JPH0615621B2 - Method for producing high hardness plastic molded body - Google Patents

Description

TECHNICAL FIELD The present invention relates to a novel method for producing a high hardness plastic molded body. More specifically, the present invention relates to
Two types of solid-state polymerizable diacetylene nylon salt compounds, which proceed in two different ways, are first solid-phase polymerized at the diacetylene part, then filled in a mold and subjected to heat polycondensation under high pressure. The present invention relates to a method for easily manufacturing a plastic molding having extremely high hardness.

2. Description of the Related Art In recent years, new materials have been actively developed in various fields, and one of them is expected to be a lightweight and easy-to-process strength material that replaces metals and inorganic materials. Research and development of high-performance polymer materials with high efficiency are being actively conducted.

Conventionally, as a polymer material having high strength and high elastic modulus,
Whisker crystals of polyoxymethylene and polyarylamides, such as Kevlar (trade name of DuPont) and Nomex (trade name of DuPont), are known to be rigid polymer fibrous oriented crystals. The strength is about several GPa (gigapascal) to tens of GPa, and the elastic modulus is about several tens GPa to 100 GPa. In order to make these polymer materials excellent in strength and elastic modulus, various studies have been made on techniques for orienting and crystallizing the polymer materials, for example, a super-drawing method, a liquid crystal spinning method, a gel spinning method.・ Technologies such as gel hot drawing method and carbonization method have been developed. However, a perfect crystal body has not been obtained by any of these techniques, and therefore the polymer material is not always satisfactory in strength and elastic modulus.

On the other hand, the diacetylene compound represented by the general formula R-C≡C-C≡C-R (I) has a main chain when the crystal is excited by heat, ultraviolet rays, or γ rays by selecting the substituent R. It is known to exhibit solid-state polymerizability such that it becomes a polymer compound having a conjugated system. The polymer compound obtained by this method is characterized by being a perfect single crystal that reflects the crystal arrangement of the monomer as it is. It is also reported that the polymer compound has an elastic modulus of about 60 GPa in the direction in which the polymer chains are oriented. "[Polymer] Vol. 24, No. 10
23-1030 (1983)].

By the way, since the material having the strongest strength existing in nature is diamond, in the molecular design of a polymer material having a high strength and a high elastic modulus, the molecular occupied cross-section is small and multidimensional covalent bonds are present. Although it has been theoretically shown that it is necessary to produce a single crystal body,
The current situation is that such a thing has not been found.

All of the highly oriented and highly crystalline polymer compounds that have been synthesized and molded for the purpose of obtaining high-strength materials are one-dimensional chain polymer compounds. Although it has an elastic modulus, it has the drawback of low strength and elastic modulus in the direction perpendicular to it.
In particular, polydiacetylene obtained as a perfect single crystal is
For example, it has the drawback that it is fragile enough to cleave into a fiber shape in the direction perpendicular to the polymer chain.

On the other hand, as a polymer compound having a multidimensional covalent bond, a compound synthesized by a method such as intermolecular cross-linking is known, but it is extremely difficult to highly crystallize by such a method, and an amorphous network Only the polymer compound is obtained.

Thus, a polymer material having isotropically high strength and high elastic modulus has not been found so far, and its development has been strongly desired.

Therefore, the inventors of the present invention have conducted extensive studies to develop such a polymer material, and have first made the general formula The diacetylene nylon salt compound represented by the formula (wherein R ₁ and R ₂ are alkylene groups or arylene groups having or not having a substituent) is a solid phase polymerizability of the diacetylene moiety and a solid phase of the nylon salt moiety. It was found that polycondensation, which is a solid-state polymerizability that advances in two different directions, is used. Further, from this, a method for producing a highly crystalline polymer compound having a network structure having a two-dimensional covalent bond is described. Proposed.

Problems to be Solved by the Invention However, since the two-dimensional polymer crystal body obtained by the above method has high strength and high elastic modulus, it is difficult to obtain a molded body.

The present invention solves the above problems and uses a diacetylene nylon salt compound represented by the general formula (II), and has a network structure having a two-dimensional covalent bond and high crystallinity,
The object of the present invention is to provide a method for easily producing a molded product made of a high hardness polymer compound having excellent hardness and elastic modulus.

Means for Solving the Problems As a result of intensive studies to achieve the above-mentioned object, the present inventors have found that the diacetylene nylon salt compound shows that the diacetylene moiety has a solid phase polymerizability and a nylon salt moiety has a solid phase. Focusing on polycondensation, which is a solid-state polymerizability that progresses in two different directions, the diacetylene nylon salt compound was preliminarily subjected to solid-phase polymerization of the diacetylene moiety, and then formed into a molding die of a desired shape. It was found that the purpose can be achieved by filling and heating and polycondensing under high pressure, and the present invention has been completed based on this finding.

That is, the present invention is based on the general formula (Wherein R ₁ and R ₂ are each an alkylene group, a cycloalkylene group or an arylene group having or not having a substituent), and a diacetylene moiety is first solid-phase polymerized. After that, it was filled in a molding die having a desired shape, and was placed under a pressure of 0.5 × 10 ⁴ to 15 × 10 ⁴ atm for 1
The present invention provides a method for producing a high-hardness plastic molded article, which comprises performing heat polycondensation at a temperature of 00 to 400 ° C.

Hereinafter, the present invention will be described in detail.

In the method of the present invention, the diacetylene nylon salt compound used as a raw material has a structure represented by the above general formula (II) (Wherein R ₁ has the same meaning as described above) and a general formula H ₂ N—R ₂ —NH ₂ (IV) (wherein R ₂ has the same meaning as described above) And a diamine represented by the formula (1) are mixed in equimolar amounts to quantitatively obtain a crystalline substance. When mixing the diacetylene carboxylic acid and the diamine,
When both are liquids, they may be mixed as they are, but when at least one is a solid, both are added and dissolved in a suitable organic solvent such as methanol, tetrahydrofuran, chloroform, ethyl acetate or dimethylformamide, It is desirable to mix them uniformly. The concentration of this solution is not particularly limited, but usually 1 mmol / ~ 1
It is selected in the range of 0 mol / degree.

In this way, by mixing the diacetylenecarboxylic acid and the diamine, the diacetylene nylon salt compound represented by the general formula (II) is formed with heat generation due to salt formation. This diacetylene nylon salt compound is
It may precipitate immediately after mixing as a crystal, may precipitate after several hours, or may not precipitate in some cases. When the crystals do not precipitate by mixing alone, the crystals may be precipitated by heating the solution to near the boiling point of the solvent and then cooling it, or by concentrating the solution and then cooling it. The precipitated crystal may be filtered and dried as it is, or may be recrystallized using a suitable solvent such as an ethanol-water mixed solvent, if desired.

R ₁ in the diacetylenecarboxylic acid represented by the general formula (III) and R ₂ in the diamine represented by the general formula (IV) are each an alkylene group having no substituent, a cycloalkylene group or an arylene group. Also, having at least one kind of substituent such as halogen atom, cyano group, alkyl group, aryl group, nitro group, ether group, ester group, amide group, hydroxyl group, carbonyl group, sulfonyl group, alkylene group, cyclo It may be an alkylene group or an arylene group.

In the method of the present invention, the diacetylene nylon salt compound represented by the general formula (II) obtained as described above is first subjected to solid phase polymerization of the diacetylene moiety and then formed into a molding die having a desired shape. The desired molded product can be obtained by filling and heating and polycondensation under high pressure. Regarding the solid-state polymerization of the diacetylene portion at this time, a vacuum sealed tube was used and cobalt 60 gamma rays were irradiated for 10 MRad to several hundred MRa.
The polydiacetylene nylon salt crystals are obtained by irradiating d or dispersing them in a solvent in which a diacetylene nylon salt compound such as methanol, chloroform or benzene is not dissolved and irradiating with ultraviolet rays for several hours to several hundred hours. . In addition, the pressurizing method at this time is not particularly limited as long as isotropic pressurizing conditions can be obtained, and any method can be used. It is advantageous to use a method in which the polydiacetylene nylon salt crystal is filled in a molding die using as a pressure medium and pressure is applied in a link type cubic arrangement anvil device. The figure is an oblique cross-sectional view showing an example of the structure in which a molding die using pyroferrite 1 as a pressure medium is filled with polydiacetylene nylon salt crystal 4, 2 is a nickel current ring, and 3 is a molybdenum plate. , 5 are polydiacetylene nylon salt crystals 4
The sample tube made of Teflon filled with is a carbon heater 6 for heating the sample tube.

The pressure in the method of the present invention is selected in the range of 0.5 × 10 ⁴ to 15 × 10 ⁴ atm. If this pressure is less than 0.5 × 10 ⁴ atm, a high-hardness plastic molded article, which is the object of the present invention, cannot be obtained, and a pressure higher than 15 × 10 ⁴ atm is not required, which is rather economically disadvantageous. .

On the other hand, the heating method is not particularly limited as long as the steady temperature can be maintained for a certain period of time. For example, a method of supplying a constant current to the carbon heater 6 having the structure shown in the figure to heat it can be used. The temperature in the polycondensation reaction of the method of the present invention is selected in the range of 100 to 400 ° C. If this temperature is less than 100 ° C, the reaction rate is too slow to be practical, and if it exceeds 400 ° C, the temperature is too high and the molded product may be deteriorated.

Furthermore, the reaction time depends on the type of raw material, pressure, temperature, etc., but 20 to 180 minutes is usually sufficient. Regarding the shape of the obtained molded body, it is possible to obtain an arbitrary shape by devising a molding die.

The plastic molded product thus obtained has a network structure having a two-dimensional covalent bond and a high crystallinity, has high strength and high elastic modulus, and is extremely hard. is doing. For example, according to the method of the present invention, the hardness H _v measured by a Vickers micro altimeter is 60-
A molded body of 300 kg / mm ² can be obtained. The Vickers hardness is about three times the yield stress and has a proportional relationship with the elastic modulus. The molded body is made of copper (H _v = 95), iron (H _v
= 130), and has reached a high hardness comparable to platinum (H _v = 150).

EFFECTS OF THE INVENTION According to the method of the present invention, a diacetylene nylon salt compound is first subjected to solid-state polymerization of the diacetylene moiety and then subjected to heat polycondensation under high pressure in a desired molding die, A reticulated and highly crystalline plastic molded product having a two-dimensional covalent bond can be easily manufactured.

The plastic molded body is excellent in strength and elastic modulus as compared with the conventional one, and has a hardness as high as that of a metal, so that it is extremely useful as a lightweight and highly hard material.

EXAMPLES Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

Example 1 Formula When the diacetylene nylon salt compound represented by the formula (1) was sealed in a vacuum tube and irradiated with 50 MRad of cobalt 60 gamma rays, the diacetylene portion was subjected to solid-state polymerization to produce black-blue polydiacetylene nylon salt crystals. The crystal,
With the configuration as shown in the figure, while filling the molding die, pressurizing at 50,000 atm in the link type cubic arrangement anvil device, energize the carbon heater built in the molding die,
It was heated to 230 ° C. and reacted for 20 minutes.

After completion of the reaction, the sample was taken out to obtain a cylindrical plastic molded body of about 3 mmφ × 3 mm. Since the infrared carbonyl absorption band of this product was shifted from 1550 cm ^-1 to 1630 cm ^-1 , it was confirmed that the nylon salt portion was also solid-phase polycondensed to form polyamide. From the X-ray diffraction pattern, this sample was found to be a two-dimensional polymer crystal with a surface spacing of 4.2Å, and the Vickers hardness H _v was about 190 kg / mm ² .

Example 2 Formula The diacetylene nylon salt compound represented by is dispersed in benzene and stirred, and a high pressure mercury lamp (100
Upon irradiation with W) for 10 hours, the color changed to dark blue, and the diacetylene portion was solid-phase polymerized to produce polydiacetylene nylon salt crystals. The crystal was filled in a mold as shown in the figure, and the carbon heater built in the mold was energized and heated to 300 ° C while pressurizing at 30,000 atm in a link type cubic anvil device. For 30 minutes.

After completion of the reaction, the sample was taken out to obtain a cylindrical plastic molded body of about 3 mmφ × 2 mm. This was confirmed to be a two-dimensional polymer crystal by the same method as in Example 1, and its Vickers hardness was about 160 kg / mm ² .

Example 3 Formula When the diacetylene nylon salt compound represented by the formula (1) was sealed in a vacuum tube and irradiated with 200 MRad of cobalt 60 gamma rays, the diacetylene portion was solid-phase polymerized to produce red polydiacetylene nylon salt crystals. With the structure shown in the figure, the crystal was filled in a molding die, and while being pressurized at 80,000 atm in a link type cubic arrangement anvil device, a carbon heater incorporated in the die was energized,
A two-dimensional polymer crystal compact similar to that in Example 1 was obtained by heating at 0 ° C. and reacting for 20 minutes. The Vickers hardness H _{v of} this product was about 260 kg / mm ² .

Example 4 Formula When the diacetylene nylon salt compound represented by the formula (1) was sealed in a vacuum tube and irradiated with 80 MRad of cobalt 60 gamma rays, the diacetylene portion was solid-state polymerized to form a blue polydiacetylene nylon salt crystal exhibiting a metallic luster.
The crystal was packed in a molding die with the structure as shown in the figure, and a carbon heater built in the die was energized while pressurizing at 100,000 atm in a link type cubic arrangement anvil device, at 120 ° C. By heating to 120 ° C. and reacting for 120 minutes, a two-dimensional polymer crystal compact similar to that of Example 1 was obtained. The Vickers hardness H _{v of} this product is 200 kg / mm ²
Met.

Example 5 Formula When the diacetylene nylon salt compound represented by the formula (1) was sealed in a vacuum tube and irradiated with 300 MRad of cobalt 60 gamma rays, the diacetylene portion was solid-phase polymerized to produce black-purple polydiacetylene nylon salt crystals. With the structure shown in the figure, the crystal was filled in a molding die, and a carbon heater built in the die was energized while being pressurized at 10,000 atm in a link type cubic arrangement anvil device.
A two-dimensional polymer crystal compact similar to that of Example 1 was obtained by heating to 50 ° C. and reacting for 30 minutes. The Vickers hardness H _{v of} this product was 300 kg / mm ² .

[Brief description of drawings]

FIG. 1 is a cross-sectional view showing an example of a structure in which a polydiacetylene nylon salt crystal is filled in a molding die in order to carry out the present invention. In the figure, reference numeral 1 is pyroferrite,
2 is a current ring, 3 is a molybdenum plate, 4 is a polydiacetylene nylon salt crystal, 5 is a Teflon sample tube, and 6 is a carbon heater.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-63-63713 (JP, A) JP-A-63-221115 (JP, A)

Claims (1)

[Claims] 1. A general formula (Wherein R ₁ and R ₂ are each an alkylene group, a cycloalkylene group or an arylene group with or without a substituent), and a diacetylene moiety is first solid phased. After the polymerization, the mixture was filled in a molding die having a desired shape and the pressure was 0.5 × 10 ⁴ to 15 × 10 ⁴ atm.
A method for producing a high-hardness plastic molded product, which comprises performing heat polycondensation at a temperature of 0 to 400 ° C.