JP2001026059A - Manufacture of norbornene-based polymer continuously molded product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve bending strength, bending elasticity and impact strength by a method wherein a base material and a specific polymerizable composition are fed to a mandrel in a draw die, and it is drawn as a polymerization molded continuos body while the polymerizable composition is being polymerized and cured integrally with the base material. SOLUTION: One layer of a base material is inserted into a draw die 3 while it is wound up in a hoop state by a hoop winder 8 to a material 3a arranged parallel to a draw direction. A polymerizable composition obtained by mixing norbornene based monomer 1 with ruthenium-carbene complex 2 expressed by the formula is injected into the draw die 3 so that the base material 10 is impregnated therewith to polymerize the polymerizable composition in the draw die 3, and it is drawn as a polymerization molded continuous body while it is cured integrally with the base material 10. In the formula, R1 and R2 each represents independently hydrogen or the like, X1 and X2 each represents independently an optional anionic ligand, and L1 and L2 each represent independently an optional neutral electron donor.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a continuous molded article of a norbornene-based polymer by using a norbornene-based monomer by a method corresponding to a so-called pultrusion molding method.

[0002]

2. Description of the Related Art As one type of continuous molding method for plastics, thermosetting resins such as unsaturated polyester resin, vinyl ester resin, phenol resin and epoxy resin are used.
There has been known a pultrusion molding method for obtaining a continuous fiber-reinforced resin molding by impregnating a reinforcing substrate such as glass fiber or the like in a prepreg state and curing in a mold while being drawn into a drawing mold ( See JP-A-61-3731).

[0003]

However, according to the study of the present inventors, for example, in the case of the above-mentioned pultruded product using a generally used unsaturated polyester resin or vinyl ester resin as a matrix resin, There was a problem. (1) Since these resins have poor flexibility and low toughness, they are vulnerable to impact. (2) Since the reinforcing base materials are arranged only in the drawing direction, the molded article has high anisotropy. Therefore, there is a problem that a vertical crack is easily generated in the drawing direction when a load is applied. This point becomes more remarkable as the molded product becomes deformed, and in the case of a round pipe or a square pipe, stress tends to concentrate,
The effect is greater.

In this case, in order to secure impact resistance, it is conceivable to use a polymer of a norbornene monomer having toughness as a resin. Techniques for polymerizing norbornene-based monomers have been generally known in the art.For example, air in a mold is replaced with an inert gas, and then the norbornene-based monomer is injected into a mold as a molding material to form a closed space. (See JP-B-7-73859).

[0005] When the norbornene-based monomer is subjected to reaction injection molding, the following two solutions, Solution A and Solution B, are used. These Solution A and Solution B are collision-mixed immediately before a mold. A polymerized product of a norbornene-based monomer was obtained by injecting a polymerizable solution into a mold and performing a polymerization reaction. (Solution A) Solution containing norbornene monomer and activator and activity regulator (Solution B) Solution containing norbornene monomer and catalyst

[0006] In such a solution, as a catalyst,
Tungsten, molybdenum, rhenium, tantalum, and other halides, oxyhalides, oxides, organic ammonium salts, etc. are used, and alkyl or alkoxy aluminum halides or organic tin compounds are used as activators. . Alcohols such as n-propyl alcohol are used as activity regulators.

However, when performing polymerization molding using norbornene-based monomers, there is an important problem that the polymerization reaction is hindered by the presence of oxygen and moisture, and good polymerization does not proceed unless the atmosphere is completely inert. Yes, for this reason, Reaction Injection Molding (RI)
As in M), molding could not be performed except by injection molding the polymerizable composition in a closed mold, and continuous molding has not been reported so far.

The present invention has been made in view of the above-mentioned problems of the conventional general technology of pultrusion molding and the problem of the technology of polymerization molding of norbornene-based monomers. Norbornene having high bending strength, bending elasticity and impact strength has been developed. An object of the present invention is to provide a method for producing a continuous polymer-based molded article that can be obtained with facilities and equipment that are not affected by the environment and have relatively low capital investment, without causing curing failure.

[0009]

In order to achieve the above object, according to the present invention, there is provided a method for drawing a metal while winding a substrate at a predetermined winding angle on a mandrel arranged in a drawing direction. While being inserted into the mold, a polymerizable composition containing a norbornene-based monomer and a ruthenium-carbene complex represented by the following general formula (I) is supplied into the drawing mold. The present invention provides a method for producing a norbornene-based polymer continuous molded article which is drawn out as a polymerization molded continuous body while polymerizing the polymerizable composition and curing integrally with the substrate.

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)

According to a second aspect of the present invention, the base material is inserted into the drawing die while being wound at a predetermined winding angle with respect to the mandrel arranged in the drawing direction. , Norbornene-based monomers and the following general formula (II)
A polymerizable composition containing a ruthenium vinylidene complex represented by is supplied, and the polymerizable composition is polymerized in the drawing die and cured integrally with the base material. A method for producing a norbornene-based polymer continuous molded article, comprising drawing.

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 together may form a polydentate chelating ligand)

Furthermore, the present invention according to claim 3 provides a method for producing a norbornene-based polymer continuous molded article according to claim 1 or 2, wherein the norbornene-based monomer is dicyclopentadiene.

Hereinafter, the method for producing a polymer continuous molded article of the present invention will be specifically described. First, a norbornene-based monomer and a ruthenium-carbene complex 4 represented by the general formula (I) or a ruthenium vinylidene complex (catalyst) represented by the general formula (II), which are stable to oxygen and moisture, are With a gear pump or the like, a predetermined amount (constant per unit time) of the obtained polymerizable composition is fed into the drawing die while mixing immediately before injection into the drawing die. The feeding amount of the polymerizable composition is determined according to the drawing speed. For example, if a pipe-shaped molded product having a diameter of 50 mm and a thickness of 5 mm is to be drawn out at a volumetric content of 50% of glass fiber of 2 m / min, the injection may be performed at 0.8 L / min. In addition, when the polymerizable composition is fed into the drawing mold, no leakage may occur.However, in order to obtain a more uniform void-free polymer continuous molded body, molding is performed in such a state that it leaks slightly from the front of the drawing mold. Is preferred.

The polymerizable composition fed into the drawing mold as described above starts polymerization while being drawn out even in the drawing mold containing air, so that a good norbornene-based polymer continuous A molded article (long body) can be obtained.

Next, a specific example of the method for producing a polymer continuous molded article of the present invention is shown in FIGS. In addition, FIG.
FIG. 2 is a schematic side view for explaining an example of a production apparatus that can suitably employ the method for producing a norbornene-based polymer continuous molded article of the present invention, and FIG. 2 is a schematic side view for explaining another example. It is. In FIG. 1, at least one of the base materials is placed on a mandrel 3a arranged in parallel with the drawing direction.
While the layer is wound up in a hoop shape (winding angle approximately 90 degrees) by a hoop winder 8 (see FIG. 3), the drawing die 3
And the polymerizable composition obtained by mixing the norbornene-based monomer 1 and the ruthenium-carbene complex or the ruthenium vinylidene complex 2 is injected into the drawing die 3 so as to impregnate the substrate 10, and the drawing die The polymerizable composition is polymerized in the mold 3 and is cured as one body with the base material 10 while being pulled out as a polymerization molded continuous body. In addition, the base material 10 in FIG. 1 is composed of two types: a roving arranged in a drawing direction along the outer peripheral surface of the mandrel 3a and a tape-shaped fiber wound around the outside thereof in a hoop shape. It is also possible to omit the use of roving.

In FIG. 2, at least one of the base materials is placed on the mandrel 3a arranged in parallel with the drawing direction.
While the layer is wound up in a helical shape (winding angle is smaller than 90 degrees) by a woven winding machine 9 (see FIG. 4) having a structure wound into a tube and a net, the layer is inserted into the drawing die 3 and In a drawing mold 3, norbornene-type monomer 1 and ruthenium-carbene complex or ruthenium vinylidene complex 2
The polymerizable composition obtained by mixing the polymerizable composition with the base material 1 is poured into the base material 10 so as to impregnate the base material 10, and the polymerizable composition is polymerized in the drawing die 3 to form the base material 1.
It is pulled out as a polymerized continuous body while being hardened integrally with zero. In addition, the base material 10 in FIG. 2 is also composed of two types: a roving arranged in the drawing direction along the outer peripheral surface of the mandrel 3a and a fiber helically wound on the outside thereof. It is also possible to omit the use of roving. 1 and 2 is a guide.

Here, the mandrel 3a, which is disposed in parallel with the drawing direction from the outside to the inside of the drawing die 3, is fixedly disposed at a fixed position, and is wound around the mandrel 3a to form a substrate. The norbornene-based polymer integrally cured with 10 is finally separated from the mandrel 3a to obtain a norbornene-based polymer continuous molded body. However, without being limited to these forms, the mandrel 3a is made of a material that can be a core material in the final molded body, and can be moved together with the wound base material so that the mandrel 3a and the mandrel 3a can be moved together. It is also possible to obtain a final molded product integrated with the polymerizable composition obtained by polymerizing and curing 3a.

The binder 8 and the woven winding machine 9
Etc., one winding machine may be arranged on the molding line,
Multiple units may be arranged. Also, when multiple units are arranged,
A plurality of the same winding machines may be arranged, or the hoop winder 8 and the woven winding machine 9 may be arranged in combination in one line.

In the method for producing a continuous polymer molded article of the present invention, the take-off speed is preferably about 30 cm / min to 5 m / min, more preferably about 50 cm / min to 3 m / min. When the take-up speed exceeds 5 m / min, the curing cannot catch up, and when the take-up speed is less than 30 cm / min, the resin is cured at the injection portion. It is preferable that the winding machine also performs the winding at a speed corresponding to the molding line speed.

In the method for producing a continuous polymer molded article of the present invention, a roving shape of a thermoplastic fiber such as glass fiber, carbon fiber, aramid fiber, or PET is used as a base material to be wound at a predetermined angle around a mandrel. A sheet-shaped member is preferably used. In the case of using a sheet, a sheet having a width of 10 mm or less is preferable from the viewpoint of shape followability. As a substrate for disposing in the drawing direction along the outer peripheral surface of the mandrel, glass fiber, carbon fiber,
Organic fibers such as aramid fibers, thermoplastic fibers such as PET, mats, cloths, rovings, and the like, and thermoplastic stretched films such as polyethylene are exemplified.

These substrates may be used as single or composite substrates depending on the required strength. Also,
The substrate may be subjected to a surface treatment or the like exhibiting good adhesiveness with the norbornene-based polymer according to the type.
The length of the drawing die used in the method for producing a continuous polymer molded article of the present invention is preferably 1 m50 cm or less from the viewpoint of processability, and most preferably about 1 m from the viewpoint of polymerization. In addition, it is preferable that the drawing die is heated to about 40 ° C. to 120 ° C.

The norbornene-based monomer used in the method for producing a polymer continuous molded article of the present invention is a monomer having a norbornene ring, and is a bicyclic compound such as norbornene or norbornadiene, dicyclodicyclopentadiene or dihydrodicyclopentadiene. Tricyclics such as, tetracyclododecene, ethylidenetetracyclododecene,
Tetracyclics such as phenyltetracyclododecene, pentacyclics such as tricyclopentadiene, heptacyclics such as tetracyclopentadiene and alkyl-substituted products thereof (for example,
Methyl, ethyl, propyl, butyl substituents, etc., alkylidene substituents (eg, ethylidene substituents), aryl substituents (eg, phenyl, tolyl substituents), epoxy groups, methacrylic groups, hydroxyl groups, amino groups,
Carboxyl group, cyano group, halogen group, ether group,
Derivatives having a polar group such as an ester bond-containing group are exemplified. Among these norbornene-based monomers, dicyclopentadiene is most preferred from the viewpoint of availability, reactivity, balance of physical properties of the polymer, price, and the like.

When it is desired to impart strength and heat resistance to the molded article, it may be cross-linked using a cross-linkable monomer, and 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-type monomers may be used alone or as a mixture of two or more kinds. Cyclobutene, cyclopentene, cyclopentadiene, cyclopentane, and cyclobutene which can be ring-opening-copolymerized with the norbornene-based monomers. 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 continuous 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. Various additives such as an imparting agent, 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 co-aggregate, EPDM, ethylene-vinyl acetate co-aggregate, and hydrides thereof. .

Next, the ruthenium-carbene complex of the 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, R 1 and R 2 independently represent hydrogen, a C 2 -C 5 -alkenyl group, a C 1 -C 5
Alkyl, phenyl, C1 -C5 -carboxylate, C1 -C5 -alkoxy, phenoxy or C2 -C5 -alkoxycarbonyl (which are
-C5 -alkyl, halogen, C1 -C5 -alkoxy, or C1 -C5 -alkoxy.
5-alkyl group, halogen, phenyl group substituted by C1 -C5 -alkoxy group), and X1 and X2 independently of one another are C1, Br, C1 -C5 -carboxy. Rate, C1
-C5 -alkoxy, phenoxy, C1 -C5 -alkylthio (which may be substituted by C1 -C5 -alkyl, halogen, C1 -C5 -alkoxy, or C1 -C5 -alkyl) L1 and L2 are independently of each other an aryl group or a C1 -C5 aryl group or a C1 -C5 alkyl group, which may be substituted by a phenyl group substituted by a C1 -C5 -alkoxy group. -C10 -alkylphosphine groups (these may be substituted by C1 -C5 -alkyl groups, halogen, C1 -C5 -alkoxy groups, or may be substituted by C1 -C5 -alkyl groups, halogen, C1 -C5 -alkoxy groups) Ruthenium-carbene, which is a neutral ligand from the group of Complexes are preferred.

Further 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.

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 because it is necessary to mix it with a certain amount of a norbornene-based monomer. A preferable example is a method of diluting the solvent for use. Examples of the solvent include toluene, benzene, tetrahydrofuran (THF), 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 represented by the general formula (II), although the stability in air is higher than that of the ruthenium-carbene complex represented by the general formula (I).

The mixing ratio of the ruthenium-carbene complex represented by the general formula (I) or the ruthenium vinylidene complex represented by the general formula (II) to the norbornene-based monomer is preferably in the range of 1/5 to 1 / 500,000 mol. ,
More preferably, it is in the range of 1/30 to 1/200000 mol. The mixing ratio of the catalyst may be set based on the necessary curing time in this range.

In the method for producing a continuous polymer molded article of the present invention, when a norbornene-type monomer and a catalyst are quantitatively kneaded and injected into a drawing die, both of them are supplied by a quantitative pump. In particular, since a strict quantitative supply is required for the supply of the catalyst, it is preferable to use a pump excellent in quantitative performance such as a gear pump.

Specific examples of the molded article formed by the pultrusion molding method of the present invention are as follows.
Examples thereof include a pipe in which an internal pressure is generated, and a hollow square member in which a shear is generated upon bending.

In the method for producing a continuously molded polymer of the present invention, when the norbornene-based monomer and the catalyst are quantitatively mixed and supplied into the drawing die, both of them are supplied by a quantitative pump. In particular, since the supply of the catalyst requires a strict quantitative supply, it is preferable to use a pump having excellent quantitative properties such as a gear pump. When kneading properties are particularly required, a kneading unit such as a static mixer or a dynamic mixer may be provided. Also,
The molded article formed by the method for producing a continuous polymer molded article of the present invention by the pultrusion molding method is suitable for use in a portion subjected to impact such as a reinforcing material for civil engineering or a road / railway reinforcing member.

<Action> In the present invention, since the norbornene-based monomer is polymerized using a ruthenium-carbene complex or a ruthenium vinylidene complex (catalyst) which is stable against oxygen and moisture, it is hardly cured even in the presence of air. It is possible to produce a norbornene-based polymer continuous molded article without causing defects. Thus, according to the present invention,
It is possible to polymerize norbornene-based monomers by applying pultrusion, a molding method in the presence of air, which was previously impossible, and obtain continuous norbornene-based polymer with high bending strength, bending elasticity and impact strength. be able to.
In addition, since there is no deactivation in the air, there can be obtained a norbornene-based polymer molded product which does not have poor curing at the interface, has no odor, and shows good physical properties.

Furthermore, since the reinforcing base material (fiber reinforced material) is drawn into the drawing die while being wound at an angle to the drawing direction, the drawing is performed. Vertical cracking at the time can be prevented. Therefore,
The manufacturing method of the present invention is very effective, for example, for forming a pipe in which a force is applied in the circumferential direction or for manufacturing a square member in which shear occurs.

[0036]

EXAMPLES Example 1 Monomer: dicyclopentadiene ruthenium-carbene complex: bis (tricyclohexylphosphine) benzylidene ruthenium dichloride Nonpolar solvent: toluene Base material: continuous mat (manufactured by Asahi Fiber Co., Ltd., 45)
Glass roving (Asahi Fiber Co., Ltd. 44)
50)

As shown in FIG. 1, a base material 10 (glass roving 12) for impregnation is inserted into the mold from the front of the drawing mold 3 along the outer peripheral surface of the mandrel 3a arranged in parallel with the drawing direction. Further, the base material 10 (continuous mat 11) is wound on the outermost layer by the hoop winder 9 at a winding angle of 90 °.
While being wound in parallel (parallel winding), a solution in which 20 parts of bis (tricyclohexylphosphine) benzylidene ruthenium chloride is dissolved in 100 parts of toluene is mixed with bis (tricyclohexylphosphine).
While quantitatively mixing with a gear pump such that the molar ratio of benzylidene ruthenium dichloride to dicyclopentadiene is 1/7000, the obtained polymerizable composition is drawn into a drawing mold 3 (60 mm × 60 mm ×
Injection into a 6 mm-thick hollow square material (length: 1 m) at a feed rate of 3 L / min., Heating and polymerization. It was withdrawn at 1.5 m / min.

The structure of the obtained molded body was as shown in the schematic sectional view of FIG. In FIG. 5, the member denoted by reference symbol P is a norbornene-based polymer. However, the fiber volume content was set to 50%. The drawing die 3 was heated to 80 ° C. by the heater 4. further,
The thickness of the outermost layer of the substrate 10 (11) was 3 mm. By the above-mentioned molding, a molded product in the shape of a hollow square member having high bending strength, bending elasticity and impact strength was obtained.

Example 2 Monomer: dicyclopentadiene ruthenium-carbene complex: bis (tricyclohexylphosphine) benzylidene ruthenium dichloride Nonpolar solvent: toluene Reinforcement substrate: continuous mat (manufactured by Asahi Fiber Co., Ltd.)
450th), glass roving (made by Asahi Fiber Co., Ltd.)
4450) Under the same conditions as in Example 1, the fiber volume content was set to 50%, and as shown in FIG. 2, the drawing die 3 was moved along the outer peripheral surface of the mandrel 3a arranged in parallel with the drawing direction. A base material 10 (glass roving 12) for impregnation is inserted into the mold from the front, and the base material 10 is added to the outermost layer by a woven winding machine 9.
(Continuous mat 11) knitting state (winding angle 4
(5 °) while being inserted into a mold, and the polymerizable composition is polymerized by injection and heating, and is cured integrally with the base material 10. 5m
/ Min. The structure of the molded body is as shown in the schematic sectional view of FIG. By the above-mentioned molding, a hollow square shaped article having high strength, rigidity and impact strength was obtained.

Example 3 Monomer: dicyclopentadiene ruthenium vinylidene complex: A compound represented by the following formula 5 was used.

[0041]

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

Non-polar solvent: Toluene Substrate: Continuous mat (Asahi Fiber Co., Ltd. 45
Glass roving (Asahi Fiber Co., Ltd. 44)
50)

As shown in FIG. 1, a base material 10 (glass roving 12) for impregnation is inserted into the mold from the front of the drawing mold 3 along the outer peripheral surface of the mandrel 3a arranged in parallel with the drawing direction. Further, the base material 10 (continuous mat 11) is wound on the outermost layer by the hoop winder 9 at a winding angle of 90 °.
While being wound in parallel (parallel winding), the ruthenium vinylidene complex 20 was added to 100 parts of toluene.
The resulting polymerizable composition was drawn out as shown in FIG. 1 while quantitatively mixing the solution in which the parts were dissolved by a gear pump so that the molar ratio of the ruthenium vinylidene complex to dicyclopentadiene was 1/3000. Mold 3 (60m
m × 60mm × thickness 6mm
In m), the mixture was injected at a feed rate of 3 L / min, polymerized by heating, and cured integrally with the base material 10 and pulled out at 1.5 m / min as a polymerization molded continuum by the drawing machine 6.

The structure of the obtained molded body was as shown in the schematic sectional view of FIG. In FIG. 5, the member denoted by reference symbol P is a norbornene-based polymer. However, the fiber volume content was set to 50%. The drawing die 3 was heated to 80 ° C. by the heater 4. further,
The thickness of the outermost layer of the substrate 10 (continuous mat 11) was 3 mm. By the above-mentioned molding, a molded product in the shape of a hollow square member having high bending strength, bending elasticity and impact strength was obtained.

Example 4 Monomer: dicyclopentadiene ruthenium-carbene complex: The same complex as in Example 3 was used. Non-polar solvent: toluene Reinforcement substrate: continuous mat (Asahi Fiber Co., Ltd.)
450th), glass roving (made by Asahi Fiber Co., Ltd.)
4450)

The fiber volume content was 50 under the same conditions as in Example 3.
2, and as shown in FIG. 2, the base material 10 (glass roving 1) for impregnating from the front of the drawing die 3 along the outer peripheral surface of the mandrel 3a disposed in parallel with the drawing direction.
2) is inserted into a mold, and further, the substrate 10 (continuous mat 11) is wound around the outermost layer in a knitting state (a winding angle of 45 °) by a woven-like winding machine 9, and inserted into the mold.
The polymerizable composition was polymerized by pouring and heating, and was integrally cured with the base material 10, and was pulled out at 1.5 m / min by a pulling machine 6 as a polymerized continuous body. The structure of the molded body is as shown in the schematic sectional view of FIG. By the above-mentioned molding, a hollow square shaped article having high bending strength, bending elasticity and impact strength was obtained.

Comparative Example 1 Resin component: Iso-unsaturated polyester Curing agent: Kayabutyl B manufactured by Kayaku Akzo Co., Ltd. Base material: Continuous mat (45 manufactured by Asahi Fiber Co., Ltd.)
Glass roving (Asahi Fiber Co., Ltd. 44)
50)

As shown in FIG. 6, a material obtained by impregnating the base material 10 with the iso-unsaturated polyester resin 15 in the impregnated layer 14 is pulled out by a drawing machine 6 into a drawing die 3 (60 mm × 6 mm).
It was drawn into a 0 mm x 6 mm thick hollow square material (length 1 m) at a speed of 0.7 m / min to perform pultrusion molding.
The drawing die 3 was heated to 145 ° C. by the heater 4. By the above-mentioned molding, a hollow square shaped article could be obtained, but the strength and impact characteristics were lower than those of Examples 1 and 2.

<Comparative Example 2> Monomer: Meton A liquid (containing dicyclopentadiene manufactured by Teijin Meton Co.), Meton B liquid (containing dicyclopentadiene manufactured by Teijin Meton Co.) Base material: Continuous mat (45 manufactured by Asahi Fiber Co., Ltd.)
Glass roving (Asahi Fiber Co., Ltd. 44)
50)

The fiber volume content was 50 under the same conditions as in Example 1.
%, And kneading the solution A and the solution B at a ratio of 1: 1 by the same injection method as in the example 1, and injects the mixture into the drawing die 3 shown in FIG. The base material 10 for impregnation (glass roving 12) is inserted into the mold from the front of the drawing die 3, and the hoop winder 8 is used to wind the base material 10 (continuous mat 11) on the outermost layer at a winding angle of 90.
Inserted into the mold while winding at a degree, and 1.
Pultrusion molding was performed at 5 m / min. In the above pultrusion molding,
The polymerizable composition was deactivated by the inhibition of oxygen due to oxygen inhibition, the methone did not cure by polymerization, and the molded product could not be pulled out.

Next, the molded products obtained in Examples 1 to 4 and Comparative Example 1 were subjected to bending strength (span 10%).
00 mm, crosshead speed 5 cm / min, jig shape conforms to JIS K 7055), flexural modulus (JIS
K 7055) and Izod impact (JIS K)
7110).

The results are shown in Table 1 below.

[0053]

[Table 1]

From the above results, it was found that the fiber-reinforced norbornene-type polymer continuous molded product obtained by the method for producing a continuous polymer molded product of the present invention by the pultrusion molding method was excellent in strength, elastic modulus and impact resistance. Also, it was found that sufficient impact strength could be obtained without reinforcing with fibers.

Further, in each of Examples 1 to 4, the polymerization proceeded sufficiently, and the result that there was almost no residual monomer was obtained. Thus, it was confirmed that a molded article having no odor could be obtained.

[0056]

As described above, the present invention uses a polymerizable composition containing a norbornene monomer and a ruthenium-carbene complex or ruthenium vinylidene complex represented by a specific general formula. According to the method for producing a polymer continuous molded article of the present invention, a norbornene-based polymer continuous molded article having high flexural strength, flexural elasticity and impact strength as compared with conventional products can be produced without causing curing failure and without being affected by the environment. In addition, equipment investment can be obtained with relatively little equipment and equipment. In addition, productivity can be improved. Further, although secondary, there is no polymerization inhibition of the norbornene-based monomer, so that the amount of residual monomer is reduced and a molded article with less odor can be obtained.

[Brief description of the drawings]

FIG. 1 is a schematic side view for explaining an example of a production apparatus that can suitably employ a method for producing a norbornene-based polymer continuous molded article of the present invention.

FIG. 2 is a schematic side view for explaining another example of a production apparatus that can suitably employ the method for producing a norbornene-based polymer continuous molded article of the present invention.

FIG. 3 is a view taken along the line XX of FIG. 1 and schematically shows a hoop winder.

4 is a view taken in the direction of arrows YY in FIG. 2 and schematically shows a woven winding machine.

FIG. 5 is an explanatory diagram of Embodiments 1 and 2 of the present invention.

FIG. 6 is an explanatory diagram of Comparative Example 1 of the present invention.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 Norbornene type monomer 2 Ruthenium-carbene complex or ruthenium vinylidene complex 3 Extraction mold 3a Mandrel 4 Heater 5 Pump 6 Extraction machine 7 Guide 8 Hoop winder 9 Textile winding machine 10 Base material 11 Continuous mat 12 Glass roving P Norbornene system polymer

Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat II (reference) C08L 65:00 F term (reference) 4F071 AA21 AB18 AB21 AB27 AH19 BA09 BB01 BB12 BC02 4F205 AA12L AB04 AD16 AH43 HA05 HA27 HA34 HA37 HA47 HB02 HF01 HF02 HL14 HT22 4J032 CA34 CA35 CA36 CA38 CA53 CA54 CB01 CB04 CC03 CC04 CD02 CE06 CE07 CE16 CG07

Claims (3)

[Claims] 1. A mandrel arranged in a drawing direction,
The substrate is inserted into a drawing mold while being wound at a predetermined winding angle, and the drawing mold contains a norbornene-based monomer and a ruthenium-carbene complex represented by the following general formula (I). Wherein the polymerizable composition is polymerized in a drawing mold and cured integrally with the base material, and is withdrawn as a polymerized and molded continuous body. Manufacturing method. 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 mandrel arranged in a drawing direction,
The substrate is inserted into a drawing die while being wound at a predetermined winding angle, and the drawing die contains a norbornene-based monomer and a ruthenium vinylidene complex represented by the following general formula (II). A polymerizable composition is supplied, and the polymerizable composition is polymerized in a drawing die and cured integrally with the base material. Production method. 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 together may form a polydentate chelating ligand) 3. The method for producing a norbornene-based polymer continuous molded article according to claim 1, wherein the norbornene-based monomer is dicyclopentadiene.