JPH11221832A - Reactive polymeric molded body and its manufacture - Google Patents

Abstract

PROBLEM TO BE SOLVED: To fill a filler by dispersing the filler uniformly in a molded body, or by filling the filler in a higher density comparing with conventional method, or allowing a plurality of fillers to have a specific filled density distribution tendency in the molded body. SOLUTION: A reactive stock solution is reacted to be polymerized in a state wherein a centrifugal force is added to a filler 7 and a reactive stock solution which exist in a mold. Therefore, even if the filler 7 is unevenly distributed peripherally in the mold, the filler 7 is dispersed uniformly peripherally in the mold by the centrifugal force. Further the reactive stock solution is also stuck to an inner peripheral surface of the mold by the centrifugal force to start a polymeric reaction. Consequently, in the obtained molded body, that in which the filler 7 is dispersed at least uniformly peripherally in the mold body is obtained. As the filler, two or more kinds of fillers of different specific gravities 7a, 7b can be also filled in the molded body. In that case, the filler of a larger specific gravity 7a becomes rich to an outer peripheral side of the molded body, and the filler of a smaller specific gravity 7b becomes rich to an inner peripheral side of the molded body.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a reactive polymerization molding method, and more particularly, to a method in which two or more reaction stock solutions and a filler are separately or simultaneously placed in a mold, and the mold is rotated. , Under the condition that centrifugal force is applied to the reaction stock solution,
The present invention relates to a reactive polymerization molding method characterized by reacting and polymerizing a reaction stock solution, and a molded article obtained by the method.

[0002]

2. Description of the Related Art In the present specification, the term "reactive polymerization molding method" broadly means a method in which a reaction stock solution is reacted and polymerized in a mold.
As an embodiment, there is a reaction injection molding (RIM) method. The RIM method is a manufacturing method in which two or more reaction stock solutions are mixed in a mixing chamber, fed into a cavity of a mold device, and injection-molded while reacting in the mold device. This RIM method is suitably used for forming a polymer (molded article) from a norbornene-based monomer.

[0003] RIM molded articles are considered to be used in various technical fields because of their excellent impact resistance, low molding pressure and easy molding.

Further, in order to improve properties such as mechanical strength and flame retardancy of the RIM molded body, a filler such as a reinforcing agent or a flame retardant may be filled in the reaction stock solution.

[0005]

However, in the conventional reaction injection molding, it is difficult to uniformly disperse the filler in the molded product because the filler tends to sink in the reaction solution. There is a problem that. In the conventional reaction injection molding, a filler is previously mixed in a reaction stock solution, and is injected into the mold together with the reaction stock solution from an injection port of the mold. For this reason, it is impossible to include a filler having a size that cannot pass through the gate of the mold in the reaction solution. Furthermore, if the filling ratio of the filler in the reaction stock solution is increased, the reaction stock solution becomes difficult to pass through the gate, and unreacted portions of the reaction stock solution tend to be formed in the mold. There is a limit to the filling ratio of the filler that can be made.

Further, a technique has been proposed in which a filler such as glass fiber is placed in a mold in advance, and then a reaction solution is injected into the mold. In addition, it is difficult to uniformly dispose the fibers in the space, and there is also a problem that unfilled portions and voids are easily generated in order to fill the gap between the fibers with the stock solution. In addition, this technique also has a problem that the granular filler cannot be uniformly arranged in the space in the mold.

Furthermore, in the conventional reaction injection molding, it was impossible to fill two or more fillers with a specific tendency in their packing density distribution.

In US Pat. No. 4,808,364, a reaction stock solution is mixed and put into a rotating mold, and the mold is rotated to apply a centrifugal force to the reaction stock solution.
A method is disclosed in which a reaction solution is reacted and polymerized in a mold.

[0009] Japanese Patent Application Laid-Open No. 3-69357 discloses that
A technology is disclosed in which a polyethylene tube having adhesiveness to a molded body is used as a mold, a reactive polymerization reaction is performed while rotating the polyethylene tube around an axis, and the obtained molded body is integrated with the polyethylene tube. I have.

However, these publications disclose a technique of uniformly dispersing a filler in a molded article, or a technique of filling a plurality of fillers in a molded article with a specific tendency of distribution of packing density. There was no one.

[0011] The present invention has been made in view of the above-mentioned circumstances, and has a feature that a filler is uniformly dispersed in a molded article, a filler is filled at a higher density than before, or a plurality of fillers are contained in a molded article. An object of the present invention is to provide a reactive polymerization molding method capable of filling a filler with a specific tendency of a distribution of packing density, and a molded article obtained by the method.

[0012]

In order to achieve the above-mentioned object, a method for producing a reactive polymer molded article according to the present invention comprises a method in which a filler and a reaction stock solution present in a mold are subjected to a centrifugal force. The method is characterized in that the reaction solution is reacted and polymerized.

In the present invention, even if the filler is present in the mold in the circumferential direction, the filler is uniformly dispersed in the mold in the circumferential direction by centrifugal force. Also, the undiluted reaction solution adheres to the inner peripheral surface of the mold by centrifugal force, and the polymerization reaction starts. In the resulting compact,
A filler in which the filler is uniformly dispersed at least in the circumferential direction of the molded body is obtained.

As the filler, it is preferable to use a filler having a specific gravity close to the specific gravity of the reaction solution, from the viewpoint of uniform dispersion of the filler in the molded product in the radial direction, but the thickness t of the molded product is 5 mm or less. When the filler is as thin as possible, even if a filler having a specific gravity considerably different from that of the reaction stock solution is used, the filler is substantially uniformly dispersed in the radial direction in the molded article.

When the filling ratio of the filler is small,
The thickness of the molded article to be obtained is, for example, the average particle diameter of the filler, the average fiber diameter or the average length of one side of the block (hereinafter, referred to as
In the case where the filler is sufficiently thick compared to “particle size, etc.”, the filler should be uniformly dispersed in the circumferential direction in the molded body and dispersed with a predetermined density gradient in the radial direction. Is also possible. For example, when the specific gravity of the filler is sufficiently large as compared with the specific gravity of the reaction solution, the filling ratio is relatively small, and the thickness of the molded body is large, the packing density of the filler at the radially outer side of the molded body And the packing density is low on the radially inner side. Further, when the specific gravity of the filler is sufficiently smaller than the specific gravity of the reaction stock solution, the filling ratio is relatively small, and when the thickness of the molded body is large,
The packing density of the filler decreases on the radially outer side of the molded body, and increases on the radially inner side.

In the present invention, two or more kinds of fillers having different specific gravities can be filled in the molded article. In that case, the filler having a higher specific gravity becomes rich on the outer peripheral side of the molded body, and the filler having a smaller specific gravity becomes rich on the inner peripheral side of the molded body.

The reactive polymer molded article according to the present invention is a reactive polymer molded article obtained by subjecting a reaction stock solution to reaction polymerization under a state where centrifugal force is applied to a filler present in a mold and a reaction stock solution. It is.

In the reactive polymer molded article according to the present invention, when two or more kinds of fillers having different specific gravities are contained as the filler, the filler having the larger specific gravity becomes rich on the outer peripheral side of the molded article. The filler having the smaller specific gravity is rich on the inner peripheral side of the molded body.

In the present invention, the lower limit of the acceleration based on the centrifugal force is not particularly limited, but is preferably 0.5 G or more, more preferably 1 G or more, and particularly preferably 1.2 G or more.
The above acceleration is good. If the acceleration is too low, the unreacted solution and the filler do not easily adhere to the inner peripheral surface of the mold uniformly, and a molded article having a uniform thickness tends to be hardly obtained.

In the present invention, the upper limit of the acceleration is not particularly limited, but when obtaining a large molded product, the acceleration is preferably 20 G or less, more preferably 10 G or less, particularly preferably 7 G or less.

In the method according to the present invention, it is preferable that the mold is rotated with a centrifugal force such that the acceleration becomes 1 G or less (preparation rotation) before the centrifugal force of the predetermined acceleration is obtained. This is for sufficiently mixing the filler and the reaction solution before molding by the polymerization reaction. From such a viewpoint, it is preferable that the time required for the preparation rotation is a time before the reaction using the reaction stock solution starts.

In the present invention, the filler is preferably placed in a mold in advance, and then the reaction solution is preferably poured into the mold. However, the filler is mixed in the reaction solution in advance. Is also good.

In the present invention, unlike the conventional method, the reaction solution is not injected through the gate of the mold, but is simply poured into the mold. Therefore, the filler is preliminarily contained in the reaction solution. Even in the case of mixing, a compact having a large particle size and the like can be filled into the molded body at a high filling density as compared with the related art. In the method of the present invention,
When the filler is put in the mold in advance, and then the undiluted reaction solution is poured into the mold, the filler having a larger particle size or the like can be filled into the molded body at a higher packing density. . Therefore, in the present invention, the characteristics (such as mechanical strength and flame retardancy) of the molded product due to the filling of the filler.
Can be effectively exhibited.

The filler used in the present invention is not particularly limited, and may be an inorganic filler or an organic filler. The form of the filler is not particularly limited, and may be any form such as a granulated, block-shaped, fibrous, chopped strand, matted, cloth-woven, or chopped.

The filler may be one which also serves as a reinforcing agent or a flame retardant.
Glass fiber, aramid fiber, carbon fiber, ultra high molecular weight polyethylene fiber, metal fiber, polypropylene fiber, aluminum coated glass fiber, cotton, acrylic fiber, boron fiber, silicon carbide fiber, alumina fiber and the like can be mentioned. In the case where a fibrous filler is used, in the present invention, a filler having a fiber diameter of 500 μm or more and a fiber length of 1 mm or more, which has been considered impossible in the past, is to be contained in the molded body. Becomes possible. In the present invention, a fibrous filler having a fiber diameter and a fiber length less than or equal to these values may be included in the molded article, and even in such a case, the fibrous filler can be uniformly dispersed in the molded article. .

As the granular or block filler, silica sand, milled glass, glass balloon, carbon black, graphite, talc, clay (aluminum silicate), diatomaceous earth, calcium carbonate, aluminum hydroxide, mica, Examples include inorganic fillers such as potassium titanate, calcium sulfate, and antimony oxide; and organic polymer fillers such as polyethylene beads and Teflon particles. In the case of using a particulate filler, in the present invention, the particle size, which was considered impossible in the past, is several mm or more (1 mm or more).
Even a filler having a size of about 50 mm, preferably 2 mm to 10 mm) can be contained in the molded article. In the present invention, a filler having a particle size of several mm or less may be contained in the molded article, and even in such a case, the filler can be uniformly dispersed in the molded article. In the present invention, when a small filler having a particle size of about 100 μm or less is used, the filler is not previously placed in a mold separately from the reaction stock solution, but may be mixed in the reaction stock solution in advance. preferable. This is to prevent the filler from scattering in the mold.

The amount of these fillers to be filled is not particularly limited, but conventionally, the upper limit is about 30% by weight of the total weight of the molded body, but in the present invention, the packing density is as high as about 40 to 80% by weight. But filling is possible.

Reaction stock solution The reaction stock solution is not particularly limited.
Examples include urea-based, nylon-based, epoxy-based, unsaturated polyester-based, phenol-based, and norbornene-based ones, with the norbornene-based being particularly preferred. The temperature of the unreacted solution before entering the mold is preferably 20 to 80 ° C, and the viscosity of the unreacted solution is, for example, 30 ° C,
Preferably 20 to 1500 cps, more preferably 3
It is about 0 to 700 cps. If the viscosity of the reaction solution is too low, the reaction solution tends to stay at the bottom without centrifugal force acting.If the viscosity is too high, it is difficult to form a free form using acceleration. There is a tendency.

Further, in the reaction stock solution, together with the filler,
Various additives such as an antioxidant, a pigment, a colorant, a foaming agent, a sliding agent, an elastomer, a dicyclopentadiene-based thermopolymerized resin and a hydrogenated product thereof may be blended. The properties of the resulting polymer can be modified by adding additives.

As the antioxidant, there are various antioxidants for plastics and rubbers such as phenol type, phosphorus type and amine type. Examples of the elastomer include natural rubber, polybutadiene, polyisoprene, styrene-butadiene copolymer (SBR), styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), and ethylene- Examples include propylene-diene terpolymer (EPDM), ethylene vinyl acetate copolymer (EVA) and hydrides thereof. The additive is usually mixed in advance with one or both of the reaction solutions.

Mold In the present invention, after the undiluted solution is put into the mold, centrifugal force can be applied to the undiluted solution inside the mold. For example, a mold is rotatable around one axis or multiple axes. By rotating the mold, an acceleration due to centrifugal force acts on the reaction solution inside the mold.

The temperature of the mold is preferably from 10 to 150
° C, more preferably 20 to 120 ° C, still more preferably 30 to 100 ° C. Temperature control of the mold is not necessarily required in the present invention, but when performing temperature control while rotating the mold, as a heating means,
Preliminary heating using a lamp, a heat gun, or the like, or a rubber heater is preferred.

Before injecting the unreacted solution into the mold,
Warm air is circulated inside the mold, and after at least the inside of the mold cavity is heated to a predetermined temperature, the circulation of the warm air is stopped, and the reaction stock solution is poured into the cavity of the mold apparatus to perform molding. Is also good.

The material of the mold used in the present invention is as follows.
Although not particularly limited, a material having good adhesiveness to the mold and a material that is non-adhesive to the molded body is preferable in order to obtain a molded body having a smooth outer peripheral surface, for example, cast iron,
Metals such as iron, stainless steel, aluminum and nickel electroformed are preferred. However, as long as the material is non-adhesive to the molded body, a synthetic resin or another material may be used. This is because reactive polymerization can be performed at a relatively low pressure, and it is not necessary to use a highly rigid mold.

When the mold is made of a synthetic resin, the synthetic resin is made of a non-adhesive resin such as fiber reinforced plastic (FRP), phenol, polyester or other polar resin. Since it is not integrated with the reactive polymer molding, the mold apparatus can be removed and used repeatedly for each reactive polymerization molding, which is preferable. However, in the present invention, a mold having adhesiveness to the molded body may be used and integrated with the molded body.

The mold is preferably a split mold that can be formed into a free shape. However, when a tube or the like is formed, a cylindrical mold that is not divided may be used. In the case of a cylindrical mold, since it is necessary to pull out the obtained molded body, in order to improve the releasability, a wax, a lubricant or the like is required in advance along the inner peripheral surface of the mold before the injection of the stock solution. Is preferably applied. Further, when the molded body is pulled out, it is possible to start drawing out the molded body after the temperature of the molded body reaches a temperature equal to or lower than the glass transition temperature (Tg) of the molded body, preferably equal to or lower than (Tg-50) ° C. preferable. This is because the shape of the molded body does not collapse and the workability is good.

The polymerization time may be appropriately selected, but when centrifugal force is applied after completion of the injection of the reaction solution, it takes several seconds to several tens of seconds to raise the mold to a predetermined rotation speed. Is 5 to 30 seconds, more preferably 5 to 15 seconds.
Seconds.

[0038]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below based on embodiments shown in the drawings.

FIGS. 1A and 1B are schematic perspective views of a mold used in a reactive polymerization molding method according to one embodiment of the present invention.
FIG. 2C is a schematic perspective view showing an example of a molded product, FIG. 2 is a side view of a driving device for rotating a mold, FIG. 3 is a plan view of the driving device, and FIG. IV of the molded article shown in C)
FIG. 4B is a cross-sectional view taken along a line IV, FIG. 4B is a cross-sectional view of an enlarged main part thereof, and FIG. 6C is an enlarged cross-sectional view of a main part of a molded body obtained by a method according to another embodiment of the present invention. .

First Embodiment In this embodiment, a method for producing a tube (containing a filler) having an outer diameter of 400 mm or more by reacting and polymerizing a reaction solution containing a norbornene-based monomer will be described.
In this embodiment, a mold 2 shown in FIGS. 1A and 1B is used to apply a centrifugal force to the reaction stock solution.

The mold 2 is attached to the outer periphery of both ends of the mold 4 from the axial direction in a state in which the mold 4 can be divided into two along the dividing surface 3 in the vertical direction. And a pair of rolling rings 8. The split mold 4 is made of, for example, an aluminum casting, and the rolling ring 8 is made of cast iron.

It is preferable that a sealing material is mounted on the split surface 3 of the split mold 4. By installing the sealant, it is possible to prevent inconvenience such as leakage of the undiluted reaction solution from the split surface 3. Suitable sealing materials used in the present embodiment include:
There is no particular limitation, and a silicone rubber sealing material or the like can be used.

An inner peripheral surface is formed inside the split mold 4 combined with the split surface 3, and a reaction stock solution having a predetermined viscosity is pressed against the inner peripheral surface by centrifugal force having a predetermined acceleration. It is supposed to be. End plates 6 and 6 are formed at both ends in the axial direction of the split mold 4 so that the through holes 5 are formed.
A nozzle for supplying the undiluted reaction solution is inserted from the through hole 5, so that the undiluted reaction solution can be supplied into the mold 2.

As shown in FIGS. 2 and 3, a pair of flanged drive rollers 12 is engaged with one of the rolling rings 8 of the mold 2, and the other of the rolling rings 8 has no pair of flanges. Drive rollers 14 are engaged with each other. These drive rollers 12 and 14 are connected to a transmission 16 and a constant torque inverter motor 18 and all rotate at substantially the same rotational speed. When these drive rollers 12 and 14 are all rotated at substantially the same rotational speed, the rolling ring 8 engaged with them is also rotated around its axis, and the mold 2 composed of the split dies 4 and 4 is also rotated. At the same time, it rotates around the axis. The driving rollers 12, 14,
The transmission 16 and the motor 18 are mounted on a base 20. The reason why the one driving roller 12 in the axial direction is provided with a flange is that the flange restricts the axial movement of the rolling ring 8, thereby restricting the axial movement of the mold 2. The drive rollers 12, 14 in both axial directions may be provided with flanges, but only one of them can sufficiently limit the axial movement of the mold 2.

Next, a method of forming a tube by the reactive polymerization molding method using the mold 2 will be described.

First, as shown in FIG.
Then, as shown in FIG. 1A, the rolling rings 8, 8 are attached to both ends of the combined split dies 4, 4, and the mold 2 is assembled. Next, the mold 2 is rotatably mounted on the drive rollers 12 and 14 shown in FIGS.

Thereafter, reactive polymerization molding is performed. The reactive polymerization molding performed in the present embodiment is a molding using a norbornene-based monomer. Specific examples of the norbornene-based monomer to be used include bicyclics such as norbornene and norbornadiene; dicyclopentadiene (cyclopentadiene dimer). ), Tricyclics such as dihydrodicyclopentadiene; tetracyclics such as tetracyclododecene; pentacyclics such as cyclopentadiene trimers; heptacyclics such as cyclopentadiene tetramers; methyl, ethyl, Substituents such as alkyl such as propyl and butyl, alkenyl such as vinyl, alkylidene such as ethylidene, and aryl such as phenyl, tolyl and naphthyl; and further having polar groups such as ester group, ether group, cyano group and halogen atom. Substitutes are exemplified. These monomers may be used in combination of one or more kinds. It is easy to obtain, excellent in reactivity,
From the viewpoint of excellent heat resistance of the obtained resin molded body, tricyclic,
Tetracyclic or pentacyclic monomers are preferred.

The ring-opening polymer to be produced is preferably of a thermosetting type. For this purpose, among the norbornene-based monomers, it has two or more reactive double bonds such as cyclopentadiene trimer. Those containing at least a crosslinkable monomer are used. The proportion of the crosslinkable monomer in all the norbornene monomers is preferably from 2 to 30% by weight.

It should be noted that, 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.

The metathesis catalyst which can be used in the molding using the norbornene-based monomer includes a norbornene-based catalyst such as tungsten hexachloride or an organic ammonium molybdate such as tridodecyl ammonium molybdate or tri (tridecyl) ammonium molybdate. There is no particular limitation as long as it is a known metathesis catalyst as a catalyst for bulk polymerization of monomers, but an organic ammonium molybdate is preferred.

As the activator (co-catalyst), JP-A-58-1983
127728, JP-A-4-226124,
JP-A-58-129003, JP-A-4-1452
There is no particular limitation as long as it is a known activator as disclosed in Japanese Patent No. 47, for example, alkyl aluminum halides such as ethyl aluminum dichloride and diethyl aluminum chloride, organic aluminum compounds such as alkoxyalkyl aluminum halides, and organic tin. And the like.

As preparation for molding, a molding material mainly composed of a norbornene-based monomer, a metathesis catalyst and an activator was mixed with a solution B composed of a norbornene-based monomer and a metathesis catalyst, and the aforementioned norbornene-based monomer and activator. The liquid is divided into two stable liquids and the liquid A, each of which is placed in a separate tank.

In this embodiment, the average particle size is 0.1%.
A filler such as silica sand of about 3 mm is put in the mold in advance. The filling ratio of the filler is not particularly limited, but is 20 to 80% by weight, preferably 30 to 80% by weight when the total weight of the reaction stock solution put in the mold is 100% by weight.
Preferably, the filling ratio is as high as about 60% by weight.

To start molding, control the mixer,
The solution A and the solution B from the tank are mixed, and the mixed solution is used as a reaction stock solution by using a nozzle or the like to form the through-hole 5 of the mold 2.
From the mold 2. The viscosity of the reaction solution supplied into the mold 2 is 50 cps to 15 at 30 ° C.
00 cps.

In the present embodiment, the mold 2 does not necessarily need to be heated, but may be heated using a heating medium or hot air from the viewpoint of facilitating the polymerization reaction.

The number of revolutions of the mold 2 is 1 G or more and 5
G or less, and it depends on the diameter of the inner peripheral surface of the mold 2.
When the thickness is set to about 600 mm, the rotational speed of the mold 2 around the axis is preferably about 80 to 150 rpm. Mold 2
The initial start-up (preparation rotation) time required to rotate at a constant rotation speed around the axis is about several seconds to 30 seconds. During this preparation rotation time, the reaction stock solution and the filler are
An acceleration of about 1 G or less is applied, and the unreacted solution and the filler are uniformly mixed. Then, increase the rotation speed of the mold,
At a constant rotation speed, an acceleration of about 1 G to 5 G is applied to the reaction solution and the filler in the mold. After the mold 2 is rotated around the axis thereof at a constant rotation speed, a nozzle may be inserted through the through-hole 5 to supply the reaction solution.

By rotating the mold 2 around the axis thereof at a constant rotational speed, the reaction stock solution supplied into the mold 2 is formed into a tube-like shape on the inner peripheral surface of the mold 2 by centrifugal force. It will stick. The filler is uniformly dispersed at least in the circumferential direction in the reaction solution. By maintaining this state for, for example, 1 to 10 minutes, the reaction in the reaction stock solution proceeds, and bulk polymerization is performed.

Thereafter, the rotation of the mold 2 is stopped, and after the mold 2 is cooled, the rolling ring 8 is removed from the state shown in FIG. 1 (A) to the state shown in FIG. 1 (B). , Split mold 4,4
Is opened, it is possible to obtain a tubular molded body 10 as shown in FIG. This tubular shaped body 10
Is composed of a reactive polymer molded product of a norbornene-based monomer, and as shown in FIGS.
Are uniformly dispersed in the resin layer 9. In particular, in the present embodiment, even if the filler 7 has a large particle size or the like, the filler 7 can be uniformly dispersed in the resin layer 9.
In addition, it can be filled with high filling. Therefore,
In the present embodiment, the improvement of the properties (mechanical strength, flame retardancy, etc.) of the molded body by filling the filler 7 can be effectively exhibited. The thickness of the obtained molded body 10 is not particularly limited, but is 5 to 10 in the present embodiment.
It is about 0 mm.

Further, in the method according to the present embodiment, by applying a centrifugal force to the reaction stock solution, bubbles are separated from the reaction stock solution by the centrifugal force during molding, and voids are eliminated in the obtained molded body.

The inner peripheral surface of the tubular molded body 10 shown in FIG. 1 (C) obtained by the method of this embodiment is a surface obtained by centrifugal force without touching anything during the molding process. Therefore, there is no inconvenience such as poor curing of the reaction stock solution during molding, and the inner peripheral surface is smooth. The obtained tubular molded body is used, for example, as a fluid pipe or the like, and a fluid flows through the pipe. Therefore, it is convenient to use the pipe as a pipe having a smooth inner peripheral surface.

Further, since the tubular molded article obtained by the method according to the present embodiment is a polymer obtained by utilizing a bulk polymerization reaction of a norbornene-based monomer, the tubular molded article has poor impact resistance and durability. Excellent mechanical properties. Further, according to this method, even a relatively large-diameter tubular molded body can be molded relatively easily.

Further, in the present embodiment, split dies 4 are used, and rolling rings 8 are mounted on the outer periphery thereof. Since it is rotated around, it is possible to realize both the free-form molding of the molded body by using the split mold and the rotation using the ring with little rotational fluctuation. In addition, if rotational blur occurs, the rotational blur can be suppressed by shaving the outer circumference of the rings 8 during rotation. Further, replacement of the rings 8, 8 is also easy.

The use of the tube-shaped molded article obtained by the present embodiment is not particularly limited. Particularly, as a pipe having a large diameter (400 mm or more, 1000 to 2000 mm), sewage pipes, water pipes for agricultural roads, and pipes for dams are used. It can be suitably used as a water pipe, a water distribution pipe for building land development, and other pipes.

Second Embodiment In this embodiment, the same reactive polymerization molding as in the first embodiment is performed using two types of fillers having different specific gravities as the filler.

The combination of fillers having different specific gravities is not particularly limited, but a combination of silica sand and glass balloon, a combination of silica sand and polyethylene beads,
Combination of calcium carbonate and polyethylene beads,
Examples include a combination of aluminum hydroxide and carbon black, and a combination of aluminum hydroxide and brominated polystyrene.

By using such a combination of fillers, as shown in FIG.
Is that the filler 7a having a higher specific gravity becomes rich on the outer peripheral side of the molded body 10a, and the filler 7b having a lower specific gravity is
It becomes rich on the inner peripheral side of the molded body 10a. The specific use of such a molded body 10a is not particularly limited, but a pipe for a special use in which different characteristics (for example, conductivity, insulation, mechanical characteristics, etc.) are required on the outer peripheral side and the inner peripheral side. Can be preferably used.

Other Embodiments The present invention is not limited to the above-described embodiments, but can be variously modified within the scope of the present invention. For example, the mold that can be used in the present invention is not limited to the above-described embodiment, and can be variously modified.

Further, in the above-described embodiment, the mold is rotated around one axis, but may be rotated around two or more axes.

[0069]

EXAMPLES Hereinafter, the present invention will be described based on more detailed examples, but the present invention is not limited to these examples.

Example 1 A mold 2 shown in FIG. 1A was prepared and set on drive rollers 12 and 14 of a mold rotating device shown in FIGS. The pair of split molds 4 and 4 were made of an aluminum casting, had an outer diameter of 500 mm, an inner diameter of 400 mm, and an axial length of 1200 mm. The inner diameter of the through hole 5 of the end plate 6 formed at both ends of the split dies 4 and 150 was 150 mm.

The split dies 4 and 4 were combined on the split surface 3.
The split surface 3 was provided with a silicone rubber sealing material.

The rolling rings 8, 8 were attached with the split surfaces 3 of the split dies 4, 4 sealed. Rolling ring 8,8
Was made of cast iron, its outer diameter was 700 mm, and its axial thickness was 50 mm.

The rolling rings 8, 8 are connected to the driving rollers 12, 14,
5 kg of silica sand (RS-silica made by Tatsumori, average particle size: 1 mm) as a filler is put into the mold 2, and then the nozzle is inserted from the axial through hole 5 of the split mold using a nozzle. A total of 5 kg of the reaction stock solution was supplied into the mold 2. The preparation of the reaction stock solution was performed as follows. 85% by weight of dicyclopentadiene (DCP) and 15% of tricyclopentadiene
A styrene-isoprene-styrene block copolymer (Clayton 1170, manufactured by Shell Co.) was used in an amount of 5 parts by weight, based on 100 parts by weight of the total amount of the monomer, and a phenolic antioxidant. 2 parts by weight of Irganox 1010 (manufactured by Ciba Geigy) were dissolved and placed in two containers. One of them was mixed with diethyl aluminum chloride (DEA) based on the mixed monomer.
C) was added to a concentration of 40 mmol, n-propanol to a concentration of 44 mmol, and silicon tetrachloride to a concentration of 20 mmol (solution A). On the other hand, tri (tridecyl) ammonium molybdate was added to the mixed monomer at a concentration of 10 mmol (solution B).

The solution A and the solution B are sent to the mixer by a gear pump so as to have a volume ratio of 1: 1 and then supplied from the through hole 5 of the mold 2 to the inside of the mold 2 using a nozzle. did. The temperature of the reaction stock solution was 30 ° C., and its viscosity was 300 cps at 30 ° C.

Immediately after the completion of the supply of the reaction solution, the driving rollers 12 and 14 were rotated, and the mold 2 was rotated about its axis. In 15 seconds, the rotation speed of the mold 2 becomes 120 rpm
And maintained that speed. The acceleration acting on the reaction stock solution was calculated to be 3G.

After maintaining this state for 5 minutes, the rotation was stopped, the mold 2 was taken out, the rolling rings 8, 8 were removed, and the split dies 4, 4 were opened. As shown in FIG. Such a tubular molded body 10 was obtained. Molded body thickness t
(See FIG. 4B) was 10 mm.

For confirmation, the tubular molded body 10 was cut at a plurality of locations and the cross-sectional state was examined. No voids were confirmed, and it was confirmed that silica sand as a filler was uniformly dispersed. Was. Further, when the inner peripheral surface of the tube molded body 10 was observed, it was confirmed that there was no trouble such as poor curing and the tube was smooth. Further, when the roundness of the cross section of the hollow portion of the tubular molded body was measured, it was close to the roundness, and it was confirmed that good roundness was obtained.

Example 2 8 kg of silica sand as a filler was put into the mold 2, and then a total of 5 kg of the undiluted reaction solution was poured into the mold 2 through the axial through hole 5 of the split mold 4 using a nozzle. Except for internal supply,
A tubular molded body was formed in the same manner as in Example 1.

For confirmation, this tube-shaped molded body was cut at a plurality of locations and the cross-sectional state was examined. No void was confirmed, and it was confirmed that silica sand as a filler was uniformly dispersed. . Further, when the inner peripheral surface of the tube molded body 10 was observed, it was confirmed that there was no trouble such as poor curing and the tube was smooth. Further, when the roundness of the cross section of the hollow portion of the tubular molded body was measured, it was close to the roundness, and it was confirmed that good roundness was obtained.

Example 3 5 kg of silica sand as a filler was put into the mold 2, and then a total of 20 kg of the undiluted reaction solution was poured into the mold 2 through the axial through hole 5 of the split mold 4 using a nozzle. Except for the supply inside, a tubular molded body was formed in the same manner as in Example 1.

For confirmation, this tube-shaped molded body was cut at a plurality of locations and the cross-sectional state was examined. No void was confirmed, and silica sand as a filler was uniformly dispersed in the circumferential direction. As a result, it was confirmed that the filling density of the silica sand was high and the density was low on the inner peripheral side. Further, when the inner peripheral surface of the tube molded body 10 was observed, it was confirmed that there was no trouble such as poor curing and the tube was smooth. Further, when the roundness of the cross section of the hollow portion of the tubular molded body was measured, it was close to the roundness, and it was confirmed that good roundness was obtained.

Example 4 The same silica sand as that used in Example 1 was used as a filler for 5 k.
g, and 0.5 kg of a glass balloon having a mean particle size of 50 mm and a product number of B38 / 4000 manufactured by Sumitomo 3M Ltd., and these fillers were charged into a mold.
A tubular molded body was formed in the same manner as in Example 1 except that a total of 5 kg of the undiluted reaction solution was supplied to the inside of the mold 2 using a nozzle from the axial through hole 5. The thickness t of the obtained molded body was 14 mm.

For confirmation, the tubular molded body was cut at a plurality of locations and the cross-sectional state was examined. No voids were confirmed, and the silica sand was richly and uniformly dispersed in the circumferential direction on the outer peripheral side.
It was confirmed that the glass balloon was richly and uniformly dispersed in the circumferential direction on the inner circumferential side. In addition, the tube molding 10
Observation of the inner peripheral surface confirmed that the film was smooth without defects such as poor curing. Further, when the roundness of the cross section of the hollow portion of the tubular molded body was measured, it was close to the roundness, and it was confirmed that good roundness was obtained.

[0084]

As described above, according to the present invention, the filler is uniformly dispersed in the reactive polymer molded article, the filler is filled at a higher density than before, or the molding is performed. A plurality of fillers can be filled in the body with a specific packing density distribution tendency.

[Brief description of the drawings]

1 (A) and 1 (B) are schematic perspective views of a mold used in a reactive polymerization molding method according to an embodiment of the present invention, and FIG. 1 (C) is a schematic perspective view showing an example of a molded article. FIG.

FIG. 2 is a side view of a driving device for rotating a mold.

FIG. 3 is a plan view of a driving device.

FIG. 4 (A) is an IV-IV of the molded article shown in FIG. 1 (C).
FIG. 3B is a cross-sectional view taken along a line, FIG. 3B is a cross-sectional view of an enlarged main part thereof, and FIG.

[Explanation of symbols]

 Reference Signs List 2 Mold 3 Split face 4 Split mold 7, 7a, 7b Filler 8 Rolling ring 9 Resin layer 10, 10a Molded body 12, 14 Drive roll

Claims (3)

[Claims] 1. A reactive polymer molded product obtained by subjecting a reaction stock solution to reaction polymerization under a state where centrifugal force is applied to a filler present in a mold and a reaction stock solution. 2. As the filler, two or more fillers having different specific gravities are included, and the filler having a higher specific gravity becomes rich on the outer peripheral side of the molded body, and the filler having a lower specific gravity, The reactive polymer molded article according to claim 1, which is rich on the inner peripheral side of the molded article. 3. A reactive polymerization molding method characterized by reacting and reacting a reaction stock solution under a state in which centrifugal force is applied to a filler and a reaction stock solution present in a mold.