CN111153435A

CN111153435A - Preparation method of antimony pentoxide crystal flame retardant

Info

Publication number: CN111153435A
Application number: CN202010000444.0A
Authority: CN
Inventors: 于淮旭
Original assignee: Individual
Current assignee: Individual
Priority date: 2020-01-06
Filing date: 2020-01-06
Publication date: 2020-05-15

Abstract

With the continuous development of flame retardant technology, antimony trioxide is widely used as a flame retardant synergist, but antimony trioxide is poor in flame retardant effect when used alone, and can only be used together with halogen compounds to achieve a synergistic effect, and moreover, high-quality antimony trioxide is expensive in price, even if part of arsenic trioxide exists in high-quality antimony trioxide, and because arsenic trioxide is high in toxicity, hidden dangers harmful to body health are buried in the production and use processes. The antimony pentoxide crystal prepared by the invention has crystal water (about four crystal water), is small in single use amount, good in flame retardant effect, low in toxicity (arsenic trioxide in the antimony trioxide is oxidized into arsenic pentoxide), low in cost, safe and environment-friendly in production and use processes, and suitable for large-scale industrial production.

Description

Preparation method of antimony pentoxide crystal flame retardant

Technical Field

The invention belongs to the technical field of flame retardants, and particularly relates to a preparation method of an antimony pentoxide crystal flame retardant.

Background

With the continuous development of flame retardant technology, flame retardant materials have become a new research direction, and the traditional antimony trioxide product is widely applied to the industries of epoxy resin, polyurethane, polystyrene, polyvinyl chloride, polyester, rubber, plastics and the like as a flame retardant synergist. When the antimony trioxide is used alone, the flame retardant effect is poor, and the synergistic effect can be achieved only by using the antimony trioxide together with halogen compounds, because the antimony trioxide reacts with the halogen compounds to generate the flame-retardant antimony halide, so that the good flame retardant effect is achieved.

Antimony trioxide itself does not contain crystal water and cannot play a role in flame retardance by releasing crystal water. In the flame-retardant formula of some manufacturers, the antimony trioxide can be used together with compounds containing crystal water (such as aluminum hydroxide, magnesium hydroxide, zinc borate and the like), so that a better flame-retardant effect is achieved in the product. However, antimony trioxide with high quality is expensive, so that the production cost is high, and the flame retardant effect is not ideal when the antimony trioxide is used alone. Even in the high-quality antimony trioxide, part of arsenic trioxide still exists, and because the toxicity of the arsenic trioxide is high, the hidden trouble of harming the health of a human body is buried in the production and use processes. The search for flame retardant products capable of replacing antimony trioxide is the research direction of flame retardant technical materials.

Disclosure of Invention

In view of the above problems, an object of the present invention is to provide a method for preparing an antimony pentoxide crystal flame retardant, the antimony pentoxide crystal prepared by the method of the present invention has crystal water (about four crystal water), a small amount of single use (which can replace antimony trioxide and reduce a part of the amount of crystal water-containing compound in the formula), good flame retardant effect, low toxicity (arsenic trioxide in antimony trioxide is oxidized into arsenic pentoxide), low cost, safe and environment-friendly production and use processes, and suitability for large-scale industrial production.

The invention provides a preparation method of an antimony pentoxide crystal flame retardant, which comprises the following specific steps:

1) sequentially adding water, a stabilizer and antimony trioxide into a reaction container with a reflux stirring device, and stirring and heating to obtain a mixed solution; the mass ratio of the raw materials is water to stabilizer: antimony trioxide 2-3.5: 0.1-1.8: 0.6-2.5.

2) Dropwise adding hydrogen peroxide into the mixed solution obtained in the step 1) at the speed of 0.02-0.15ML/s to obtain antimony pentoxide hydrosol; the concentration of the used hydrogen peroxide is generally 25 to 32 percent.

3) Keeping the temperature of the mixture obtained in the step 2) at 80-120 ℃ in a reaction vessel for reacting for two hours, then discharging the mixture while the mixture is hot at 80-120 ℃, and sealing the mixture in the vessel until the mixture becomes antimony pentoxide gel.

4) Drying the antimony pentoxide gel into crystals in a drying device at 90-120 ℃.

5) Grinding the obtained crystal powder into powder to obtain the antimony pentoxide crystal flame retardant.

The stabilizer in the step 1) is preferably a mixture of organic amine and phosphate or phosphoric acid, and can also be a phosphate of fatty alcohol amine, wherein the mass ratio of the organic amine to the phosphate or the phosphate is 1.5-2.5: 0.1-1.8;

the organic amine is preferably formamide or acetamide or N, N-dimethylethylamine or ethylenediamine or ethanolamine or diethanolamine or triethanolamine or methoxyethanol amine or N-methyldiethanolamine or aniline or any combination thereof.

The phosphate or phosphoric acid comprises ammonium monohydrogen phosphate or ammonium dihydrogen phosphate or ammonium phosphate or sodium monohydrogen phosphate or sodium dihydrogen phosphate or sodium phosphate or phosphoric acid or potassium monohydrogen phosphate or potassium dihydrogen phosphate or phosphoric acid or any combination thereof;

the phosphate of the fatty alcohol amine comprises formamide phosphate, acetamide phosphate, N-dimethylethylamine phosphate, ethylenediamine phosphate, methoxyethanol amine phosphate, N-methyldiethanolamine phosphate, aniline phosphate, ethanolamine phosphate, diethanolamine phosphate, triethanolamine phosphate or any combination thereof;

the sealed container in the step 3) is a reaction kettle, a plastic barrel with a cover, an iron barrel with a cover, a trough with a cover or any combination thereof.

The drying equipment in the step 4) comprises an air-blast drying box, spray drying equipment, reduced-pressure drying equipment and the like.

The preferable reagents are industrial products, wherein the content of antimony trioxide is more than or equal to 98 percent, the purity of the selected organic amine is more than or equal to 70 percent, and the concentration of the selected hydrogen peroxide is 25 to 32 percent. The industrial reagent is used, so that the cost can be saved in the actual production, and the method is suitable for large-scale production.

The antimony pentoxide crystal prepared by the method has crystal water (about four crystal water), is small in single use amount (the part of crystal water compound in the formula can be reduced while antimony trioxide is replaced), good in flame retardant effect, low in toxicity (arsenic trioxide is oxidized into arsenic pentoxide), low in cost, safe and environment-friendly in production and use processes, and suitable for large-scale industrial production.

Detailed Description

The technical solutions in the embodiments of the present invention are clearly and completely described, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Example 1

The invention provides a preparation method of an antimony pentoxide crystal flame retardant, which comprises the following steps:

a preparation method of antimony pentoxide crystal flame retardant comprises the steps of adding 160g of deionized water into a container with a reflux device, adding 26g of ammonium monohydrogen phosphate and 59g of diethanolamine into the container respectively, heating the mixture to react completely under continuous stirring, adding 79 g of antimony trioxide until the antimony trioxide is dispersed uniformly, dropwise adding 101g of hydrogen peroxide at the speed of 0.02ml/s, and continuing heating the mixture to react until the antimony trioxide is completely dissolved to obtain light yellow transparent liquid, wherein the content of antimony in the mixed liquid is about 15%. And (3) preserving the product in a reaction container at 90 ℃ for 2 hours, discharging the obtained product into a plastic bucket with a cover when the product is hot at 90 ℃ until the product becomes gel, drying the gel into crystals through an air drying oven, and grinding the crystals into powder according to actual needs.

Example 2

a preparation method of antimony pentoxide crystal flame retardant comprises the steps of adding 164g of deionized water into a container with a reflux device, adding 32g of sodium monohydrogen phosphate and 75g of ethanolamine into the container respectively, heating the mixture to react completely under continuous stirring, adding 107 g of antimony trioxide until the antimony trioxide is uniformly dispersed, dropwise adding 137g of hydrogen peroxide into the reaction container at the speed of 0.04ml/s, and continuing heating the mixture to react until the antimony trioxide is completely dissolved to obtain light yellow transparent liquid, wherein the content of antimony in the product is about 23%. And (3) preserving the product in a reaction kettle at 105 ℃ for 2 hours, discharging the obtained product into a plastic bucket with a cover when the product is hot at 105 ℃ until the product becomes gel, drying the gel into crystals by a spray dryer, and grinding the crystals into powder according to actual needs.

The antimony pentoxide crystal flame retardant prepared by the method provided by the invention has good performance.

The antimony pentoxide crystal product prepared by the invention contains crystal water (about four crystal water), is small in single use amount (the part of crystal water compound in the formula can be reduced while antimony trioxide is replaced), good in flame retardant effect, small in toxicity (arsenic trioxide is oxidized into arsenic pentoxide), low in cost, safe and environment-friendly in production and use processes, and suitable for large-scale industrial production.

Claims

1. The invention provides a preparation method of an antimony pentoxide crystal flame retardant, which comprises the following specific steps:

1) sequentially adding water, a stabilizer and antimony trioxide into a reaction container with a reflux stirring device, and stirring and heating to obtain a mixed solution; the mass ratio of the raw materials is water to stabilizer: antimony trioxide 2-3.5: 0.1-1.8: 0.6-2.5;

2) dropwise adding hydrogen peroxide into the mixed solution obtained in the step 1) at the speed of 0.02-0.15ML/s to obtain antimony pentoxide hydrosol; the concentration of the used hydrogen peroxide is generally 25 to 32 percent;

3) keeping the temperature of the mixture obtained in the step 2) at 80-120 ℃ in a reaction container for reacting for two hours, then discharging the material while the material is hot at 80-120 ℃, and sealing the material in the container until the material becomes antimony pentoxide gel;

4) drying the antimony pentoxide gel into crystals in drying equipment at 90-120 ℃;

2. The preparation method of antimony pentoxide crystal flame retardant according to claim 1, wherein the stabilizer in step 1) is preferably a mixture of organic amine and phosphate or phosphoric acid, and optionally a phosphate of fatty alcohol amine, wherein the mass ratio of organic amine to phosphoric acid or phosphate is 1.5-2.5: 0.1-1.8.

3. The method of claim 1, wherein the organic amine is preferably formamide, acetamide, N-dimethylethylamine, ethylenediamine, ethanolamine, diethanolamine, triethanolamine, methoxyethanolamine, N-methyldiethanolamine, aniline, or any combination thereof.

4. The method of claim 1, wherein the phosphate or phosphoric acid includes ammonium monohydrogen phosphate or ammonium dihydrogen phosphate or ammonium phosphate or sodium monohydrogen phosphate or sodium dihydrogen phosphate or sodium phosphate or phosphoric acid or potassium monohydrogen phosphate or potassium dihydrogen phosphate or phosphoric acid or any combination thereof.

5. The method of claim 1, wherein the phosphate of the fatty alcohol amine comprises formamide phosphate, acetamide phosphate, N-dimethylethylamine phosphate, ethylenediamine phosphate, methoxyethanolamine phosphate, N-methyldiethanolamine phosphate, aniline phosphate, ethanolamine phosphate, diethanolamine phosphate, triethanolamine phosphate, or any combination thereof.

6. The method for preparing antimony pentoxide crystal flame retardant according to claim 1, wherein the sealed container of step 3) is a reaction kettle or a plastic bucket with a cover or an iron bucket with a cover or a silo with a cover or any combination thereof.

7. The method for preparing antimony pentoxide crystal flame retardant according to claim 1, wherein the drying equipment of step 4) includes an air-blast drying oven, a spray drying equipment, a reduced pressure drying equipment, and the like.