Spherical potassium perchlorate and preparation method and application thereof

Abstract

The invention relates to the field of inorganic materials, in particular to spherical potassium perchlorate and a preparation method and application thereof. Modified nano graphite powder is evenly divided into two parts, and the parts are respectively added into a potassium chloride aqueous solution and a sodium perchlorate aqueous solution to obtain a suspension A and a suspension B. A surfactant and n-butanol are added into cyclohexane to obtain an oil phase, and the oil phase is evenly divided into two parts, and the suspension A and the suspension B are respectively added into the oil phase to obtain a microemulsion A and a microemulsion B. The microemulsion A and the microemulsion B are mixed and reacted, and then centrifuged. The product is collected, washed and dried. The potassium perchlorate prepared by the invention has high stability and low accident risk during production, storage, transportation and use.

Description

Technical Field

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

[0002] Potassium perchlorate is a strong oxidant with the characteristics of high combustion temperature, fast combustion speed and strong oxidizing property. It is one of the important raw materials in the production of fireworks and firecrackers. It can be used as an ignition agent, oxidant, luminescent agent, etc., making the fireworks and firecrackers more brilliant. Potassium perchlorate is inevitably subject to friction and impact during production, storage, transportation and use, which can easily cause combustion and explosion, resulting in accidents. How to improve the stability of potassium perchlorate during production, storage, transportation and use and reduce the risk of accidents has become an urgent problem to be solved. Summary of the invention

[0003] Purpose of the invention: In view of the above technical problems, the present invention provides a spherical potassium perchlorate and a preparation method and application thereof.

[0004] The technical solutions adopted are as follows:

[0005] A preparation method of spherical potassium perchlorate is as follows:

[0006] S1: Activate the nanographite powder with hydrogen peroxide solution and add it to DMF, then add diisocyanate, stir and mix, stir and react at 80-100°C for 12-48h under nitrogen atmosphere, then add polyethylene glycol, continue to react for 12-48h, return to room temperature, pour the reaction solution into acetone, let it stand for 1-10h and then centrifuge, wash and dry the obtained product, divide it into two parts and add them to potassium chloride aqueous solution and sodium perchlorate aqueous solution respectively to obtain suspension A and suspension B;

[0007] S2: Add surfactant and n-butanol to cyclohexane to obtain an oil phase, divide the oil phase into two equal parts, add suspension A and suspension B to the oil phase respectively to obtain microemulsion A and microemulsion B, mix microemulsion A and microemulsion B, react, centrifuge, collect the product, wash and dry.

[0008] Furthermore, the mass fraction of the hydrogen peroxide solution is 10-30%.

[0009] Furthermore, the diisocyanate is any one or a combination of two or more of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, and lysine diisocyanate.

[0010] Furthermore, the surfactant consists of Triton X-100 and dodecyltrimethylammonium bromide.

[0011] Furthermore, the mass ratio of Triton X-100 to dodecyltrimethylammonium bromide is 1-9:1-9.

[0012] Furthermore, the mixed reaction temperature in S2 is 25-35°C.

[0013] Furthermore, the mixing reaction time in S2 is 1-10h.

[0014] The content of graphite in the spherical potassium perchlorate prepared by the above preparation method is ≤20wt%.

[0015] Furthermore, the particle size of the spherical potassium perchlorate prepared by the above preparation method is 1-100 μm.

[0016] The invention also provides an application of spherical potassium perchlorate in energetic materials.

[0017] Beneficial effects of the present invention:

[0018] The invention provides spherical potassium perchlorate. Graphite has strong lubricity and good thermal conductivity, can reduce friction between potassium perchlorate particles, make edge effect less likely to occur, reduce friction sensitivity, can quickly transfer heat of hot spots, play a role in inhibiting hot spot propagation, and reduce impact sensitivity. Activation with hydrogen peroxide solution can increase the number of surface active groups such as hydroxyl and carboxyl groups of nano graphite powder, so as to better achieve grafting with polyethylene glycol. The surfactant composed of TritonX-100 and dodecyltrimethylammonium bromide can provide "micro reactors" for double decomposition reaction, so that the nucleation and growth of potassium perchlorate are both carried out in these droplet micro cavities, and the graphite is connected and entangled with polyethylene glycol segments grafted on the graphite surface through hydrogen bonds and van der Waals forces, so that the generated potassium perchlorate and nano graphite powder are fully wrapped to form a sphere, and the surface defects of potassium perchlorate are reduced, so that hot spots are relatively less likely to be formed, and the friction sensitivity and impact sensitivity are reduced. The potassium perchlorate prepared by the invention has high stability and low accident risk during production, storage, transportation and use. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] Figure 1 This is the SEM image of the spherical potassium perchlorate prepared in Example 1. DETAILED DESCRIPTION

[0020] 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.

[0021] Embodiment 1:

[0022] A preparation method of spherical potassium perchlorate:

[0023] Take 1g of nanographite powder (Deco Island gold, average particle size 35nm) and add it to 20ml of 30% hydrogen peroxide solution for immersion activation for 24h, then centrifuge it, dry it to constant weight, then add it to 20ml DMF, add 1.5g of diphenylmethane diisocyanate, stir and mix well, stir and react at 85℃ under nitrogen atmosphere for 24h, then add 2.5g of polyethylene glycol 6000, continue to react for 24h and return to room temperature, pour the reaction solution into 100ml of acetone, let it stand for 8h and then centrifuge it. The product is washed with acetone and dried to constant weight, divided into two parts and added to 50ml of 1.6mol / L potassium chloride aqueous solution and 50ml of 1.6mol / L sodium perchlorate aqueous solution respectively, ultrasonically oscillate for 10min to obtain suspension A and suspension B, and 2.5g of Triton X-100, 2.5g dodecyltrimethylammonium bromide and 15ml n-butanol are added to 500ml cyclohexane to obtain an oil phase, the oil phase is divided into two parts, suspension A and suspension B are added to the oil phase respectively, stirred and mixed to obtain microemulsion A and microemulsion B, microemulsion A and microemulsion B are mixed and stirred at 30°C at a speed of 60r / min for 5h, then an appropriate amount of acetone is added to break the emulsion, and the mixture is centrifuged at a speed of 2000r / min for 5min. The product is collected, rinsed with cold water and dried.

[0024] Embodiment 2:

[0025] A preparation method of spherical potassium perchlorate:

[0026] Take 1g of nanographite powder (Deco Island gold, average particle size 35nm) and add it to 20ml of 30% mass fraction hydrogen peroxide solution for immersion activation for 24h, then centrifuge it, dry it to constant weight, then add it to 20ml DMF, add 1.5g of diphenylmethane diisocyanate, stir and mix, stir and react at 85℃ under nitrogen atmosphere for 24h, then add 2.5g of polyethylene glycol 6000, continue to react for 24h and return to room temperature, pour the reaction solution into 100ml of acetone, let it stand for 8h and then centrifuge it. The obtained product is washed with acetone and dried to constant weight, divided into two parts and added to 50ml of 1.6mol / L potassium chloride aqueous solution and 50ml of 1.6mol / L sodium perchlorate aqueous solution respectively, ultrasonically oscillate for 10min to obtain suspension A and suspension B, and 1g of Triton X-100, 4g dodecyltrimethylammonium bromide and 15ml n-butanol are added to 500ml cyclohexane to obtain an oil phase, the oil phase is divided into two parts, suspension A and suspension B are added to the oil phase respectively, stirred and mixed to obtain microemulsion A and microemulsion B, microemulsion A and microemulsion B are mixed and stirred at 30°C at a speed of 60r / min for 5h, then an appropriate amount of acetone is added to break the emulsion, and the mixture is centrifuged at a speed of 2000r / min for 5min. The product is collected, rinsed with cold water and dried.

[0027] Example 3

[0028] A preparation method of spherical potassium perchlorate:

[0029] Take 1g of nanographite powder (Deco Island gold, average particle size 35nm) and add it to 20ml of 30% hydrogen peroxide solution for immersion activation for 24h, then centrifuge it, dry it to constant weight, then add it to 20ml DMF, add 1.5g of diphenylmethane diisocyanate, stir and mix well, stir and react at 85℃ under nitrogen atmosphere for 24h, then add 2.5g of polyethylene glycol 6000, continue to react for 24h and return to room temperature, pour the reaction solution into 100ml of acetone, let it stand for 8h and then centrifuge it. The obtained product is washed with acetone and dried to constant weight, divided into two parts and added to 50ml of 1.6mol / L potassium chloride aqueous solution and 50ml of 1.6mol / L sodium perchlorate aqueous solution respectively, ultrasonically oscillate for 10min to obtain suspension A and suspension B, and 2g of Triton X-100, 3g dodecyltrimethylammonium bromide and 15ml n-butanol are added to 500ml cyclohexane to obtain an oil phase, the oil phase is divided into two parts, suspension A and suspension B are added to the oil phase respectively, stirred and mixed to obtain microemulsion A and microemulsion B, microemulsion A and microemulsion B are mixed and stirred at 30°C at a speed of 60r / min for 5h, then an appropriate amount of acetone is added to break the emulsion, and the mixture is centrifuged at a speed of 2000r / min for 5min. The product is collected, rinsed with cold water and dried.

[0030] Embodiment 4:

[0031] A preparation method of spherical potassium perchlorate:

[0032] Take 1g of nanographite powder (Deco Island gold, average particle size 35nm) and add it to 20ml of 30% mass fraction hydrogen peroxide solution for immersion activation for 24h and then centrifuge it, dry it to constant weight, then add it to 20ml DMF, add 1.5g of diphenylmethane diisocyanate, stir and mix well, stir and react at 85℃ under nitrogen atmosphere for 24h, then add 2.5g of polyethylene glycol 6000, continue to react for 24h and then return to room temperature, pour the reaction solution into 100ml of acetone, let it stand for 8h and then centrifuge it, wash the product with acetone and dry it to constant weight, divide it into two parts and add them to 50ml of 1.6mol / L potassium chloride aqueous solution and 50ml of 1.6mol / L sodium perchlorate aqueous solution respectively, ultrasonically oscillate for 10min to obtain suspension A and suspension B, and 3g of Triton X-100, 2g dodecyltrimethylammonium bromide and 15ml n-butanol are added to 500ml cyclohexane to obtain an oil phase, the oil phase is divided into two parts, suspension A and suspension B are added to the oil phase respectively, stirred and mixed to obtain microemulsion A and microemulsion B, microemulsion A and microemulsion B are mixed and stirred at 30°C at a speed of 60r / min for 5h, then an appropriate amount of acetone is added to break the emulsion, and the mixture is centrifuged at a speed of 2000r / min for 5min. The product is collected, rinsed with cold water and dried.

[0033] Embodiment 5:

[0034] A preparation method of spherical potassium perchlorate:

[0035] Take 1g of nanographite powder (Deco Island gold, average particle size 35nm) and add it to 20ml of 30% hydrogen peroxide solution for immersion activation for 24h, then centrifuge it, dry it to constant weight, then add it to 20ml DMF, add 1.5g of diphenylmethane diisocyanate, stir and mix well, stir and react at 85℃ under nitrogen atmosphere for 24h, then add 2.5g of polyethylene glycol 6000, continue to react for 24h and return to room temperature, pour the reaction solution into 100ml of acetone, let it stand for 8h and then centrifuge it. The product is washed with acetone and dried to constant weight, divided into two parts and added to 50ml of 1.6mol / L potassium chloride aqueous solution and 50ml of 1.6mol / L sodium perchlorate aqueous solution respectively, ultrasonically oscillate for 10min to obtain suspension A and suspension B, and 4g of Triton X-100, 1g dodecyltrimethylammonium bromide and 15ml n-butanol are added to 500ml cyclohexane to obtain an oil phase, the oil phase is divided into two parts, suspension A and suspension B are added to the oil phase respectively, stirred and mixed to obtain microemulsion A and microemulsion B, microemulsion A and microemulsion B are mixed and stirred at 30°C at a speed of 60r / min for 5h, then an appropriate amount of acetone is added to break the emulsion, and the mixture is centrifuged at a speed of 2000r / min for 5min. The product is collected, rinsed with cold water and dried.

[0036] Comparative Example 1:

[0037] The method is basically the same as Example 1, except that the nano-graphite powder is not activated by the hydrogen peroxide solution;

[0038] A preparation method of potassium perchlorate:

[0039] Take 1g of nanographite powder (Deco Island gold, average particle size 35nm) and add it to 20ml of DMF, add 1.5g of diphenylmethane diisocyanate, stir and mix, stir and react at 85℃ under nitrogen atmosphere for 24h, then add 2.5g of polyethylene glycol 6000, continue to react for 24h and return to room temperature, pour the reaction solution into 100ml of acetone, stand for 8h and then centrifuge, wash the product with acetone and dry to constant weight, divide it into two parts and add them to 50ml of 1.6mol / L potassium chloride aqueous solution and 50ml of 1.6mol / L sodium perchlorate aqueous solution respectively, ultrasonically oscillate for 10min to obtain suspension A and suspension B, add 2.5g of Triton X-100, 2.5g dodecyltrimethylammonium bromide and 15ml n-butanol are added to 500ml cyclohexane to obtain an oil phase, the oil phase is divided into two parts, suspension A and suspension B are added to the oil phase respectively, stirred and mixed to obtain microemulsion A and microemulsion B, microemulsion A and microemulsion B are mixed and stirred at 30°C at a speed of 60r / min for 5h, then an appropriate amount of acetone is added to break the emulsion, and the mixture is centrifuged at a speed of 2000r / min for 5min. The product is collected, rinsed with cold water and dried.

[0040] Comparative Example 2:

[0041] The method is basically the same as Example 1, except that the nano-graphite powder is not modified.

[0042] A preparation method of potassium perchlorate:

[0043] Take 1g of nano-graphite powder (Deco Island gold, average particle size 35nm), divide it into two parts, add them into 50ml 1.6mol / L potassium chloride aqueous solution and 50ml 1.6mol / L sodium perchlorate aqueous solution respectively, and ultrasonically oscillate for 10min to obtain suspension A and suspension B. Add 2.5g Triton X-100, 2.5g dodecyltrimethylammonium bromide and 15ml n-butanol into 500ml cyclohexane to obtain oil phase, divide the oil phase into two parts, add suspension A and suspension B into the oil phase respectively, stir and mix to obtain microemulsion A and microemulsion B, mix microemulsion A and microemulsion B, stir and react at 30℃ at 60r / min for 5h, add appropriate amount of acetone to demulsify, centrifuge at 2000r / min for 5min, collect the product, rinse with cold water and dry.

[0044] Comparative Example 3:

[0045] The process is basically the same as Example 1, except that 5 g of Triton X-100 is added, and dodecyltrimethylammonium bromide is not added.

[0046] A preparation method of potassium perchlorate:

[0047] Take 1g of nanographite powder (Deco Island gold, average particle size 35nm) and add it to 20ml of 30% mass fraction hydrogen peroxide solution for immersion activation for 24h and then centrifuge it, dry it to constant weight, then add it to 20ml DMF, add 1.5g of diphenylmethane diisocyanate, stir and mix well, stir and react at 85℃ under nitrogen atmosphere for 24h, then add 2.5g of polyethylene glycol 6000, continue to react for 24h and then return to room temperature, pour the reaction solution into 100ml of acetone, let it stand for 8h and then centrifuge it. The product is washed with acetone and dried to constant weight, divided into two parts and added to 50ml of 1.6mol / L potassium chloride aqueous solution and 50ml of 1.6mol / L sodium perchlorate aqueous solution respectively, ultrasonically oscillate for 10min to obtain suspension A and suspension B, and 5g of Triton X-100 and 15 ml of n-butanol were added to 500 ml of cyclohexane to obtain an oil phase, and the oil phase was divided into two parts. Suspension A and suspension B were added to the oil phase respectively and stirred to obtain microemulsion A and microemulsion B. Microemulsion A and microemulsion B were mixed and stirred at 30°C at a speed of 60 r / min for 5 hours, and then an appropriate amount of acetone was added to break the emulsion. The mixture was centrifuged at a speed of 2000 r / min for 5 minutes, and the products were collected, rinsed with cold water and dried.

[0048] Comparative Example 4:

[0049] The process is basically the same as Example 1, except that 5 g of dodecyltrimethylammonium bromide is added, and Triton X-100 is not added.

[0050] A preparation method of potassium perchlorate:

[0051] Take 1g of nanographite powder (Deco Island gold, average particle size 35nm) and add it to 20ml of 30% hydrogen peroxide solution for immersion activation for 24h, then centrifuge it, dry it to constant weight, then add it to 20ml DMF, add 1.5g of diphenylmethane diisocyanate, stir and mix well, stir and react at 85℃ under nitrogen atmosphere for 24h, then add 2.5g of polyethylene glycol 6000, continue to react for 24h and return to room temperature, pour the reaction solution into 100ml acetone, let it stand for 8h and then centrifuge it, wash the product with acetone and dry it to constant weight, divide it into two parts and add them to 50ml 1.6 mol / L potassium chloride aqueous solution and 50 ml 1.6 mol / L sodium perchlorate aqueous solution were ultrasonically oscillated for 10 min to obtain suspension A and suspension B. 5 g dodecyltrimethylammonium bromide and 15 ml n-butanol were added to 500 ml cyclohexane to obtain an oil phase. The oil phase was equally divided into two parts, and suspension A and suspension B were added to the oil phase respectively, and stirred to obtain microemulsion A and microemulsion B. Microemulsion A and microemulsion B were mixed and stirred at 30 ° C at a speed of 60 r / min for 5 h, and then an appropriate amount of acetone was added to break the emulsion. The mixture was centrifuged at a speed of 2000 r / min for 5 min. The product was collected, rinsed with cold water and dried.

[0052] Comparative Example 5:

[0053] The method is basically the same as Example 1, except that no nano graphite powder is added.

[0054] A preparation method of potassium perchlorate:

[0055] Add 2.5g Triton X-100, 2.5g dodecyltrimethylammonium bromide and 15ml n-butanol to 500ml cyclohexane to obtain an oil phase, divide the oil phase into two parts, add 50ml 1.6mol / L potassium chloride aqueous solution and 50ml 1.6mol / L sodium perchlorate aqueous solution to the oil phase respectively, stir and mix to obtain microemulsion A and microemulsion B, then mix microemulsion A and microemulsion B, stir and react at 30°C at 60r / min for 5h, add appropriate amount of acetone to break the emulsion, centrifuge at 2000r / min for 5min, collect the product, rinse with cold water and dry.

[0056] Performance Test:

[0057] The potassium perchlorate prepared in Examples 1-5 of the present invention and Comparative Examples 1-5 was used as a test sample.

[0058] According to GJB 5891.24-2006 standard, test conditions: 90°, 3.92MPa, 20mg sample weight, pendulum mass (1500±1)g, ambient temperature (20±5)℃, relative humidity 50-65%;

[0059] According to GJB 5891.22-2006 standard, a 5kg drop weight, 20mg charge, 58.8MPa pressure, 20℃ ambient temperature, and 50-65% relative humidity are used. The impact sensitivity H is calculated by the lifting method test. 50 (50% ignition height), the above test results are shown in Table 1 below:

[0060] ;

[0061] It can be seen from Table 1 above that the potassium perchlorate prepared by the present invention has high stability and low accident risk during production, storage, transportation and use.

[0062] By comparing the data of Examples 1-5, it can be seen that changing the mass ratio of Triton X-100 and dodecyltrimethylammonium bromide will affect the friction sensitivity and impact sensitivity of potassium perchlorate. When the mass ratio of Triton X-100 and dodecyltrimethylammonium bromide is 1:1, the prepared potassium perchlorate has the highest stability.

[0063] By comparing the data of Example 1 with Comparative Examples 1 and 2, it can be seen that the stability of the prepared potassium perchlorate can be improved by activating and modifying the nano-graphite powder.

[0064] By comparing the data of Example 1 with Comparative Examples 3 and 4, it can be seen that the addition of Triton X-100 and dodecyltrimethylammonium bromide plays a positive role in improving the stability of potassium perchlorate.

[0065] By comparing the data of Example 1 with Comparative Example 5, it can be seen that the addition of nano-graphite powder in the present invention can greatly improve the stability of potassium perchlorate.

[0066] 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 spherical potassium perchlorate, characterized in that: The details are as follows: S1: Activate the nanographite powder with hydrogen peroxide solution and add it to DMF, then add diisocyanate, stir and mix, stir and react at 80-100°C for 12-48h under nitrogen atmosphere, then add polyethylene glycol, continue to react for 12-48h, return to room temperature, pour the reaction solution into acetone, let it stand for 1-10h and then centrifuge, wash and dry the obtained product, divide it into two parts and add them to potassium chloride aqueous solution and sodium perchlorate aqueous solution respectively to obtain suspension A and suspension B; S2: adding a surfactant and n-butanol to cyclohexane to obtain an oil phase, dividing the oil phase into two equal parts, adding suspension A and suspension B to the oil phase to obtain microemulsion A and microemulsion B respectively, mixing microemulsion A and microemulsion B, centrifuging after reaction, collecting the product, washing, and drying; The mass fraction of the hydrogen peroxide solution is 10-30%; The diisocyanate is any one or a combination of two or more of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, and lysine diisocyanate; The surfactant consists of Triton X-100 and dodecyltrimethylammonium bromide; The mass ratio of Triton X-100 to dodecyltrimethylammonium bromide is 1-9:1-9; The mixed reaction temperature in S2 is 25-35°C; The mixing reaction time in S2 is 1-10h.

2. A spherical potassium perchlorate prepared by the method for preparing spherical potassium perchlorate according to claim 1, characterized in that: The content of graphite is ≤20wt%.

3. The spherical potassium perchlorate according to claim 2, characterized in that: The particle size of the spherical potassium perchlorate is 1-100 μm.

4. Use of the spherical potassium perchlorate as claimed in claim 3 in energetic materials.

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