Preparation method of fine-particle potassium perchlorate

Abstract

The invention relates to the field of inorganic materials, in particular to a preparation method of fine-particle potassium perchlorate, which comprises the following steps: adding double-bond ionic liquid, (perfluorocyclohexyl) methacrylate, a radical initiator, a surfactant and n-butyl alcohol into cyclohexane to obtain an oil phase, averagely dividing the oil phase into two parts, the preparation method comprises the following steps: respectively adding a potassium chloride aqueous solution and a sodium perchlorate aqueous solution into an aqueous solution of potassium chloride and a sodium perchlorate aqueous solution to obtain a microemulsion A and a microemulsion B, mixing the microemulsion A and the microemulsion B for reaction, centrifuging, collecting a product, washing and drying, the friction sensitivity of the prepared potassium perchlorate is 0, and the potassium perchlorate is high in safety in production, transportation and storage processes.

Description

Technical Field

[0001] The invention relates to the field of inorganic materials, in particular to a method for preparing fine-particle potassium perchlorate. 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 effect of fireworks and firecrackers more brilliant. However, potassium perchlorate is inevitably subject to friction 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 method for preparing fine-particle potassium perchlorate.

[0004] The technical solutions adopted are as follows: A method for preparing fine-particle potassium perchlorate is as follows: Adding a double-bonded ionic liquid, (perfluorocyclohexyl) methacrylate, a free radical initiator, a surfactant and n-butanol to cyclohexane to obtain an oil phase, dividing the oil phase into two equal parts to obtain an oil phase A and an oil phase B, adding a potassium chloride aqueous solution to the oil phase A to obtain a microemulsion A, adding a sodium perchlorate aqueous solution to the oil phase B to obtain a microemulsion B, mixing the microemulsion A and the microemulsion B for reaction, centrifuging, collecting the product, washing and drying; The structure of the double bond ionic liquid is as follows: ; Wherein, R is an alkyl group having ≤4 carbon atoms; n is a positive integer greater than or equal to 5; The mass ratio of the double-bond ionic liquid to (perfluorocyclohexyl) methacrylate is 1:0.1-1.

[0005] Furthermore, R is a butyl group, and R is preferably a n-butyl group (-Bu).

[0006] Furthermore, n is 5, 6, 7 or 8, and n is preferably 5.

[0007] Furthermore, the surfactant is composed of Span80 and Tween20.

[0008] Furthermore, the mass ratio of Span80 to Tween20 is 1-4:1-4.

[0009] Furthermore, the free radical initiator is azobisisobutyronitrile and / or azobisisoheptanenitrile.

[0010] Furthermore, the temperature of the mixed reaction is 35-45°C, and the temperature of the mixed reaction is preferably 40°C.

[0011] Furthermore, the mixing reaction time is 1-10 hours.

[0012] The invention has the beneficial effects as follows: the invention provides a method for preparing fine-particle potassium perchlorate. In the invention, a double-bond ionic liquid and (perfluorocyclohexyl) methacrylate are added for copolymerization while preparing potassium perchlorate by a microemulsion method, so that the size of potassium perchlorate can be limited during nucleation and growth, and the generated copolymer has quaternary ammonium salt cations, long-chain carboxyl anions and fluorine-containing segments, and can play an excellent friction reduction effect, reduce the friction between potassium perchlorate particles, make the edge effect less likely to occur, reduce the surface defects of potassium perchlorate, and is relatively less likely to form hot spots, thereby improving its stability. The potassium perchlorate prepared by the invention has a friction sensitivity of 0, a small particle size, and high safety during production, transportation and storage. DETAILED DESCRIPTION

[0013] 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.

[0014] Embodiment 1: A method for preparing fine-particle potassium perchlorate: 1g of double-bond ionic liquid, 0.1g of (perfluorocyclohexyl) methacrylate, 0.01g of azobisisobutyronitrile, 7.5g of Span80, 7.5g of Tween20 and 40g of n-butanol were added to 500g of cyclohexane, and the mixture was stirred to obtain an oil phase. The oil phase was evenly divided into two parts, recorded as oil phase A and oil phase B. 100ml of 1.6mol / L potassium chloride aqueous solution and 100ml of 1.6mol / L sodium perchlorate aqueous solution were added to oil phase A and oil phase B respectively, and ultrasonicated for 30min to obtain microemulsion A and microemulsion B. Microemulsion A and microemulsion B were mixed, stirred at 40°C at a speed of 60r / min for reaction for 5h, and then an appropriate amount of acetone was added to break the emulsion, and the mixture was centrifuged at a speed of 2000r / min for 5min. The product was collected, rinsed with cold water and dried.

[0015] The potassium perchlorate prepared in this example was used as a sample, and a circulating dispersion sampling system was used to disperse the sample. A laser particle size distribution analyzer was used to test the particle size of the sample. The equivalent particle size (D10, D50, D90) was used to measure the change in the particle size of potassium perchlorate, and the particle size D90 was 50.22 μm, the particle size D50 was 34.65 μm, and the particle size D10 was 19.04 μm.

[0016] Among them, the structure of the double bond ionic liquid is as follows: ; The preparation method of double bond ionic liquid is as follows: Take 0.5 mol 4-vinylphenylhexanoic acid and 0.55 mol sodium hydroxide and place them in a round-bottom flask, add 1200 ml deionized water, stir vigorously at 50°C for 6 hours, then add 0.5 mol tetrabutylammonium bromide to the mixed solution, stir and react for 12 hours, add chloroform, extract the product into the organic phase, separate the liquid to remove the aqueous phase, wash the organic phase with deionized water several times, use a rotary evaporator to remove the organic solvent, and then dry the obtained product in a vacuum drying oven at 50°C for 24 hours.

[0017] Embodiment 2: A method for preparing fine-particle potassium perchlorate: 1g of double-bond ionic liquid, 0.2g of (perfluorocyclohexyl) methacrylate, 0.01g of azobisisobutyronitrile, 7.5g of Span80, 7.5g of Tween20 and 40g of n-butanol were added to 500g of cyclohexane, and the mixture was stirred to obtain an oil phase. The oil phase was evenly divided into two parts, recorded as oil phase A and oil phase B. 100ml of 1.6mol / L potassium chloride aqueous solution and 100ml of 1.6mol / L sodium perchlorate aqueous solution were added to oil phase A and oil phase B respectively, and ultrasonicated for 30min to obtain microemulsion A and microemulsion B. Microemulsion A and microemulsion B were mixed, stirred at 40°C at a speed of 60r / min for reaction for 5h, and then an appropriate amount of acetone was added to break the emulsion, and the mixture was centrifuged at a speed of 2000r / min for 5min. The product was collected, rinsed with cold water and dried.

[0018] The structure and preparation method of the double-bonded ionic liquid are the same as those in Example 1.

[0019] The potassium perchlorate prepared in this example was used as a sample, and a circulating dispersion sampling system was used to disperse the sample. A laser particle size distribution analyzer was used to test the particle size of the sample. The equivalent particle size (D10, D50, D90) was used to measure the change in the particle size of potassium perchlorate, and the particle size D90 was 48.05 μm, the particle size D50 was 33.17 μm, and the particle size D10 was 18.52 μm.

[0020] Embodiment 3: A method for preparing fine-particle potassium perchlorate: 1g of double-bond ionic liquid, 0.3g of (perfluorocyclohexyl) methacrylate, 0.01g of azobisisobutyronitrile, 7.5g of Span80, 7.5g of Tween20 and 40g of n-butanol were added to 500g of cyclohexane, and the mixture was stirred to obtain an oil phase. The oil phase was evenly divided into two parts, recorded as oil phase A and oil phase B. 100ml of 1.6mol / L potassium chloride aqueous solution and 100ml of 1.6mol / L sodium perchlorate aqueous solution were added to oil phase A and oil phase B respectively, and ultrasonicated for 30min to obtain microemulsion A and microemulsion B. Microemulsion A and microemulsion B were mixed, stirred at 40°C at a speed of 60r / min for reaction for 5h, and then an appropriate amount of acetone was added to break the emulsion, and the mixture was centrifuged at a speed of 2000r / min for 5min. The product was collected, rinsed with cold water and dried.

[0021] The structure and preparation method of the double-bonded ionic liquid are the same as those in Example 1.

[0022] The potassium perchlorate prepared in this example was used as a sample, and a circulating dispersion sampling system was used to disperse the sample. A laser particle size distribution analyzer was used to test the particle size of the sample. The equivalent particle size (D10, D50, D90) was used to measure the change in the particle size of potassium perchlorate, and the particle size D90 was 46.64 μm, the particle size D50 was 33.61 μm, and the particle size D10 was 17.73 μm.

[0023] Embodiment 4: A method for preparing fine-particle potassium perchlorate: 1g of double-bond ionic liquid, 0.4g of (perfluorocyclohexyl) methacrylate, 0.01g of azobisisobutyronitrile, 7.5g of Span80, 7.5g of Tween20 and 40g of n-butanol were added to 500g of cyclohexane, and the mixture was stirred to obtain an oil phase. The oil phase was evenly divided into two parts, recorded as oil phase A and oil phase B. 100ml of 1.6mol / L potassium chloride aqueous solution and 100ml of 1.6mol / L sodium perchlorate aqueous solution were added to oil phase A and oil phase B respectively, and ultrasonicated for 30min to obtain microemulsion A and microemulsion B. Microemulsion A and microemulsion B were mixed, stirred at 40°C at a speed of 60r / min for reaction for 5h, and then an appropriate amount of acetone was added to break the emulsion, and the mixture was centrifuged at a speed of 2000r / min for 5min. The product was collected, rinsed with cold water and dried.

[0024] The structure and preparation method of the double-bonded ionic liquid are the same as those in Example 1.

[0025] The potassium perchlorate prepared in this example was used as a sample, and a circulating dispersion sampling system was used to disperse the sample. A laser particle size distribution analyzer was used to test the particle size of the sample. The equivalent particle size (D10, D50, D90) was used to measure the change in the particle size of potassium perchlorate, and the particle size D90 was 46.89 μm, the particle size D50 was 32.14 μm, and the particle size D10 was 17.06 μm.

[0026] Embodiment 5: A method for preparing fine-particle potassium perchlorate: 1g of double-bond ionic liquid, 0.5g of (perfluorocyclohexyl) methacrylate, 0.01g of azobisisobutyronitrile, 7.5g of Span80, 7.5g of Tween20 and 40g of n-butanol were added to 500g of cyclohexane, and the mixture was stirred to obtain an oil phase. The oil phase was evenly divided into two parts, recorded as oil phase A and oil phase B. 100ml of 1.6mol / L potassium chloride aqueous solution and 100ml of 1.6mol / L sodium perchlorate aqueous solution were added to oil phase A and oil phase B respectively, and ultrasonicated for 30min to obtain microemulsion A and microemulsion B. Microemulsion A and microemulsion B were mixed, stirred at 40°C at a speed of 60r / min for reaction for 5h, and then an appropriate amount of acetone was added to break the emulsion, and the mixture was centrifuged at a speed of 2000r / min for 5min. The product was collected, rinsed with cold water and dried.

[0027] The structure and preparation method of the double-bonded ionic liquid are the same as those in Example 1.

[0028] The potassium perchlorate prepared in this example was used as a sample, and a circulating dispersion sampling system was used to disperse the sample. A laser particle size distribution analyzer was used to test the particle size of the sample. The equivalent particle size (D10, D50, D90) was used to measure the change in the particle size of potassium perchlorate, and the particle size D90 was 48.66 μm, the particle size D50 was 33.05 μm, and the particle size D10 was 17.94 μm.

[0029] Embodiment 6: A method for preparing fine-particle potassium perchlorate: 1g of double-bond ionic liquid, 0.6g of (perfluorocyclohexyl) methacrylate, 0.01g of azobisisobutyronitrile, 7.5g of Span80, 7.5g of Tween20 and 40g of n-butanol were added to 500g of cyclohexane, and the mixture was stirred to obtain an oil phase. The oil phase was evenly divided into two parts, recorded as oil phase A and oil phase B. 100ml of 1.6mol / L potassium chloride aqueous solution and 100ml of 1.6mol / L sodium perchlorate aqueous solution were added to oil phase A and oil phase B respectively, and ultrasonicated for 30min to obtain microemulsion A and microemulsion B. Microemulsion A and microemulsion B were mixed, stirred at 40°C at a speed of 60r / min for reaction for 5h, and then an appropriate amount of acetone was added to break the emulsion, and the mixture was centrifuged at a speed of 2000r / min for 5min. The product was collected, rinsed with cold water and dried.

[0030] The structure and preparation method of the double-bonded ionic liquid are the same as those in Example 1.

[0031] The potassium perchlorate prepared in this example was used as a sample, and a circulating dispersion sampling system was used to disperse the sample. A laser particle size distribution analyzer was used to test the particle size of the sample. The equivalent particle size (D10, D50, D90) was used to measure the change in the particle size of potassium perchlorate, and the particle size D90 was 49.27 μm, the particle size D50 was 34.30 μm, and the particle size D10 was 18.82 μm.

[0032] Embodiment 7: A method for preparing fine-particle potassium perchlorate: 1g of double-bonded ionic liquid, 0.7g of (perfluorocyclohexyl) methacrylate, 0.01g of azobisisobutyronitrile, 7.5g of Span80, 7.5g of Tween20 and 40g of n-butanol were added to 500g of cyclohexane, and the mixture was stirred to obtain an oil phase. The oil phase was evenly divided into two parts, recorded as oil phase A and oil phase B. 100ml of 1.6mol / L potassium chloride aqueous solution and 100ml of 1.6mol / L sodium perchlorate aqueous solution were added to oil phase A and oil phase B respectively, and ultrasonicated for 30min to obtain microemulsion A and microemulsion B. Microemulsion A and microemulsion B were mixed, stirred at 40°C and 60r / min for reaction for 5h, and then an appropriate amount of acetone was added to break the emulsion, and the mixture was centrifuged at 2000r / min for 5min. The product was collected, rinsed with cold water and dried.

[0033] The structure and preparation method of the double-bonded ionic liquid are the same as those in Example 1.

[0034] The potassium perchlorate prepared in this example was used as a sample, and a circulating dispersion sampling system was used to disperse the sample. A laser particle size distribution analyzer was used to test the particle size of the sample. The equivalent particle size (D10, D50, D90) was used to measure the change in the particle size of potassium perchlorate, and the particle size D90 was 50.06 μm, the particle size D50 was 34.55 μm, and the particle size D10 was 19.10 μm.

[0035] Embodiment 8: A method for preparing fine-particle potassium perchlorate: 1g of double-bonded ionic liquid, 0.8g of (perfluorocyclohexyl) methacrylate, 0.01g of azobisisobutyronitrile, 7.5g of Span80, 7.5g of Tween20 and 40g of n-butanol were added to 500g of cyclohexane, and the mixture was stirred to obtain an oil phase. The oil phase was evenly divided into two parts, recorded as oil phase A and oil phase B. 100ml of 1.6mol / L potassium chloride aqueous solution and 100ml of 1.6mol / L sodium perchlorate aqueous solution were added to oil phase A and oil phase B respectively, and ultrasonicated for 30min to obtain microemulsion A and microemulsion B. Microemulsion A and microemulsion B were mixed, stirred at 40°C at a speed of 60r / min for reaction for 5h, and then an appropriate amount of acetone was added to break the emulsion, and the mixture was centrifuged at a speed of 2000r / min for 5min. The product was collected, rinsed with cold water and dried.

[0036] The structure and preparation method of the double-bonded ionic liquid are the same as those in Example 1.

[0037] The potassium perchlorate prepared in this example was used as a sample, and a circulating dispersion sampling system was used to disperse the sample. A laser particle size distribution analyzer was used to test the particle size of the sample. The equivalent particle size (D10, D50, D90) was used to measure the change in the particle size of potassium perchlorate, and the particle size D90 was 50.80 μm, the particle size D50 was 35.12 μm, and the particle size D10 was 19.94 μm.

[0038] Embodiment 9: A method for preparing fine-particle potassium perchlorate: 1g of double-bond ionic liquid, 0.9g of (perfluorocyclohexyl) methacrylate, 0.01g of azobisisobutyronitrile, 7.5g of Span80, 7.5g of Tween20 and 40g of n-butanol were added to 500g of cyclohexane, and the mixture was stirred to obtain an oil phase. The oil phase was evenly divided into two parts, recorded as oil phase A and oil phase B. 100ml of 1.6mol / L potassium chloride aqueous solution and 100ml of 1.6mol / L sodium perchlorate aqueous solution were added to oil phase A and oil phase B respectively, and ultrasonicated for 30min to obtain microemulsion A and microemulsion B. Microemulsion A and microemulsion B were mixed, stirred at 40°C at a speed of 60r / min for reaction for 5h, and then an appropriate amount of acetone was added to break the emulsion, and the mixture was centrifuged at a speed of 2000r / min for 5min. The product was collected, rinsed with cold water and dried.

[0039] The structure and preparation method of the double-bonded ionic liquid are the same as those in Example 1.

[0040] The potassium perchlorate prepared in this example was used as a sample, and a circulating dispersion sampling system was used to disperse the sample. A laser particle size distribution analyzer was used to test the particle size of the sample. The equivalent particle size (D10, D50, D90) was used to measure the change in the particle size of potassium perchlorate, and the particle size D90 was 51.25 μm, the particle size D50 was 35.09 μm, and the particle size D10 was 21.45 μm.

[0041] Embodiment 10: A method for preparing fine-particle potassium perchlorate: 1g of double-bonded ionic liquid, 1g of (perfluorocyclohexyl) methacrylate, 0.01g of azobisisobutyronitrile, 7.5g of Span80, 7.5g of Tween20 and 40g of n-butanol were added to 500g of cyclohexane, and the mixture was stirred to obtain an oil phase. The oil phase was evenly divided into two parts, recorded as oil phase A and oil phase B. 100ml of 1.6mol / L potassium chloride aqueous solution and 100ml of 1.6mol / L sodium perchlorate aqueous solution were added to oil phase A and oil phase B respectively, and ultrasonicated for 30min to obtain microemulsion A and microemulsion B. Microemulsion A and microemulsion B were mixed, stirred at 40°C and 60r / min for reaction for 5h, and then an appropriate amount of acetone was added to break the emulsion, and the mixture was centrifuged at 2000r / min for 5min. The product was collected, rinsed with cold water and dried.

[0042] The structure and preparation method of the double-bonded ionic liquid are the same as those in Example 1.

[0043] The potassium perchlorate prepared in this example was used as a sample, and a circulating dispersion sampling system was used to disperse the sample. A laser particle size distribution analyzer was used to test the particle size of the sample. The equivalent particle size (D10, D50, D90) was used to measure the change in the particle size of potassium perchlorate, and the particle size D90 was 55.35 μm, the particle size D50 was 36.12 μm, and the particle size D10 was 22.01 μm.

[0044] Comparative Example 1: The process is basically the same as Example 1, except that (perfluorocyclohexyl) methacrylate is not added.

[0045] A method for preparing fine-particle potassium perchlorate: Add 1g of double-bonded ionic liquid, 0.01g of azobisisobutyronitrile, 7.5g of Span80, 7.5g of Tween20 and 40g of n-butanol to 500g of cyclohexane, stir and mix to obtain an oil phase, divide the oil phase into two equal parts, record them as oil phase A and oil phase B, add 100ml of 1.6mol / L potassium chloride aqueous solution and 100ml of 1.6mol / L sodium perchlorate aqueous solution to oil phase A and oil phase B respectively, and ultrasonicate for 30min to obtain microemulsion A and microemulsion B, mix microemulsion A and microemulsion B, stir and react at 40°C at a speed of 60r / min for 5h, then add appropriate amount of acetone to break the emulsion, centrifuge at a speed of 2000r / min for 5min, collect the product, rinse with cold water and then dry.

[0046] The potassium perchlorate prepared in this comparative example was used as a sample, and a circulating dispersed sampling system was used to disperse the sample. A laser particle size distribution analyzer was used to test the particle size of the sample. The equivalent particle size (D10, D50, D90) was used to measure the change in the particle size of potassium perchlorate, and the particle size D90 was 60.06 μm, the particle size D50 was 40.69 μm, and the particle size D10 was 25.58 μm.

[0047] Performance test: The potassium perchlorate prepared in Examples 1-10 of the present invention and Comparative Example 1 was used as a test sample.

[0048] According to GJB 5891.24-2006 standard, the test conditions are: 90°, 3.92MPa, 20mg sample weight, pendulum mass of (1500±1)g, ambient temperature of (20±5)℃, relative humidity of 50-65%. During the test, any sample that changes color, smells, emits smoke, makes an explosion sound, or has ablation marks on the surface of the impact column is judged as explosion, otherwise it is judged as non-explosion. Each group of samples is measured 25 times in parallel, and the measurement results are expressed as explosion percentage; ; It can be seen from Table 1 above that the friction sensitivity of potassium perchlorate prepared by the present invention is 0, and it is highly safe during production, transportation and storage.

[0049] By comparing Examples 1-10, it can be seen that when the mass ratio of the double-bonded ionic liquid to (perfluorocyclohexyl) methacrylate is 1:0.1-1, the prepared potassium perchlorate not only has a friction sensitivity of 0, but also has a smaller particle size; By comparing Example 1 with Comparative Example 1, it can be seen that without adding (perfluorocyclohexyl) methacrylate, the friction sensitivity of the prepared potassium perchlorate increases to 12%, and the particle size also increases slightly.

[0050] 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 fine-particle potassium perchlorate, characterized in that: The details are as follows: Adding a double-bonded ionic liquid, (perfluorocyclohexyl) methacrylate, a free radical initiator, a surfactant and n-butanol to cyclohexane to obtain an oil phase, dividing the oil phase into two equal parts to obtain an oil phase A and an oil phase B, adding a potassium chloride aqueous solution to the oil phase A to obtain a microemulsion A, adding a sodium perchlorate aqueous solution to the oil phase B to obtain a microemulsion B, mixing the microemulsion A and the microemulsion B for reaction, centrifuging, collecting the product, washing and drying; The structure of the double bond ionic liquid is as follows: ； Wherein, R is an alkyl group having ≤4 carbon atoms; n is a positive integer greater than or equal to 5; The mass ratio of the double-bond ionic liquid to (perfluorocyclohexyl) methacrylate is 1:0.1-1.

2. The method for preparing fine-particle potassium perchlorate according to claim 1, characterized in that: R is butyl.

3. The method for preparing fine-particle potassium perchlorate according to claim 1, characterized in that: n is 5, 6, 7 or 8.

4. The method for preparing fine-particle potassium perchlorate according to claim 1, characterized in that: The surfactant is composed of Span80 and Tween20.

5. The method for preparing fine-particle potassium perchlorate according to claim 4, characterized in that: The mass ratio of Span80 to Tween20 is 1-4:1-4.

6. The method for preparing fine-particle potassium perchlorate according to claim 1, characterized in that: The free radical initiator is azobisisobutyronitrile and / or azobisisoheptanenitrile.

7. The method for preparing fine-particle potassium perchlorate according to claim 1, characterized in that: The temperature of the mixed reaction is 35-45°C.

8. The method for preparing fine-particle potassium perchlorate according to claim 1, characterized in that: The mixing reaction time is 1-10h.

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