JP2003040983A - Expanded polymerization molded body and its production method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an expanded polymerization molded body having minute bubbles which is lightweight and excellent in durability. SOLUTION: In a method for producing a molded body obtained by polymerizing and molding a polymerizable monomer at the same time in the presence of a polymerization catalyst, gas is dissolved in the monomer and a surfactant is also added to produce.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a foamed polymer which is obtained by polymerizing and molding a polymerizable monomer in the presence of a polymerization catalyst at the same time and which is excellent in uniformity and has minute foam, which is lightweight and has excellent rigidity. The present invention relates to a composite molded body and a method for manufacturing the same.

[0002]

2. Description of the Related Art Heretofore, various methods have been known as a production method for producing a foamed and polymerized molded article in so-called reaction molding, in which polymerization and molding of a polymerizable monomer are simultaneously carried out in the presence of a polymerization catalyst. Known methods include a method of mechanically mixing gas to foam, a method of adding a low boiling point compound or a capsule-like compound, and using this as a foaming agent. Further, the two chemical components are dissolved in gas at a predetermined pressure and temperature, and then the gas is injected into a mold and reacted at a predetermined pressure and temperature to form a foamed polymer molded article. Methods to create are also being developed.

In recent years, there has been a growing demand for a foamed polymer molded article which is more and more excellent in uniformity and has fine foam, and which is lightweight and has excellent durability.

[0004]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a foamed polymer molded article which has fine bubbles, is lightweight and has excellent durability.

[0005]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors produced a molded product obtained by simultaneously polymerizing and molding a polymerizable monomer in the presence of a polymerization catalyst. In the method, a gas is dissolved in the polymerizable monomer, and a surfactant is allowed to coexist, so that the reaction molding includes a large number of bubbles having excellent uniformity, and as a result, it is lightweight and excellent in durability. The present invention has been accomplished by finding that a foam-polymerized molded article can be obtained.

That is, the present invention is as follows. 1. In a method for producing a molded product obtained by simultaneously polymerizing and molding a polymerizable monomer in the presence of a polymerization catalyst, a gas that does not affect the polymerization reaction is dissolved in the polymerizable monomer, and the polymerization reaction is affected. A method for producing a foam-polymerized molded article, which comprises performing the treatment by incorporating a surfactant which does not extend. 2. The method for producing a foam-polymerized molded article according to the above 1, wherein the polymerizable monomer is a metathesis-polymerizable cyclic olefin. 3. Monomer liquid A consisting of a metathesis polymerizable cyclic olefin containing a metathesis polymerization catalyst system catalyst component as a polymerizable monomer (solution A) and a metathesis polymerizable cyclic olefin containing a metathesis polymerization catalyst system activator component B (solution B) is used, and these are mixed to produce a molded article, wherein the foamed polymerized molded article is produced. 4. The method for producing a foamed polymer according to any one of 1 to 3 above, wherein the surfactant is a fluorine-containing surfactant or a silicone-containing surfactant. 5. 1 above, characterized in that the gas is nitrogen, argon, helium, carbon dioxide, or a mixture thereof.
The manufacturing method of the foaming-polymerization molded body of 3-3. 6. Content of this surfactant is 0.001 weight% -2 weight% with respect to the whole polymerizable monomer, The manufacturing method of said foam-polymerization molded body of said 1-4 characterized by the above-mentioned. 7. A polymerizable monomer composed of a metathesis-polymerizable cyclic olefin is used as a surfactant which dissolves a gas that does not affect the polymerization reaction in the polymerizable monomer in the presence of a metathesis polymerization catalyst system and does not affect the polymerization reaction. A foamed and polymerized molded product obtained by simultaneously polymerizing and molding by mixing these, and having an average diameter of 100 μm.
Contains a large number of bubbles of the following size and has a specific gravity of 0.55
A foamed polymerized molded product in the range of 0.95.

The present invention will be described in more detail below.

The foamed polymer molded article of the present invention is a crosslinked polymer molded article containing a large number of bubbles therein, and is obtained by simultaneously polymerizing and molding a polymerizable monomer in the presence of a polymerization catalyst. Examples of such crosslinked polymers include polyurethane foams, polyamide foams, dicyclopentadiene foams, unsaturated polyester foams, epoxy foams, and the like, and the reaction of dicyclopentadiene resin proceeds relatively quickly. In addition, since it is excellent in impact resistance and strength, it can be cited as a suitable one as a foamed polymerized molded article.

The dicyclopentadiene foam will be described below as a more specific example.

The dicyclopentadiene foam is obtained by injecting a monomer composed of a metathesis-polymerizable cyclic olefin containing a metathesis polymerization catalyst system into a mold, and polymerizing and crosslinking reaction in the mold. Such a monomer liquid may be one liquid, or two or more liquids may be mixed and injected into the mold. Preferably, a monomer liquid A containing a metathesis polymerizable cyclic olefin containing a catalyst component of a metathesis polymerization catalyst system (solution A) and a monomer liquid B containing a metathesis polymerizable cyclic olefin containing an activator component of a metathesis polymerization catalyst system ( A method of mixing two solutions B) and injecting the mixed solution into the mold is preferable. Further, the monomer liquid containing the metathesis-polymerizable cyclic olefin may be mixed and injected as the second component or the third component.

A metathesis-polymerizable cyclic olefin is used as the polymerizable monomer of the dicyclopentadiene foam. As the metathesis-polymerizable cyclic olefin, one having 1 to 2 metathesis-polymerizable cycloalkene groups in the molecule is used. A compound having at least one norbornene skeleton in the molecule is preferable. Specific examples thereof include dicyclopentadiene, tricyclopentadiene, cyclopentadiene-methylcyclopentadiene co-dimer, 5-ethylidene norbornene, norbornene, norbornadiene, 5-cyclohexenyl norbornene, 1,4,5,8-dimethano -1, 4, 4a,
5,6,7,8,8a-octahydronaphthalene, 1,
4-methano-1,4,4a, 5,6,7,8,8a-octahydronaphthalene, 6-ethylidene-1,4,5,5
8-Dimethano-1,4,4a, 5,6,7,8,8a-
Octahydronaphthalene, 6-ethylidene-1,4-methano-1,4,4a, 5,6,7,8,8a, -octahydronaphthalene, 1,4,5,8-dimethano-1,
4,4a, 5,8,8a-hexahydronaphthalene, ethylene bis (5-norbornene) and the like can be mentioned, and a mixture thereof can also be used. Particularly, dicyclopentadiene or a mixture thereof containing 50 mol% or more, preferably 70 mol% or more is suitably used.

If necessary, a metathesis-polymerizable cyclic olefin having a polar group containing a different element such as oxygen and nitrogen can be used as a copolymerization monomer. Such a copolymerizable monomer also preferably has a norbornene structural unit, and the polar group is an ester group,
Ether groups, cyano groups, N-substituted imide groups, halogen groups and the like are preferable. Specific examples of the copolymerization monomer include 5-methoxycarbonylnorbornene and 5- (2-
Ethylhexyloquine) carbonyl-5-methylnorbornene, 5-phenyloxymethylnorbornene, 5-cyanonorbornene, 6-cyano-1,4,5,8-dimethano-1,4,4a, 5,6,7, Examples thereof include 8,8a-octahydronaphthalene, N-butyl nadic acid imide, and 5-chloronorbornene.

The metathesis catalyst system includes halides of metals such as tungsten, rhenium, tantalum and molybdenum as catalyst components, salts such as ammonium salts, and alkylated compounds of metals of groups I to III of the periodic table as activator components. Examples thereof include a composite catalyst composed of an organometallic compound mainly containing a compound such as tetraalkyltin, an alkylaluminum compound, and an alkylaluminum halide compound, or a catalyst composed of a ruthenium carbene complex.

The former is generally polymerized by mixing two liquids of a monomer liquid A containing a catalyst component and a monomer liquid B containing an activator component B. The latter is generally polymerized by mixing a monomer solution and a catalyst component.

In the latter, the polymerization generally does not proceed instantaneously, but the polymerization reaction can be accelerated by increasing the temperature. However, in the former, the polymerization reaction is fast and the polymerization moldability is excellent. It is suitable.

The monomer solution A (solution A) contains a catalyst component of a metathesis polymerization catalyst system. As such a catalyst component, a halide or ammonium salt of a metal such as tungsten, rhenium, tantalum or molybdenum is used, but a tungsten compound is particularly preferable from the viewpoint of reactivity of dicyclopentadiene. As such a tungsten compound, tungsten hexahalide, tungsten oxyhalide, etc. are preferable, and more specifically, tungsten hexachloride, tungsten oxychloride, etc. are preferable. Further, organic ammonium tungstate or the like can also be used. It has been found that when such a tungsten compound is directly added to the monomer, it immediately starts cationic polymerization, which is not preferable. Therefore, such a tungsten compound is preferably suspended in an inert solvent such as benzene, toluene, chlorobenzene and the like in advance and solubilized by adding a small amount of an alcohol compound and / or a phenol compound to be used. Further, as described above, it is preferable to add about 1 to 5 mol of Lewis base or chelating agent to 1 mol of the tungsten compound in order to prevent undesired polymerization. Examples of such additives include acetylacetone, acetoacetic acid alkyl esters, tetrahydrofuran, and benzonitrile. When a polar monomer is used, it may be a Lewis base itself as described above, and it may have its action even if the above compound is not added.
As described above, the monomer liquid A (solution A) containing the catalyst component has substantially sufficient stability.

On the other hand, the monomer solution B (solution B) contains an activator component of the metathesis polymerization catalyst system.
The activator component is preferably an organometallic compound centered on an alkylated compound of a metal of Group I to Group III of the periodic table, particularly tetraalkyltin, an alkylaluminum compound, and an alkylaluminum halide compound, and specifically, a chlorinated compound. Diethyl aluminum, diethyl aluminum chloride,
Examples thereof include trioctylaluminum, dioctylaluminum iodide, and tetrabutyltin. A monomer liquid B (solution B) is formed by dissolving the organometallic compound as the activator component in the monomer.

Basically, the solution A and / or the solution B to which a foaming agent or a foaming gas, which is a feature of the present invention described later, is mixed and injected into a mold to obtain the desired crosslinking. A polymer molded product can be obtained. However, if the above composition is left as it is, the polymerization reaction is initiated very quickly, so that curing may occur before it sufficiently flows into the molding die, which may cause a problem. In such a case, it is preferable to use an activity regulator. As such a regulator, Lewis bases are generally used, and above all, ethers, esters, nitriles and the like are used.
Specific examples include ethyl benzoate, butyl ether, diglyme and the like. Such a regulator is generally used by adding it to the solution (solution B) side of the component of the activator of the organometallic compound. When a monomer having a Lewis base is used as described above, it can also serve as a regulator.

The amount of the metathesis polymerization catalyst system used is, for example, when a tungsten compound is used as the catalyst component, the ratio of the tungsten compound to the raw material monomer is
It is about 1,000 to 1 to 15,000, preferably about 2,000 to 1 on a molar basis, and when an alkylaluminum is used as the activator component, the aluminum compound to the above raw material monomer is used. The ratio of about 100: 1 to 10,000: 1, preferably 2 on a molar basis.
The vicinity of 00: 1 to 1,000: 1 is used. Further, the chelating agent and the activity controlling agent as described above can be appropriately adjusted and used depending on the amount of the catalyst system used by experiments.

The molded product of the crosslinked polymer obtained by the present invention may further contain various additives depending on the purpose thereof in order to improve or maintain the properties thereof in practical use. Such additives include fillers, pigments, antioxidants, light stabilizers, flame retardants, polymer modifiers and the like.
Such additives cannot be added after the crosslinked polymer of the present invention has been molded, and therefore, when added, it is necessary to add them to the above-mentioned raw material solution in advance.

The easiest method is the solution A described above.
And a solution B may be added in advance to either or both of them, but in that case, they do not react to a certain extent with the catalyst component and activator component having strong reactivity in the liquid and do not react to some extent. In addition, it must not interfere with the metathesis polymerization. Inevitably, even if the reaction is unavoidable, if it does not substantially inhibit the polymerization or does not inhibit it in a short time, it is mixed with a monomer to prepare a third liquid, and immediately before the polymerization. Mixtures can also be used. A method in which the polymerization catalyst or activator is used as the third liquid and the above additives are added to solution A or solution B not containing the third liquid is also conceivable. Further, in the case of a solid filler, when the two components are mixed and the shape is such that the voids can be sufficiently filled immediately before starting the polymerization reaction or during the polymerization, it is filled in the molding die. It is also possible to keep it. In addition, it is preferable to add an antioxidant to the molded product according to the present invention. Therefore, it is desirable to add a phenol-based or amino-based antioxidant to the solution in advance. Specific examples of these antioxidants include 2,6-di-t-butyl-p-cresol,
N, N'-diphenyl-p-phenylenediamine, tetrakis [methylene (3,5-di-t-butyl-4-hydroxycinnamate)] methane and the like can be mentioned.

In the molded product of the present invention, another polymer may be added in the monomer solution state. As such a polymer additive, the elastomer is effective in enhancing the impact resistance of the molded product and controlling the viscosity of the solution. As the elastomer used for this purpose,
There can be mentioned a wide range of elastomers such as styrene-butadiene-styrene triblock rubber, styrene-isoprene-styrene triblock rubber, polybutadiene, polyisoprene, butyl rubber, ethylene propylene-diene-terpolymer, nitrile rubber.

The surfactant used in the present invention may be any one that does not affect the polymerization reaction and does not adversely affect the molding. Specific examples include fluorine-based surfactants and silicone-based surfactants. The fluorinated surfactant is a surfactant containing fluorine, and examples thereof include a fluorinated alkyl ester, a fluorinated alkyl ester addition polymer, a perfluoroalkyl-containing oligomer, a perfluoroalkylethylene oxide, a perfluoroalkyl. Examples include ethylene oxide adducts, fluorinated methacrylate copolymers, fluorinated acrylate copolymers, and the like. The silicone-based surfactant is a surfactant containing silicone, and examples thereof include polydioxyalkylene / dimethylpolysiloxane copolymer, polysilicone / polyether graft copolymer, block copolymer and the like. Of these, fluorine-based surfactants are preferable. These surfactants are used by adding them to the monomer liquid, and may be used by adding them to both or one of the monomer liquid A and the monomer liquid B. The amount of such a surfactant added is 0.0
It is preferably from 01% to 2% by weight. By setting it in such a range, it is possible to reduce the size of the bubbles in the foamed polymerized molded article and to evenly distribute the bubbles. Two
If it exceeds 5% by weight, it remains unreacted in the molded product, which deteriorates the physical properties of the molded product and is not preferable. 0.
If it is less than 001% by weight, the size of the cells in the foamed and polymerized molded product is reduced, and the effect of uniformly distributing the cells is less likely to appear, which is not preferable. A more preferable addition amount is 0.0
05% to 1% by weight, and further 0.01% by weight
It is preferably about 0.5% by weight.

In the foamed polymerized molding, a gas (gas) is dissolved in a monomer solution (one or both of solution A and solution B) under high pressure, and the gas is injected into the mold and then the gas is foamed in the mold. It can be preferably produced by the method.

A typical foaming reaction injection molding apparatus of the present invention has a device for supplying foaming gas added to a normal reaction injection molding (RIM) apparatus, and further has pressure resistance such as a mold and a monomer liquid tank. This is a structure with improved pressure controllability. Before the foam molding, the raw material monomer liquid A and the monomer liquid B are divided so as not to cause a reaction, and are stored in the A tank and the B tank which can be sealed and stored. A containing each of these monomer liquids
Gas is introduced from the gas supply device into the tank and / or the B tank, and the introduced gas is dissolved in the respective monomer liquids in the A tank and / or the B tank at a predetermined pressure. Alternatively, a mixing device is provided in the supply pipe for the liquid A and / or the liquid B, and gas is introduced into the portion from the gas supply device, and the introduced gas is dissolved in each monomer liquid at a predetermined pressure. In this case, the gas to be introduced is carbon dioxide gas, nitrogen gas, argon gas,
Any gas that acts as a foaming gas such as helium gas may be used, but nitrogen gas or carbon dioxide gas is preferably used. Since carbon dioxide gas has a higher diffusivity than other gases, it was easy to saturate and dissolve it in the monomer liquid. However, when dicyclopentadiene is used as a raw material monomer using carbon dioxide gas, there is a disadvantage that the reactivity is impaired, and the monomer liquid has a short shelf life. On the other hand, since nitrogen gas is inert and does not hinder the polymerization reaction, it is more preferably used in the present invention.

Further, in order to dissolve the foaming gas in each of the monomer liquids, for example, when only the pressure is applied at room temperature to dissolve the foaming gas, the gas is supplied to the A tank and / or the gas supply means equipped with a pressurizing device. The pressure is fed to the B tank and the A tank and / or the B tank are pressurized. For example, it is performed by applying a pressure of 6 MPa or more in about 10 hours, or by applying a pressure of 8 MPa or more in about 3 to 5 hours. Alternatively, the gas may be liquefied or densified at an extremely low temperature, and a predetermined pressure may be applied while A
A mixing device is provided in the liquid and / or liquid B supply pipe, and gas is introduced into the portion from the gas supply device, and the introduced gas is dissolved in each monomer liquid while pressurizing. For example, a gas having a pressure of 6 MPa or higher and a temperature of −60 ° C. is introduced and melted.

The pressure at which the gas is dissolved is preferably high, but from the practical point of view, the range is preferably 2 MPa to 20 MPa. More preferably 5 MPa to 18 MP
The range is a.

Next, each of the monomer liquids is sent to a mixing head for mixing the two monomer liquids, and the two liquids are uniformly mixed in the mixing head portion. At this time, it is preferable that the temperature of the monomer liquid during mixing is adjusted to a temperature range of 10 ° C. to 45 ° C. by controlling the temperature of the tanks and pipes of the monomer liquids. More preferably, it is in the range of 15 ° C to 30 ° C.

Each component (each monomer liquid) is transported by using a pump or the like. Then, the mixed two liquids are sent to a mold, and the mixed components undergo a polymerization and crosslinking reaction to be solidified to obtain a molded product. The foamed polymerized molded article of the present invention containing a large number of bubbles is foamed at the stage of solution state just before solidification in this mold and / or at the stage of increasing viscosity due to progress of polymerization reaction. can get.

That is, the monomer liquid in which the gas is previously dissolved undergoes a rapid change in pressure and / or temperature in the mold,
The solubility of the gas decreases and foaming occurs. In this case, either the pressure or the temperature may be changed, but when the gas is saturated by high pressure, a device equipped with a pressure adjusting valve is used as a mold pressure control device, and the pressure adjusting valve is used to It is preferable to control the pressure in the mold so as to sharply decrease it.
The temperature and pressure of the mold are controlled, but the temperature rapidly rises and the pressure also changes due to the polymerization reaction of the mixed two liquids. Such rapid changes in temperature and pressure also contribute to foaming. The mold temperature is 20 immediately before the polymerization reaction starts.
The temperature is set to ℃ to 120 ℃. Preferably, 30 ° C to 11
It is in the range of 0 ° C. The pressure inside the cavity (cavity) is set within the range of 0 to 5 MPa. Preferably,
It is in the range of 0.05 to 4 MPa.

In order to adjust the bubble diameter and the number of bubbles in the polymer, the temperature and pressure of the mold are adjusted by using the mold pressure control device and / or the mold temperature control device. And / or by appropriately controlling the temperature. The cell diameter and the number of cells in the foamed polymer (molded article) can also be adjusted by controlling the gas concentration in the monomer liquid.

The greatest feature of the above method is that it contains a large number of relatively uniform and fine bubbles to achieve weight reduction, thickness increase, and rigidity increase. The average size of the bubbles should be smaller than 100 μm diameter. 100μ
If it is larger than m, it becomes brittle and the strength decreases. Bubbles smaller than 1 μm are generally difficult to produce, and the effect is small. The number of bubbles per unit volume is 1 × 10 ⁶ cells / c
m ³ or more seemed necessary, but since it was difficult to measure, in the present invention, it was defined by the specific gravity of the polymer (molded product).
When the specific gravity is less than 0.55, the polymer has many relatively large bubbles (cavities) or small bubbles are connected to each other, resulting in deterioration of strength and impact resistance. When the specific gravity is larger than 0.95, the weight reduction of the polymer, which is the object of the present invention, is not effective. In the present invention, fine bubbles are formed in a polymer (in a molded product).
By utilizing the phenomenon that the original mechanical strength of the material is not significantly reduced when the bubbles have the same size or small defects as the inevitable defects in the polymer, while achieving the weight reduction by being generated. However, this is applied to a large-scale septic tank that is required to be lightweight and have high bending rigidity. Therefore, as described above, the bubble size of the present invention needs to be 100 μm or less, preferably 50 μm or less, and more preferably 30 μm or less. Further, the majority of the bubbles of the present invention (about 70% or more) need to be independent bubbles.

The average size of the bubbles in the present invention is obtained by cutting out a cross section in the plate thickness direction of the polymer (molded product) of the present invention and observing with a microscope such as an electron microscope at a magnification of 100 to 200 times. Is the average of the diameters of. 1
The observed and measured sample portion when observed at a magnification of 00 was an area of 1 mm × 0.8 mm. Further, in this experiment, observation samples were taken from three locations in the plate thickness direction. The size of the bubbles observed when the cross section was cut out was
Not all are the diameter of that bubble. That is, when the bubbles are formed into spheres, the cross section to be cut has various cut surfaces from the diameter portion of the sphere to the end of the sphere. Assuming that all the bubbles are perfect spheres of uniform size, the average diameter of the cut surfaces observed when randomly cut is calculated to be about 0.74 times the diameter of the spheres. The "average size of bubbles" is not corrected or considered. That is, in the present invention, as described above, there is no problem in practical use for confirming the effect of the present invention, which is a simple average of all cut surfaces observed under a microscope.

The foamed polymer molding of the present invention contains a large number of cells produced by such a method, thereby achieving weight reduction and saving the amount of expensive resin used as compared with a molded article of the same size. . The specific gravity of the bubble-free dicyclopentadiene polymer is about 1.03, but in the present invention, the specific gravity is 0.55 to 0.95, and significant reduction in weight and production cost can be achieved without lowering strength and rigidity. Can be reduced. Further, the weight reduction makes it possible to increase the plate thickness, and the bending rigidity can be greatly improved.

[0035]

EXAMPLES The foamed polymerized molded article of the present invention will be described more specifically with reference to the following examples.

[Example 1] (Production of raw material liquid: Preparation of solution A) Tungsten hexachloride 2
8 parts by weight was added to 80 parts by weight of dry toluene under a nitrogen stream, and then 1.3 parts by weight of t-butanol was added to 1 part of toluene.
The solution dissolved in 1 part by weight was added and stirred for 1 hour, then a solution consisting of 18 parts by weight of nonylphenol and 14 parts by weight of toluene was added and stirred for 5 hours under a nitrogen purge. Further, 14 parts by weight of acetylacetone was added. Stirring was continued overnight under a nitrogen purge while expelling by-produced hydrogen chloride gas to prepare a polymerization catalyst solution. Next, with respect to a monomer mixture consisting of 95 parts by weight of purified dicyclopentadiene (purity 99.7% by weight, the same below) and 5 parts by weight of purified ethylidene norbornene (purity 99.5% by weight, the same below), ethylene-containing 70 mol% Ethylene-propylene-
The above polymerization catalyst solution was added to a solution containing 3 parts by weight of ethylidene norbornene copolymer rubber and 2 parts by weight of Etanox 702 as an oxidation stabilizer, and a tungsten content of 0.01 mo.
l / litter was added. Further, 0.075 parts by weight of a fluorinated alkyl methacrylate copolymer was added to 100 parts by weight of this solution to prepare a monomer solution A.
(Solution A) was prepared.

(Preparation of Solution B) 70 mol% of ethylene content based on a monomer mixture consisting of 83 parts by weight of purified dicyclopentadiene and 5 parts by weight of purified ethylidene norbornene.
3 parts by weight of ethylene-propylene-ethylidene norbornene copolymer rubber was dissolved in a solution of trioctyl aluminum 85 and dioctyl aluminum iodide 1
5, the activator mixture for polymerization prepared by mixing the diglyme at a molar ratio of 100 has an aluminum content of 0.03 mol /
It was added at a rate of becoming a litter. Further this solution 1
A monomer liquid B (solution B) was prepared by adding 0.075 parts by weight of a fluorinated alkyl methacrylate copolymer to 00 parts by weight.

(Molding) Using an aluminum mold for molding, using a foaming reaction injection molding machine, the thickness is 4.5 mm × 500 m.
A m × 500 mm foamed polymer plate was prepared. Nitrogen gas was dissolved at 13 MPa in both monomer liquids at 25 ° C. Fixed side mold temperature is 90 ℃, movable side mold temperature is 60 ℃,
Reaction injection molding was performed with the cavity internal pressure set to 0.5 MPa. The obtained foamed and polymerized molded plate had a density of 0.66, and the average cell size inside the polymer was 33 μm.

[Example 2] Foam polymerization molding was performed in the same manner as in Example 1 except that 0.8% by weight of the fluorinated alkyl methacrylate copolymer was added only to the solution B and not added to the solution A. I made a board. The foamed polymer obtained had a density of 0.64 and an average cell size inside the polymer of 30.
It was μm.

[Comparative Example 1] The thickness was measured using a foaming reaction injection molding machine with an aluminum mold for molding in the same manner as in Example 1 except that the fluorinated alkyl methacrylate copolymer was not added to the solutions A and B. 4.5mm x 500m
A m × 500 mm foamed polymer plate was prepared. The obtained foamed and polymerized plate had a density of 0.70 and the average cell size inside the polymer was 45 μm.

[Comparative Example 2] In the same manner as in Example 1 except that the gas was not dissolved in the solutions A and B, a reaction injection molding machine was used with a molding aluminum die to obtain a thickness of 3 mmX.
A 500 mm x 500 mm non-foaming polymer molded plate was prepared. The obtained polymerized molded plate had a density of 1.03 and no bubbles were found inside the polymer.

[Comparative Example 3] Reaction injection molding was carried out using an aluminum mold for molding in the same manner as in Example 1 except that the fluorinated alkyl methacrylate copolymer was not added to the solutions A and B and the gas was not dissolved. Machine thickness 3
A non-foamed polymer plate of mm × 500 mm × 500 mm was prepared. The obtained polymerized molded plate had a density of 1.03 and no bubbles were found inside the polymer.

(Evaluation of Physical Properties) Using the molded plates produced in the above examples, samples for measuring physical properties were cut out, and the bending strength and the bending elastic modulus were evaluated according to JISK7203. The evaluation results are shown in Table 1.

[0044]

[Table 1]

Note: [Rigidity] is [bending elastic modulus x plate thickness 3
Squared].

As shown in the evaluation results of Table 1, Examples 1 and 2 are superior to Comparative Examples 1 to 3 in that the weight is kept light and the decrease in bending strength is suppressed and the bending rigidity is excellent. Recognize. That is, by dissolving the gas in the polymerizable monomer and coexisting with the surfactant (Examples 1 and 2), it is possible to uniformly generate small bubbles as compared with the case where the surfactant is not included (Comparative Example 1). And many could be formed. As a result, the specific gravity can be reduced and high bending rigidity can be realized while keeping the weight light. In addition, when gas was not used (Comparative Examples 2 and 3), air bubbles were not generated, and thus the lightness and bending rigidity were poor. From this result, the effect of the present invention was proved.

[0047]

According to the present invention, in the polymerizable monomer,
A gas that does not affect the polymerization reaction is dissolved, and a surfactant that does not affect the polymerization reaction coexists in the polymerizable monomer, and polymerization and molding are performed at the same time, resulting in a light weight and rigidity. An excellent foam-polymerized molded article can be provided.

The foamed polymer molding of the present invention is excellent in weight reduction, impact resistance and rigidity, and also has good productivity.
Construction and civil engineering materials such as septic tanks, water tanks, drainage channels, concrete panels, water meter covers, trash cans, bumpers for cars and trucks, air deflectors, vehicle parts such as body exteriors, chassis for shovel cars, bodies, bumpers, etc. , Construction equipment parts such as generator covers, medical equipment parts such as diagnostic machine bodies, waterproof pans, bathtub pans, wash bowl housing materials, recreational applications such as outboard motor covers and golf cart bodies. Is useful for various covers, exterior members such as bodies, and the like.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 4F204 AA12 AA45 AB02 AB10 AG20                       EA01 EB01 EF01 EF02                 4F206 AA12L AB10 AB15 AG20                       AR12 AR15

Claims (7)

[Claims] 1. A method for producing a molded article obtained by simultaneously polymerizing and molding a polymerizable monomer in the presence of a polymerization catalyst, wherein a gas that does not affect the polymerization reaction is dissolved in the polymerizable monomer, and A method for producing a foamed and polymerized molded article, which comprises performing the polymerization by incorporating a surfactant that does not affect the polymerization reaction. 2. The method for producing a foam-polymerized molded article according to claim 1, wherein the polymerizable monomer is a metathesis-polymerizable cyclic olefin. 3. A monomer solution A (solution A) composed of a metathesis-polymerizable cyclic olefin containing a metathesis polymerization catalyst system catalyst component as a polymerizable monomer, and a metathesis polymerization cyclic product containing a metathesis polymerization catalyst system activator component. The method for producing a foam-polymerized molded article according to claim 2, wherein a molded article is produced by using a monomer liquid B (solution B) containing an olefin and mixing these. 4. The method for producing a foamed polymer according to claim 1, wherein the surfactant is a fluorine-containing surfactant or a silicone-containing surfactant. 5. The method for producing a foamed polymer molded article according to claim 1, wherein the gas is nitrogen, argon, helium, carbon dioxide, or a mixture thereof. 6. The production of a foam-polymerized molded article according to claim 1, wherein the content of the surfactant is 0.001% by weight to 2% by weight based on the whole polymerizable monomer. Method. 7. A polymerizable monomer comprising a metathesis-polymerizable cyclic olefin is dissolved in a gas which does not affect the polymerization reaction in the presence of a metathesis polymerization catalyst system, and the polymerization reaction is affected. A foamed polymer molded article obtained by containing a surfactant which does not extend and mixing these to perform polymerization and molding at the same time, which contains a large number of bubbles having an average diameter of 100 μm or less and a specific gravity of 0. A foamed polymer molded article having a range of 55 to 0.95.