compound having a nitrogen atom as the component (B),
(4) The curable composition according to the above (1) or (2), which is at least one selected from pyridine, 4-vinylpyridine, acetonitrile, ethylenediamine, and N-benzylidenemethylamine; and (4) the above (1) to (3). A) a cured product obtained from any of the curable compositions.

[0006]

DETAILED DESCRIPTION OF THE INVENTION (A) used in the present invention
The metathesis polymerization catalyst of the component is represented by the following general formula (I) or the following general formula (II), and the compound represented by the formula (I) and the compound represented by the formula (II) may be used alone. , May be used together.

Embedded image (Where M is ruthenium or osmium, X ^{1 to} X ⁴ are anionic ligands, L ^{1 to} L ⁴ are neutral electron donating groups, and R ^{1 to} R ⁴ are each independently hydrogen, carbon, Numbers 1-20
An alkyl group, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an aryl group having 2 to 20 carbon atoms, a carboxylate group having 1 to 20 carbon atoms,
20 alkoxy groups, alkenyloxy group having 2 to 20 carbon atoms, aryloxy group having 1 to 20 carbon atoms, 2 to 2 carbon atoms
20 alkoxycarbonyl group, C1-20 alkylthio group, C1-20 alkylsulfonyl group, C1-20 alkylsulfinyl group, C1-20 alkylseleno group, C1-20 Selected from an alkyl seleninyl group having 1 to 20 carbon atoms, and an alkyl group having 1 to 5 carbon atoms, a halogen, an alkoxy group having 1 to 5 carbon atoms or an aryl having 2 to 20 carbon atoms. The aryl group may be substituted with a halogen, an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms. )

[0007] The catalyst represented by the general formula (I) or the catalyst represented by the general formula (II) is a two-part metathesis catalyst system comprising a combination of a conventionally known catalyst component and an activator. Unlike this, the metathesis polymerizable monomer can be subjected to ring-opening polymerization by metathesis reaction without easily losing catalytic activity due to oxygen or moisture in the air. Specific examples of such a catalyst include, for example, compounds represented by the following general formulas (III) to (X), and among them, among the compounds represented by the formulas (III), (IV), (V) and (IV) Compounds are preferred.

[0008]

Embedded image

The coordinating compound having a nitrogen atom of the component (B) used in the present invention acts as a deactivator for the metathesis polymerization catalyst of the component (A), and is used for the metal atom ruthenium or osmium. Is a compound that can be a ligand. Coordinating compound having nitrogen atom (B)
It is preferred that the compound does not have a substituent that hinders sterically around the nitrogen atom as a coordinating atom, and that coordination can occur efficiently, and pyridine, 4-vinylpyridine,
At least one selected from acetonitrile, ethylenediamine and N-benzylidenemethylamine is more preferred. These may be used alone or in combination of two or more. The boiling point of the coordinating compound (B) having a nitrogen atom is 5
The temperature is preferably within a range from 0 ° C. or higher to the boiling point or decomposition point of the metathesis polymerizable monomer (C). Specifically, 5
0 ° C to 300 ° C is preferred, and 70 ° C to 200 ° C is more preferred. Here, the decomposition point of the metathesis polymerizable monomer (C) refers to the temperature at which the weight starts to decrease in a thermobalance (TGA) measurement.

The compounding amount of the coordinating compound (B) having a nitrogen atom is 1 to 1 with respect to the metathesis polymerization catalyst of the component (A).
It is necessary to be 1000 molar equivalents, preferably 5 to 300 molar equivalents.

The metathesis polymerizable monomer (C) used in the present invention is a metathesis polymerizable compound, and a cycloolefin monomer capable of metathesis polymerization can be used. Above all, norbornene-based monomers such as substituted or unsubstituted norbornene, dicyclopentadiene and dihydrodicyclopentadiene are preferably used.

Examples of the norbornene-based monomer include, for example, norbornene, norbornadiene, methylnorbornene, dimethylnorbornene, ethylnorbornene, ethylidene norbornene, butylnorbornene, 5-acetyl-2-norbornene, dimethyl-5-norbornene-2,3-dicarboxy. Rate, N-hydroxy-5-
Norbornene-2,3-dicarboximide, 5-norbornene-2-carbonitrile, 5-norbornene-2
-Carboxaldehyde, 5-norbornene-2,3-
Dicarboxylic acid monomethyl ester, 5-norbornene-
2,3-dicarboxylic acid dimethyl ester, 5-norbornene-2,3-dicarboxylic acid diethyl ester, 5-norbornene-2,3-dicarboxylic acid di-n-butyl ester, 5-norbornene-2,3-dicarboxylic acid dicyclohexyl Esters, 5-norbornene-2,3-dicarboxylic acid dibenzyl ester, 5-norbornene-2,
3-dicarboxylic anhydride, 3,6-epoxy-1,2,2
Bicyclic rings such as 3,6-tetrahydrophthalic anhydride, 5-norbornene-2,3-dicarboxylic acid, 5-norbornene-2-methanol, 6-triethoxysilyl-2-norbornene, and 5-norbornen-2-ol Tricyclic norbornene such as norbornene, dicyclopentadiene (a dimer of cyclopentadiene), dihydrodicyclopentadiene, methyldicyclopentadiene, dimethyldicyclopentadiene, tetracyclododecene, methyltetracyclododecene, dimethylcyclotetradodecene Pentacyclic or norbornene such as tricyclopentadiene (trimer of cyclopentadiene) and tetracyclopentadiene (tetramer of cyclopentadiene). Further, a compound having two or more norbornene groups, for example, tetracyclododecadiene, symmetric tricyclopentadiene, or the like can also be used.

Cyclobutenes other than norbornene, cyclopentene, cyclooctene, cyclododecene, 1,5
-Cyclooctadiene, 1,3,5,7-cyclooctatetraene, 1,5,7-cyclododecatriene, 5,
6-epoxy-1-cyclooctene, 3,4-epoxy-1-cyclooctene, 5-methoxy-1-cyclooctene, 5-bromo-1-cyclooctene, 5-isopropoxy-1-cyclooctene, 5- Formyl-1-cyclooctene, 5-methoxy-1-cyclooctene, ethylcyclooct-1-ene-5-carboxylate,
Cycloolefins such as (trimethylsilyl) cyclooct-1-ene-5-carboxylate, tetrahydroindene and methyltetrahydroindene can also be used. The above metathesis polymerizable monomers can be used alone or in combination of a plurality of monomers.

The compounding amount of the metathesis polymerizable monomer (C) is from 1 to 100,000 weight per 100 parts by weight of the total amount of the metathesis polymerization catalyst (A) and the coordinating compound having a nitrogen atom (B). It is preferable to use a part.

The filler of the component (D) used in the present invention is used for the purpose of improving mechanical properties such as shrinkage and elastic modulus and electric properties such as dielectric constant and dielectric loss of the obtained cured product. And powdery, granular or fibrous inorganic fillers and organic fillers.

As the filler (D), for example, titanium oxide, zircon oxide, antimony oxide, zinc oxide, magnesium oxide, aluminum oxide, magnesium hydroxide,
Aluminum hydroxide, calcium carbonate, talc, kaolin clay, mica, nepheline sinite, silica, silica gel, fused silica, synthetic silicic acid, quartz powder, quartzite powder, silicate earth, barium sulfate, calcium sulfate, pumice powder, glass balun, whisker And inorganic fillers such as wood flour, polyester, polystyrene, acrylic resin, resin beads such as urea resin, and organic fillers such as carbon fiber and carbon black. These may be used alone or in combination of two or more. Can be used. The compounding amount of the filler (D) can be appropriately determined depending on the physical properties of the target cured product, the viscosity of the curable composition, and the like. Usually, the amount is 0 to 100 parts by weight of the metathesis polymerizable monomer (C). .1 to
300 parts by weight.

The filler (D) used in the present invention may be subjected to a surface treatment with a silane coupling agent or the like.
The silane coupling agent for surface treatment is usually YSiX
(Y is a monovalent group having a functional group and binding to Si, and X is a monovalent group having hydrolyzability and binding to Si). Examples of the functional group in Y include groups such as vinyl, amino, methacryloxy, cyano, carbamate, pyridine, sulfonyl azide, urea, styryl, chloromethyl, ammonium salt, and alcohol.
Examples thereof include chloro, methoxy, ethoxy, methoxyethoxy and the like.

Specific examples of the silane coupling agent include vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, vinyltriacetoxysilane, γ-chloropropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ- (2-aminoethyl) -aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ) Ethyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, N, N-dimethylaminophenyltriethoxysilane, trimethoxysilylbenzoic acid, chloromethylphenethyltrimethoxysilane, 2-styrylethyl Triethoxysilane, aminoethyl aminomethyl phenethyltrimethoxysilane, gamma
-Chlorophenyltrimethoxysilane, N-phenylaminopropyltrimethoxysilane, allyltriethoxysilane, 3-aminopropylmethyldiethoxysilane,
3-aminotrimethoxysilane, bis (2-hydroxyethyl) aminopropyltriethoxysilane, bis @ 3
-(Triethoxysilyl) propyl {amine, bis} 3
-(Triethoxysilyl) propyl} ethylenediamine, 2-chloroethyltriethoxysilane, chloromethyltriethoxysilane, chlorophenyltriethoxysilane, 3-cyanopropyltriethoxysilane, N, N
-Diethyl-3-aminopropyltrimethoxysilane,
N, N-diethylaminophenyltriethoxysilane,
1- (dimethylchlorosilyl) -2- (chloromethylphenyl) ethane, isocyanatopropyltriethoxysilane, mercaptoethyltriethoxysilane, methacryloxyethyldimethyl (3-trimethoxysilylpropyl) ammonium chloride, N-methylaminopropyl Triethoxysilane, 3- (N-styrylmethyl-
2-aminoethylamino) propyltrimethoxysilane hydrochloride, 1-trichlorosilyl-2- (chloromethylphenyl) ethane, β-trichlorosilyl-4-ethylpyridine, triethoxysilylpropylethylcarbamate, N- (triethoxysilyl Propyl) urea, 1-trimethoxysilyl-2- (aminomethyl) phenylethane, 1-trimethoxysilyl-2- (chloromethyl) phenylethane, 2- (trimethoxysilyl) ethylphenylsulfonyl azide, trimethoxysilylpropyl Diethylenetriamine, p-aminophenyltrimethoxysilane, 2-styrylethyltrimethoxysilane, aminoethylmethylphenethyltrimethoxysilane, 6-triethoxysilyl-2-norbornene and derivatives thereof, and the like. Alone or may be used in combination of two or more.

When the silane coupling agent itself is in a liquid state, it can be used as it is as a treatment liquid used for surface treatment of the filler (D), but it is usually used as a solution of water or an organic solvent. Preferably, it is used. The organic solvent is not particularly limited as long as it can dissolve the silane coupling agent and other components. Examples thereof include alcohols such as methanol, ethanol, propyl alcohol, and isopropyl alcohol, acetone, methyl ethyl ketone, methyl isobutyl ketone, benzene, and toluene. , Xylene, dimethylformamide, N-methyl-2
-Pyrrolidone, methyl cellosolve, ethyl cellosolve,
Examples thereof include dioxane, tetrahydrofuran, and ethylene glycol dimethyl ether. Each of these may be used alone, or two or more of them may be used in combination. When water is used, water may be used alone or in combination with one or more organic solvents.

The amount of the silane coupling agent used is preferably 0.001 to 10% by weight as the concentration in the processing solution.
0.01 to 5% by weight is more preferred. When the concentration of the silane coupling agent is less than 0.001% by weight, when a resin is blended in the curable composition of the present invention, the effect of improving the adhesive strength between the resin and the filler interface is small and 10% by weight. % Is not economically preferable. The temperature and time of the surface treatment are not particularly limited, but are usually 0 to 10
0 ° C., 0.5 to 10 minutes, preferably 20 to 50 ° C., 5
Seconds to 3 minutes.

The curable composition of the present invention is obtained by blending a resin such as an epoxy resin, a phenol resin, a polyimide, a polyester, a polyethylene, a rubber-based elastomer, an acrylic resin, a methacryl resin, and a vinyl resin in addition to the filler (D). It can be a resin composition.

In addition to the curable composition of the present invention, a glass fiber, a glass mat, a release agent, a coloring agent, a weathering agent, a flame retardant, and the like can be added as required.

Examples of the release agent include zinc stearate, silicon oil, and fluorine oil. Usually, 0.01 to 5 parts by weight is added to 100 parts by weight of the metathesis polymerizable monomer as component (C). be able to.
Examples of the coloring agent include inorganic pigments such as titanium dioxide, cobalt blue, and cadmium yellow; and organic pigments such as carbon black, aniline black, phthalocyanine, and quinacdrine.

Examples of the weather resistance imparting agent include an ultraviolet absorber and a light stabilizer. Examples of the ultraviolet absorber include salicylic acid-based ultraviolet absorbers such as phenyl salicylate and pt-butylphenyl salicylate, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,2′-dihydroxy-4, Benzophenone-based ultraviolet absorbers such as 4'-dimethoxybenzophenone, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-
3 ', 5'-di-t-butylphenyl) benzotriazole, 2- (2'-hydroxy-3', 5'-di-t-
Amylphenyl) benzotriazole ultraviolet absorbers such as benzotriazole, 2-ethylhexyl-2-cyano-3,3′-diphenylacrylate, ethyl-2-
And cyanoacrylate-based ultraviolet absorbers such as cyano-3,3'-diphenylacrylate. These may be used alone or in combination of two or more.
As a light stabilizer, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,2)
6,6-pentamethyl-4-piperidinyl) sebacate, dimethyl succinate 1- (2-hydroxyethyl)
And hindered amine light stabilizers such as -4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate. These may be used alone or in combination of two or more, and may be used in combination with an ultraviolet absorber.

As the flame retardant, hexabromobenzene,
Tetrabromobisphenol A, decabromodiphenyl oxide, tribromophenol, dibromophenyl glycidyl ether, perchloropentacyclodecane,
Halogen-based compounds such as heptonic acid derivatives are used alone or in combination of two or more. Also, tris (dichloropropyl) phosphate, tris (dibromopropyl) phosphate
And boric acid compounds. Further, examples of the auxiliary flame retardant include antimony trioxide, iron oxide, aluminum hydride and the like. When these are used in combination with the flame retardant, the flame retardant effect is further enhanced. Halogen flame retardants are
Usually, 1 to 50 parts by weight per 100 parts by weight of the metathesis polymerizable monomer (C), and an auxiliary flame retardant such as antimony trioxide is 1 to 15 parts by weight based on 100 parts by weight of the metathesis polymerizable monomer (C). Used in the range. Also, hydrates such as aluminum hydroxide and magnesium hydroxide can be used in combination as a filler for flame retardancy, and these are used in an amount of 10 to 30 parts by weight per 100 parts by weight of the metathesis polymerizable monomer.
It is preferable to use in the range of parts by weight.

The method for producing the curable composition of the present invention comprises:
There are no particular restrictions on the order of addition of the components (A), (B) and (C). However, in order to deactivate the metathesis polymerization catalyst of the component (A), the metathesis polymerization catalyst of the component (A) and ( Before mixing the metathesis polymerizable monomer of component C),
It is necessary to mix at least the coordinating compound having a nitrogen atom of the component (B) with the component (A). The order of addition of the other components is not particularly limited,
Even if all the other components are added to the mixture of the components (A) and (B) simultaneously or in an arbitrary order and mixed,
Even if the component (C) is mixed with the mixture of the component (A) and the component (B), and then the other components are added simultaneously and in an arbitrary order and mixed, the components (A) and (B) Is mixed with the mixture obtained by adding other components simultaneously or in an arbitrary order, and mixing the mixture. Parts or all at the same time or in a mixture added and mixed in any order,
The remaining components including the component (C) may be added at the same time or in any order and mixed. The mixing method and mixing time of the various components may be such that all the components are uniformly mixed.
Although there is no particular limitation, stirring may be performed using a stirrer, a mix rotor, an agitator, a stirring motor, or the like.

The metathesis polymerization catalyst of component (A) and (B)
The method for preparing the mixture with the coordinating compound having a nitrogen atom as a component is not particularly limited, but the minimum amount of toluene, acetone, benzene, xylene, methyl ethyl ketone, cyclohexanone, tetrahydrofuran, and N-methylpyrrolidone necessary for mixing the two are mixed. , Γ-butyrolactone, N,
N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, ethyl acetate, methyl acetate, n-butyl acetate, chloroform, methylene chloride,
1,2-dichloroethane, n-pentane, cyclopentane, cyclopentene, n-hexane, cyclohexane,
When cyclohexene, n-heptane, cycloheptane, cycloheptene, n-octane, cyclooctane, cyclooctene, diethyl ether and the like are added as a solvent,
A homogeneous solution can be prepared, which is preferable. Also,
The components (A) and (B) are mixed at 25 ° C. without heating.
It is preferable to carry out at about normal temperature. (A) component and (B)
The mixture with the component is preferably in a liquid state when mixed with the metathesis polymerizable monomer of the component (C).

Mixing of the mixture of the components (A) and (B) with the component (C) is preferably carried out while the component (C) is a liquid at room temperature of about 25 ° C. while cooling. Can be used as appropriate. When the component (C) is solid at room temperature, it is preferably used as a solution appropriately dissolved in a solvent. The method of mixing other components is not particularly limited, but it is preferable to perform the mixing in a liquid state at normal temperature.

The metathesis polymerization catalyst of the component (A)
It is inactivated by being mixed with the coordinating compound having a nitrogen atom as the component (B). Here, inactivating the metathesis polymerization catalyst means that the polymerization of the polymerizable monomer does not proceed under the reaction conditions under which the monomer polymerizable by the metathesis polymerization catalyst is polymerized. Specifically, a mixed system of 1 mol of a metathesis polymerization catalyst deactivated with respect to 1000 mol of a metathesis polymerizable monomer is used.
This means that no more than 30-mer compounds are formed after minutes. That is, for example, 1 mol of the metathesis polymerization catalyst and 500 mol or less of a basic substance (a coordinating compound having a nitrogen atom of the component (B) in the present invention) per 1000 mol of the metathesis polymerizable monomer at room temperature.
And that after 30 minutes, no more than 30-mer compound of the monomer was formed. In addition, for example, 1 mol of the metathesis polymerization catalyst and 500 mol or less of a basic substance (a coordinating compound having a nitrogen atom of the component (B) in the present invention) per 1000 mol of the metathesis polymerizable monomer in a homogeneous solution state. And a mixture consisting of
This indicates that 90 mol% or more of the unreacted monomer remains when the reaction is performed for 10 times the polymerization time at which the residual ratio of the unreacted monomer when the basic compound is not added is 90 mol%.

The curable composition of the present invention maintains the state in which the polymerization of the metathesis polymerizable monomer (C) does not proceed because the metathesis polymerization catalyst of the component (A) is inactivated as described above. be able to. The fact that the polymerization of the metathesis polymerizable monomer does not proceed in the present invention means that the polymerization of the metathesis polymerizable monomer does not substantially occur, and specifically, a compound of 30 or more mer of the metathesis polymerizable monomer is not generated. Or 90 mol% or more of the unreacted metathesis polymerizable monomer remains. The curable composition of the present invention can maintain a state where the polymerization of the metathesis polymerizable monomer does not progress at 25 ° C. for 10 minutes to 7 days. That is, the curable composition is at 25 ° C. for 10 minutes or more.
The fluidity is maintained without gelling for 7 days. When the curable composition is immediately gelled, it is necessary to mix various components immediately before each production of the cured product and to produce the curable composition, but the curable composition of the present invention is: Since such labor is omitted and a low-viscosity liquid is maintained, the handleability when using a cured product having a complicated shape or various molding methods is good.

When the curable composition of the present invention is used, it is necessary to reactivate the deactivated metathesis polymerization catalyst (A). The curable composition of the present invention can obtain a cured product by reactivating the deactivated metathesis polymerization catalyst (A). Here, reactivating the deactivated metathesis polymerization catalyst means that the polymerization of the compound polymerizable by the metathesis polymerization catalyst starts. When the polymerization starts, the polymerizable compound and the metathesis catalyst undergo a chemical reaction. Specifically, after 30 minutes in a mixed system of 1 mol of the reactivated metathesis polymerization catalyst per 1000 mol of the metathesis polymerizable monomer. It means that a compound of 100 monomers or more of a monomer is formed. That is, the reactivation means, for example, a mixture of an inactivated monomer, a metathesis polymerization catalyst, and a deactivator thereof (a coordinating compound having a nitrogen atom of the component (B) in the present invention). , The polymerization is initiated by adding or contacting the fourth component. Reactivation means, for example, that the reaction rate at the polymerization initiation stage obtained from the reaction rate is restored to 50% or more of the reaction rate at the same stage when the polymerization is not inactivated.

Reactivation methods include a method of dissociating a coordinating compound (B) having a nitrogen atom, which is a deactivator, as a salt from a catalyst by adding an acid, and a method of irradiating light in the presence of a photoacid generator. Activation method by sending the deactivated mixture to a column packed with a strongly acidic ion exchange resin or by batch processing with a resin, such as forming a deactivating agent and a stable metal complex. There is a method of activation by adding a metal ion salt and the like. In these methods, as the reactivating agent, concentrated hydrochloric acid, trifluoroacetic acid, acetic acid, p-toluenesulfonic acid, trifluoromethanesulfonic acid, a strongly acidic ion exchange resin, a photoacid generator, or the like can be used.

The curable composition of the present invention can be easily reactivated by heating. The curable composition is preferably heated in an open system at a temperature in the range of 50 ° C. to the decomposition point of the metathesis polymerizable monomer. The polymerization of the metathesis polymerizable monomer (C) proceeds by heating. For efficient polymerization of the metathesis polymerizable monomer (C), it is preferable to increase the area of the gas-liquid interface of the curable composition.

The curable composition of the present invention contains an epoxy resin,
When a resin such as phenolic resin, polyimide, polyester, polyethylene, rubber-based elastomer, acrylic resin, methacrylic resin, and vinyl resin is blended and used as a resin composition, the blending of these resins is performed before heating the curable composition. Alternatively, it can be performed in a heating step and / or after heating.

The curable composition of the present invention and the cured product obtained therefrom can be used in the fields of films, reinforced plastics, cast products, molded products, coating materials, electronic component sealing materials and the like.

[0036]

Next, the present invention will be described with reference to examples, but the present invention is not limited to these examples. Example 10 g of silica gel filler (trade name: Fuselex RD-8, manufactured by Tatsumori Co., Ltd.) in a glass 100 ml beaker.
And 10 g of dicyclopentadiene, and stirred at 40 ° C. for 30 minutes with a stirring motor.
bis (tricyclohexylphosphine) benzylidene ruthenium dichloride 1 in a glass screw bottle
0 mg, 10 mg of 4-vinylpyridine and 0.1 mg of toluene.
A uniform mixture prepared by stirring 18 g of the mixture at a room temperature of about 25 ° C. for 5 minutes with a mix rotor was added, and the mixture was stirred at a room temperature for 15 minutes with a stirring motor to obtain a uniform curable composition. This curable composition did not show an increase in viscosity even after being left at room temperature for 15 minutes, and it was confirmed that polymerization did not start. Next, the curable composition is transferred to a casting mold and placed in an oven for 6 hours.
After heating at 0 ° C. for 5 minutes, an orange opaque cured product was obtained.

[0037]

As described in Examples, the curable composition obtained by the present invention can be stored in a stable state without polymerization progressing even when left in an open system for a certain period of time, and can be easily heated. Since the polymerization can be started, it is easy to handle in the polymerization reaction, and it is applicable to a molding method in which a metathesis catalyst and a metathesis polymerizable monomer are pre-mixed and molded in a predetermined mold. Available and its industrial value is great.

 ──────────────────────────────────────────────────の Continued on the front page (72) Inventor Masaki Yusa 48 Wadai, Tsukuba, Ibaraki F-term in Hitachi Chemical Co., Ltd. Research Laboratories (reference) 4J032 CA23 CA24 CA27 CA28 CA34 CA35 CA36 CA38 CA43 CA45 CA46 CB01 CB03 CD02 CD07 CE03 CE05 CF01 CG06 CG07 CG08

Claims (4)

[Claims] (A) a metathesis polymerization catalyst represented by the following general formula (I) and / or a metathesis polymerization catalyst represented by the following general formula (II) and (B) a metathesis polymerization catalyst (A): A curable composition containing, as an essential component, a mixture of a coordinating compound having a nitrogen atom of 1000 molar equivalents and (C) a metathesis polymerizable monomer. Embedded image (Where M is ruthenium or osmium, X ^{1 to} X ⁴ are anionic ligands, L ^{1 to} L ⁴ are neutral electron donating groups, and R ^{1 to} R ⁴ are each independently hydrogen, carbon, Numbers 1-20
An alkyl group, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an aryl group having 2 to 20 carbon atoms, a carboxylate group having 1 to 20 carbon atoms,
20 alkoxy groups, alkenyloxy group having 2 to 20 carbon atoms, aryloxy group having 1 to 20 carbon atoms, 2 to 2 carbon atoms
20 alkoxycarbonyl group, C1-20 alkylthio group, C1-20 alkylsulfonyl group, C1-20 alkylsulfinyl group, C1-20 alkylseleno group, C1-20 Selected from an alkyl seleninyl group having 1 to 20 carbon atoms, and an alkyl group having 1 to 5 carbon atoms, a halogen, an alkoxy group having 1 to 5 carbon atoms or an aryl having 2 to 20 carbon atoms. The aryl group may be substituted with a halogen, an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms. ) 2. The curable composition according to claim 1, further comprising 0.1 to 300 parts by weight of a filler (D) based on 100 parts by weight of the metathesis polymerizable monomer. 3. The curable composition according to claim 1, wherein the coordinating compound having a nitrogen atom is at least one selected from pyridine, 4-vinylpyridine, acetonitrile, ethylenediamine and N-benzylidenemethylamine. object. 4. A cured product obtained from the curable composition according to claim 1.