A preparation method and application of ultrafine potassium perchlorate

Abstract

The invention relates to the field of inorganic materials, and in particular to a method for preparing ultrafine potassium perchlorate and an application thereof. A potassium chloride aqueous solution is added to an oil phase containing a sulfonate type gemini surfactant to obtain a microemulsion A; a sodium perchlorate aqueous solution is added to an oil phase containing a sulfonate type gemini surfactant to obtain a microemulsion B; the microemulsion A and the microemulsion B are simultaneously added to an organic solvent, reacted at a constant temperature of 50-100 DEG C for 1-10 hours, and then centrifuged, and the product is collected, washed, and dried. The method prepares potassium perchlorate with a hollow rod-shaped structure by combining a microemulsion method with a sulfonate type gemini surfactant, and the potassium perchlorate is used as a smoke generator oxidant and has broad application prospects in the military and civil rescue fields.

Description

Technical Field

[0001] The invention relates to the field of inorganic materials, and in particular to a preparation method of ultrafine potassium perchlorate and application thereof. Background Art

[0002] Smoke agents are chemical smoke-forming substances used for purposes such as masking, blinding, interference and signaling. They are widely used in both military and civilian fields. For example, blue smoke bombs are used by the armed police force, orange smoke agents are used for maritime rescue, and white smoke agents are used for filming. The principle of smoke generation is to use the heat and gas products released by the combustion of oxidants and combustibles in the agent to sublimate the dye and carry it into the air, thereby producing smoke of various colors.

[0003] In traditional smoke agents, potassium chlorate, which is easily decomposed at low temperatures, is usually selected as the oxidant. However, potassium chlorate has safety hazards during storage and transportation. Potassium perchlorate has shown stronger safety and higher effective oxygen content, and has gradually replaced potassium chlorate. However, potassium perchlorate often exhibits a higher decomposition temperature and a slower reaction rate when reacting with combustibles (such as lactose, sucrose, starch and other carbohydrates), making its application in smoke agents unsatisfactory. Problems such as short smoking time, thin smoke, poor smoke continuity, and more agent residues often occur. Summary of the invention

[0004] Purpose of the invention: In view of the above technical problems, the present invention provides a preparation method and application of ultrafine potassium perchlorate.

[0005] The technical solutions adopted are as follows:

[0006] A method for preparing ultrafine potassium perchlorate is as follows:

[0007] A method for preparing ultrafine potassium perchlorate is as follows:

[0008] A potassium chloride aqueous solution is added to an oil phase containing a sulfonate-type gemini surfactant to obtain a microemulsion A;

[0009] A sodium perchlorate aqueous solution is added to an oil phase containing a sulfonate type gemini surfactant to obtain a microemulsion B;

[0010] Add microemulsion A and microemulsion B into an organic solvent at the same time, react at a constant temperature of 50-100°C for 1-10 hours, centrifuge, collect the product, wash it, and dry it to obtain ultrafine potassium perchlorate;

[0011] The structural formula of the sulfonate type gemini surfactant is as follows:

[0012] ;

[0013] Wherein, n is a positive integer greater than or equal to 10.

[0014] Furthermore, the oil phase consists of sulfonate type gemini surfactant, n-butanol and n-octane.

[0015] Furthermore, the mass ratio of the sulfonate type gemini surfactant, n-butanol and n-octane is 1-5:4-8:15-30.

[0016] Furthermore, n is 10, 11, 12, 13, 14 or 15.

[0017] Furthermore, the preparation method of the sulfonate type gemini surfactant is as follows:

[0018] S1: adding bromohydrocarbon and triethylenetetramine to anhydrous ethanol for mixed reaction, and the obtained product is recrystallized from anhydrous ethanol to obtain an intermediate;

[0019] S2: Add the intermediate and 1,3-propane sultone to ethyl acetate, heat to reflux and react with stirring for 1-5 days, then return to room temperature and filter, dissolve the obtained product in aqueous sodium hydroxide solution, then add hydrochloric acid solution drop by drop with continuous stirring, filter out the precipitated flocculent solid, dissolve it with methanol and adjust the pH of the solution to 10, then add acetone for crystallization, and finally filter out the precipitated product and dry it.

[0020] Furthermore, in S1, the reaction temperature is 70-75°C, and the reaction time is 10-15h.

[0021] Furthermore, the organic solvent is n-octane.

[0022] Furthermore, the prepared ultrafine potassium perchlorate has a hollow rod-like structure.

[0023] Application of the ultrafine potassium perchlorate prepared by the ultrafine potassium perchlorate preparation method in smoke generating agent.

[0024] Beneficial effects of the present invention:

[0025] The invention provides a method for preparing ultrafine potassium perchlorate. Potassium perchlorate with a hollow rod-shaped structure is prepared by combining a microemulsion method with a sulfonate type gemini surfactant. The special microstructure improves the reaction rate of the potassium perchlorate with a combustible agent. The prepared smoke agent has the advantages of high burning rate, long smoke generation time, large smoke generation amount and less residue. The smoke agent has broad application prospects in the military and civil rescue fields as a smoke agent oxidant. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1 This is a SEM image of potassium perchlorate prepared in Example 1;

[0027] Figure 2 This is the TEM image of potassium perchlorate prepared in Comparative Example 1. DETAILED DESCRIPTION

[0028] If the specific conditions are not specified in the examples, the experiments were carried out under conventional conditions or the conditions recommended by the manufacturer. If the manufacturer of the reagents or instruments is not specified, they are all conventional products that can be purchased commercially. The techniques not mentioned in the present invention are all referenced to the prior art. Unless otherwise specified, the following examples and comparative examples are parallel experiments, using the same processing steps and parameters.

[0029] Embodiment 1:

[0030] A method for preparing ultrafine potassium perchlorate is as follows:

[0031] 15g of sulfonate type Gemini surfactant, 25g of n-butanol and 75g of n-octane were mixed to obtain an oil phase, 50ml of 0.8mol / L potassium chloride aqueous solution was slowly added dropwise to the oil phase, and the mixture was fully stirred to obtain microemulsion A. Another 15g of sulfonate type Gemini surfactant, 25g of n-butanol and 75g of n-octane were mixed to obtain an oil phase, 50ml of 0.8mol / L sodium perchlorate aqueous solution was slowly added dropwise to the oil phase, and the mixture was fully stirred to obtain microemulsion B. Microemulsion A and microemulsion B were simultaneously added to 250ml of n-octane, reacted in a constant temperature water bath at 60°C for 8h, and then centrifuged. The product was collected, washed with anhydrous ethanol, and then vacuum dried to obtain ultrafine potassium perchlorate. It was observed by scanning electron microscopy and transmission electron microscopy, respectively, and it was found to be a hollow rod-like structure. The SEM and TEM images are shown in Figure 1 and Figure 2 .

[0032] Among them, the structural formula of the sulfonate type gemini surfactant is as follows:

[0033] ;

[0034] The preparation method of the above-mentioned sulfonate type gemini surfactant is as follows:

[0035] ;

[0036] S1: 0.2 mol 1-bromo-n-undecane and 0.1 mol triethylenetetramine were added to 500 ml anhydrous ethanol, mixed and reacted at 70°C for 15 hours, then returned to room temperature and filtered. The obtained crude product was heated and dissolved with 100 ml anhydrous ethanol, then crystallized at 0-5°C for 5 hours, and then filtered again. The obtained product was vacuum dried to obtain an intermediate;

[0037] S2: Add 0.05 mol of the intermediate and 0.2 mol of 1,3-propane sultone to 500 ml of ethyl acetate, heat to reflux and react with stirring for 5 days, then return to room temperature and filter. Add the obtained product to 200 ml of 0.1 mol / L sodium hydroxide aqueous solution and ultrasonically oscillate to dissolve it. Then add 0.1 mol / L hydrochloric acid solution drop by drop and stir continuously until the pH of the system reaches 6. Filter out the precipitated flocculent solid, dissolve it with 100 ml of methanol and adjust the pH of the solution to 10 with sodium hydroxide. Add 1000 ml of acetone to crystallize. Finally, filter out the precipitated product and dry it in vacuum.

[0038] Embodiment 2:

[0039] A method for preparing ultrafine potassium perchlorate is as follows:

[0040] 15g of sulfonate type gemini surfactant, 25g of n-butanol and 75g of n-octane are mixed to obtain an oil phase, 50ml of 0.8mol / L potassium chloride aqueous solution is slowly added dropwise to the oil phase, and the mixture is fully stirred to obtain microemulsion A. Another 15g of sulfonate type gemini surfactant, 25g of n-butanol and 75g of n-octane are mixed to obtain an oil phase, 50ml of 0.8mol / L sodium perchlorate aqueous solution is slowly added dropwise to the oil phase, and the mixture is fully stirred to obtain microemulsion B. Microemulsion A and microemulsion B are simultaneously added to 250ml of n-octane, reacted in a constant temperature water bath at 60°C for 8h, and then centrifuged. The product is collected, washed with anhydrous ethanol, and then vacuum dried to obtain ultrafine potassium perchlorate. It is observed by scanning electron microscopy and transmission electron microscopy, respectively, and it can be seen that it has a hollow rod-like structure.

[0041] Among them, the structural formula of the sulfonate type gemini surfactant is as follows:

[0042] ;

[0043] The preparation method of the above-mentioned sulfonate type gemini surfactant is as follows:

[0044] ;

[0045] S1: Add 0.2 mol 1-bromo-n-dodecane and 0.1 mol triethylenetetramine to 500 ml anhydrous ethanol, mix and react at 70°C for 15 hours, then return to room temperature and filter. Dissolve the obtained crude product in 100 ml anhydrous ethanol, crystallize at 0-5°C for 5 hours, and filter again. The obtained product is vacuum dried to obtain an intermediate.

[0046] S2: Add 0.05 mol of the intermediate and 0.2 mol of 1,3-propane sultone to 500 ml of ethyl acetate, heat to reflux and react with stirring for 5 days, then return to room temperature and filter. Add the obtained product to 200 ml of 0.1 mol / L sodium hydroxide aqueous solution and ultrasonically oscillate to dissolve it. Then add 0.1 mol / L hydrochloric acid solution drop by drop and stir continuously until the pH of the system reaches 6. Filter out the precipitated flocculent solid, dissolve it with 100 ml of methanol and adjust the pH of the solution to 10 with sodium hydroxide. Add 1000 ml of acetone to crystallize. Finally, filter out the precipitated product and dry it in vacuum.

[0047] Embodiment 3:

[0048] A method for preparing ultrafine potassium perchlorate is as follows:

[0049] 15g of sulfonate type gemini surfactant, 25g of n-butanol and 75g of n-octane are mixed to obtain an oil phase, 50ml of 0.8mol / L potassium chloride aqueous solution is slowly added dropwise to the oil phase, and the mixture is fully stirred to obtain microemulsion A. Another 15g of sulfonate type gemini surfactant, 25g of n-butanol and 75g of n-octane are mixed to obtain an oil phase, 50ml of 0.8mol / L sodium perchlorate aqueous solution is slowly added dropwise to the oil phase, and the mixture is fully stirred to obtain microemulsion B. Microemulsion A and microemulsion B are simultaneously added to 250ml of n-octane, reacted in a constant temperature water bath at 60°C for 8h, and then centrifuged. The product is collected, washed with anhydrous ethanol, and then vacuum dried to obtain ultrafine potassium perchlorate. It is observed by scanning electron microscopy and transmission electron microscopy, respectively, and it can be seen that it has a hollow rod-like structure.

[0050] Among them, the structural formula of the sulfonate type gemini surfactant is as follows:

[0051] ;

[0052] The preparation method of the above-mentioned sulfonate type gemini surfactant is as follows:

[0053] ;

[0054] S1: Add 0.2 mol 1-bromotridecane and 0.1 mol triethylenetetramine to 500 ml anhydrous ethanol, mix and react at 70°C for 15 hours, then return to room temperature and filter. Dissolve the obtained crude product in 100 ml anhydrous ethanol, crystallize at 0-5°C for 5 hours, and filter again. The obtained product is vacuum dried to obtain an intermediate.

[0055] S2: Add 0.05 mol of the intermediate and 0.2 mol of 1,3-propane sultone to 500 ml of ethyl acetate, heat to reflux and react with stirring for 5 days, then return to room temperature and filter. Add the obtained product to 200 ml of 0.1 mol / L sodium hydroxide aqueous solution and ultrasonically oscillate to dissolve it. Then add 0.1 mol / L hydrochloric acid solution drop by drop and stir continuously until the pH of the system reaches 6. Filter out the precipitated flocculent solid, dissolve it with 100 ml of methanol and adjust the pH of the solution to 10 with sodium hydroxide. Add 1000 ml of acetone to crystallize. Finally, filter out the precipitated product and dry it in vacuum.

[0056] Embodiment 4:

[0057] A method for preparing ultrafine potassium perchlorate is as follows:

[0058] 15g of sulfonate type gemini surfactant, 25g of n-butanol and 75g of n-octane are mixed to obtain an oil phase, 50ml of 0.8mol / L potassium chloride aqueous solution is slowly added dropwise to the oil phase, and the mixture is fully stirred to obtain microemulsion A. Another 15g of sulfonate type gemini surfactant, 25g of n-butanol and 75g of n-octane are mixed to obtain an oil phase, 50ml of 0.8mol / L sodium perchlorate aqueous solution is slowly added dropwise to the oil phase, and the mixture is fully stirred to obtain microemulsion B. Microemulsion A and microemulsion B are simultaneously added to 250ml of n-octane, reacted in a constant temperature water bath at 60°C for 8h, and then centrifuged. The product is collected, washed with anhydrous ethanol, and then vacuum dried to obtain ultrafine potassium perchlorate. It is observed by scanning electron microscopy and transmission electron microscopy, respectively, and it can be seen that it has a hollow rod-like structure.

[0059] Among them, the structural formula of the sulfonate type gemini surfactant is as follows:

[0060] ;

[0061] The preparation method of the above-mentioned sulfonate type gemini surfactant is as follows:

[0062] ;

[0063] S1: Add 0.2 mol 1-bromo-n-tetradecane and 0.1 mol triethylenetetramine to 500 ml anhydrous ethanol, mix and react at 70°C for 15 hours, then return to room temperature and filter. Dissolve the obtained crude product in 100 ml anhydrous ethanol, crystallize at 0-5°C for 5 hours, and filter again. Dry the obtained product in vacuum to obtain an intermediate.

[0064] S2: Add 0.05 mol of the intermediate and 0.2 mol of 1,3-propane sultone to 500 ml of ethyl acetate, heat to reflux and react with stirring for 5 days, then return to room temperature and filter. Add the obtained product to 200 ml of 0.1 mol / L sodium hydroxide aqueous solution and ultrasonically oscillate to dissolve it. Then add 0.1 mol / L hydrochloric acid solution drop by drop and stir continuously until the pH of the system reaches 6. Filter out the precipitated flocculent solid, dissolve it with 100 ml of methanol and adjust the pH of the solution to 10 with sodium hydroxide. Add 1000 ml of acetone to crystallize. Finally, filter out the precipitated product and dry it in vacuum.

[0065] Embodiment 5:

[0066] A method for preparing ultrafine potassium perchlorate is as follows:

[0067] 15g of sulfonate type gemini surfactant, 25g of n-butanol and 75g of n-octane are mixed to obtain an oil phase, 50ml of 0.8mol / L potassium chloride aqueous solution is slowly added dropwise to the oil phase, and the mixture is fully stirred to obtain microemulsion A. Another 15g of sulfonate type gemini surfactant, 25g of n-butanol and 75g of n-octane are mixed to obtain an oil phase, 50ml of 0.8mol / L sodium perchlorate aqueous solution is slowly added dropwise to the oil phase, and the mixture is fully stirred to obtain microemulsion B. Microemulsion A and microemulsion B are simultaneously added to 250ml of n-octane, reacted in a constant temperature water bath at 60°C for 8h, and then centrifuged. The product is collected, washed with anhydrous ethanol, and then vacuum dried to obtain ultrafine potassium perchlorate. It is observed by scanning electron microscopy and transmission electron microscopy, respectively, and it can be seen that it has a hollow rod-like structure.

[0068] Among them, the structural formula of the sulfonate type gemini surfactant is as follows:

[0069] ;

[0070] The preparation method of the above-mentioned sulfonate type gemini surfactant is as follows:

[0071] ;

[0072] S1: Add 0.2 mol 1-bromopentadecane and 0.1 mol triethylenetetramine to 500 ml anhydrous ethanol, mix and react at 70°C for 15 hours, then return to room temperature and filter. Dissolve the obtained crude product in 100 ml anhydrous ethanol, crystallize at 0-5°C for 5 hours, and filter again. Dry the obtained product in vacuum to obtain an intermediate.

[0073] S2: Add 0.05 mol of the intermediate and 0.2 mol of 1,3-propane sultone to 500 ml of ethyl acetate, heat to reflux and react with stirring for 5 days, then return to room temperature and filter. Add the obtained product to 200 ml of 0.1 mol / L sodium hydroxide aqueous solution and ultrasonically oscillate to dissolve it. Then add 0.1 mol / L hydrochloric acid solution drop by drop and stir continuously until the pH of the system reaches 6. Filter out the precipitated flocculent solid, dissolve it with 100 ml of methanol and adjust the pH of the solution to 10 with sodium hydroxide. Add 1000 ml of acetone to crystallize. Finally, filter out the precipitated product and dry it in vacuum.

[0074] Embodiment 6:

[0075] A method for preparing ultrafine potassium perchlorate is as follows:

[0076] 15g of sulfonate type gemini surfactant, 25g of n-butanol and 75g of n-octane are mixed to obtain an oil phase, 50ml of 0.8mol / L potassium chloride aqueous solution is slowly added dropwise to the oil phase, and the mixture is fully stirred to obtain microemulsion A. Another 15g of sulfonate type gemini surfactant, 25g of n-butanol and 75g of n-octane are mixed to obtain an oil phase, 50ml of 0.8mol / L sodium perchlorate aqueous solution is slowly added dropwise to the oil phase, and the mixture is fully stirred to obtain microemulsion B. Microemulsion A and microemulsion B are simultaneously added to 250ml of n-octane, reacted in a constant temperature water bath at 60°C for 8h, and then centrifuged. The product is collected, washed with anhydrous ethanol, and then vacuum dried to obtain ultrafine potassium perchlorate. It is observed by scanning electron microscopy and transmission electron microscopy, respectively, and it can be seen that it has a hollow rod-like structure.

[0077] Among them, the structural formula of the sulfonate type gemini surfactant is as follows:

[0078] ;

[0079] The preparation method of the above-mentioned sulfonate type gemini surfactant is as follows:

[0080] ;

[0081] S1: Add 0.2 mol 1-bromohexadecane and 0.1 mol triethylenetetramine to 500 ml anhydrous ethanol, mix and react at 70°C for 15 hours, then return to room temperature and filter. Dissolve the obtained crude product in 100 ml anhydrous ethanol, crystallize at 0-5°C for 5 hours, and filter again. The obtained product is vacuum dried to obtain an intermediate.

[0082] S2: Add 0.05 mol of the intermediate and 0.2 mol of 1,3-propane sultone to 500 ml of ethyl acetate, heat to reflux and react with stirring for 5 days, then return to room temperature and filter. Add the obtained product to 200 ml of 0.1 mol / L sodium hydroxide aqueous solution and ultrasonically oscillate to dissolve it. Then add 0.1 mol / L hydrochloric acid solution drop by drop and stir continuously until the pH of the system reaches 6. Filter out the precipitated flocculent solid, dissolve it with 100 ml of methanol and adjust the pH of the solution to 10 with sodium hydroxide. Add 1000 ml of acetone to crystallize. Finally, filter out the precipitated product and dry it in vacuum.

[0083] Performance Test:

[0084] The potassium perchlorate prepared in Examples 1-6 of the present invention and the commercially available potassium perchlorate (Aladdin) were respectively mixed with lactose, cobalt oxide powder, and a phenolic resin binder in a mass ratio of 57:38:2:3 for granulation, and the mixture was passed through a 100-mesh sieve to obtain a pyrotechnic powder. The pyrotechnic powder and 40% by mass of methylene blue dye were added to prepare a blue smoke agent. 1.5 g of the blue smoke agent was taken and pressed into a powder column with a diameter of 12 mm, and a smoke effect test was performed.

[0085] The test was carried out in a smoke box, where the smoke agent was burned. The smoke box was 3.1m long and 9.1m in volume. 2 , one end is a visible light source, the other end is a visible light infrared scanning radiometer, to measure the time of ignition and combustion to produce smoke and the attenuation of visible light band radiation over time. The test results are shown in Table 1 below:

[0086] ;

[0087] As can be seen from Table 1 above, the potassium perchlorate prepared in the present invention can be used in a smoke generator to significantly increase its burning rate, smoke generation time and smoke generation amount and reduce residue.

[0088] The above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit the same. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that the technical solutions described in the aforementioned embodiments may still be modified, or some of the technical features may be replaced by equivalents. However, these modifications or replacements do not deviate the essence of the corresponding technical solutions from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. A method for preparing ultrafine potassium perchlorate, characterized in that: The details are as follows: A potassium chloride aqueous solution is added to an oil phase containing a sulfonate-type gemini surfactant to obtain a microemulsion A; A sodium perchlorate aqueous solution is added to an oil phase containing a sulfonate type gemini surfactant to obtain a microemulsion B; Add microemulsion A and microemulsion B into an organic solvent at the same time, react at a constant temperature of 50-100°C for 1-10 hours, centrifuge, collect the product, wash it, and dry it to obtain ultrafine potassium perchlorate; The structural formula of the sulfonate type gemini surfactant is as follows: ； wherein n is 10, 11, 12, 13, 14 or 15; The oil phase is composed of sulfonate type gemini surfactant, n-butanol and n-octane; The mass ratio of the sulfonate type gemini surfactant, n-butanol and n-octane is 1-5:4-8:15-30; The prepared ultrafine potassium perchlorate has a hollow rod-like structure.

2. The method for preparing ultrafine potassium perchlorate according to claim 1, characterized in that: The preparation method of the sulfonate type gemini surfactant is as follows: S1: adding bromohydrocarbon and triethylenetetramine to anhydrous ethanol for mixed reaction, and the obtained product is recrystallized from anhydrous ethanol to obtain an intermediate; S2: Add the intermediate and 1,3-propane sultone to ethyl acetate, heat to reflux and react with stirring for 1-5 days, then return to room temperature and filter, dissolve the obtained product in aqueous sodium hydroxide solution, then add hydrochloric acid solution drop by drop with continuous stirring, filter out the precipitated flocculent solid, dissolve it with methanol and adjust the pH of the solution to 10, then add acetone for crystallization, and finally filter out the precipitated product and dry it.

3. The method for preparing ultrafine potassium perchlorate according to claim 2, characterized in that: The reaction temperature in S1 is 70-75°C and the reaction time is 10-15h.

4. The method for preparing ultrafine potassium perchlorate according to claim 1, characterized in that: The organic solvent is n-octane.

5. Use of ultrafine potassium perchlorate prepared by the method for preparing ultrafine potassium perchlorate as claimed in any one of claims 1 to 4 in a smoke generating agent.

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