JP2000301558A - Method for producing norbornene-based polymer molded article - Google Patents

Abstract

(57) [Abstract] [Problem] Strength, rigidity, and good quality without curing failure
Provided is a method for producing a norbornene-based polymer molded article that can obtain a norbornene-based polymer molded article having excellent dimensional accuracy by press molding. SOLUTION: A solution obtained by dissolving a fixed amount of norbornene-based monomer (preferably dicyclopentadiene) 4 and a ruthenium-carbene complex or a ruthenium vinylidene complex represented by a specific general formula that is stable to oxygen and moisture in a solvent. 5 is mixed with a mixing device such as a dynamic mixer 6 to obtain a polymerizable composition. The polymerizable composition is immediately poured into the lower mold 2 by the resin material supply device 7 immediately. The upper mold 3 is lowered and pressed toward the lower mold 2 (mold closed), and the polymerizable composition supplied into the mold and undergoing polymerization and curing is heated and pressurized, shaped while defoaming, and formed into norbornene. To obtain a base polymer molded article.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a method for producing a norbornene-based polymer molded article.

[0002]

2. Description of the Related Art As a molding method having high strength, rigidity and dimensional accuracy, a sheet of unsaturated polyester resin or the like is placed in a previously opened mold and heated and pressed, as in sheet molding compound (SMC) press molding. Thus, there is a technique for obtaining a molded article (Japanese Patent Publication No. 6-17036). However, the SMC molded product molded by such a method has a problem that it is liable to crack due to poor impact strength. In order to solve the problem, there is known a method of obtaining a molded article by polymerizing a norbornene-based monomer.

As a technique for polymerizing norbornene monomers, for example, the inside of a mold is replaced with an inert gas,
There is a reaction injection molding method in which a norbornene-type monomer is injected into a mold as a molding material and reacted.
3859).

[0004]

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 compounding 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 solutions, Solution A and Solution B, have been used. These Solution A and Solution B are collision-mixed 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, an activator and an activity regulator (Solution B) A solution containing a norbornene-based monomer and a catalyst In such a solution, as a catalyst, tungsten, molybdenum, rhenium, tantalum, etc. Halides, oxyhalides, oxides, organic ammonium salts and the like are used.

As the activator, an alkylaluminum halide, an alkoxyalkylaluminum halide, an aryloxyalkylaluminum halide, an organotin 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 a catalyst, an activator and an activity regulator with the norbornene-based monomer, Injection Molding (RI)
As in M), it can only be handled by a method of injection-molding the polymerizable composition in a closed mold.
There were problems such as complicated shapes required for press molding and the inability to carry out fiber reinforcement. Further, since the molding method is limited to RIM, the alignment of the molding dies becomes loose, so that only molded products having poor mold accuracy and poor dimensional accuracy were obtained.

On the other hand, a molded product obtained by press-molding SMC is as follows:
As described above, there is a drawback that it is brittle and easily broken.

The present invention has been made in view of the problems in the case of performing polymerization molding using the above-mentioned conventional norbornene-based monomer, and is excellent in strength, rigidity and dimensional accuracy with good quality without curing failure. An object of the present invention is to provide a method for producing a norbornene-based polymer molded article that can obtain a norbornene-based polymer molded article by press molding.

[0012]

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) as a catalyst. It is characterized by supplying the polymerizable composition into a mold in an open state, polymerizing the norbornene-based monomer while closing the mold, and pressing and shaping.

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 The method for producing a norbornene-based polymer molded product according to claim 2 includes a norbornene-based monomer and a ruthenium vinylidene complex represented by the following general formula (II) as a catalyst. The polymerizable composition is supplied into a mold in an open state, and the norbornene-based monomer is polymerized while the mold is closed, and is pressed and shaped.

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
-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)

[0013] The method for producing a norbornene-based polymer molded product according to claim 3 is characterized in that the polymerizable composition is supplied into the mold while the fiber reinforcing material is arranged in the mold. Further, the method for producing a norbornene-based polymer molded article according to claim 4 is characterized in that the norbornene-based monomer is dicyclopentadiene.

Next, a more specific example of the method for producing a norbornene-based polymer molded article of the present invention will be described with reference to FIG. First, a fixed amount of the norbornene-based monomer 4 and a ruthenium-carbene complex represented by the general formula (I) or a ruthenium vinylidene complex represented by the general formula (II), which are stable to oxygen and moisture, were dissolved in a solvent. A certain amount of the solution 5 is mixed with a mixing device such as a dynamic mixer 6 to obtain a polymerizable composition.
Thereby, the liquid is continuously poured into the lower mold 2. Next, the upper mold 3 is lowered by the press machine 1 and pressed toward the lower mold 2 (mold closing), and the polymerizable composition supplied into the mold and being partially polymerized and cured is heated and pressurized to be defoamed. While shaping.
In this case, the heating and pressurizing conditions are not particularly limited, but a temperature of 30 to 100 ° C. and a pressure of about 0.3 to 4 MPa are preferably employed. The polymerizable composition supplied and pressurized in the mold in this way starts polymerization promptly even in the presence of air, so that a good norbornene-based polymer molded article with less curing failure can be obtained.

Here, the lower mold 2 and the upper mold 3 used in the method for producing a polymer molded article of the present invention are
As shown in FIG. 2, a clearance C is formed on a mating surface of the lower mold 2 and the upper mold 3, that is, a side circumference of a polymer molded product (not shown). Internal air can be efficiently degassed. This clearance C is 0.005 mm to 1 mm
And more preferably about 0.07 mm to 0.5 mm.

The resin raw material supply apparatus used in the method for producing a polymer molded article of the present invention comprises a norbornene-based monomer and the above-mentioned ruthenium-carbene complex or the above-mentioned ruthenium vilinidene complex immediately before the discharge section by a mixer such as a dynamic mixer. Is preferred.

Examples of the norbornene-based monomer to be polymerized include bicyclic norbornene-based monomers such as norbornene and norbornene, tricyclics such as dicyclopentadiene and dihydrodicyclopentadiene, tetracyclics such as tetracyclododecene, and tricyclone. Pentacycles such as pentadiene, heptacycles such as tetracyclopentadiene, and their alkyl-substituted (eg, methyl, ethyl, propyl, butyl-substituted, etc.), alkylidene-substituted (eg, ethylidene-substituted), aryl-substituted Derivatives having polar groups such as epoxy groups, methacrylic groups, hydroxyl groups, amino groups, carboxyl groups, cyano groups, halogen groups, ether groups, and ester bond-containing groups, as well as derivatives (eg, phenyl and tolyl substituents) Is mentioned. These may be used alone or as a mixture of two or more. The norbornene-based monomer is preferably dicyclopentadiene from the viewpoint of availability, reactivity, balance of physical properties of the polymer, cost, and the like.

When it is desired to impart strength and heat resistance to the molded article, crosslinking may be carried out using a crosslinking monomer. Examples thereof include polycyclic norbornene monomers having a reactive double bond. Specifically, dicyclopentadiene, tetracyclopentadiene and the like can be mentioned.
Here, when the norbornene monomer and the crosslinkable monomer are the same, it is not particularly necessary to use another crosslinkable monomer.

These norbornene-based monomers may be used alone or in combination of two or more. Cyclobutene, cyclopentene, cyclopentadiene, cyclopentane, and cyclobutene which can be ring-opening copolymerized with the norbornene-based monomer. Monocyclic cycloolefins such as octene and cyclododecene may be used without impairing the object of the present invention.

The polymerizable composition used in the method for producing a norbornene-based 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,
Various additives such as a thixotropic agent, an antistatic agent, a molecular weight regulator, 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 co-aggregate, EPDM, ethylene-vinyl acetate co-aggregate, 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 Phenoxy, C1 -C5 -alkylthio groups (these are C1 -C5
It may be substituted by a 5-alkyl group, halogen, C1 -C5 -alkoxy group, or C1 -C5
An alkyl group, a halogen, a phenyl group substituted by a C1 -C5 -alkoxy group).
1 and L2 independently of one another are an aryl group or a C1 to
C10 -alkylphosphine groups (these are C1 -C5-
(It may be substituted by an alkyl group, halogen, a C1 -C5 -alkoxy group, or may be substituted by a C1 -C5 -alkyl group, a halogen, a phenyl group substituted by a C1 -C5 -alkoxy group.) Ruthenium-carbene complexes which are neutral ligands from the group of are preferred.

More preferred ruthenium-carbene complexes represented by the general formula (I) are 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 vilinidene complex represented by the general formula (II) is preferably liquid because it is poured into the mold while being mixed. For example, it is preferable to use it after diluting it in a solvent. Examples of the solvent include toluene, benzene, tetrahydrofuran (TH
F), dichloromethane and the like. It is not preferable to dissolve the ruthenium-carbene complex in a solvent or an acid in which active hydrogen is present, since the stability of the complex is impaired. The same can be said for the ruthenium vinylidene complex of the general formula (II), although the stability in air is higher than that of the ruthenium-carbene complex of the general formula (I).

In the method for producing a norbornene-based polymer molded article of the present invention, the mixing ratio of the ruthenium-carbene complex or the ruthenium vinylidene 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. The mixing ratio of the catalyst may be set based on the necessary curing time in this range.

In the present invention, when producing a fiber-reinforced norbornene-based polymer molded article, for example, a method in which a polymerizable composition is poured into a mold while a fiber reinforcing material is disposed in the mold is adopted. I just need.

As a specific example, as shown in FIG.
The fiber reinforcing material 8 is placed in the lower mold 2 in advance, and in this state, the norbornene-based monomer and bis-tricyclohexylphosphine benzylidine ruthenium (I
V) A method in which a polymerizable composition containing dichloride is supplied by a resin raw material supply device, and then a mold is closed, and a monomer that is starting to be polymerized is pressed and shaped. .

Also in this example, the polymerizable composition starts polymerization in the mold, so that a norbornene-based polymer molded product can be obtained. Moreover, since the norbornene-based monomer is polymerized under the fiber reinforcing material 8, a molded product having higher strength and higher elastic modulus can be obtained.

As the fiber reinforcing material, it is preferable to use mats such as chopped strand mats, continuous mats, and cloth mats, or to use preform mats in which fibers are previously formed into a product shape.

Examples of the type of the fiber reinforcing material include inorganic fibers and organic fibers, and preferable examples thereof include glass fibers, carbon fibers, polyethylene terephthalate fibers such as aramid fibers and jute fibers.

<Function> In the method for producing a norbornene-based polymer molded article of the present invention, a norbornene-based monomer is polymerized using a ruthenium-carbene complex or a ruthenium vinylidene complex (catalyst) stable against oxygen and moisture. Therefore, poor curing is reduced even in the presence of air. Therefore, according to the present invention, it is possible to press the norbornene-based monomer supplied into the mold in an open state while polymerizing it in the presence of air. That is, it is possible to produce a norbornene-based polymer molded article by press molding, which is a molding method in the presence of air, which was conventionally impossible.

Further, it is possible to obtain a norbornene-based polymer molded article having good dimensional accuracy and excellent impact strength as compared with conventional reaction injection molding. In addition, even if a reinforcing material such as fiber reinforcement is mixed with a filler, poor curing at the interface does not occur, so that it is possible to manufacture a molded product having a high strength and a high elastic modulus, which has been conventionally difficult to obtain. It becomes possible. Moreover, SMC
Conventional fiber-reinforced plastic (FR
P) It is possible to obtain a molded product which is superior in impact strength and hard to crack as compared with a molded product.

Hereinafter, "parts" means "parts by weight". <Example 1> (Raw materials) Monomer: dicyclopentadiene ruthenium-carbene complex: bis (tricyclohexylphosphine) benzylidene ruthenium dichloride Solvent: toluene (Production of molded article) As shown in FIG. A solution 5 in which 20 parts of tricyclohexylphosphine) benzylidene ruthenium dichloride were dissolved was mixed with dicyclopentadiene 4 so that the molar ratio of bis (tricyclohexylphosphine) benzylidene ruthenium dichloride to dicyclopentadiene was 1/5000. While mixing with mixer 6,
The obtained polymerizable composition was continuously supplied in an amount of 50 g into the lower mold 2 for forming a flat plate, and while the upper mold 3 was lowered and closed, the monomers were polymerized and pressed to shape. At this time, the temperature of the mold was 80 ° C., and the press pressure was 0.7 MPa.
Met.

After 3 minutes, the mold was released, and a plate made of polydicyclopentadiene (100 mm × 100 mm × 5
mm). The obtained molded product had good curability despite being in contact with air at the time of molding.

<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.)

(Production of molded article) A mixture of a conventional dicyclopentadiene A solution containing an activator and a dicyclopentadiene B solution containing a conventional catalyst (the compound names of the catalyst and the activator are unknown) is 1 As in Example 1, the mixture was continuously supplied into the lower mold while mixing the A liquid and the B liquid with the dynamic mixer in the molding die shown in FIG. Most of the molded articles were uncured and could not be used as products. The mold temperature during molding was 80 ° C.

<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 (Product name: (Production of molded article) Dicyclopentadiene A solution containing conventional activator and dicyclopentadiene B containing conventional catalyst)
The liquid (the names of the compounds of the catalyst and the activator are unknown) was injection-filled into a molding die using a reaction injection (RIM) molding machine so that the mixing ratio became 1/1. As a result, a cured molded product could be obtained, but the dimensional accuracy was lower than that of Example 1 as shown in Table 1. The mold temperature during molding was 8
It was 0 ° C. The injection and filling of the AB liquid was performed on a mold in which nitrogen was supplied and air was purged in advance.

<Example 2> (Raw materials) Monomer: dicyclopentadiene ruthenium-carbene complex: bis (tricyclohexylphosphine) benzylidene ruthenium dichloride Solvent: toluene Fiber reinforcing material: continuous mat (glass fiber: # 450 manufactured by Asahi Fiber Co., Ltd.)

(Production of molded article) A polymerizable composition obtained by mixing dicyclopentadiene and the above-mentioned catalyst in the same manner as in Example 1 with five continuous mats laminated in the lower mold 2 Are continuously poured into the lower mold 2 and polymerized, while the upper mold 3 is lowered and pressed to obtain a fiber-reinforced polydicyclopentadiene molded product (flat plate).
I got The mold temperature during molding was 80 ° C. The obtained molded product was excellent in strength and elastic modulus as shown in Table 1.

<Comparative Example 3> An SMC in which an iso-based polyester, calcium carbonate and glass fiber were mixed at a ratio of 100: 100: 30 was used in the same manner as in Example 1 by using a mold shown in FIG. Pressing with a press for a minute resulted in a fiber-reinforced resin molded product. The obtained molded product had the same strength and rigidity as the fiber-reinforced dicyclopentadiene molded product obtained in Example 2, but had a poor impact strength.

<Example 3> (Raw materials) Monomer: dicyclopentadiene ruthenium vinylidene complex: A compound represented by the following formula (III) was used.

[0041]

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

Solvent: toluene

(Production of molded article) As shown in FIG. 1, a solution prepared by dissolving 20 parts of a ruthenium vinylidene complex in 200 parts of toluene was prepared so that the molar ratio of the ruthenium vinylidene complex to dicyclopentadiene became 1/3000. , And 50 g of the polymerizable composition obtained by mixing with the dicyclopentadiene in the dynamic mixer 6 is continuously supplied into the lower mold 2 for flat plate forming, and the lower mold 3 is lowered and closed, The monomers were polymerized and pressed and shaped. The upper mold 3 is closed, and after 3 minutes, the mold is released, and a flat plate made of polydicyclopentadiene (100 m
m × 100 mm × 5 mm). The resulting molded product is
Despite being in contact with air during molding, the curability was good. The mold temperature during molding was 100 ° C.

<Example 4> (Raw materials) Monomer: dicyclopentadiene ruthenium vinylidene complex: The same one as in Example 3 was used. Solvent: toluene Fiber reinforcement: continuous mat (glass fiber: Asahi Fiber Co., Ltd. # 450)

(Production of Molded Article) A polymerizable composition obtained by mixing dicyclopentadiene and a catalyst in the same manner as in Example 3 with five continuous mats laminated in the lower mold 2 The mixture was poured into the lower mold 2, polymerized with dicyclopentadiene, and pressed with the upper mold 3 to obtain a fiber-reinforced polydicyclopentadiene molded product (flat plate). The mold temperature during molding was 100 ° C. The obtained molded article was excellent in strength elastic modulus.

Next, with respect to the molded products obtained in Examples 1 to 4 and Comparative Examples 2 and 3, the bending strength (JI
SK 7055), flexural modulus (JIS K 7)
055), Izod impact (JIS K 711)
0) and dimensional errors were measured, and the results were
The results are shown in Table 1 below. The Izod impact was measured using a notched test piece. The dimensional error is a percentage difference between the design dimension of the long side of the flat molded product and the actual product.

[0047]

[Table 1]

From the above results, it was found that the norbornene-type polymer molded product obtained by the method for producing a norbornene-based polymer molded product of the present invention was excellent not only in strength and elastic modulus but also particularly in impact resistance and heat resistance. It was also found that the dimensional accuracy was higher than that of the conventional reaction injection molding method.

[0049]

As described above, the present invention provides a polymerizable composition containing a norbornene-based monomer and a ruthenium-carbene complex or ruthenium vinylidene complex as a catalyst in an open mold. In the present invention, the norbornene-based monomer is polymerized while the mold is closed, and the mixture is pressed and shaped.According to the present invention, a norbornene-type polymer molded product can be easily obtained with high productivity even in the presence of air. it can.

The obtained norbornene-type polymer molded product has better impact resistance than the conventional press-formed product of fiber-reinforced plastic (FRP), and has higher strength and rigidity than the norbornene-type polymer molded product obtained by the conventional reaction injection molding. And excellent dimensional accuracy. In addition, according to the present invention as set forth in claim 3, the use of the fiber reinforcing material does not cause interfacial adhesion failure due to poor curing at the time of compounding with the fiber reinforcing material.
A molded product having high strength and high elastic modulus can be easily obtained.
Further, according to the present invention as set forth in claim 4, wherein the norbornene-based monomer is dicyclopentadiene, the above effects are more reliably exhibited by the characteristics of dicyclopentadiene.

[Brief description of the drawings]

FIG. 1 is an illustration of an example of a method for producing a norbornene-based polymer molded product according to the present invention.

FIG. 2 is a schematic cross-sectional view showing an example of a mold used in the method for producing a norbornene-based polymer molded article according to the present invention.

FIG. 3 is an explanatory view of an example of a method for producing a fiber-reinforced norbornene-based polymer molded product according to the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Press machine 2 Lower mold 3 Upper mold 4 Norbornene-based monomer 5 Ruthenium-carbene complex 6 Dynamic mixer 7 Resin supply device 8 Fiber reinforcing material C Mold mold clearance

Continued on the front page F term (reference) 4F202 AA12L AB03 AB04 AB17 AB25 AG01 AK01 AK02 AM30 CA09 CB01 CL50 CN01 CN05 CN25 4F204 AA12L AB03 AB04 AB17 AB25 AG01 AK01 AK02 AM30 FA01 FB01 FH21 FN11 FN15 FN17 CA43 CA06 CG07

Claims (4)

[Claims] 1. A polymerizable composition containing a norbornene-based monomer and a ruthenium-carbene complex represented by the following general formula (I) as a catalyst is supplied into a mold in an open state, A method for producing a norbornene-based polymer molded article, comprising polymerizing a norbornene-based monomer while pressing a mold, and pressing and shaping. 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) 2. A polymerizable composition containing a norbornene-based monomer and a ruthenium vinylidene complex represented by the following general formula (II) as a catalyst is supplied into a mold in an open state, and molded. A method for producing a norbornene-based polymer molded article, comprising polymerizing a norbornene-based monomer while closing a mold. 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
-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) 3. The method for producing a norbornene-based polymer molded product according to claim 1, wherein the polymerizable composition is supplied into the molding die in a state where the fiber reinforcing material is arranged in the molding die. 4. The method for producing a norbornene-based polymer molded article according to claim 1, wherein the norbornene-based monomer is dicyclopentadiene.