JP2000290355A - Reaction injection molding method or norbornene monomer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a reaction injection molding method whereby a good molded article similar to one obtained by the conventional method wherein a norbornene monomer is polymerized in a mold filled with nitrogen in place of air can be obtain while the polymerization is conducted in the presence of air by conducting the polymerization by mixing a norbornene monomer with a ruthenium-carbene complex or a ruthenium-vinylidene complex and simultaneously injecting the resultant mixture into a mold. SOLUTION: A norbornene monomer is polymerized by mixing it with a ruthenium-carbene complex of formula I or a ruthenium-vinylidene complex of formula II, as the catalyst, and simultaneously injecting the resultant mixture into a mold. Preferably, the mixing ratio of the catalyst to the monomer is (1/5)-(1/50,000). In the formulas, R1 and R2 are each H, 2-20C alkenyl, 1-20C alkyl, aryl, 1-20C carboxylate or the like; X1 to X4 are each an anionic ligand; L1 to L4 are each a neutral electron donor; and R3 and R4 are each the same as R1 or are each a ferrocene derivative group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a reaction injection molding method using a norbornene-based monomer.

[0002]

2. Description of the Related Art Techniques for polymerizing norbornene monomers have been generally known. For example, there is a reaction injection molding method in which air in a mold is replaced with an inert gas, and then a norbornene-based monomer is injected into the mold as a molding material to cause a polymerization reaction (Japanese Patent Publication No. 7-73859).
Reference).

[0003] However, when performing polymerization molding using a norbornene-based monomer, there is an important problem that the polymerization reaction is hindered by the presence of oxygen and water, and good polymerization does not proceed unless the atmosphere is completely inert. there were. That is, polymerization molding using a norbornene-based monomer can promote polymerization only in a closed space, and therefore, reaction injection molding (Reaction injection molding:
RIM) cannot be molded except by injection-molding the polymerizable composition in a closed mold. In particular, unless the inside of the mold is filled with an inert gas, polymerization is inhibited. And polymerized molded articles could not be obtained. When such a 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 the mold, and the solution is mixed in the mold. By injecting it as a polymerizable solution and causing a polymerization reaction,
A polymer molded product of a norbornene-based monomer was obtained. (Solution A) Solution containing norbornene monomer and activator and activity regulator (Solution B) Solution containing norbornene monomer and catalyst

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.

[0005] The above polymerizable solution is stored at a manufacturing site or the like until the reaction injection molding is performed after the catalyst, activator and activity regulator are mixed with the norbornene-based monomer. It was necessary to make the storage tank, the molding machine, and the like a structure capable of preventing the entry of moisture and air. Specifically, the air in the path through which the norbornene-based monomer passes, including the piping, is replaced with an inert gas (eg, nitrogen) as much as possible.
In addition, extra capital investment is required, and careful management is required.

Further, 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 of the inert gas in the mold, which is troublesome and has a problem that the quality is not stable. When a reinforcing material or the like is mixed, since the presence of water as well as air inhibits the polymerization reaction, it is necessary to evaporate the water by sufficient drying and the like.

[0007]

[Problems to be solved by the invention]

The present invention has been made in view of the above-mentioned problems of the conventional reaction injection molding method using a norbornene-based monomer, and is directed to a reaction injection molding machine or a reaction injection molding die in the presence of air. It is an object of the present invention to provide a reaction injection molding method capable of obtaining a molded product equivalent to a conventional reaction injection molding method in which air inside the mold is replaced with nitrogen even when polymerization is performed.

[0009]

The reaction injection molding method of the norbornene-based monomer 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] While mixing with a ruthenium vinylidene complex represented by
It is characterized by injecting a polymerizable composition containing both into a mold and polymerizing the norbornene-based monomer.

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 together may form a polydentate chelating ligand)

The norbornene monomer used in the reaction injection molding method of the present invention is preferably dicyclopentadiene from the viewpoint of easy availability, reactivity, balance of polymer properties, and the like.

As a more specific example of the reaction injection molding method of the present invention, as shown in FIG. 1, a norbornene-based monomer 1 and a ruthenium-based compound represented by the general formula [I], which is stable to oxygen and moisture, The solution 2 of the carbene complex or the ruthenium vilinidene complex represented by the general formula [II] is supplied to the mixing head 5 by a constant amount using the metering pumps 3 and 4, and mixed under high pressure by the mixing head 5. A method of continuously injecting a given amount of a polymerizable composition obtained continuously and containing a norbornene-based monomer 1 and a ruthenium-carbene complex or a ruthenium vilinidene complex into a mold 6. Can be mentioned. And the polymerizable composition injected into the mold in this way rapidly initiates polymerization even in an air atmosphere, so that even without nitrogen replacement, a good quality norbornene-based polymer molded article can be obtained. Can be.

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.

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.

The ruthenium represented by the general formula [I]
As for the carbene complex or the ruthenium vinylidene complex represented by the general formula [II], the polymerizable composition obtained by continuously mixing with a certain amount of a norbornene-based monomer to form a polymerizable composition is converted into a liquid form by continuous mixing. It is preferable to make it liquid so that it can be poured into a molding die. 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 reaction injection molding method of the norbornene monomer of the present invention, the mixing ratio of the ruthenium-carbene complex to the norbornene monomer is 1/5 to 1/5.
A range of 00000 moles is preferred. More preferably, 1
/ 30 to 1/200000 mol. In this range, the mixing ratio of the catalyst may be set to the necessary curing time.

In order to mix and inject and inject a monomer and a catalyst into a mold, for example, a solution obtained by dissolving a catalyst in a solvent such as toluene while sucking a norbornene-based monomer in a tank by a pump is used. There is a method in which the mixture is subjected to collision mixing at a high pressure by a mixing head while being supplied in a fixed amount by a pump, and then injected into a molding die. Also, while pumping up the norbornene-based monomer in the tank and similarly supplying a solution of the dissolved catalyst to the norbornene-based monomer by the pump at a constant rate, the mixture is subjected to high-pressure collision mixing, and then injected into the mold. May be adopted. Mixing of the monomer and the catalyst may be performed by impingement mixing using a pump pressure or by a dynamic mixer.

Although the injection amount of the polymerizable composition depends on the shape of the mold, it is 10 cc / sec to 40 L / sec, preferably 100 cc / sec.
cc / sec to 20 L / sec is desirable. If it is less than 10 cc / sec, it hardens during injection and it is difficult to completely fill it. If it exceeds 40 L / sec, there is a possibility of backflow. The mold may or may not be heated.

Here, in the reaction injection molding method of the present invention, when a fiber-reinforced norbornene-based polymer molded article is molded, the polymerizable composition is injected into the mold with the fiber reinforcing material disposed in the mold. -The method of injection may be adopted.

As the fiber reinforcing material, it is preferable to use a fibrous body in a mat state, a cross state or a knit state, or a preforming material produced by spraying chopped strands. In particular, in consideration of the impregnation property, it is preferable to use a fibrous body in a mat state (for example, continuous mat) or a preformed material using chopped strands.

In the fiber-reinforced norbornene polymer molded article obtained by the reaction injection molding method of the present invention, the fiber volume content of the fiber reinforcing material is preferably 3% to 60%, more preferably 7% to 40%. %. If it exceeds 60%, the resin does not impregnate well and backflow is likely to occur, and if it is less than 3%, the reinforcing effect is hardly exhibited.

Examples of the type of the fiber reinforcing material include inorganic fibers, organic fibers, and natural fibers. Preferred examples thereof include glass fibers, carbon fibers, aramid fibers, jute fibers, and kenaf fibers. .

<Action> The present invention relates to a method for reaction injection molding of norbornene monomers. That is, the present invention provides a method for producing a reaction injection molded article by a polymerization reaction of a norbornene-based monomer. According to the present invention, even in the presence of air, that is, even in a reaction injection molding machine or a reaction injection mold in the presence of air, the same as that obtained by performing polymerization of the norbornene-based monomer by replacing the internal air with nitrogen. A high quality norbornene-based polymer molded article can be obtained. In addition, even when compounded with a fiber reinforcing material, a fiber-reinforced norbornene-based polymer molded product showing good physical properties without curing failure at the interface can be obtained. Furthermore, since the curing failure can be greatly reduced as compared with the conventional norbornene-based polymer molded product, a molded product having less residual monomer and less odor can be obtained.

[0024]

EXAMPLES <Example 1> Monomer: dicyclopentadiene ruthenium-carbene complex: bis (tricyclohexylphosphine) benzylidene ruthenium dichloride Solvent: toluene The reaction injection molding apparatus shown in FIG. 1 was used. The operation of purging the air inside and in the tank with an inert gas such as nitrogen gas was not performed (hereinafter, the examples are the same as in Example 4).

Bis (tricyclohexylphosphine) benzylidene ruthenium chloride 20 was added to 200 parts of toluene.
Part 2 of the solution 2 (tank storage) was dissolved in bis (tricyclohexylphosphine) benzylidene ruthenium chloride at a molar ratio of 1/8 to dicyclopentadiene 1.
000, together with dicyclopentadiene 1
It is supplied to the mixing head 5 by the gear pumps 3 and 4,
While performing high-pressure quantitative collision mixing with the mixing head 5, the polymerizable composition was placed in a mold 6 for molding a flat plate (thickness 6 mm, size 200 mm □) at a pressure of 0.3 MPa.
40 cc was injected and injected in 3 seconds.

After 2 minutes, the mold was released to obtain a flat plate 7 (see FIG. 2) which was a molded product made of polydicyclopentadiene. The resulting molded article had a low odor, no stickiness on the surface, and good curability was confirmed. The mold temperature during molding was 20 ° C.

<Comparative Example 1> 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 and dicyclo Solution composed of pentadiene (trade name: Meton: manufactured by Teijin Meton Co., Ltd.) The above-mentioned raw material was molded using the apparatus shown in FIG. Most of the molded articles were uncured and could not be used as products. The air was not purged by nitrogen in the mold and the piping.

<Comparative Example 2> In the apparatus shown in FIG. 1, only the tank for storing the liquid A and the liquid B was purged with nitrogen or the like in advance. Thereafter, when molding was performed under the same molding conditions as in Comparative Example 1, a cured molded product could be obtained, but a strong monomer odor remained in the molded product.

<Example 2> Monomer: dicyclopentadiene Fiber reinforcing material: continuous mat (450 # manufactured by Asahi Fiber Co., Ltd.) Four continuous mats were laminated in a mold 6 shown in FIG. 1 under the same conditions as in Example 1. Then, it was molded by a reaction injection molding method using dicyclopentadiene. As a result, a molded article made of polydicyclopentadiene having high strength and high rigidity with little monomer odor was obtained.

<Comparative Example 3> Fiber reinforcing material: glass continuous mat (450 # manufactured by Asahi Fiber Co., Ltd.) Four continuous mats were laminated in a mold 6 shown in FIG. 1 and dicyclopentadiene was obtained under the same conditions as in Comparative Example 2. Was molded by reaction injection molding, but polymerization failure occurred partially due to air entrainment in the glass mat, and a molded product with high strength and high rigidity could not be obtained.

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

[0032]

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

Solvent: Toluene The reaction injection molding apparatus shown in FIG. 1 was used, but the operation of purging the air in the mold and the tank with an inert gas such as nitrogen gas in advance as in the prior art was not performed.

A solution 2 (tank storage) obtained by dissolving 20 parts of a ruthenium vinylidene complex in 200 parts of toluene was mixed with dicyclopentadiene 1 so that the molar ratio of the ruthenium vinylidene complex to dicyclopentadiene 1 was 1/4000. While being supplied to the mixing head 5 by the gear pumps 3 and 4 and performing constant-quantity collision mixing by the mixing head 5, a flat plate (thickness: 6 mm, size: 200 mm)
□) The polymerizable composition was placed in a mold 6 for molding at a pressure of 0.
240 cc was injected and injected at 3 MPa for 3 seconds.

After 2 minutes, the mold was released, and a flat plate 7 (see FIG. 2) of a molded article made of polydicyclopentadiene was obtained.
The resulting molded article had a low odor, no stickiness on the surface, and good curability was confirmed. The mold temperature during molding was 60 ° C.

Example 4 Monomer: dicyclopentadiene Fiber reinforcement: continuous mat (450 # manufactured by Asahi Fiber Co., Ltd.) Four continuous mats were laminated in a mold 6 shown in FIG. 1 under the same conditions as in Example 3. Then, it was molded by a reaction injection molding method using dicyclopentadiene. As a result, a flat plate 7 of a high-strength and high-rigidity molded article of polydicyclopentadiene having a low monomer odor was obtained.

Examples 1 and 2 and Comparative Example 1
The bending strength (JIS
K 7055), flexural modulus (JIS K 705)
5) and Izod impact (JIS K 711)
Each physical property value of 0) was measured. The Izod impact was measured using a notched test piece.

The results are shown in Table 1 below. From the above results, it is apparent that the fiber-reinforced norbornene-based polymer obtained by the reaction injection molding method of the present invention is excellent not only in strength and elastic modulus but also particularly in impact resistance and heat resistance.

[0039]

[Table 1]

[0040]

As described above, according to the present invention,
Even in the presence of air, that is, by a reaction injection molding machine or a reaction injection mold in the presence of air, the same good norbornene-based as obtained by polymerizing norbornene-based monomers by replacing the air inside with nitrogen. A polymer molded article can be obtained. Since it is not necessary to replace the storage tank, the molding machine, and the mold with nitrogen, equipment can be simplified as compared with the conventional reaction injection molding method. Furthermore, since the curing failure can be greatly reduced as compared with the conventional norbornene-based polymer molded product, a molded product having less residual monomer and less odor can be obtained. In addition, since interfacial adhesion failure due to curing failure does not occur at the time of fiber composite, a fiber-reinforced norbornene-based polymer molded article having high strength and high elastic modulus can be easily obtained.

[Brief description of the drawings]

FIG. 1 is an explanatory view of one example of a reaction injection molding method of a norbornene-based monomer of the present invention.

FIG. 2 is a perspective view showing a flat plate (molded body) obtained in Example 1 of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Dicyclopentadiene (norbornene-type monomer) 2 Solution (catalyst) 3, 4 Gear pump 5 Mixing head 6 Mold 7 Mold plate (molded article)

Claims (3)

[Claims] 1. A mixture obtained by mixing 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. And a polymerizable composition containing both of them is injected into a mold to polymerize the norbornene-based monomer. 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
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) 2. The method for reaction injection molding of norbornene-based monomers according to claim 1, wherein the polymerizable composition is injected into the mold while the fiber reinforcement is placed in the mold. 3. The method according to claim 1, wherein the norbornene-based monomer is dicyclopentadiene.