KR100403904B1 - Curable Molding Material and Method for Producing Molded Article - Google Patents

Abstract

In the present invention, the cycloolefins capable of metathesis polymerization are reacted in the presence of a metathesis polymerization catalyst to produce a semi-cured molding material, while the semi-degradable polymerization product is introduced into a mold for molding while maintaining the semi-cured state, and the cured article is molded. To prepare. Advantageous Effects of Invention According to the present invention, molded articles can be easily produced in an atmosphere (ordinary air without special treatment) using cycloolefins capable of metathesis polymerization as raw materials. In addition, various existing molding machines can be used.

Description

Curable Molding Material and Method for Producing Molded Article}

It is known that cycloolefins ring-opening-polymerize with a metathesis catalyst system. For example, J. Am. Chem. Soc., Vol. 82, p. 2337 (l960), describes the ring-opening polymerization of norbornene by a metathesis catalyst system, Angew. Chem. Int. Edn., Vol. 3, pp. 723 (l964), describes the cyclopentene ring-opening polymerization by a metathesis catalyst system [MoCl ₅ / Al (C ₂ H ₅ ) ₃ ].

Moreover, the method of ring-opening-polymerizing cycloolefins and manufacturing a polymer is also known. For example, Japanese Patent Application Laid-Open No. 50-l30900 or Japanese Patent Laid-Open No. 52-33000 discloses a method for producing a ring-opening polymerized polymer using a metathesis catalyst system composed of an halide such as tungsten or molybdenum and an organoaluminum compound.

On the other hand, a method of bulk polymerizing norbornene-type cycloolefins (monomers) such as dicyclopentadiene or tricyclopentadiene is also known. For example, Japanese Patent Application Laid-Open No. 58-l27728 or Japanese Patent Laid-Open No. 58-l290l3 discloses a solution A consisting of a mixture of a catalyst component and a monomer of a metathesis catalyst system, and a solution B consisting of a mixture of an activator and a monomer of a metathesis catalyst system. A method for producing crosslinked polymer moldings by reaction injection molding (RIM) is disclosed.

Japanese Patent Application Laid-Open No. 59-51911 discloses crosslinking by reaction injection molding a norbornene-type monomer using a metathesis catalyst system combining a catalyst component selected from organic ammonium salts of tungsten and molybdenum and an activator selected from alkoxyalkylaluminum halide and aryloxyaluminum halide. A method of making a polymer molding is disclosed.

Also, Japanese Patent Laid-Open No. 3-205409 discloses a dicyclolinked crosslinked by reaction injection molding using a metathesis catalyst system combining a catalyst component selected from tungsten hexachloride and tungsten oxytetrachloride and an activator selected from diethylaluminum chloride and ethylaluminum dichloride. A method of making a pentadiene polymer is disclosed.

In the metathesis catalyst system, it is known that the catalyst component is activated by an activator and ring-opening-polymerizes norbornene-type monomers. In the reaction injection molding, the solution A and the solution B are subjected to impingement mixing, and the mixed solution is immediately injected into the liquid phase into the mold to be ring-opened and polymerized.

However, the organoaluminum compound used as the activator is highly reactive and, if water or oxygen is present, reacts with them immediately, thus losing the catalytic activation action. Therefore, in the case of performing reaction injection molding, it is necessary to carry out bulk polymerization in a space formed in a state in which the divided mold is closed in order to eliminate the mixing of water or oxygen in the air as much as possible. Therefore, there existed a problem that there was a restriction | limiting in the shape of a shaping | molding method or a molded article.

Japanese Patent Application Laid-Open No. 2-225518 or Japanese Patent Laid-Open No. 3-292124 discloses a method of making a primary molded product obtained by bulk polymerization of a norbornene-type monomer in a mold, and then a secondary molding (molding) of the primary molded product. have.

But. In the manufacturing method of the said primary molded object, the obtained primary molded object has completed metathesis reaction, it is hardened | cured, and cannot be easily deformed. Therefore, it is necessary to carry out shaping | molding after making a primary molded object high temperature (normally 100 degreeC or more) beforehand, and there existed various problems, such as the need for troublesome work | work at the time of secondary molding. In addition, since the primary molded body is a cured product in which the metathesis reaction is completed, it is difficult to make a complicated shape in the secondary molding.

The present invention relates to a molding material for producing a molded article from metathesis polymerizable cycloolefins, and a method for producing a molded article from the molded article.

It is explanatory drawing (sectional schematic drawing) which shows the process of manufacturing a molded article with the casting for compression molding using a semi-hardened material. In Fig. 1, reference numeral l denotes a radial cargo, reference numeral 2 denotes a compression molding mold (female mold), reference numeral 3 denotes a compression molding mold (male mold), and reference numeral 4 denotes a compression molding apparatus for a sheet mold compound (SMC). (Hydraulic press), the code | symbol 5 represents air | atmosphere, respectively.

<Best Mode for Carrying Out the Invention>

As the cycloolefins capable of metathesis polymerization used in the present invention, one or more kinds selected from bicyclic or higher norbornenes and monocyclic cycloolefins having 4 or more carbon atoms can be used. Especially, norbornene, such as substituted or unsubstituted norbornene, dicyclopentadiene, and dihydrodicyclopentadiene, is used suitably.

Norbornenes include norbornene, norbornenadiene, methylnorbornene, dimethyl norbornene, ethyl norbornene, ethylidene norbornene, butyl norbornene, 5-acetyl-2-norbornene, dimethyl -5-norbornene-2,3-dicarboxylate, N-hydroxy-5-norbornene-2,3-dicarboxyimide, 5-norbornene-2-carbonitrile, 5-norborne N--2-carboxyaldehyde, 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 ester, 5- Norbornene-2,3-dicarboxylic acid dibenzyl ester, 5-norbornene-2,3-dicarboxylic acid anhydride, 3,6-epoxy-l, 2,3,6-tetrahydrophthalic anhydride, 5-norbornene-2,3-dicarboxylic acid, 5-norbornene-2-meth Bicyclic norbornene such as tanol, 6-triethoxysilyl-2-norbornene, 5-norbornene-2-ol,

Tricyclic norbornene such as dicyclopentadiene (ie, dimer of cyclopentadiene), dihydrodicyclopentadiene, methyldicyclopentadiene, dimethyldicyclopentadiene,

Tetracyclic norbornene such as tetracyclododecene, methyltetracyclododecene, dimethylcyclotetradodecene,

And norbornene having five or more rings such as tricyclopentadiene (that is, a trimer of cyclopentadiene) and tetracyclopentadiene (that is, a tetramer of cyclopentadiene). Compounds having two or more norbornene groups, for example, tetracyclododecadiene, symmetric tricyclopentadiene and the like can be used.

Cyclobutene, cyclopentene, cyclooctene, cyclododecene, l, 5-cyclooctadiene, l, 3,5,7-cyclooctatetraene, 1,5,7-cyclododecatene other than norbornene-based, 5,6-epoxy-l-cyclooctene, 3,4-epoxy-l-cyclooctene, 5-methoxy-l-cyclooctene, 5-bromo-l-cyclooctene, 5-isopropoxy-l- Cyclooctene, 5-formyl-l-cyclooctene, 5-methoxy-l-cyclooctene, ethyl-cyclooct-1-ene-5-carboxylate, (trimethylsilyl) -cyclooct-1-ene- Cycloolefins, such as 5-carboxylate, tetrahydroindene, and methyl tetrahydroindene, can also be used.

The above compounds may be used alone or as a plurality of mixtures. When used as a plurality of mixtures, preference is given to mixtures comprising at least 50% by weight of dicyclopentadiene and in addition tricyclopentadiene and / or tetracyclopentadiene.

The metathesis polymerization catalyst used in the present invention, unlike the metathesis catalyst system combining a catalyst component and an activator as is known in the art, does not easily lose its catalytic activity by oxygen or moisture in the air and is a metathesis polymerizable cycloolefin system. It is a catalyst which can ring-open-polymerize a compound by metathesis reaction. Preferable as such a metathesis polymerization catalyst is one or more kinds of metathesis polymerization catalysts represented by the following general formulas (a) and (b).

<Formula a>

<Formula b>

Where

M is ruthenium or osmium,

R ¹ and R ² are each independently hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an aryl group, a carboxylate group having 1 to 20 carbon atoms, and 1 to 20 carbon atoms. Alkoxy group of 20, alkenyloxy group of 2 to 20 carbon atoms, aryloxy group, alkoxycarbonyl group of 2 to 20 carbon atoms, alkylthio group of 1 to 20 carbon atoms, alkylsulfonyl group of 1 to 20 carbon atoms, alkyl of 1 to 20 carbon atoms A sulfinyl group, an alkyl selenino group having 1 to 20 carbon atoms, an alkyl seleninyl group having 1 to 20 carbon atoms, or an alkyl selenonyl group having 1 to 20 carbon atoms, each of which is an alkyl group having 1 to 5 carbon atoms, halogen, or 1 to 5 carbon atoms. May be substituted with an alkoxy group or phenyl, the phenyl may be substituted with a halogen, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms,

X ¹ and X ² are anionic ligands,

L ¹ and L ² each represent a neutral electron donating group.

As such a metathesis polymerization catalyst, a compound (catalyst) represented by the following general formula (A) is preferable.

Wherein M represents ruthenium or osmium,

R ³ and R ⁴ each independently represent a hydrogen, an alkyl group, an alkenyl group or an aromatic group, an alkyl group having 1 to 20 carbon atoms as an alkyl group, an alkenyl group having 2 to 20 carbon atoms as an alkenyl group, an aryl group as an aromatic group, etc. The alkyl group, alkenyl group or aromatic group may have a substituent,

X ³ and X ⁴ are anionic ligands, i.e., groups having a negative charge when excluding coordination to a central metal, for example hydrogen, halogen, alkyl groups of 1 to 5 carbon atoms, alkoxy groups of 1 to 5 carbon atoms, phenyl group Etc.

L ³ and L ⁴ are neutral electron donating groups, ie groups having a neutral charge when excluding coordination to a central metal, for example PR ⁵ R ⁶ R ⁷ (where R ⁵ is a secondary alkyl group or cyclo Alkyl groups, R ⁶ and R ⁷ each independently represent an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group, an alkoxy group having 1 to 10 carbon atoms or an aromatic group), or a phosphine-based electron donor group represented by pyridine, p-fluoropyridine, or the like. There is this.

Specific examples of such a compound (catalyst) are Ru carbene catalysts represented by the following Chemical Formulas 1 to 8. In particular, compounds of formula 3 are preferably used.

Synthesis of such compounds (catalysts) is already known.

For example, the Journal of American Chemical Society, Vol. 118, page 100 (1996), discloses the use of cyclopropene derivatives (Scheme 1).

Moreover, the method of using the diazo compound represented by following Formula in the same literature as the above is also disclosed.

Organometallics, Vol. 16, No. 18, page 3867 (1997) also discloses the use of propargyl chloride represented by the following formula.

Also, according to Organometallics Vol. 16, No. 18, page 400l (1997), the following method is also indicated.

Synthesis Example (see Scheme 3, R ⁹ and R ¹⁰ ; methyl group)

Hydrogen 2 atmospheres by adding cyclooctadiene ruthenium dichloride (21 mmo1), tricyclohexylphosphine (42 mmol), sodium hydroxide (7.2 g) and deoxygenated sec-butanol in 50OmL Fisher-Porter Bottle. To 90 ° C. under Pressurization is repeated several times until absorption of hydrogen is complete and stirring is continued overnight. It cooled to room temperature under the pressure of hydrogen, and obtained the pale yellow precipitate. 30 ml of water is added, and the precipitate is filtered and dried in a hydrogen stream to obtain Ru (H) ₂ (H ₂ ) ₂ (Pcy ₃ ) ₂ (yield about 80%).

Next, this Ru (H) ₂ (H ₂ ) ₂ (Pcy ₃ ) ₂ (1.5 mmol) is dissolved in 30 ml of dichloroethane solution and cooled to -30 ° C. 3-chloro-3-methyl-1-butyne (l.5 mmol) is added. The solution immediately turns reddish purple and reacts as it is for 15 minutes. Remove the cooling bath and add degassed methanol (20 ml) to precipitate purple crystals. Washing with methanol and drying gives the desired catalyst (compound of formula 3) (yield 95%). (Reference: Organometallics Vol. 16, 18, p. 3867 (1997)).

A metathesis polymerization catalyst can be used individually or in combination of 2 or more types. At this time, the amount of the catalyst is 0.001 to 20 parts by weight, preferably 0.01 to 5 parts by weight based on 100 parts by weight of the cyclodegradable polymerizable cycloolefins.

When the metathesis polymerization catalyst as described above is used, the rate of polymerization (metathesis) reaction can be arbitrarily adjusted by appropriately selecting conditions (amount of catalyst used, reaction temperature, use of reaction control (inhibitor) agent, etc.). Therefore, the state in which the polymerization (metathesis) reaction of raw material cycloolefins is not completed can be created. This state is called a "semi-curing" state. Heating of the semi-cured molding material resumes the polymerization (metathesis) reaction, thereby completing hardening.

The semi-molded molding material is a liquid phase with a fluidity or a solid shape with no fluidity and can be appropriately selected according to the shaping method. When the semi-cured molding material is in the liquid phase, its viscosity is usually several tens of poises or more, and can be appropriately selected according to the shaping method.

If the semi-cured molding material is solid, there is no particular limitation on its hardness (bending stiffness), and it can be appropriately selected according to the shaping method.

By appropriately selecting the viscosity or hardness condition (the amount of catalyst used, reaction temperature, use of reaction control (inhibitor) agent, etc.) of the semi-molded molding material, it can be designed and adjusted in a desired range. In addition, the time from semi-curing to shaping to a predetermined shape is appropriately selected depending on the type of production. In addition, the time holding the semi-hardened state can be adjusted according to storage temperature.

In the manufacturing method of the molded article of this invention, after shape | molding a molding material to a predetermined shape, you may heat-harden the molded molding material, and you may heat-harden while shaping | molding a molding material to a predetermined shape.

Cycloolefins such as cyclobutene, cyclopentene, cyclooctene, cyclododecene, tetrahydroindene and methyltetrahydroindene which can be ring-opened copolymerized with the norbornene-based cycloolefins It can mix and use in the range which does not impair the objective of this invention.

In addition, resins such as polyimide, saturated polyester, polyethylene, rubber elastomers, acrylic resins, methacryl resins, and vinyl resins can be mixed and used.

In the present invention, antioxidants, reaction regulators, fillers in consideration of physical properties, appearance, and workability, in addition to cycloolefins capable of metathesis polymerization of essential components (normally liquid monomers at normal temperature) and metathesis polymerization catalysts (normally solid at normal temperature) Can be reacted by adding an additive (or a third component) such as a modifier, a releasing agent, a coloring agent, a light stabilizer, a flame retardant, and a reinforcing material.

Antioxidant can be added in addition to the quantity previously contained in a raw material monomer. Examples of the antioxidants include hindered phenol-based antioxidants, for example, 2,6-di (t-butyl) -4-methylphenol, 2,6-di (t-butyl) -4-ethylphenol and stearyl- β- (3,5-di (t-butyl) -4-hydroxyphenyl) propionate, tetrakis- [methylene-3- (3 ', 5'-di (t-butyl) -4'-hydride Oxyphenyl) propionate] methane, 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2,2'-methylenebis (4-ethyl-6-t-butylphenol), 4 , 4'-methylenebis (2,6-di (t-butyl) phenol), l, 3,5-trimethyl-2,4,6-tris (3,5-di (t-butyl) -4-hydrate Oxybenzyl) benzene, 1,3,5-tris (3 ', 5'-di (t-butyl) -4'-hydroxybenzyl) -S-triazine-2,4,6- (lH, 3H, 5H) trione etc. are mentioned.

The amount of the newly added antioxidant is usually 10,000 ppm or less, but addition of more than 10,000 ppm does not interfere.

Moreover, the dicyclopentadiene of the raw material monomer used for the general purpose is usually already adding antioxidants, such as 2, 6- di (t-butyl) -4-methylphenol and 4-t- butylcatechol. In the manufacturing method of this invention, this antioxidant may be used as it is, and may be added newly. In some cases, it may be removed.

Examples of the reaction regulator include reaction inhibitors such as triphenylphosphine, tricyclohexylphosphine, tricyclopentylphosphine, tributylphosphine, and triisopropylphosphine, and are generally O.001 to 100 parts by weight in a DCPD resin solution. 10 parts by weight may be added.

Examples of the filler include inorganic fillers such as silica sand, calcium carbonate, aluminum hydroxide and clay, and organic fillers such as wood powder, polyester or polystyrene beads. The usage-amount can be suitably determined by the physical property of a polymer, the viscosity of a semi-hardened state, etc.

Examples of the modifier include elastomers, natural rubbers, butadiene rubbers, polymethyl methacrylate, polyvinyl acetate, polystyrene, and the like. Although the usage-amount changes with the physical property of the target polymer, it can be used normally in 1-50 weight part with respect to 100 weight part of resin.

Examples of the release agent include zinc stearate, silicone oil, fluorine oil, and the like, and can be added in an amount of 0.01 to 5 parts by weight based on 100 parts by weight of the resin.

As a coloring agent, organic pigments, such as inorganic pigments, such as titanium dioxide, cobalt blue, and a doped yellow, carbon black, aniline black, phthalocyanine, quinactoline, are mentioned.

Examples of weathering imparting agents include ultraviolet absorbers and light stabilizers. As a ultraviolet absorber, salicylic acid type ultraviolet absorbers, such as phenyl salicylate and para-t- butylphenyl salicylate, 2, 4- dihydroxy benzophenone, 2-hydroxy-4- methoxy benzophenone, 2, for example. Benzophenone ultraviolet absorbers, such as 2, 2- di-hydroxy- 4,4'- dimethoxy benzophenone, 2- (2'- hydroxy- 5'- methylphenyl) benzotriazole, 2- {2'- hydride Benzotria, such as oxy-3 ', 5'-di (t-butyl) phenyl} benzotriazole and 2- {2'-hydroxy-3', 5'-di (t-amyl) phenyl} benzotriazole Cyanoacrylate ultraviolet absorbers, such as a sol type ultraviolet absorber, 2-ethylhexyl-2-cyano-3,3'- diphenyl acrylate, and ethyl-2-cyano-3,3'- diphenyl acrylate, Can be mentioned. You may use these individually or in combination of 2 or more types.

In addition, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-pipepe, together with the ultraviolet absorbent to increase weather resistance Hindamine light stabilizers such as ridinyl) sebacate and dimethyl succinate-l- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate Also good.

As the flame retardant, halogen-based compounds such as hexabrombenzene, tetrabrombisphenol A, decabrom diphenyloxide, tribromphenol, dibromophenyl glycidyl ether, perchloropentacyclodecane, and a hete acid derivative are used alone or in combination. It is used together. Moreover, phosphoric acid compounds, such as a tris phosphate (dichloropropyl) and a tris phosphate (dibromopropyl), a boric acid compound, etc. can also be used together. Examples of the flame retardant include antimony trioxide, iron oxide, aluminum hydride and the like, and when used in combination with a flame retardant, the flame retardant effect is increased. The halogen-based flame retardant is usually 1 to 50 parts by weight with respect to 100 parts by weight of the resin, and a flame retardant such as antimony trioxide is used in the range of 1 to l5 parts by weight. Hydrates, such as aluminum hydroxide and magnesium hydroxide, can also be used together as a filler for the purpose of flame retardancy. It is preferable to use these addition amount in the range of 10-300 weight part with respect to 100 weight part of resin.

As the reinforcing material, inorganic fiber reinforcing materials such as glass and carbon, organic fibers such as PAN, pitch, rayon carbon fiber, PET, polyethylene, and Kevlar can be used. These reinforcing materials may be in any form such as mats, rovings, and crosses. These reinforcing materials can be mixed with the material and may be provided in a molding mold in advance.

The molding material of the present invention can be used in the composition of a solventless solvent, and a solvent can also be used as needed.

In this invention, it heats in order to perform a polymerization reaction. Operation of heating is normally performed in two steps. The heating in one step is carried out to bring it to a semi-cured state, the temperature of which is usually 0 to 100 캜, preferably 20 to 40 캜, and the time is appropriately determined according to the amount of the catalyst and the reaction temperature. The heating in two stages molds to the desired shape and completes curing. The temperature at that time is normally 80-250 degreeC, Preferably it is 100-200 degreeC, and reaction time is suitably determined according to the quantity of a catalyst and reaction temperature.

The shape of the molding material in the semi-cured state of the present invention may be any of plate shape, sheet shape, rod shape, and the like.

As a molded article obtained by heat-hardening the molding material of a hardened state, any of planar objects, such as a pipe, a semicircle tube, and a laminated body, and a three-dimensional object may be sufficient.

In the case of using a molding mold for shaping into a predetermined shape, a mold for compression molding, a conventional mold mold compound (SMC) or a bulk mold compound (BMC) molding can be used. Moreover, various shaping | molding methods, such as compression, injection compression, and a matched metal die, can be used. The molding method can be appropriately selected according to the use or production amount of the molded article, and the shape and material of the mold can be selected.

FIG. 1 shows an explanatory diagram (sectional schematic view) of manufacturing a molded article from a semi-cargo by using an SMC molding die.

The atmosphere in the molding of the present invention may be a normal air atmosphere (including oxygen and moisture in the atmosphere). Of course, special treatment may be performed, such as replacing the atmosphere with nitrogen gas, but this is uneconomical.

Hereinafter, an Example demonstrates this invention. In addition, in an Example, a part means a weight part unless there is particular limitation.

The molding material of the present invention is a curable molding material which is made into a semi-cured state by reacting cycloolefins capable of metathesis polymerization in the presence of a metathesis polymerization catalyst.

It is preferable that the shape of a molding material is 1 or more types chosen from plate shape, sheet shape, and rod shape.

The cycloolefins capable of metathesis polymerization are preferably one or more selected from bicyclic or higher norbornenes and monocyclic cycloolefins having 4 or more carbon atoms.

As the metathesis polymerization catalyst, one or more kinds of metathesis polymerization catalysts represented by the following general formulas (a) and (b) are preferably used.

Where

M is ruthenium or osmium,

R ¹ and R ² are each independently hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an aryl group, a carboxylate group having 1 to 20 carbon atoms, and 1 to 20 carbon atoms. Alkoxy group of 20, alkenyloxy group of 2 to 20 carbon atoms, aryloxy group, alkoxycarbonyl group of 2 to 20 carbon atoms, alkylthio group of 1 to 20 carbon atoms, alkylsulfonyl group of 1 to 20 carbon atoms, alkyl of 1 to 20 carbon atoms A sulfinyl group, an alkyl selenino group having 1 to 20 carbon atoms, an alkyl seleninyl group having 1 to 20 carbon atoms, or an alkyl selenonyl group having 1 to 20 carbon atoms, each of which is an alkyl group having 1 to 5 carbon atoms, halogen, or 1 to 5 carbon atoms. May be substituted with an alkoxy group or phenyl, the phenyl may be substituted with a halogen, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms,

X ¹ and X ² are anionic ligands,

L ¹ and L ² each represent a neutral electron donating group.

The manufacturing method of the molded article of this invention heat-hardens the said hardenable molding material, and it shape | molds to a predetermined shape. The manufacturing method of this invention is equipped with the 1st process of preparing a molding material, and the 2nd process of shaping | molding a molding material to a predetermined shape and heat-hardening.

In the presence of the metathesis polymerization catalyst, cycloolefins capable of metathesis polymerization can be reacted to produce a semi-cured molded material, and the molded product can be prepared by introducing the molded product into a molding mold and curing while maintaining the semi-cured polymerized state.

A compression molding mold may be used as the molding mold, and the molding atmosphere may be atmosphere.

<Example l>

A commercially available 99 wt.% Dicyclopentadiene (DCPD) was heated to about 35 ° C., and then dissolved by adding 0.13 parts of triphenylphosphine to 100 parts of DCPD, followed by addition of 0.1 parts of Ru carbene catalyst of the formula (3). It was. The reaction was carried out while maintaining the temperature at 35 ° C. At the time when the surface of the reaction solution was brought into contact with the glass rod having a diameter of 2 mm (the semi-cured state), this was introduced into a mold for compression molding, and the following molding was performed.

The compression molding mold was installed in a hydraulic press capable of vertical movement, and the temperature of the mold was set at 12 ° C. As shown in FIG. 1, the above semi-cured state was introduced into the mold while the mold was opened, and then the hydraulic press was operated to close the mold and to be molded. The pressure at this time was 80 kg per l square cm of plate area. After about 2 hours, the mold was opened and the molded article was taken out. The obtained molded article was a molded article having sufficient strength and hardness.

In addition, the molding for compression molding used the metal mold | die for flat shaping | molding (the size of flat plate 300 mm in length, 300 mm in width, and 4 mm in height) for SMC. This mold consists of a water column mold and a female mold.

<Example 2>

The reaction solution was adjusted by the same formulation as in Example 1, and the reaction solution was placed in a mold frame (300 mm long, 300 mm wide, 2 mm deep) of an aluminum product. The reaction solution was put into a 40 ° C. warming chamber for each mold frame and allowed to react. After 3 hours, the reaction solution was taken out of the warming chamber. At this time, the reactants in the mold frame had a solid state without fluidity. This reactant was taken out of the mold frame to prepare a molding material in a semi-cured state. This molded material was stored at room temperature for one day and then wound by hand along the outside of a glass tube with an outer diameter of 50 mm. Next, the molded material was molded into a curing furnace together with a glass tube and reacted at 120 ° C. to cure. After 1 hour, the cured product was taken out of the curing furnace, and the cured product was separated from the glass tube to obtain a cylindrical (pipe) molded product.

According to the present invention, molded articles can be produced easily and safely in an atmosphere (ordinary air without special treatment) using cycloolefins capable of metathesis polymerization as raw materials. In addition, conventional molding machines such as various compression molding apparatuses can be used.

Claims (12)

At least one metathesis polymerization selected from bicyclic or higher norbornenes and monocyclic cycloolefins having 4 or more carbon atoms in the presence of 0.001 to 20 parts by weight of at least one metathesis polymerization catalyst which is a compound represented by the following formula (a) or (b): A curable molding material produced in a semi-cured state by reacting 100 parts by weight of cycloolefins. <Formula a> <Formula b> Where M is ruthenium or osmium, R ¹ and R ² are each independently hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an aryl group, a carboxylate group having 1 to 20 carbon atoms, and 1 to 20 carbon atoms. Alkoxy group of 20, alkenyloxy group of 2 to 20 carbon atoms, aryloxy group, alkoxycarbonyl group of 2 to 20 carbon atoms, alkylthio group of 1 to 20 carbon atoms, alkylsulfonyl group of 1 to 20 carbon atoms, alkyl of 1 to 20 carbon atoms A sulfinyl group, an alkyl selenino group having 1 to 20 carbon atoms, an alkyl seleninyl group having 1 to 20 carbon atoms, or an alkyl selenonyl group having 1 to 20 carbon atoms, each of which is an alkyl group having 1 to 5 carbon atoms, halogen, or 1 to 5 carbon atoms. May be substituted with an alkoxy group or phenyl, the phenyl may be substituted with a halogen, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, X ¹ and X ² are anionic ligands, L ¹ and L ² each represent a neutral electron donating group. The molding material according to claim 1, wherein the shape is at least one selected from a plate shape, a sheet shape, and a rod shape. delete delete The 1st process of preparing the molding material of Claim 1 or 2, and the 2nd process of shaping | molding the said molding material to a predetermined shape immediately after the said 1st process or after storing at 0 degreeC-room temperature, Method for producing a molded article comprising a. The manufacturing method of the molded article of Claim 5 in which the said 2nd process includes the process of shaping | molding the said molding material to a predetermined shape, and the process of heat-hardening the said molding material in order. The manufacturing method of the molded article of Claim 5 with which the said 2nd process includes the process of heating and hardening, shaping the said molding material to a predetermined shape. The manufacturing method of the molded article which introduce | transduces and hardens | cures the molding material of the semi-hardened state of Claim 1 or 2 to the molding die, maintaining a semi-hardened state. The manufacturing method of the molded article of Claim 5 which uses the compression molding mold as a molding mold. The manufacturing method of the molded article of Claim 5 whose atmosphere at the time of shaping | molding is air | atmosphere. The manufacturing method of the molded article of Claim 8 which uses the compression molding mold as a molding mold. The manufacturing method of the molded article of Claim 8 whose atmosphere at the time of shaping | molding is air | atmosphere.