JPH0369288B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The metal salt polymer molded product of the present invention has high heat resistance and compressive elastic modulus, and is useful as gears, aircraft materials, architectural structural materials, and electronic/electrical materials. [Prior Art] Polystyrene sulfonic acid metal salts and polystyrene carboxylic acid metal salts are infusible and do not soften or melt even when heated, so they cannot be injection molded or compression molded. If the metal is an alkali metal,
Although it can be cast from an aqueous solution, it can only be made into a thin film and its strength is weak. Furthermore, when the metal is a lanthanide element, cast polymerization can be performed from monomers (see Japanese Patent Laid-Open No. 57-5705), but the degree of polymerization is low and the strength is low. [Problems to be Solved by the Invention] The present invention seeks to provide a method for producing a molded article of the metal salt polymer having high strength and high modulus of elasticity in an arbitrary shape, which has not been previously possible. be. [Specific means for solving the problem] In the present invention, by press-molding the metal salt polymer powder, it is possible to obtain a molded article with good mold releasability, high strength, and high elastic modulus. can. That is, in the present invention, after filling a powder of infusible polystyrene sulfonic acid metal salt and/or polystyrene carboxylic acid metal salt into a mold, a powder of 1000 kg/cm ² or more 10
The present invention provides a method for producing a molded body of a metal salt polymer, which is characterized in that the molded body is formed by compacting the powder at a pressure of 10,000 kg/cm ² or less. (Metal salt polymer) Metal salt polymer is produced by mixing, for example, polystyrene sulfonic acid and/or polystyrene carboxylic acid in an aqueous solution of an alkali metal hydroxide such that the amount of metal ions is 0.1 to 20 equivalents per equivalent of the acidic group of the polymer. It can be obtained by adding a solution of a metal compound such as a metal chloride to and reacting it. The polymers used to produce metal salt polymers are:
It can be obtained by copolymerizing or polymerizing only styrene sulfonic acid and/or styrene carboxylic acid. The degree of polymerization of this polymer is 50 to 300,000, and in order to make the molded product high in strength, a higher degree of polymerization is better, so a degree of polymerization of 100 or more is preferable, and the polymer solution used when producing the metal salt polymer should have a lower degree of polymerization. It is preferably 50,000 or less because it has a low viscosity and is easy to handle. Metal ions include Li ⁺ , Na ⁺ , K ⁺ , Pb ⁺ ,
Cs ⁺ , Be ²⁺ , Mg ²⁺ , Ca ²⁺ , Sr ²⁺ , Ba ²⁺ , La ³⁺ ,
Ti ⁴⁺ , Cr ³⁺ , Mn ²⁺ , Fe ²⁺ , Fe ³⁺ , Co ²⁺ , Ni ²⁺ ,
Cu ⁺ , Zn ²⁺ , Al ³⁺ , Sn ⁴⁺ , Pb ²⁺ etc. can be used.
These may be used in combination. After the reaction, the precipitated metal salt polymer is filtered to separate the solvent, and then washed to remove unreacted materials and
By-products are removed, then dried and, if necessary, ground to form a powder of 0.01 to 500 microns, which is used as a molding material. In order to obtain a dense molded body, the smaller the particle size, the better it is, so the particle size is preferably 200 microns or less.In terms of handling, the larger the particle size, the easier it is, so the particle size is preferably 0.1 micron or more. The molded body is obtained by filling a cavity 1 of a compression mold shown in FIG. 1 with metal salt polymer powder, and heating and pressurizing the powder. Molding temperature is room temperature ~ 500℃
℃, and above 100℃ to promote molding.
In order to prevent decomposition of the polymer, the temperature is preferably 400°C or lower. The molding pressure must be adjusted to obtain a compact molded product.
It is preferably 1000 Kg/cm ² or more, and 100,000 Kg/cm ² or less from the viewpoint of pressure resistance of a mold that is easily available and can be used repeatedly. In the figure, 1 is a cavity, 2 is a housing material for forming the cavity, 3 is a piston rod, 4 is a cylinder, 5 is an O-ring, 6 is an O-ring holder, 7 is an outer cylinder, 8 is an outer cylinder planting part, 9 1 is a lower part of the outer cylinder, and 10 is an exhaust pipe. The atmosphere during pressurized powder molding may be any atmosphere such as nitrogen gas, helium gas, air, etc., but it is preferably carried out under vacuum (0.0001 to 100 mmHg). The shape of the molded body is arbitrary, such as a rod shape, a plate shape, and a gear shape. This molded body can be subjected to heat treatment, cutting, cutting, perforation, etc., as necessary. (Effects of the Invention) The effects obtained by the manufacturing method of the present invention are summarized as follows. It is possible to obtain a molded article of any shape, not only a film shape, but also a rod shape, a plate shape, a block shape, a cam shape, a tooth shape, etc. The obtained molded body has a high flexural modulus (e.g. 3
gigapascal or higher), heat resistant, and free from cracks and cracks. [Example] Hereinafter, the present invention will be explained in more detail with reference to Examples. Production example of metal salt polymer powder Powder ZnCl 2 0.1 in 300 c.c. of water is added to a polymer solution in which 0.1 equivalent of polystyrene sulfonic acid and 0.1 equivalent of NaOH are dissolved in a solution consisting of 200 c.c. of water and 300 c.c. of _methanol . An equivalent amount of the metal compound solution was added dropwise with stirring, and 200 c.c. of methanol was further added. The resulting precipitate was filtered, washed, dried, and ground to obtain polystyrene zinc sulfonate powder having an equivalent ratio of 1:1. Powder - Powder - was made to drip a metal compound solution to the polymer solution shown in Table 1, stirring, and also added methanol at 200 °C. The resulting precipitate was filtered, washed, dried and pulverized to obtain metal salt polymer powder shown in Table 1. The formation of metal salts is observed in the infrared absorption spectrum.
CO double bond absorption of 1700 cm ^-1 is COO of 1500 cm ^-1
This was confirmed because the absorption shifted to a resonance structure and the X-ray diffraction spectrum showed an amorphous pattern. Example 1 The powder shown in Table 1 was filled into the cavity 1 formed by the housing materials 2, 2 of the mold shown in FIG. 1 and the cylinder 4 having an inner diameter of 2 cmφ. Next, while exhausting the air inside the cavity through the exhaust pipe 10 using a vacuum pump, the air was heated at 200°C for 60 minutes.
Molded by applying pressure of 6000Kg/ ^cm2 , wall pressure 3mm, diameter
I got a 20mm disc. This disk had a specific gravity of 1.86 and a light brown color. This disk was cut into a rectangular parallelepiped with a length of 15 mm, width of 8 mm, and thickness of 2 mm, and the compressive elastic modulus at 20°C was measured using an autograph manufactured by Shimadzu Corporation at a crosshead speed of 0.5 mm. It was 15.7 gigapascals (GPa). The compressive strength was 0.21GPa. Examples 2 to 20 The powders shown in Table 1 were wedged into a mold, and pressure molded under the molding conditions shown in Table 2 to obtain molded bodies having the physical properties shown in Table 2. Comparative Example 1 A mixture of 100 parts of zinc styrene sulfonate monomer (commercially available, white powder with an equivalent ratio of 1:1) and 1 part of AIBN was placed in a silicone mold and heated at 80 to 100°C for 3 hours, but the casting could not be cured. Ta. Comparative Example 2 The same procedure as in Comparative Example 1 was carried out using aluminum styrene sulfonate (commercially available, white powder with an equivalent ratio of 1:1), but casting hardening could not be achieved. Comparative Example 3 When 1 g of powder was added to 100 g of water, it was insoluble in water and no cast film was obtained. Comparative Example 4 The same procedure as Comparative Example 3 was carried out using powder, and the results were as follows.
It was insoluble in water and no cast film was obtained. Comparative Example 5 A push mold with a cavity of 63.2 x 12.7 x 3.15 mm was heated to 400°C and filled with the powder shown in Table 1,
Compression molding was attempted at 90 kg/cm ² but no molded product was obtained. Furthermore, even when this sample was heated to 600°C, it did not soften or melt.

【table】

【table】 [Brief explanation of drawings]

FIG. 1 is a cross section of the pressurizing device used in Example 1. DESCRIPTION OF SYMBOLS 1...Sample, 2...Housing member, 3...Upper piston rod, 4...Cylinder, 5...O ring, 6...O
Ring holder, 7...Outer cylinder, 8...Outer cylinder upper part, 9...Outer cylinder lower part, 10...Exhaust pipe.

Claims (1)

[Claims] 1. After filling the powder of infusible polystyrene sulfonic acid metal salt and/or polystyrene carboxylic acid metal salt into a mold, 1000 kg/cm 2 or more 100,000 kg/cm ² or more
1. A method for producing a molded body, which comprises forming a molded body by pressurizing powder at a pressure of cm ² or less. 2. The method according to claim 1, wherein the metal is Ca, Zn, or Al. 2. The manufacturing method according to claim 1, wherein the pressurized powder molding is performed under vacuum. 2. The method according to claim 1, wherein the compacting of the powder is carried out at a temperature of room temperature to 500°C. 2. The method according to claim 1, wherein the molded article has a compressive modulus of elasticity of 3 gigapascals (3 GPa) or more as measured in accordance with JIS K7208-1975.