JP2001126944A - Production of coil molding - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a production of coil molding, which reduces the occurrence of molding defects and is industrially advantageous. SOLUTION: A undiluted reaction solution at least containing (a) a norbornane monomer and (b) a complex, with which a neutral electron donor and/or heteroatom contained carbene compound is coordinated in ruthenium as a ligand, is fed into a metal die, where a wiring coil is located, and is bulk- polymerized. It is preferable the undiluted reaction solution further contain (c) Lewis acid.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method of manufacturing a coil formed body used as a ground coil for a magnetic levitation railway, for example.

[0002]

2. Description of the Related Art A molded article obtained by a reaction injection molding (RIM) method has excellent mechanical properties, impact resistance and weather resistance, and has been proposed for application to a wide range of fields. RIM
As one of the application examples of the molded product, a magnetically levitated railway coil molded product is manufactured by supplying a stock solution containing a norbornene-based monomer and a metathesis catalyst into a mold in the presence of a winding coil and performing bulk polymerization. (For example, Japanese Patent Application Laid-Open No. 4-168704, Japanese Patent Application Laid-Open
JP-A-5-2845, JP-A-10-96593, JP-A-10-296792, JP-A-10-3
No. 15267).

Further, the above publication discloses a molybdenum-based or tungsten-based metathesis catalyst (main catalyst) such as tridodecylammonium molybdate, tri (tridecyl) ammonium molybdate, tungsten hexachloride, etc.
JP-A-58-127728, JP-A-4-2261
No. 24, JP-A-58-129003 and JP-A-6-145247, which are used together with a metathesis cocatalyst such as an alkyl aluminum, an alkyl aluminum halide, an alkoxyalkyl aluminum halide and an arylalkyl aluminum halide. Thus, a method for forming a metathesis catalyst system and performing RIM molding is disclosed.

However, in such a conventional production method, the metathesis catalyst system is extremely sensitive and unstable to water, oxygen, and a compound having a polar group in the atmosphere. Deformation is likely to occur due to deactivation. (2) A step of thoroughly drying a reinforcing material such as glass fiber is required. (3) The surface of the reinforcing material is subjected to coupling treatment with a silane coupling agent or the like. However, there is a problem that the cost of the auxiliary material is increased because the required material is required.

[0005]

In recent years, various ruthenium complexes have been reported as catalysts for ring-opening polymerization of cyclic olefins. For example, Japanese Translation of International Patent Publication No. 10-5088
No. 91 describes a complex compound in which a tertiary phosphine ligand or the like is bound to at least one kind of divalent cationic compound of ruthenium or osmium. Japanese Patent Publication No. 9-512828 discloses a ruthenium or osmium metal carbene complex compound having various ligands, and describes an experimental example in which the compound is used as a catalyst for bulk polymerization of dicyclopentadiene. These publications state that ruthenium complex catalysts have the advantage of being relatively less susceptible to the effects of deactivators such as water and air during the polymerization of cyclic olefins.

Japanese Patent Application Laid-Open No. 10-338839 discloses a method for producing a molded article in which a curable two-component system comprising a ruthenium complex and a tensioned cycloolefin is introduced into a mold by the RIM method, and the cured product is cured. Have been. Also described is the use of a curable two-component system as encapsulating material for electrical or electronic components.

[0007] JP-A-10-80933 discloses the production of a fiber-reinforced composite material comprising injecting a reactive resin mixture comprising a ruthenium complex into a molding die into which a woven fabric has been charged, and then curing the mixture. A method is disclosed.
It also describes the use of fiber reinforced composite materials to produce molding tools or articles for building automobiles, aircraft or sports facilities.

[0008] However, the above publication does not mention at all that the curable two-component system or the reactive resin mixture is used for producing a coil molding for a magnetically levitated railway or the like. As described above, it has not yet been achieved to supply a reaction stock solution containing a ruthenium complex into a mold and perform reaction injection molding to produce a coil molded body on an industrial scale. There was a need to establish a method of manufacturing the body.

SUMMARY OF THE INVENTION An object of the present invention is to solve the problems of the prior art and to provide a method for producing a coil molded product which is industrially advantageous in that the occurrence of molding defects is extremely small.

[0010]

In order to achieve the above object, a method for producing a coil molded product according to the present invention comprises: (a) a norbornene-based monomer; and (b) a ruthenium-containing neutral electron donor. Supply of a reaction solution containing at least a complex (ruthenium complex) in which a carbohydrate compound and / or a heteroatom-containing carbene compound is coordinated to a mold in which a winding coil is disposed to perform bulk polymerization It is characterized by.

Preferably, the unreacted solution further contains (c) a Lewis acid.

As the winding coil, for example, a winding coil used for a magnetic levitation railway is used. A winding coil used in a magnetic levitation railway is an air-core coil without an iron core wound around a conductive wire, and the wire is usually coated with an insulating material or the like and used as an insulated wire. Specific examples of the conductive wire used for the winding coil include aluminum, copper, iron, nickel, gold, silver and other general magnetic metals and mixtures thereof as materials, and the winding coil reduces cost, Aluminum is preferred for reasons such as weight reduction and workability. The cross-sectional shape of the conductive wire is
Although a polygon, a circle, etc. are mentioned, a rectangle is preferable from workability, and the width of a rectangle is 1-20 mm, preferably 3-10 m.
m, the thickness is 1 to 20 mm, preferably 3 to 10 mm. Examples of insulated coated wire include epoxy powder coated flat wire, polyethylene powder coated flat wire, paper wound flat wire, Nomex flat wire, Kapton wound flat wire, laminated mica flat wire, glass wound flat wire, flat formal A wire with an epoxy powder coating is particularly preferable because it does not inhibit the bulk ring-opening polymerization reaction of the norbornene-based monomer and its processability. The coating thickness of the insulated wire is 0.01
１1 mm, preferably 0.03 to 0.5 mm, more preferably 0.05 to 0.1 mm.

[0013]

The present inventors have conducted extensive studies and found that the use of a reaction stock solution containing at least a norbornene-based monomer and a ruthenium complex reduces the possibility of deactivating the catalyst system under the influence of moisture or air in the atmosphere. Even if surface treatment (silane coupling treatment) of glass fiber or the like used as a reinforcing material is not required, and the reinforcing material is not sufficiently dried before forming, it can be efficiently used, for example, coil forming used in a magnetic levitation railway. It has been found that the body can be manufactured. That is, according to the present invention, it is possible to provide an industrially advantageous method for manufacturing a coil molded body, in which the occurrence of molding defects is significantly reduced.

Further, by further containing a Lewis acid in the reaction stock solution, the polymerization reactivity of the reaction stock solution is further increased, and it is possible to produce a coil molding more efficiently.

Examples of the coil molded body include a wound coil molded body used in a magnetic levitation railway.

[0016]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, an embodiment of a method for manufacturing a coil formed body according to the present invention will be described.

In this embodiment, a method for manufacturing a coil-formed body used as a magnetic levitation type railway coil will be described as an example of a method for manufacturing a coil-formed body.

The wound coil molded body according to the present embodiment comprises:
It contains at least (a) a norbornene-based monomer and (b) a complex (ruthenium complex) in which a neutral electron donor and / or a heteroatom-containing carbene compound is coordinated as a ligand with ruthenium, and preferably ( c) It is produced by supplying a reaction stock solution also containing a Lewis acid into a mold in which a winding coil is arranged and performing bulk polymerization.

(A) Norbornene Monomer The norbornene monomer may be any as long as it has a norbornene ring. However, since a molded article excellent in heat resistance can be obtained, a polycyclic norbornene monomer having three or more rings is used. Is preferred.

Specific examples of norbornene-based monomers include bicyclics such as norbornene and norbornadiene; tricyclics such as dicyclopentadiene and dihydrodicyclopentadiene; tetracyclics such as tetracyclododecene; and pentacyclics such as tricyclopentadiene. Ring; heptacyclic such as tetracyclopentadiene; substituted products such as alkyl such as methyl, ethyl, propyl and butyl; alkenyl such as vinyl; alkylidene such as ethylidene; aryl such as phenyl, tolyl and naphthyl; Ester group, ether group,
Substituents having a polar group such as a cyano group and a halogen atom are exemplified. These monomers may be used in combination of one or more kinds. Tricyclic, tetracyclic, or pentacyclic monomers are preferred from the viewpoints of easy availability, excellent reactivity, and excellent heat resistance of the obtained resin molded article.

Among the norbornene-based monomers, the ring-opening polymer produced is preferably of a thermosetting type. For this purpose, a reactive double-opening polymer such as dicyclopentadiene, tricyclopentadiene or tetracyclopentadiene is used. Those containing at least a crosslinkable monomer having two or more bonds are used. The proportion of the crosslinkable monomer in all the norbornene monomers is usually at least 10% by weight, preferably at least 30% by weight.

Incidentally, within a range not to impair the object of the present invention,
Monocyclic cycloolefins such as cyclobutene, cyclopentene, cyclopentadiene, cyclooctene and cyclododecene, which can be ring-opening copolymerized with norbornene monomers,
It may be used as a comonomer.

(B) Ruthenium Complex The ruthenium complex is not particularly limited.
Ruthenium complexes represented by the following general formulas [1] to [3] are used.

[0024]

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(In the formula [1], X ₁ independently represents any anionic ligand, and L ₁ independently represents any neutral electron donor and / or a heteroatom-containing carbene compound. Two, three or four of X ₁ and L ₁ may be linked together to form a polydentate chelating ligand, m is an integer from 0 to 2 and n is 1 to 3 It is an integer. Z is 1 or 2.)

[0026]

Embedded image

(In the formula [2], R₁And R₂Is
Independently hydrogen, halogen, oxygen, nitrogen
May contain atoms, sulfur atoms, phosphorus atoms, silicon atoms
C₁~ C₂₀X represents a hydrocarbon group of₂And X₃
Each independently represents an anionic ligand. L
₂And L₃Any, neutral children independent of each other
A donor and / or heteroatom containing carbene compound
You. R₁, R₂, X ₂, X₃, L₂, L₃
2, 3, 4 or 5 of
A rated ligand may be formed. )

[0028]

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(In the formula [3], R ₃ and R ₄ independently represent hydrogen, or C ₁ -C ₂₀ which may contain a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, or a silicon atom. X ₄ and X ₅
Each independently represents an anionic ligand. L
₄ and L ₅ each independently represent any neutral electron donor and / or heteroatom-containing carbene compound. R
₃ , R ₄ , X ₄ , X ₅ , L ₄ , and L ₅
The three, four, or five may be joined together to form a polydentate chelating ligand. The "carbene compound" is a generic term for compounds having a methylene free radical, and refers to a compound having an uncharged divalent carbon atom represented by (> C :). The carbene is generally present as an unstable intermediate generated during the reaction, but can be isolated as a relatively stable carbene compound having a hetero atom. The “hetero atom” refers to an atom belonging to Group 15 and Group 16 of the periodic table, and specifically includes a nitrogen atom, oxygen atom, phosphorus atom, sulfur atom, arsenic atom, selenium atom, and the like. Can be mentioned. Among them, a nitrogen atom, an oxygen atom, a phosphorus atom, and a sulfur atom are preferable for obtaining a stable carbene compound, and a nitrogen atom and a phosphorus atom are particularly preferable.

Specific examples of the hetero atom-containing carbene compound include 1,3-diisopropyl-imidazole-2-
Ilidene, 1,3-dicyclohexyl-imidazole-
2-ylidene, 1,3-di (methylphenyl) -imidazole-2-ylidene, 1,3-di (methylnaphthyl)
-Imidazole-2-ylidene, 1,3-diadamantyl-imidazole-2-ylidene, 1,3-diphenyl-imidazole-2-ylidene, 1,3,4,5-tetramethyl-imidazole-2-ylidene, 1 , 3,4
5-tetraphenyl-imidazole-2-ylidene, bis (diisopropylamino) carbene, 1,2,4-triazine-5-ylidene, 3- (2,6-diisopropylphenyl) -2,3-thiazol-2-ylidene And the like.

Of these, those in which the heteroatom adjacent to the carbene has a bulky substituent, specifically 1,3-diispropyl-imidazole-2-ylidene, 1,3-dicyclohexyl-imidazole-2 −
Ylidene, 1,3-di (methylphenyl) -imidazole-2-ylidene, 1,3-di (methylnaphthyl) -imidazole-2-ylidene, 1,3-diadamantyl-
Imidazole-2-ylidene, 1,3-diphenyl-imidazole-2-ylidene, 1,3,4,5-tetraphenyl-imidazole-2-ylidene, 1,2,4-triazine-5-ylidene, 3- ( 2,6-diisopropylphenyl) -2,3-thiazol-2-ylidene.

The anionic ligand in the formulas [1] to [3] may be any ligand as long as it has a negative charge when separated from the central metal. The neutral electron donating compound may be any ligand as long as it is a ligand having a neutral charge when separated from the central metal, that is, a Lewis base.

X ₁ , X ₂ , X ₃ , X ₄ and X
Specific examples of ₅ include halogen atoms such as F, Br, Cl and I, hydrogen, acetylacetonato group, diketonate group, substituted cyclopentadienyl group, substituted allyl group,
Alkenyl, alkyl, aryl, alkoxy, aryloxy, alkoxycarbonyl, carboxyl, alkyl or arylsulfonate, alkylthio, alkenylthio, arylthio, alkylsulfonyl, alkylsulfinyl, etc. Can be mentioned.

Specific examples of the neutral electron donor include oxygen,
Water, carbonyl, amines, pyridines, ethers,
Nitriles, esters, phosphines, phosphinites, phosphites, stibines, sulfoxides,
Examples include thioethers, amides, aromatic compounds, cyclic diolefins, olefins, isocyanides, thiocyanates, and the like.

Specific examples of R ₁ , R ₂ , R ₃ and R ₄ include hydrogen, alkenyl, alkynyl, alkyl, aryl, carboxyl, alkoxy, alkenyloxy, alkynyloxy, aryloxy Groups, alkoxycarbonyl groups, alkylthio groups, arylthio groups, alkylsulfonyl groups, alkylsulfinyl groups, and the like.

Specific examples of the ruthenium complexes represented by the above formulas [1] to [3] include the following.

That is, as an example of the general formula [1],
(P-cumene) tricyclohexylphosphine ruthenium dichloride, bis (tricyclohexylphosphine)
Ruthenium dichloride, [1,3-di (methylphenyl) -imidazole-2-ylidene] (p-cymene) ruthenium dichloride and the like; Examples of the general formula [2] include:
Benzylidenebis (tricyclohexylphosphine) ruthenium dichloride, (phenylthiomethylene) bis (triisopropylphosphine) ruthenium dichloride, bis (1,3-diisopropyl-imidazole-2)
-Ylidene) benzylidene ruthenium dichloride, bis (1,3-dicyclohexyl-imidazole-2-ylidene) benzylidene ruthenium dichloride, [1,3-
Bis (2,4,6-trimethylphenyl) -imidazole-2-ylidene] (tricyclohexylphosphine)
Benzylidene ruthenium dichloride, [1,3-bis (2,4,6-trimethylphenyl) -imidazole-
2-ylidene] (pentamethylcyclopentadienyl)
Benzylidene ruthenium dichloride; general formula [3]
Specific examples of phenylvinylidenebis (tricyclohexylphosphine) ruthenium dichloride, bis (1,3-diisopropyl-imidazole-2-ylidene) phenylvinylideneruthenium dichloride, [1,
3-bis (2,4,6-trimethylphenyl) -imidazole-2-ylidene] (tricyclohexylphosphine) t-butylvinylidene ruthenium dichloride.

In the present invention, the ratio of the ruthenium complex to the norbornene-based monomer is usually from 1: 100 to 2,000,000, preferably from 1: 500 to 1, as represented by the molar ratio of (metal ruthenium in the ruthenium compound: norbornene-based monomer). 1,000,000, more preferably 1: 1000 to 500,000. If the amount of the ruthenium complex is too large, the cost increases, and if it is too small, sufficient activity cannot be obtained.

The ruthenium complex can be used by dissolving it in a monomer under conditions where the polymerization of the norbornene monomer does not proceed. In addition, as long as the properties of the product are not essentially impaired, the product may be suspended or dissolved in a small amount of a solvent without dissolving in the monomer.

Examples of the solvent for suspending or dissolving the ruthenium complex include aliphatic hydrocarbons such as pentane, hexane and heptane; cyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane,
Alicyclic hydrocarbons such as trimethylcyclohexane, ethylcyclohexane, diethylcyclohexane, decahydronaphthalene, norbornane, tricyclodecane, and cyclooctane; aromatic hydrocarbons such as benzene, toluene, and xylene; nitrogen-containing such as nitromethane, nitrobenzene, and acetonitrile Ethers such as diethyl ether and tetrahydrofuran; and halogen-containing hydrocarbons such as chloroform, dichloromethane, chlorobenzene and dichlorobenzene.

Among these solvents, industrially used aromatic, aliphatic and alicyclic hydrocarbons and ethers are preferred, and alicyclic hydrocarbons such as cyclohexane are more preferred.

(C) Lewis Acid The Lewis acid is not particularly limited as long as it is an electron pair acceptor defined by Lewis, and usually includes Lewis acids represented by the following general formulas [4] to [5]. .

[0043]

Embedded image

[0044]

Embedded image(In the formulas [4] and [5], M₁Is the third group of the periodic table
Or a group 13 element, for example, aluminum,
Element and scandium. M₂Is the periodic table
Periphery of Group 4 element or third period or less (below germanium)
Shows Group 14 elements in the Periodic Table, for example, titanium, tin, zircon
For example. X₆, X₇, X₈ , X₉,
X₁₀, X₁₁And X₁₂Are, independently of each other,
Atom, halogen atom, oxygen atom, nitrogen atom, sulfur atom
C which may contain a yellow atom, a phosphorus atom and a silicon atom₁~
C₂₀Represents a hydrocarbon group. ) X₆, X₇, X₈, X₉, X₁₀, X₁₁And
And X₁₂Specific examples of F, Br, Cl and I
Such as halogen atom, acetylacetonato group, diketone
, A substituted cyclopentadienyl group, a substituted allyl group,
Alkenyl group, alkyl group, aryl group, alkoxy
Group, aryloxy group, alkoxycarbonyl group, car
Boxyl group, alkyl or aryl sulfonate
Group, alkylthio group, alkenylthio group, arylthio
Group, alkylsulfonyl group, alkylsulfinyl group
Can be mentioned.

Preferred examples of the above formula [4] include trialkoxyaluminum, triphenoxyaluminum, dialkoxyalkylaluminum, alkoxydialkylaluminum, trialkylaluminum, dialkoxyaluminum chloride, alkoxyalkylaluminum chloride, dialkylaluminum chloride, trialkylaluminum chloride and trialkylaluminum chloride. Alkoxy scandium.

Preferred examples of the formula [5] include tetraalkoxytitanium, tetraalkoxytin, and tetraalkoxyzirconium.

Examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group and an n-octoxy group. If a halogen-containing alkoxy group having a halogen bonded to the β-position is used in addition to these alkoxy groups, not only the reaction rate is improved but also the reaction rate is increased, so that it is particularly preferably used.

Specific examples of such a halogen-containing alkoxy group include 2-chloroethoxy group, 2,2-dichloroethoxy group, 2,2,2-trichloroethoxy group,
-Chloro-1-propoxy group, 1,3-dichloro-2-
A propoxy group, a 1,1-dichloro-2-propoxy group,
1,1,1-trichloro-2-propoxy group, hexachloro-2-propoxy group, 2-chloro-2-propene-
1-oxy group, 2-chloro-1-butoxy group, 1-chloro-3-methoxy-2-propoxy group, 1,3-dibromo-2-propoxy group, 1,3-diiodo-2-propoxy group, 2 -Chlorocyclohexoxy group and the like. Among these, a 1,3-dichloro-2-propoxy group is particularly preferred.

The alkyl group includes a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-
Examples thereof include a butyl group and a sec-butyl group.

In the present invention, the ratio of the Lewis acid to the ruthenium complex is usually 1: 0.0 when expressed by the molar ratio of (metal ruthenium in the ruthenium compound: Lewis acid).
It is 5-100, preferably 1: 0.2-20, more preferably 1: 0.5-10. Even with too much Lewis acid,
If the amount is too small, a sufficiently high polymerization activity cannot be obtained. In this way, by providing a catalyst system comprising a combination of a ruthenium complex and a Lewis acid, the catalytic activity is further enhanced.

Other Ingredients In the present invention, an antioxidant, a filler, a pigment, a colorant, a foaming agent, a sliding agent, a flame retardant, a combustible, an elastomer, and the like may be added to the reaction stock solution, if necessary. Can be blended, and the properties of the resulting molded article can be modified.

Examples of the antioxidant include various antioxidants for plastics and rubbers such as phenol, phosphorus and amine. As fillers, glass, talc,
Inorganic fillers such as calcium carbonate, mica, potassium titanate and calcium sulfate are exemplified. Examples of the flame retardant include various flame retardants such as halogen-based, phosphorus-based, and inorganic-based flame retardants.

In particular, for the purpose of obtaining a molded article having high mechanical strength, a fiber reinforcing material may be filled in a mold in advance, and then a reaction stock solution may be injected into the mold and cured.

As the fiber reinforcing material, a material having good mechanical strength and heat resistance is used.
Examples include glass fiber, aramid fiber, ultrahigh molecular weight polyethylene fiber, polypropylene fiber, cotton, acrylic fiber, boron fiber, silicon carbide fiber, and alumina fiber. In addition, these reinforcing materials can be used in various shapes, such as those obtained by matting a long fiber or chopped strand, those woven into a cloth, and those in a chopped shape. The filling amount of the reinforcing material is not particularly limited, but is usually 10% by weight or more, preferably 20 to 60% by weight based on the weight of the molded body. If the filling amount is small, the ratio of the mechanical strength is small, and if the filling amount is too large, there is a tendency that uniform filling is not achieved and unevenness occurs or filling is hindered.

For the purpose of adjusting the viscosity of the reaction stock solution, an elastomer may be blended with the reaction stock solution. As the elastomer used, natural rubber, polybutadiene, polyisoprene, styrene-butadiene copolymer, styrene-butadiene-styrene block copolymer, styrene-isoprene-styrene copolymer, ethylene-propylene-
Examples include diene-based elastomers such as diene-based polymers, ethylene-vinyl acetate copolymers, and hydrides thereof. Preferably, a diene-based elastomer, more preferably a butadiene-based elastomer, particularly preferably, a block copolymer of styrene and butadiene or isoprene or cis-1,4-polybutadiene is used. By adding these elastomers to the reaction stock solution, the impact resistance of the resulting molded article is also improved. The amount of the elastomer to be added is appropriately selected so that the viscosity of the reaction solution at 30 ° C. is in the range of 5 cps or more, preferably 50 cps or more, and 1000 cps or less, preferably 500 cps or less.

These additives may be preliminarily mixed with the reaction stock solution or may be put in the mold cavity.

Undiluted Reaction Solution As the undiluted reaction solution in the present invention, the above-mentioned norbornene-based monomer, ruthenium catalyst, Lewis acid and optional components prepared by dividing into two or more solutions are used. The bulk unreacted solution is not bulk-polymerized with only one solution, but if all of the solutions are mixed, each component has a predetermined ratio, and the norbornene-based monomer may be separated so as to undergo bulk polymerization, and the method of separation is not particularly limited.

Each of the liquids thus divided constitutes a reaction stock solution in the present invention. For example, a first liquid comprising a norbornene-based monomer and a Lewis acid and a second liquid in which a ruthenium complex is dissolved in a solvent do not polymerize as they are, but the total amount of each component contained in the two liquids is the present invention. If the amounts of the components are used, these two solutions are the reaction stock solutions used in the present invention, respectively, and when they are mixed, they react to form bulk polymerization of the norbornene-based monomer.

From the viewpoint of workability, bulk polymerization is usually performed using two reaction stock solutions, but three or more reaction stock solutions may be used.

Bulk Polymerization Method In the present invention, for bulk polymerization of the norbornene-based monomer, for example, a resin transfer molding (RTM) method or a reaction injection molding (RIM) method can be used. These methods need only be substantially lumpy and may have small amounts of inert compounds present. In these methods, a known molding machine conventionally known as an RTM machine or RIM machine can be used for mixing two or more kinds of reaction stock solutions.

The RTM machine is generally composed of an unreacted solution tank, a catalyst-mixed solution tank, a measuring pump, a mixer and the like.
The mixture is fed into a mixer at a volume ratio of 0: 1 to 10: 1, and then poured into a molding die heated to a predetermined temperature, where it is immediately subjected to bulk polymerization to obtain a molded product.

[0062] A preferred molding method using an RTM machine is a reaction solution comprising a norbornene-based monomer and a complex obtained by coordinating ruthenium with a neutral electron donor and / or a heteroatom-containing carbene compound as a ligand. This is a method of preparing a catalyst blended solution dissolved in, and mixing and molding them. In this method, it is preferable to add a Lewis acid to the reaction stock solution composed of the norbornene-based monomer.

The RIM machine is configured so that two or more kinds of undiluted reaction solutions are sent to a mixing head, mixed by collision energy, and then injected into a high-temperature molding die, where they are immediately subjected to bulk polymerization to obtain a molded product. Is done.

A preferable molding method using an RIM machine is to divide a norbornene-based monomer into two parts, and to further coordinate a ruthenium with a neutral electron donor or / and a heteroatom-containing carbene compound as a ligand as a third liquid. This is a method in which a liquid obtained by dissolving the resulting complex in a solvent is used, and these three liquids are mixed by collision mixing to be molded. In this method, it is preferable to add a Lewis acid to at least one of the two divided norbornene monomers.

[0065] In the production the present invention of the coil molded product, usually split mold structure, that is using a molding die having a core mold and a cavity mold, the interior of the mold, placing the winding coils, wound in such a spacer A gap is formed between the wire coil and the inner peripheral surface of the mold, and two or more of the above-mentioned reaction stock solutions are supplied thereto to cause bulk polymerization of the norbornene-based monomer. It is preferable that, in addition to the winding coil, a reinforcing material for reinforcement is previously arranged inside the mold.

The core mold and the mold are manufactured so as to form a cavity (cavity) in accordance with the shape of a target molded product. There is no particular limitation on the shape, material, and size of the mold. Since it can be molded at a relatively low temperature and a low pressure using a low-viscosity reaction liquid, not only a metal mold but also various materials such as various synthetic resins and low melting point alloys can be used.

In the present embodiment, the wound coil is made of a metal wire such as aluminum having a linear expansion coefficient substantially equal to that of the norbornene-based polymer after bulk polymerization. 1000m
m, preferably 100-800 mm, more preferably 2
00 to 300 mm, vertical 50 to 500 mm, preferably 1
00 to 400 mm, more preferably 200 to 300 mm
In the winding form, 1 to 50 volumes, preferably 5 to 30 volumes, more preferably 10 to 20 volumes wound as it is,
Alternatively, 0.1 to 3 mm is obtained by stacking 2 to 10 steps,
It preferably has a shape in which unit coils obtained by stacking two sets at a distance of 0.5 to 2 mm are connected in a figure eight shape.

In the present embodiment, the cross-sectional shape of the metal wire is
A rectangle is adopted from the viewpoint of workability, and the width of the rectangle is 1 to 20 mm, preferably 3 to 10 mm, and the thickness is 1 to 20 mm, preferably 3 to 10 mm.

The winding coil is disposed so as to completely enter the inside of the mold. However, the terminals of the winding coil are attached to the mold so as to be exposed outside the mold.

The temperature of the reaction solution before it is fed into the mold cavity is preferably 20 to 80 ° C. The viscosity of the reaction stock solution is, for example, at 30 ° C., usually 2 to 1000 c.
ps, preferably 5 to 300 cps. The collision pressure when filling the reaction stock solution into the cavity by the RIM method is as follows:
Usually 5 to 120 kgf / cm ² , preferably 10 to 8
0 kgf / cm ² .

The mold temperature is usually at least room temperature, preferably from 40 to 200 ° C., particularly preferably from 50 to 130 ° C. The mold clamping pressure is usually in the range of 0.1 to 100 kg / cm ² . The polymerization time may be appropriately selected, but usually,
It is from 10 seconds to 20 minutes, preferably within 5 minutes.

When the undiluted reaction solution mixed by the above RTM machine or RIM machine is injected into the cavity of the mold, the bulk polymerization reaction is immediately started and hardened. The polymerization reaction is an exothermic reaction, and the temperature of the molded article in the mold gradually decreases as the curing time (curing time) increases. When a Lewis acid is not used, a post-curing (post-curing) step may be separately provided. The molded body obtained by the bulk polymerization may be released from the mold by using an air ejector or a mold removal device provided in the mold.

When the reaction solution is supplied, the atmosphere in the mold may be an inert atmosphere by purging with an inert gas such as N ₂ , but this is not always necessary in the present invention. Even in an air atmosphere, there is little possibility of causing a problem such as deactivation of the catalyst.

Before placing the coil in the mold, the coil is preliminarily placed in an oven or the like for 50 to 100 minutes.
Although it may be heated to about ° C., the necessity is not always required in the present invention, and the adhesiveness to the resin can be sufficiently maintained even if the heating and drying are not performed before molding.

Further, when the reinforcing material is placed inside the mold, the surface of the reinforcing material may be treated in advance with a coupling agent such as a silane coupling agent, so that the reinforcing material absorbs the adsorbed water. When it is contained, the adsorbed water may be removed by heating and drying in advance, but the necessity of these is not always the present invention. Adhesion can be sufficiently maintained.

In the present embodiment, as described above, a wound coil formed body as a formed body in which the winding coil is integrated can be obtained. This wound coil formed body can be suitably used as a ground coil for a magnetically levitated railway.

According to the present embodiment, the catalyst system is less likely to be deactivated due to the influence of moisture or air in the atmosphere, and a surface treatment (silane coupling treatment) of glass fiber used as a reinforcing material is unnecessary. In addition, even if the reinforcing material is not sufficiently dried before molding, a wound coil molded body can be efficiently manufactured. In addition, by further containing the Lewis acid in the reaction solution, the polymerization reactivity of the reaction solution is further increased, and it is possible to more efficiently produce a wound coil formed body.

Although the embodiments of the present invention have been described above, the present invention is not limited to these embodiments at all, and can be implemented in various modes without departing from the gist of the present invention. Of course.

[0079]

EXAMPLES Hereinafter, the present invention will be described based on examples in which the present invention is further embodied, in comparison with comparative examples. However, the present invention is not limited to these examples. In the following Examples and Comparative Examples, parts and percentages are by weight unless otherwise specified.

Example 1 The size of the cavity was 876 mm × 982 mm × 50
An aluminum mold (upper mold and lower mold) having a diameter of 0.1 mm was prepared. The winding coil and the reinforcing material are arranged so as to completely enter the inside of the mold between the upper mold and the lower mold, and there is a gap between the winding coil and the inner peripheral surface of the mold with a spacer or the like. And the mold was closed. However,
The terminals of the coil were mounted on the mold so as to be exposed outside the mold. The winding coil has a width of 8.5 m.
A rectangular aluminum wire having a thickness of m and a thickness of 6.2 mm was used. The wire is 273 horizontal in a rectangular shape
24 mm wound around a 263 mm long winding die, and the two layers are stacked with a gap of 0.5 mm.
A unit coil obtained by assembling the unit coils connected in a figure eight shape was used. As the reinforcing material, a glass fiber not subjected to the silane coupling treatment was used. No heating was performed on these wound coils and reinforcing material before molding.

At the time of reaction injection molding, norbornene monomers composed of dicyclopentadiene (including about 5% of cyclopentadiene trimer) were placed in two tanks (Solution A and Solution B). Separately from these liquids A and B, bis (tricyclohexylphosphine)
Solution C containing benzylidene ruthenium dichloride was prepared. Liquid C was prepared by blending bis (tricyclohexylphosphine) benzylidene ruthenium dichloride (manufactured by Strem Chemical Co.) so that the molar ratio of ruthenium metal to norbornene-based monomer was 10000: 1. A 2% dichloromethane solution was prepared.

Next, these three solutions were used as a solution A: solution B: C
Liquid = 1000: 1000: 11 to the mixing head at a volume ratio of collision mixing (collision pressure 60 kgf / cm
² ) The mixture was injected into a mold (air atmosphere) heated to a mold temperature of 60 ° C. and a core mold temperature of 60 ° C. The bulk polymerization reaction time was about 300 seconds. Thereafter, a reaction injection molded body (coil molded body) in which the winding coil was integrated was taken out of the mold. After that, post-curing was performed at 140 ° C. for 10 minutes.

The obtained molded body was cut, and the adhered surface between the winding coil and the resin was observed. As a result, it was confirmed that the resin was cured well and adhered well.

Example 2 As in Example 1, a norbornene-based monomer composed of dicyclopentadiene (containing about 5% of cyclopentadiene trimer) was used and placed in two tanks (solution A and solution B). liquid). Bis (1,3-dichloro-2-propoxy) aluminum chloride as Lewis acid was added to these two tanks such that the molar ratio of Lewis acid to ruthenium complex was 1: 5. Was added. Note that the same liquid as in Example 1 was used as the liquid C.

Next, these three liquids were used as a liquid A: liquid B: C
The liquid was sent to a mixing head at a volume ratio of 1000: 1000: 11, and was subjected to collision mixing and injected into a mold (air atmosphere) in the same manner as in Example 1. The bulk polymerization reaction time was about 150 seconds. Thereafter, a reaction injection molded body (coil molded body) in which the winding coil was integrated was taken out of the mold. No subsequent post cure was performed.

The obtained molded body was cut, and the adhered surface between the winding coil and the resin was observed. As a result, it was confirmed that the resin was cured well and adhered well.

Comparative Example 1 A norbornene-based monomer composed of dicyclopentadiene (containing about 5% of cyclopentadiene trimer) as in Example 1 was used and placed in two tanks (solutions A and B). liquid). One of these two tanks contains
Diethylaluminum chloride (DEAC) was added to the norbornene-based monomer in a concentration of 40 mmol, n-propanol in a concentration of 44 mmol, and silicon tetrachloride in a concentration of 20 mmol (solution A). On the other side, tri (tridecyl) ammonium molybdate was added to the norbornene-based monomer so as to have a concentration of 10 mmol (solution B).

Next, these two solutions were mixed with A solution: B solution = 1:
Example 1 by feeding into the mixing head at a capacity ratio of 1
In the same manner as described above, the mixture was subjected to collision mixing and injected into the mold (air atmosphere). The bulk polymerization reaction time was about 60 seconds. Thereafter, a reaction injection molded body (coil molded body) in which the winding coil was integrated was taken out of the mold.

When the obtained molded body was cut and the contact surface between the wound coil and the resin was observed, the unreacted solution remained unreacted, resulting in molding failure.

Thereafter, post-curing was carried out at 140 ° C. for 10 minutes, but again the unreacted stock solution was not completely cured.

Consideration As described above, in Example 1, the conditions that were conventionally considered to be difficult to form (the winding coil and the reinforcing material were not heated and dried before forming, and the surface of Even if the coupling process is not performed and the atmosphere in the mold is an air atmosphere), it is confirmed that the occurrence of molding defects can be prevented by performing post-curing on the molded body after demolding. Was done. This is considered to be due to the fact that the use of the ruthenium complex as the catalyst increased the polymerization reactivity of the norbornene-based monomer.

Further, in Example 2, it was confirmed that occurrence of molding defects could be prevented without performing post-curing on the molded product after demolding. This is considered to be because the polymerization reactivity of the norbornene-based monomer was further increased by using a Lewis acid in addition to the ruthenium complex as the catalyst.

On the other hand, in Comparative Example 1, molding failure occurred. This is considered to be due to the use of a conventional molybdenum-based catalyst.

[0094]

As described above, according to the present invention, it is possible to provide an industrially advantageous method for manufacturing a coil molded product, which is extremely less likely to cause molding defects and is industrially advantageous.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Yasuhiro Mitsuda 1-2-1 Yoko, Kawasaki-ku, Kawasaki-shi, Kanagawa Prefecture F-term in the Zeon Corporation General Development Center 5E044 AA02 AB01 AB07 AC01 AD02

Claims (2)

[Claims] (1) (a) a norbornene-based monomer,
(B) a mold in which a reaction solution containing at least a complex formed by coordinating ruthenium with a neutral electron donor and / or a heteroatom-containing carbene compound is placed in a mold in which a winding coil is disposed; A method for producing a coil molded product, wherein the coil molded product is supplied to the inside and polymerized in bulk. 2. The method according to claim 1, wherein the undiluted reaction solution further contains (c) a Lewis acid.