JP2000290404A - Method for producing norbornene-based polymer molded article - Google Patents

Abstract

(57) [Summary] [PROBLEMS] To obtain a good polymerized product of a norbornene-type monomer which is not affected by the environment and has no curing failure,
In addition, the method for producing a polymer molded article can be used not only for a single molded article but also for reinforcing an existing article or another molded article, thereby reducing capital investment. SOLUTION: A fibrous body 3 impregnated with a polymerizable composition 1 containing a norbornene-type monomer and a ruthenium-carbene complex or a ruthenium vinylidene complex represented by a specific general formula as a catalyst is laminated. Mold 4
Alternatively, a method for producing a norbornene-based polymer molded article in which a norbornene-type monomer in an adherend is polymerized.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing a norbornene-based polymer molded article.

[0002]

2. Description of the Related Art Conventionally, a technique of polymerizing norbornene monomers has been known. As an example, there is a reaction injection molding method in which the interior of a mold is replaced with an inert gas, and then a norbornene-based monomer is injected into the mold as a molding material and reacted (see Japanese Patent Publication No. 7-73859).

[0003]

In the case of polymerization molding using a norbornene-based monomer, the polymerization reaction is inhibited by the presence of oxygen and moisture, and good polymerization proceeds unless the atmosphere is completely inert. There is a problem not to do. In other words, the polymerization molding using a norbornene-based monomer can only favorably proceed polymerization in a closed space, and injection-molding the polymerizable composition in a closed mold as in reaction injection molding. In addition to this, polymerization molding of norbornene monomers cannot be performed.

When a molded article is formed by forming a composite with a reinforcing material such as a reinforcing fiber, instead of obtaining a molded article using a norbornene-based monomer alone, the reinforcing fiber is set in a mold in advance and then reinforced. The air contained in the fiber must be removed, which requires careful purging with an inert gas in the mold, which is troublesome and has a problem in that the quality is not stable. When a reinforcing material or the like is mixed, the presence of water as well as air impedes the polymerization reaction, so that it is necessary to evaporate the water by sufficient drying and the like.

Conventionally, when a norbornene-based monomer is subjected to reaction injection molding, the following two types of solutions A and B have been used. These solutions A and B are subjected to collision mixing immediately before a mold. A polymerized product of a norbornene-based monomer is obtained by injecting a polymerizable solution into a mold and performing a polymerization reaction.

(Solution A) A solution containing a norbornene-based monomer and an activator and an activity regulator (Solution B) A solution containing a norbornene-based monomer and a catalyst In such a solution, examples of the catalyst include tungsten, molybdenum, rhenium, and tantalum. Halides, oxyhalides, oxides, organic ammonium salts and the like are used.

As the activator, an alkyl aluminum halide, an alkoxyalkyl aluminum halide, an aryloxyalkyl aluminum halide, an organic tin compound and the like are used. Alcohols such as n-propyl alcohol are used as activity regulators.

The above-mentioned polymerizable solution is stored at a production site or the like until the reaction injection molding after mixing the catalyst, the activator and the activity modifier with the norbornene-based monomer. It is necessary that the storage tank, the molding machine, and the like have a structure that can prevent the entry of moisture and air. Specifically, the path through which the norbornene-based monomer passes, including the piping, must be purged with an inert gas (eg, nitrogen) as much as possible. This requires extra capital investment and requires careful attention to management. is necessary. In addition, conventionally, when performing reaction injection molding after an interval from the previous molding, such as after production suspension, the catalyst and activator blended in the norbornene-based monomer have deteriorated due to the influence of oxygen and moisture, Even if the reaction injection molding is performed, the curing quality becomes poor, the required quality cannot be satisfied, and the odor peculiar to the norbornene monomer remains considerably in the molded product.

Furthermore, reaction injection molding has a problem that the investment in equipment is larger than open mold molding (for example, hand lay-up molding or spray-up molding).

[0010] The present invention has been made in view of such circumstances, and it is possible to obtain a good norbornene-based polymer molded product that is not affected by the environment and that has no curing failure. An object of the present invention is to provide a method for producing a norbornene-based polymer molded article that can be used for on-site construction and reinforcement of existing products and other molded articles, and requires less capital investment.

[0011]

The process for producing a norbornene-based polymer molded article of the present invention comprises a norbornene-based monomer and a ruthenium-carbene complex represented by the following general formula [I] or a catalyst represented by the following general formula [II] And the polymerizable composition containing the ruthenium vinylidene complex represented by the formula (1) is laminated with a fibrous body impregnated with the polymerizable composition.

Embedded image (Wherein R ₁ and R ₂ are each independently hydrogen, C _2-
A C20-alkenyl group, a C1-C20-alkyl group, an aryl group, a C1-C20-carboxylate, a C1-C20-alkoxy group, a C2-C20-alkenyloxy group, an aryloxy group, a C2-C20-alkoxycarbonyl group, or C1 -C20 -alkylthio groups (these are C1 -C5
An alkyl group, a halogen, a C1 -C5 -alkoxy group, or a C1 -C5-
X ₁ and X ₂ independently of one another represent an anionic ligand, and may represent an anionic ligand, which may be substituted by an alkyl group, halogen, or a phenyl group substituted by a C 1 -C 5 -alkoxy group. ₁ and L ₂ independently of one another represent any neutral electron donor; of X ₁ , X ₂ , L ₁ and L ₂ , two or three are together a polydentate chelating ligand May be formed)

Embedded image Wherein R ₃ and R ₄ are independently hydrogen, C 2-
C20 -alkenyl, C1 -C20 -alkyl, aryl, C1 -C20 -carboxylate, C1 -C20 -alkoxy, C2 -C20 -alkenyloxy, aryloxy, C2 -C20 -alkoxycarbonyl, C1
To C20 -alkylthio groups (these may be substituted by C1 -C5 -alkyl groups, halogen, C1 -C5 -alkoxy groups or by C1 -C5 -alkyl groups, halogen, C1 -C5 -alkoxy groups) X ₃ and X ₄ may be substituted by a substituted phenyl group) or a ferrocene derivative,
L ₃ and L ₄ independently of one another represent any anionic ligand; L ₃ and L ₄ independently represent any neutral electron donor; of X ₃ , X ₄ , L ₃ and L ₄ , Or three of them may form a polydentate chelating ligand together.) The method for producing a norbornene-based polymer molded article according to claim 2 is characterized in that the norbornene-based monomer is dicyclopentadiene. Has features.

Hereinafter, the present invention will be described in more detail. As an embodiment of a method for producing a polymer molded product of a norbornene-based polymer according to the present invention, as shown in FIG. 1, a fibrous body 3 as a fiber reinforcing material placed and laminated on a molding die 4 includes a norbornene-based monomer Impregnated with a polymerizable composition 1 containing a ruthenium-carbene complex represented by the general formula [I] or a ruthenium vinylidene complex represented by the following general formula [II], which is stable to oxygen and moisture. A method of impregnating with a roller 2 and defoaming as necessary, and laminating several layers on the mold 4 sequentially can be mentioned. That is, the fibrous body is laminated on the mold while the fibrous body is impregnated with the polymerizable composition.

The impregnation of the fibrous body 3 with the polymerizable composition 1 may be carried out before laminating the fibrous body 3 on the mold 4 or after laminating the fibrous body 3 on the mold 4. In the case of impregnation after lamination in the mold 4, the impregnation roller can be easily used by using the impregnation roller as described above. In addition, when the impregnation is performed before lamination in the mold 4, the impregnation with the polymerizable composition is performed. A method in which the fibrous body 3 is immersed in a tank may be used.

The norbornene-based monomer may be additionally adhered and impregnated on a molding die or an adherend in which an appropriate number of fibrous bodies impregnated with the polymerizable composition are laminated. The number of fibrous bodies laminated on the mold or adherend is
It is not particularly limited, and is appropriately set depending on the required physical properties of the molded article. As the specific number of sheets, for example, 3 to 6
In many cases, the number is about one, but in some cases, it can be one. Then, the polymerizable composition 1 in the fibrous body 3 laminated as described above rapidly starts polymerization even in the air, so that a polymer molded product of a norbornene-based monomer can be obtained by open molding.

The norbornene-based monomer used in the method for producing a polymer molded article of the present invention may be dicyclopentadiene from the viewpoints of reactivity, a balance of physical properties of a polymer, availability, and the like. preferable.

In the method for producing a polymer molded article according to the present invention, a part such as a mortar / concrete material, wood, plastic, metal or the like in an existing molded article or on-site construction is used as an adherend other than a mold, usually a mold. A reinforcing material or a backing material may be used. Furthermore, the use of the method for producing a polymer molded article of the present invention is not particularly limited, and a molded article obtained by laminating a polymer on various objects can be obtained.

The norbornene-based monomer used in the method for producing a polymer molded article of the present invention is a monomer having a norbornene ring, such as a bicyclic compound such as norbornene or norbornadiene, or dicyclopentadiene or dihydrodicyclopentadiene. Tricyclic, tetracyclododecene, ethylidenetetracyclododecene, tetracyclic such as phenyltetracyclododecene, pentacyclic such as tricyclopentadiene, heptacyclic such as tetracyclopentadiene, and alkyl substitution thereof (Eg, methyl, ethyl, propyl, butyl substituents), alkylidene substituents (eg, ethylidene substituents), aryl substituents (eg, phenyl, tolyl substituents), epoxy groups, methacrylic groups, Hydroxyl group, amino group, carboxyl group, cyano group A halogen group, an ether group, such as derivatives having a polar group such as an ester bond-containing group. These may be used alone or as a mixture of two or more.

The polymerizable composition used in the method for producing a polymer molded article of the present invention includes an antifoaming agent, an antioxidant, a filler, a coloring agent, a polymer modifier, a flame retardant, a foaming agent, and a thixotropic agent. Agent,
Various additives such as an antistatic agent, a molecular weight modifier, a pigment, a dye, and an elastomer as an impact resistance improver may be blended. Examples of the filler include calcium carbonate, aluminum hydroxide, magnesium carbonate, sodium hydrogen carbonate, clay, talc, mica, kaolin, fly ash, montmorillonite, glass balloon, silica balloon, and thermally expandable vinylidene chloride particles. Examples of the elastomer include natural rubber, polybutadiene, polyisoprene, styrene-butadiene-styrene block copolymer, styrene-isoprene-styrene block copolymer, EPDM, ethylene-vinyl acetate copolymer, and hydrides thereof. .

Next, the ruthenium-carbene complex represented by the general formula [I] will be described in detail below. Among the ruthenium-carbene complexes represented by the above general formula [I], preferred complexes are as follows. That is, in the formula, R1
And R2 independently of one another are hydrogen, C2 -C5 -alkenyl, C1 -C5 -alkyl, phenyl, C1 -C5
C5 -carboxylate, C1 -C5 -alkoxy,
A phenoxy group or a C2 -C5 -alkoxycarbonyl group (these are C1 -C5 -alkyl groups, halogen,
It may be substituted by a 1-C5-alkoxy group, or may be a C1-C5-alkyl group, halogen, C1
Or a phenyl group substituted by a C5 -alkoxy group), and X1 and X2 independently of one another are C1, Br, C1 -C5 -carboxylate, C1 -C5 -alkoxy groups A phenoxy group or a C1 -C5 -alkylthio group (these are
May be substituted by a C -alkyl group, halogen, a C1-C5-alkoxy group, or
C5 -alkyl, halogen, phenyl which may be substituted by C1 -C5 -alkoxy, and L1 and L2 independently of one another Aryl groups or C1 -C10 -alkylphosphine groups (these are C1 -C10
It may be substituted by C5 -alkyl, halogen, C1 -C5 -alkoxy or C1 -C5
A ruthenium-carbene complex, which is a neutral ligand from the group consisting of a 5-alkyl group, halogen, and a phenyl group substituted by a C1 -C5 -alkoxy group).

More preferred ruthenium-carbene complexes represented by the general formula [I] include those represented by the formula:
Are, independently of one another, hydrogen, methyl, ethyl, phenyl or vinyl optionally substituted by methyl, ethyl or phenyl, and X
1 and X2 are, independently of one another, C1 or Br;
Furthermore, mention may be made of ruthenium-carbene complexes wherein L1 and L2 independently of one another are a trimethylphosphine group, a triethylphosphine group, a triphenylphosphine group or a tricyclohexylphosphine group.

Next, the ruthenium vinylidene complex represented by the general formula [II] will be described in detail below. Among the ruthenium vinylidene complexes represented by the above general formula [II], preferred complexes are as follows. That is, in the formula, R3 and R4 independently represent hydrogen, a methyl group, an ethyl group,
A phenyl group, a ferrocenyl group, or a methyl group, an ethyl group, a vinyl group optionally substituted by a phenyl group or a ferrocenyl group, X3 and X4 are each independently Cl, Br, and L3 and L4 are And a ruthenium vinylidene complex which is independently a trimethylphosphine group, a triethylphosphine group, a triphenylphosphine group or a tricyclohexylphosphine group.

The ruthenium represented by the above general formula [I]
The carbene complex or the ruthenium vinylidene complex represented by the general formula [II] is preferably liquid from the viewpoint of dispersibility in the monomer. For example, it is preferable to use it after diluting it in a solvent. Examples of solvents include
Toluene, benzene, tetrahydrofuran (THF),
Dichloromethane and the like. In addition, ruthenium-
It is not preferable to dissolve the carbene complex in a solvent or an acid in which active hydrogen exists, since the stability of the complex is impaired. The same can be said for the ruthenium vinylidene complex represented by the general formula [II], although the stability is higher than that of the ruthenium-carbene complex represented by the general formula [I].

In the method for producing a polymer molded article of the present invention,
The mixing ratio of the ruthenium-carbene complex to the norbornene-based monomer is preferably in the range of 1/5 to 1 / 500,000 mol. More preferably, 1/30 to 1/2000
It is in the range of 00 moles. Within this range, the mixing ratio of the catalyst may be set based on the necessary pot life and curing time.

The polymerizable composition impregnated in the fibrous body is more preferably defoamed by a defoaming roller or the like in order to improve the compatibility with the fibrous body. By defoaming, a molded article of good quality with few voids can be obtained.

In the method for producing a polymer molded article of the present invention, the number of the fibrous bodies to be laminated can be freely changed depending on the laminating portion. As described above.

Examples of the form of the fibrous body include chopped strand mat, continuous mat, roving cloth, and blind roving. Examples of the type of the fibrous body include inorganic fibers and organic fibers, and preferable examples thereof include glass fibers, carbon fibers, aramid fibers, and jute fibers.

The fibrous body may be subjected to a surface treatment or the like exhibiting good adhesiveness with the norbornene-based polymer depending on the type of the fibrous body.

The norbornene-based polymer molded article obtained by the present invention is excellent in heat resistance and impact resistance.
It is suitable for use in housing materials such as bathtubs and waterproof pans, pipework equipment such as pipes and joints, and civil engineering materials.

<Function> The present invention provides a molding method comprising laminating a fibrous body impregnated with a polymerizable composition containing a norbornene-based monomer and a catalyst represented by the above general formula [I] or [II]. Since the mold or the adherend is once formed and the norbornene-based monomer in the fibrous body is polymerized, the method for producing a norbornene-based polymer molded article of the present invention cures even in the presence of air or moisture. A norbornene-based polymer molded article excellent in heat resistance and impact resistance without defects can be obtained. In addition, even when compounded with a fibrous body, a fiber-reinforced norbornene-based polymer molded body showing good physical properties without curing failure at the interface can be obtained.

Further, since the number of fibrous bodies to be laminated can be freely changed, strength design according to the shape becomes possible. In addition, since poor curing can be significantly reduced as compared with a conventional norbornene-based polymer molded article, a molded article with less residual monomer and less odor can be obtained.

[0031]

Hereinafter, "parts" means "parts by weight". <Example 1> (Raw materials) Monomer: dicyclopentadiene ruthenium-carbene complex: bis (tricyclohexylphosphine) benzylidene ruthenium dichloride Solvent: toluene Fiber: glass chopped strand mat (counter 45)
(Preparation of polymerizable composition) A solution prepared by dissolving 20 parts of bis (tricyclohexylphosphine) benzylidene ruthenium dichloride in 200 parts of toluene was mixed with a solution of bis (tricyclohexylphosphine) benzylidene ruthenium dichloride to dicyclopentadiene. Ratio is 1/10
And mixed with dicyclopentadiene so as to obtain a polymerizable composition.

(Production of molded article) Next, a flat mold (200 m in width)
mx 200 mm) along with a glass chopped strand mat, impregnating the polymerizable composition with a glass impregnated roller on the glass chopped strand mat,
After defoaming, the lamination, impregnation and defoaming of a glass chopped strand mat impregnated with the polymerizable composition are repeated twice in the same manner, and completely cured by heating in a curing oven at 60 ° C. for 10 minutes. I let it. In this way, on a flat mold,
A cured product of a 3-ply laminate of a glass chopped strand mat impregnated with the polymerizable composition was formed. Thereafter, demolding was performed to obtain a flat plate (molded body) made of fiber reinforced polydicyclopentadiene. The curability of the obtained polymer molded product was good and there was no stickiness on the surface.

Example 2 Molding was carried out under exactly the same conditions as in Example 1 except that bis (tricyclohexylphosphine) benzylidene ruthenium dichloride left in the air for one week was used as the ruthenium-carbene complex. A flat plate made of glass fiber reinforced polydicyclopentadiene having comparable good mechanical and thermal properties was obtained.

Example 3 (Raw materials) Monomer: dicyclopentadiene ruthenium-carbene complex: bis (tricyclohexylphosphine) benzylidene ruthenium dichloride Solvent: toluene Fiber: glass roving cloth (450 g / count
m ² ) (Preparation of polymerizable composition) A solution prepared by dissolving 20 parts of bis (tricyclohexylphosphine) benzylidene ruthenium dichloride in 200 parts of toluene was used to prepare a molar ratio of bis (tricyclohexylphosphine) benzylidene ruthenium dichloride to dicyclopentadiene. Is 1/10
000 and mixed with dicyclopentadiene and stirred.

(Production of molded article) Next, the polymerizable composition was impregnated with an impregnating roller while a chopped strand mat was placed along a rotating cylindrical mold (φ75, length 300 mm). After the defoaming, the lamination, impregnation and defoaming of the chopped strand mat impregnated with the polymerizable composition were repeated twice, and completely cured by heating in a curing oven at 60 ° C. for 10 minutes. In this way, a cured product of a three-ply laminate of the polymerizable composition-impregnated chopped strand mat was formed along the cylinder. Thereafter, demolding was performed to obtain a φ75 pipe made of fiber-reinforced polydicyclopentadiene.

<Example 4> (Raw materials) Monomer: dicyclopentadiene ruthenium vinylidene complex: a complex represented by the following formula 5 was used.

[0037]

Embedded image (In the formula, Cy represents a cyclohexyl group, and Fc represents a ferrocenyl group.)

Solvent: toluene Fiber body: glass chopped strand mat (count 45)
0 g / m ² ) (Preparation of polymerizable composition) First, a solution prepared by dissolving 20 parts of the above ruthenium vinylidene complex in 200 parts of toluene was prepared so that the molar ratio of the ruthenium vinylidene complex to dicyclopentadiene was 1/5000. Was mixed with dicyclopentadiene and stirred. (Production of molded article) Next, the obtained polymerizable composition was impregnated into a chopped strand mat with an impregnating roller, defoamed, and then flat-molded (width 200 mm).
mm × 200 mm in depth), and in the same manner, two plies of a chopped strand mat impregnated with the polymerizable composition were laminated thereon, and cured in an 80 ° C. curing oven at 30 ° C.
Heated for a minute to completely cure. On the flat mold, a cured product of a three-ply laminate of a polymerizable composition-impregnated chopped strand mat was formed. Thereafter, demolding was performed to obtain a flat plate (molded body) made of fiber reinforced polydicyclopentadiene having good mechanical and thermal properties.

<Example 5> Molding was performed under exactly the same conditions as in Example 1 except that the same ruthenium vinylidene complex as in <Example 4> was used after standing in air for one month. A flat plate made of glass fiber reinforced polydicyclopentadiene having excellent mechanical and thermal properties was obtained.

Example 6 (Raw materials) Monomer: dicyclopentadiene ruthenium-carbene complex: the same as in Example 4 Solvent: toluene Fiber: glass roving cloth (count 450 g /
m ² ) (Preparation of polymerizable composition) A solution prepared by dissolving 20 parts of the same ruthenium vinylidene complex as in <Example 4> in 200 parts of toluene was adjusted to have a molar ratio of ruthenium vinylidene complex to dicyclopentadiene of 1/2000. Mixing and stirring were performed so as to be as follows.

(Production of molded article) Next, the obtained polymerizable composition was impregnated into a chopped strand mat with an impregnating roller, and after defoaming, rotating cylindrical mold (φ75, length 3)
In a similar manner, two plies of a chopped strand mat impregnated with the polymerizable composition were laminated thereon, and completely cured by heating in a curing oven at 80 ° C. for 20 minutes. In this way, a cured product of the three-ply laminate of the polymerizable composition-impregnated chopped strand mat was formed along the cylindrical mold. Thereafter, demolding was performed to obtain a φ75 pipe made of fiber-reinforced polydicyclopentadiene.

<Comparative Example 1> (Raw materials) Monomer 1 (Solution A): solution comprising activator, activity regulator and dicyclopentadiene (trade name: Meton: manufactured by Teijin Meton Co., Ltd.) Monomer 2 (Solution B): Catalyst Solution consisting of and dicyclopentadiene (trade name: Meton: manufactured by Teijin Meton Co., Ltd.)

(Preparation of polymerizable composition and production of molded article) A conventional dicyclopentadiene A solution containing an activator,
A conventional dicyclopentadiene B solution containing a catalyst (the compound name of the catalyst and the activator is unknown) is mixed and stirred so that the mixing ratio becomes 1/1, and then the polymerized composition mixed and stirred is impregnated with a roller. Tried to impregnate the glass chopped strand mat, but the partial polymerization started rapidly, and almost all became poorly cured polymers, and a predetermined polymer molded product by lamination could not be obtained.

<Comparative Example 2> (Raw materials) Monomer 1 (Solution A): solution comprising activator, activity regulator and dicyclopentadiene (trade name: Meton: manufactured by Teijin Meton Co., Ltd.) Monomer 2 (Solution B): Catalyst (Manufactured by Teijin Meton Co., Ltd.) (manufactured by Teijin Meton Co., Ltd.) (Production of molded article) Dicyclopentadiene A solution containing conventional activator and dicyclopentadiene B containing conventional catalyst
Molding was carried out under the same conditions as in Example 1 except that the liquid (the compound names of the catalyst and activator were unknown) was allowed to stand in the air for one day. Did not. After heating in a heating furnace at 80 ° C., polymerization did not proceed. The cause may be that the catalyst has been deteriorated by air.

<Comparative Example 3> (Raw materials) Monomer 1 (Solution A): solution comprising activator, activity regulator and dicyclopentadiene (trade name: Meton: manufactured by Teijin Meton Co., Ltd.) Monomer 2 (Solution B): Catalyst (Meton: trade name: manufactured by Teijin Meton Co., Ltd.) Fiber body: glass fiber chopped strand mat (count: 450 g / m ² ) (Production of molded body) First, reaction injection controlled at 90 ° C. Three-ply set of glass fiber chopped strand mat in a molding pipe mold (φ75) (it took 4 minutes to cut the glass fiber into a predetermined shape and set it in the mold)
After that, the mold was closed, and nitrogen was supplied into the mold for 30 seconds to purge air.

Next, the mixing ratio of the conventional dicyclopentadiene A solution containing the activator and the dicyclopentadiene B solution containing the conventional catalyst (the compound names of the catalyst and the activator are unknown) is reduced to 1/1. And RIM (Reaction inj
Injection into the above mold with a molding machine. The injection time was about 6 seconds.

When the mold was opened three minutes after the completion of the injection, glass fiber reinforced polydicyclopentadiene was obtained, but the air could not be completely exhausted. In some parts, considerable curing failure was observed.

<Comparative Example 4> Molding was performed under exactly the same conditions as in Comparative Example 3 except that the air in the mold was not purged with nitrogen at the time of molding. Poor curing of the glass fiber reinforced polydicyclopentadiene revealed It became considerably worse compared to.

Comparative Example 5 Resin component: ortho-unsaturated polyester Curing agent: methyl ethyl ketone peroxide Fiber: chopped strand mat (count 450 g /
m ² ) 100 parts of ortho-unsaturated polyester was mixed and stirred so that the mixing amount of methyl ethyl ketone peroxide was 1.0 part. Next, while the polymerizable composition mixed and stirred is impregnated into a chopped strand mat with an impregnating roller, a flat mold (200 mm wide × 200 m deep) is used.
3 plies were laminated along m), and further cured in a curing oven at 70 ° C. for 40 minutes, followed by demolding to obtain a flat plate made of an unsaturated polyester resin. The curability of the obtained molded product was good and there was no stickiness on the surface.

As can be seen from the above results, the method for producing a polymer molded article of the present invention provides a fiber-reinforced norbornene-based polymer which exhibits good reactivity even in the presence of air, has a quick reaction, and is excellent in quality. A molded article can be obtained. Further, it can be polymerized more quickly than a monomer such as an unsaturated polyester resin used in conventional lamination molding.

Next, test pieces were cut out from the flat plates obtained in Examples 1, 2, 4 and 5 and Comparative Example 5, and each test piece was subjected to bending strength (according to JIS K 7055) and bending. Each physical property value of an elastic modulus (based on JIS K 7055), an Izod impact (JIS K 7110) and a heat distortion temperature (JIS K 6911) was measured. The Izod impact was measured using a notched test piece.

The results are shown in Table 1 below. However,
In Comparative Examples 1 to 4, physical properties were not measured due to poor curing.

[0053]

[Table 1]

From the above results, it was found that the fiber-reinforced norbornene-based polymer molded article obtained by the method for producing a polymer molded article of the present invention was excellent not only in strength and elastic modulus but also particularly in impact resistance and heat resistance.

[0055]

As described above, according to the present invention,
The method for producing a norbornene-based polymer molded article can be expanded from a conventional method using in-mold molding to a method using open mold molding. That is, a molding die or an adherend is once formed by laminating a fibrous body impregnated with a polymerizable composition containing a norbornene-based monomer and the catalyst represented by the general formula [I] or [II]. However, since the norbornene-based monomer in the fibrous body is polymerized, a norbornene-based polymer molded article having excellent heat resistance and impact resistance can be produced irrespective of the molding environment, product shape, size, and reinforcing portion. It can be provided simply and with little capital investment. In addition, since there is no poor interfacial adhesion due to poor curing at the time of fiber composite, a molded article having high strength and high elastic modulus can be easily obtained. Furthermore, a multilayer molded product of various materials such as plastics can be easily obtained, and a composite of two or more types of norbornene-based polymers can be easily formed by multilayering or the like. Moreover, unlike conventional two types of monomers, polymerization molding can be performed with one type of norbornene-based monomer, so that there is an advantage that a complicated apparatus, a mold, or a wide monomer storage space is not required.

[Brief description of the drawings]

FIG. 1 is an explanatory diagram illustrating an example of a method for producing a norbornene-based polymer molded article of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Polymerizable composition 2 Impregnating roller 3 Fiber body 4 Mold

Continued on the front page (72) Inventor Takeharu Morita 2-1 Hyakuyama, Shimamotocho, Mishima-gun, Osaka Sekisui Chemical Co., Ltd.

Claims (2)

[Claims] 1. A polymerizable composition comprising a norbornene-based monomer and a ruthenium-carbene complex represented by the following general formula [I] or a ruthenium vinylidene complex represented by the following general formula [II] as a catalyst: A method for producing a norbornene-based polymer molded article, comprising polymerizing a norbornene-based monomer in a mold or an adherend in which a fibrous body impregnated with an object is laminated. Embedded image (Wherein R ₁ and R ₂ are each independently hydrogen, C _2-
A C20-alkenyl group, a C1-C20-alkyl group, an aryl group, a C1-C20-carboxylate, a C1-C20-alkoxy group, a C2-C20-alkenyloxy group, an aryloxy group, a C2-C20-alkoxycarbonyl group, or C1 -C20 -alkylthio groups (these are C1 -C5
An alkyl group, a halogen, a C1 -C5 -alkoxy group, or a C1 -C5-
X ₁ and X ₂ independently of one another represent an anionic ligand, and may represent an anionic ligand, which may be substituted by an alkyl group, halogen, or a phenyl group substituted by a C 1 -C 5 -alkoxy group. ₁ and L ₂ independently of one another represent any neutral electron donor; of X ₁ , X ₂ , L ₁ and L ₂ , two or three are together a polydentate chelating ligand May be formed). Wherein R ₃ and R ₄ are independently hydrogen, C 2-
C20 -alkenyl, C1 -C20 -alkyl, aryl, C1 -C20 -carboxylate, C1 -C20 -alkoxy, C2 -C20 -alkenyloxy, aryloxy, C2 -C20 -alkoxycarbonyl, C1
-C20 -alkylthio groups (which may be substituted by C1 -C5 -alkyl groups, halogen, C1 -C5 -alkoxy groups, or by C1 -C5 -alkyl groups, halogen, C1 -C5 -alkoxy groups) (It may be substituted by a substituted phenyl group.)
Or, represents a ferrocene derivative, X ₃ and X ₄ independently represent any anionic ligand, L ₃ and L
₄ independently of one another, any neutral electron donor;
Two or three of ₃ , X ₄ , L ₃ and L ₄ may together form a multidentate chelating ligand) 2. The method for producing a norbornene-based polymer molded article according to claim 1, wherein the norbornene-based monomer is dicyclopentadiene.