KR100236610B1 - Antimony pentoxide production - Google Patents

Abstract

The present invention relates to a method for preparing high-purity antimony pentoxide that can neutralize the pH of a suspension and overcome the limited range of use due to low viscosity and high concentration, and has a purity of 99.3 to 99.6% of tetragonal antimony trioxide. A suspension process for making a colloidal state by stirring 2.5-3.5 parts by weight of ion-exchanged water and 0.02 to 0.08 parts by weight of triethylamine as a dispersant and 0.01 to 0.07 parts by weight of sodium hydroxide as a catalyst with respect to 1 µm or less of fine particles; Heating the suspension at about 20 to 30 ° C., and then exothermicly adding 1.0 to 1.6 mol of hydrogen peroxide to 1 mol of antimony trioxide; In order to prevent the generation of new reactants at the start of the exothermic reaction, the hydrogen peroxide introduced in the exothermic process is uniformly repeated for about 1 hour to 1 hour 30 minutes to maintain the exothermic reaction up to 112 to 124 ° C. Process; It consists of a cooling process to cool by natural reflux without inputting a heat source.

Description

Method of manufacturing antimony pentoxide

The present invention relates to a method for producing high purity antimony pentoxide, which can neutralize the pH of a suspension and overcome the limited range of use due to low viscosity and high concentration, and more particularly, to an antimony pentoxide in a liquid colloidal state. And a process for producing antimony pentoxide powder, which is dried and powder-treated with antimony pentoxide.

Conventionally, antimony trioxide is mainly used as a flame retardant added to a product, and antimony trioxide is added to products such as PVC resin and fiber to make a flame retardant product.

However, as described above, in the case of the antimony trioxide, an inorganic flame retardant, when the antimony trioxide solution in suspension was prepared, the particulate state was settled to ultrafine particles, so that the colloidal liquid phase was not obtained.

In order to compensate for these disadvantages, the suspension of antimony trioxide (Sb ₂ O ₃ ) made by oxidizing antimony trioxide is used to enhance the stability and flexibility of the product by excellent application of diversification, excellent flame retardant effect, transparency, and non-settling property. I can do it.

On the other hand, powder type (Powder Type), when used in a product that meets the purpose of use than antimony trioxide, excellent gloss transparency, colorability, low specific gravity, excellent dispersibility and excellent flame retardancy.

Therefore, in recent years, due to the diversity and superiority of the use, the study of the sol type (powder type) and the powder type (powder type) of antimony pentoxide was proceeded considerably.

As its typical example, Japanese Unexamined Patent Application 52-21298 discloses a portion of antimony trioxide to pentoxide particles of the large particle size of about 4000Å to make antimony after heating 90 to 105 ℃ for producing in response to gwansan hydrogen with respect to the Sb ₂ O ₃ 1 A method for producing a colloidal liquid phase by reacting with -2 mol is disclosed.

In this case, however, the particle size of antimony trioxide (Sb ₃ O ₃ ) is precipitated because of its large particle size, and the effect of dispersion is insufficient. In addition, it is difficult to control the temperature due to the rapid exothermic reaction. It was difficult to obtain antimony (Sb ₂ O ₅ ) in the colloidal liquid phase.

In addition, U.S.P.4026819 discloses a method of adding triethylamine (Triethanol amine) after the reaction using an amine system, which has a disadvantage of low concentration, low pH, and large particles to obtain a colloidal liquid phase.

In addition, Japanese Patent Application Laid-Open No. 63-285120 discloses an antimony trioxide in an active state mixed with 1 part by weight and 2 parts by weight or more of water, and then adds H ₂ O ₂ for 3 hours to react at 80 to 90 ° C. for 5 hours. However, this method has a long reaction time, requires excessive energy, has a problem of sedimentation in the colloidal state, and has a problem of utility due to its strong acidity.

The present invention solves these problems and uses an inorganic alkali catalyst in a specific range of the reaction system to provide a manufacturing method that can industrially mass-produce the colloidal state and powder state suitable for the use according to the characteristics of the product, By using an amine dispersant, antimony pentoxide can be produced industrially advantageously by dissociating in a fully colloidal state and neutralizing low viscosity and high pH.

Therefore, the object of the present invention is to use anti-sedimentation, transparency, pH enhancement, high purity fine particle diameter, antimony pentoxide powder in colloidal form by low energy, simplicity of process, ease of reaction operation, etc. It is providing antimony pentoxide which can be less than 20㎛.

For this purpose, 2.5 to 3.5 parts by weight of ion-exchanged water, 0.02 to 0.08 parts by weight of triethylamine as a dispersant, and 0.01 to 0.01% of sodium hydroxide as a catalyst for tetragonal antimony trioxide with a particle size of 99.3 to 99.6% of 1 µm or less. A suspension process for stirring to 0.07 parts by weight to make a colloidal state; Heating the suspension at about 20 to 30 ° C., and then exothermicly adding 1.0 to 1.6 mol of hydrogen peroxide to 1 mol of antimony trioxide; In order to prevent the generation of new reactants at the start of the exothermic reaction, the hydrogen peroxide introduced in the exothermic process is uniformly repeated for about 1 hour to 1 hour 30 minutes to maintain the exothermic reaction up to 112 to 124 ° C. Process; It can be achieved by a cooling process of cooling by natural reflux without inputting a heat source.

Hereinafter, a method for synthesizing colloidal antimony pentoxide and a powder (Powder) according to the present invention will be described in detail.

As the inorganic alkali material used in the present invention, inorganic salts such as hydroxide of alkaline earth metal, ammonia, sodium carbonate, ammonium carbonate and sodium phosphate can be used. Among them, NaOH, KOH, etc. can be accelerated by using an alkaline earth hydroxide, it can efficiently provide a colloidal antimony oxide having a fine particle diameter.

Therefore, the NaOH is about 0.063% in the range of 0.01 to 0.07% with respect to the amount of the suspension (Paster) used as a result of measuring the amount of the alkaline substance used.

On the other hand, dispersants and stabilizers can be used to enhance the effect by using an amine (Amine) system. Types of this amine include Alkyl amine, Alkanol amine, and Alkanol amine salt.

Alky amines include Ethyl amine, Buthyl amine and Triethamine. Alkanol amines include Monoethanol amine, Di-ethanol amine, and Tri-ethanol amine.

Alkanol salts include Triethanl + phosphate, which is effective in stabilizing foaming and reacting with antimony trioxide. It is preferably about 1-11% for antimony trioxide and about 0.3 ~ 4% for phosphoric acid.

In the above production method, triethylamine (Triethlamine; TEA) was used as a dispersant to obtain the following experimental results in a reactor capable of synthesizing at low viscosity and high concentration.

That is, triethylamine (TEA) may be used in an amount of 0.02% to 0.08% with respect to the paste, and the best condition is 0.077%.

Since the use of this amine system has a low boiling point (B.P), it is possible to improve the purity by forming only the reaction conditions during the reaction and subliming the exothermic temperature at 112 ° C to 124 ° C to remove foreign substances and impurities.

After the reaction is completed, reflux cooling is maintained to prevent internal reactions and to preserve the internal pressure. In addition, by suppressing the unreacted colloidal state and increasing the reactor pressure, high purity and low viscosity can be made by suppressing the amount of generator oxygen from the surface of the reactant. there was.

In addition, it is effective to manufacture high-concentration products suitable for use through evaporation of low-viscosity products, and to improve PH (hydrogen ion concentration), NaOH (concentration: 40%) against antimony pentoxide (concentration: 40%) 1-2.5%), and the best condition is 1.85%. In addition, 1-2% of triethanol amine is added for dispersion and dissociation, and the best condition is 1.25%.

On the other hand, the following surfactants are used to enhance the compatibility of the colloidal application and to improve the dissolution and dispersion of the action after the powder (POWDER) production. In other words, the surfactants are Dodecyl Benzene Chloride and Poly oxyethenealky amine. The former is used in the step of ion exchange by adding hydrochloric acid as a strong cationic surfactant, and the latter is a weak cationic surfactant having various characteristics by carbon and hydrogen of the alkyl group. In particular, poly oxyalkyl amine shows a satisfactory performance in the range of 0.03-0.1% in the colloidal state, preferably 0.05%.

Accordingly, the present application is a method for preparing a colloidal phase, and the catalyst dispersant neutralizing agent dissociating agent is adjusted to meet the purpose of use, such as the use of the conventional drawback of the application of high-calorie needs of the purpose of use can be solved the problem of stability of quality have.

On the other hand, in the case of powder, it is possible to maintain high purity, maintain thermal stability, and at the same time make an excellent product of transparency, coloring, and flame resistance. Application and actual production of each application can be described as follows based on the examples.

Example 1

First, install a stirrer, reflux cooler, vacuum dehydrator and thermometer (internal and external), and paste a small amount of ion-exchanged water NaOH, triethylamine (TEA), etc. into 1 μm HS antimony trioxide (Sb203). A) Liquidize and stir.

When the suspension temperature reaches 22 ° C, 1.03 mol of H ₂ O ₂ aqueous solution (purity 35%) was uniformly added to antimony trioxide (Sb ₂ O 3) for 1 hour to 30 minutes, and the exothermic reaction was 112 ° C. to It leads to 124.

When the exothermic reaction is induced, a aging process is performed for 90 minutes by natural reflux cooling while maintaining the pressure of the tank at 3-4 atm.

Next, a vacuum dewatering method was selected to dehydrate about 40% to enhance solids.

The results of the method described above are as follows.

(1) Composition of suspension and amount of oxidizing agent

(2) Synthesis result

Example 2

In order to adapt the raw material produced in Example 1 to the application, the neutralization of pH, low viscosity, and the expansion of the purpose of use through dissociation of the suspension were used. Therefore, when the suspension of Example 1 was added to the suspension solution while maintaining the suspension at 85 to 105 ° C., 1.85% of NaOH, 1.25% of TEOH.A, and 0.05% of the surfactant POAA were added. Further stabilization proceeds. On the other hand, by adopting the vacuum dehydration method, the solid content was improved through the dehydration process of about 40%. Therefore, it is possible to manufacture a product suitable for the flame-retardant treatment of various applications as SOL. Thus, the tested results are as follows.

Example 3

The sol (SOL) prepared in Example 2 provides a sufficient condition for producing a powder. It can be utilized as a substitute for antimony trioxide in flame retardant of synthetic resin system by removing H2O of colloidal phase. Therefore, the experimental results of the application of PVC resin proved the plasticity, transparency and richness of color (COLOR).

Analysis of the powder (POWDER) of antimony pentoxide (Sb ₂ O5) was as follows.

As described above, in the present invention, first, a method for preparing a sol suspension is prepared by suspending antimony trioxide having a needle-like structure and a coaxial system in water (ion-exchanged water) and adding TEA and NsOH together with the pH adjustment and viscosity of the suspension. Lowered the initial conditions for the pasting (Paste) of the liquid phase by the addition of the oxidizing agent.

In addition, after preheating the suspended material to about 22 ℃, the hydrogen peroxide for Sb ₂ O ₃ is adjusted to maintain the set temperature for a predetermined time at the start of the exothermic reaction, the natural reflux without the heat source after the exothermic reaction Cool and react to aging to form a developer of antimony pentoxide.

After deodorizing strong acid and hydrogen peroxide, the suspension was neutralized by neutralization, and then surfactants were added to make the suspension suitable for each application.

In addition, the antimony pentoxide in powder form was prepared by high-purity antimony pentoxide by fine powdering after drying by ball milling.

Therefore, in the sol type suspension of antimony pentoxide as described above, high flame retardant effect and hiding power as fine particles, small transparency, high sedimentation, no sedimentation, and when chemically produced, a uniform quality product can be obtained and excellent in flame retardancy. It can be used in combination with synthetic resin, rubber, latex, and electronic parts (PCB board) to improve the quality.

On the other hand, in the antimony pentoxide powder type, it is possible to obtain a product with good transparency when applying flame retardant products such as PVC and ABS, and has a high specific gravity, low dispersibility, excellent dispersibility, and high flame retardancy. There is an effect that can be widely applied to such fields.

Claims (3)

Stirring 2.5-3.5 parts by weight of ion-exchanged water, 0.02-0.08 parts by weight of triethamine, a dispersant, and 0.01-0.07 parts by weight of sodium hydroxide, as catalysts, for 1 µm or less particles having a purity of 99.3 to 99.6% of antimony trioxide Suspension process to make the colloidal state by; Heating the suspension at about 20 to 30 ° C., and then exothermicly adding 1.0 to 1.6 mol of hydrogen peroxide to 1 mol of antimony trioxide; In order to prevent the generation of new reactants at the start of the exothermic reaction, the hydrogen peroxide introduced in the exothermic process is uniformly repeated for about 1 hour to 1 hour 30 minutes to maintain the exothermic reaction up to 112 to 124 ° C. Process; A method for producing a colloidal antimony pentoxide comprising a cooling step of cooling by a natural reflux method without adding a heat source. The method of claim 1, wherein 1.85% NaOH, 1.25% TEOH.A, and 0.05% surfactant POAA are added while maintaining the colloidal suspension prepared through the suspension, exothermic, maintenance and cooling processes at 85 ° C to 105 ° C. An addition step of performing; A method for producing a colloidal antimony pentoxide, characterized in that the solid content is improved through a vacuum dehydration process with a dehydration rate of about 40%. The method for producing antimony pentoxide according to claim 2, wherein the colloidal suspension subjected to the vacuum dehydration process is finely powdered by a ball milling operation after removing the water component by a drying process.