A poly(vinyl ferrocene) / ammonium perchlorate / aluminum composite, its preparation method and use

Abstract

The application discloses a poly(vinyl ferrocene) / ammonium perchlorate / aluminum composite and a preparation method and application thereof. Raw materials of the composite include poly(vinyl ferrocene), ammonium perchlorate and polydopamine modified aluminum powder, the composite is of a core-shell structure, the core layer is polydopamine modified aluminum powder particles, and the shell layer includes an ammonium perchlorate layer and a poly(vinyl ferrocene) layer deposited in turn from inside to outside; the mass ratio of poly(vinyl ferrocene), ammonium perchlorate and polydopamine modified aluminum powder is 0.02-0.2:0.2-2:1; the composite can be used for preparing a composite solid propellant, and the composite and the composite solid propellant can be used for preparing a solid fuel. The poly(vinyl ferrocene) / ammonium perchlorate / aluminum composite has good combustion performance in the composite solid propellant.

Description

Technical Field

[0001] This invention belongs to the field of aerospace energy, specifically involving poly(vinyl ferrocene) / ammonium perchlorate / aluminum composites, their preparation methods, and applications. Background Technology

[0002] Ammonium perchlorate and aluminum powder are common components in composite solid propellants. The thermal decomposition properties of ammonium perchlorate and the oxidation efficiency of aluminum powder directly determine the final combustion performance. Existing composite solid propellants have relatively low combustion efficiency. Lowering the thermal decomposition temperature of ammonium perchlorate and increasing the oxidation efficiency of aluminum powder are considered effective ways to improve the combustion performance of composite solid propellants.

[0003] However, existing methods for improving the combustion performance of composite solid propellants, as well as existing composite solid propellants, still have the following shortcomings:

[0004] 1. Uneven catalyst dispersion;

[0005] 2. Large mass and heat transfer distances exist between the catalyst, oxidant, and metallic fuel;

[0006] 3. Incomplete combustion of metallic fuels. Summary of the Invention

[0007] To address the low combustion efficiency of existing composite solid propellants, this invention provides a poly(vinyl ferrocene) / ammonium perchlorate / aluminum composite, its preparation method, and its applications. The poly(vinyl ferrocene) catalyst can significantly reduce the thermal decomposition temperature of ammonium perchlorate and increase the combustion rate of the composite solid propellant. Furthermore, improving the uniformity of mixing among the poly(vinyl ferrocene), ammonium perchlorate, and aluminum powder can further enhance the combustion performance of the composite solid propellant.

[0008] The objective of this invention is achieved through the following technical solution:

[0009] I. A poly(vinyl ferrocene) / ammonium perchlorate / aluminum composite

[0010] The raw materials for the composite include poly(vinyl ferrocene), ammonium perchlorate, and polydopamine-modified aluminum powder.

[0011] The mass ratio of the poly(vinyl ferrocene), ammonium perchlorate and polydopamine-modified aluminum powder is 0.02-0.2:0.2-2:1.

[0012] The composite has a core-shell structure, with the core layer being polydopamine-modified aluminum powder particles and the shell layer comprising an ammonium perchlorate layer and a poly(vinyl ferrocene) layer deposited sequentially from the inside out. The particle size of the polydopamine-modified aluminum powder particles is 0.1–30.0 μm.

[0013] The deposition is specifically achieved using liquid phase deposition, meaning the composite is prepared by sequentially depositing ammonium perchlorate and poly(vinyl ferrocene) onto the outer surface of polydopamine-modified aluminum powder via liquid phase deposition. The poly(vinyl ferrocene) is prepared by free radical polymerization using vinyl ferrocene as a monomer.

[0014] The particle size range of the unmodified aluminum powder particles, the polydopamine-modified aluminum powder particles, and the composite particles are all 0.1–30.0 μm. The thickness of the polydopamine-modified aluminum powder and the shell layer are both in the nanometer range, and therefore negligible compared to the outer diameter of the polydopamine-modified aluminum powder particles.

[0015] II. A method for preparing a poly(vinyl ferrocene) / ammonium perchlorate / aluminum composite.

[0016] The preparation method specifically includes the following steps:

[0017] D1) Under a protective gas atmosphere, vinyl ferrocene and an initiator were dissolved in anhydrous toluene solvent and stirred at 60-80°C for 8-24 hours. After the reaction was completed, methanol was added to quench the reaction, and then poly(vinyl ferrocene) was obtained by filtration, washing and drying.

[0018] In step D1), the concentration of the vinyl ferrocene in anhydrous toluene is 0.100–0.500 g / mL;

[0019] The initiator is azobisisobutyronitrile or benzoyl peroxide, and the molar amount of the initiator is 0.02 to 0.20 times the molar amount of vinyl ferrocene. After quenching the reaction with methanol, the precipitate is collected by filtration, washed with methanol, and dried at 50 to 70°C to obtain poly(vinyl ferrocene).

[0020] D2) Add dopamine hydrochloride and aluminum powder to Tris-HCl buffer and stir at room temperature for 3-12 h; after the reaction is completed, obtain polydopamine modified aluminum powder by filtration, washing and vacuum drying.

[0021] In step D2), the concentration of the aluminum powder in the Tris-HCl buffer is 0.005–0.020 g / mL, and the concentration of the Tris-HCl buffer is 1 mol / L (pH = 8.5). The mass of dopamine hydrochloride is 0.5–2 times the mass of the aluminum powder, and the particle size of the aluminum powder is 0.1–30.0 μm. After the reaction is complete, the precipitate is collected by filtration, washed with deionized water, and then vacuum dried at 50–70°C to obtain polydopamine-modified aluminum powder.

[0022] D3) Polydopamine-modified aluminum powder and ammonium perchlorate were added to deionized water, and the deionized water was removed by rotary evaporation to obtain ammonium perchlorate / aluminum composite.

[0023] In step D3), the concentrations of the polydopamine-modified aluminum powder and ammonium perchlorate in deionized water are 0.010–0.100 g / mL and 0.010–0.100 g / mL, respectively. The mass of ammonium perchlorate is 0.2–2 times the mass of the polydopamine-modified aluminum powder.

[0024] D4) Add the ammonium perchlorate / aluminum complex and poly(vinyl ferrocene) to toluene, and remove the toluene by rotary evaporation to obtain the poly(vinyl ferrocene) / ammonium perchlorate / aluminum complex;

[0025] In step D4), the concentration of the ammonium perchlorate / aluminum complex in toluene is 0.010–0.050 g / mL; the mass of poly(vinyl ferrocene) is 0.02–0.1 times the mass of the ammonium perchlorate / aluminum complex.

[0026] The protective gas is any one or a combination of two or more of nitrogen, helium, neon, argon, krypton, and radon.

[0027] III. A composite solid propellant

[0028] The composite solid propellant comprises the above-mentioned poly(vinyl ferrocene) / ammonium perchlorate / aluminum composite.

[0029] IV. A method for preparing a composite solid propellant

[0030] The preparation method, by weight, includes the following steps:

[0031] S1) 40-50 parts of ammonium perchlorate, 1-5 parts of poly(vinyl ferrocene) and 30-40 parts of poly(vinyl ferrocene) / ammonium perchlorate / aluminum composite are dispersed in 10-30 parts of hydroxyl-terminated polybutadiene to obtain the first product;

[0032] S2) Under stirring conditions, 1 to 10 parts of isophorone diisocyanate are added to the first product and mixed evenly to obtain the second product;

[0033] S3) The second product is added to the mold, and then cured for 7-10 days to obtain a composite solid propellant. The curing temperature is 50-80℃.

[0034] IV. Application of a poly(vinyl ferrocene) / ammonium perchlorate / aluminum composite and composite solid propellant

[0035] The poly(vinyl ferrocene) / ammonium perchlorate / aluminum composite and composite solid propellant can be used to prepare or as solid fuel for aerospace equipment.

[0036] The composite prepared in this invention improves the combustion rate and flame intensity of the composite solid propellant. This invention uses a ferrocene-based catalyst and improves the mixing uniformity between the ferrocene-based catalyst, ammonium perchlorate, and aluminum powder, thereby significantly improving the combustion performance of the composite solid propellant.

[0037] The beneficial effects of this invention are as follows:

[0038] (1) In this invention, poly(vinyl ferrocene) is prepared by free radical polymerization using vinyl ferrocene as a monomer. Poly(vinyl ferrocene) has a high ferrocene content, which can effectively improve catalytic performance.

[0039] (2) In this invention, ammonium perchlorate and polyvinyl ferrocene are deposited sequentially on the outer surface of polydopamine-modified aluminum powder particles to improve the mixing uniformity between poly(vinyl ferrocene), ammonium perchlorate and aluminum powder, so that the composite solid propellant of this invention has a faster combustion rate.

[0040] (3) The present invention prepared a composite solid propellant based on poly(vinyl ferrocene) / ammonium perchlorate / aluminum composite, which exhibited good combustion performance. Attached Figure Description

[0041] Figure 1 This is a combustion comparison diagram of the composite solid propellant prepared in Example 4 and the comparative example of the present invention. Detailed Implementation

[0042] The present invention will now be described in more detail with reference to the embodiments and accompanying drawings, but the implementation of the present invention is not limited thereto.

[0043] Specific embodiments of the present invention are as follows:

[0044] Example 1

[0045] 1) Under an argon atmosphere, 2.1213 g of vinyl ferrocene and 0.0341 g of azobisisobutyronitrile were dissolved in 5 mL of anhydrous toluene solvent and stirred at 70 °C for 12 h. After the reaction was completed, 100 mL of methanol was added to quench the reaction, the precipitate was filtered and washed with methanol, and then dried at 60 °C to obtain poly(vinyl ferrocene).

[0046] 2) Add 4.0021 g of dopamine hydrochloride and 4.0007 g of aluminum powder to 300 mL of Tris-HCl buffer solution with a concentration of 1 mol / L (pH = 8.5) and stir for 6 h at room temperature. After the reaction is complete, filter to collect the precipitate, wash the precipitate with deionized water, and then vacuum dry at 60 °C to obtain polydopamine modified aluminum powder.

[0047] 3) Add 1.0023g of polydopamine-modified aluminum powder and 1.0011g of ammonium perchlorate to 20mL of deionized water, and remove the solvent deionized water by rotary evaporation to obtain ammonium perchlorate / aluminum composite.

[0048] 4) Add 0.5501g of ammonium perchlorate / aluminum complex and 0.0523g of poly(vinyl ferrocene) to 20mL of toluene, and remove the solvent toluene by rotary evaporation to obtain poly(vinyl ferrocene) / ammonium perchlorate / aluminum complex.

[0049] Example 2

[0050] 1) Under an argon atmosphere, 2.1233 g of vinyl ferrocene and 0.0821 g of azobisisobutyronitrile were dissolved in 5 mL of anhydrous toluene solvent and stirred at 70 °C for 12 h. After the reaction was completed, 100 mL of methanol was added to quench the reaction, the precipitate was filtered and washed with methanol, and then dried at 60 °C to obtain poly(vinyl ferrocene).

[0051] 2) Add 4.0011 g of dopamine hydrochloride and 4.0017 g of aluminum powder to 300 mL of Tris-HCl buffer solution with a concentration of 1 mol / L (pH = 8.5) and stir for 6 h at room temperature. After the reaction is complete, filter to collect the precipitate, wash the precipitate with deionized water, and then vacuum dry at 60 °C to obtain polydopamine modified aluminum powder.

[0052] 3) Add 1.0025g of polydopamine-modified aluminum powder and 1.0021g of ammonium perchlorate to 20mL of deionized water, and remove the solvent deionized water by rotary evaporation to obtain ammonium perchlorate / aluminum composite.

[0053] 4) Add 0.5532 g of ammonium perchlorate / aluminum complex and 0.0513 g of poly(vinyl ferrocene) to 20 mL of toluene, and remove the solvent toluene by rotary evaporation to obtain poly(vinyl ferrocene) / ammonium perchlorate / aluminum complex.

[0054] Example 3

[0055] 1) Under an argon atmosphere, 2.1220 g of vinyl ferrocene and 0.1642 g of azobisisobutyronitrile were dissolved in 5 mL of anhydrous toluene solvent and stirred at 70 °C for 12 h. After the reaction was completed, 100 mL of methanol was added to quench the reaction, the precipitate was filtered and washed with methanol, and then dried at 60 °C to obtain poly(vinyl ferrocene).

[0056] 2) Add 4.0055 g of dopamine hydrochloride and 4.0012 g of aluminum powder to 300 mL of Tris-HCl buffer solution with a concentration of 1 mol / L (pH = 8.5) and stir for 6 h at room temperature. After the reaction is complete, filter to collect the precipitate, wash the precipitate with deionized water, and then vacuum dry at 60 °C to obtain polydopamine modified aluminum powder.

[0057] 3) Add 1.0031g of polydopamine-modified aluminum powder and 1.0050g of ammonium perchlorate to 20mL of deionized water, and remove the solvent deionized water by rotary evaporation to obtain ammonium perchlorate / aluminum composite.

[0058] 4) Add 0.5512 g of ammonium perchlorate / aluminum complex and 0.0511 g of poly(vinyl ferrocene) to 20 mL of toluene, and remove the solvent toluene by rotary evaporation to obtain poly(vinyl ferrocene) / ammonium perchlorate / aluminum complex.

[0059] Example 4

[0060] 1) Under an argon atmosphere, 2.1222 g of vinyl ferrocene and 0.2465 g of azobisisobutyronitrile were dissolved in 5 mL of anhydrous toluene solvent and stirred at 70 °C for 12 h. After the reaction was completed, 100 mL of methanol was added to quench the reaction, the precipitate was filtered and washed with methanol, and then dried at 60 °C to obtain poly(vinyl ferrocene).

[0061] 2) Add 4.0015 g of dopamine hydrochloride and 4.0033 g of aluminum powder to 300 mL of Tris-HCl buffer solution with a concentration of 1 mol / L (pH = 8.5) and stir for 6 h at room temperature. After the reaction is complete, filter to collect the precipitate, wash the precipitate with deionized water, and then vacuum dry at 60 °C to obtain polydopamine modified aluminum powder.

[0062] 3) Add 1.0071g of polydopamine-modified aluminum powder and 1.0070g of ammonium perchlorate to 20mL of deionized water, and remove the solvent deionized water by rotary evaporation to obtain ammonium perchlorate / aluminum composite.

[0063] 4) Add 0.5502 g of ammonium perchlorate / aluminum complex and 0.0510 g of poly(vinyl ferrocene) to 20 mL of toluene, and remove the solvent toluene by rotary evaporation to obtain poly(vinyl ferrocene) / ammonium perchlorate / aluminum complex.

[0064] This embodiment also describes the preparation of a composite solid propellant based on a poly(vinyl ferrocene) / ammonium perchlorate / aluminum composite. The specific process is as follows:

[0065] 1) 1.4089 g of ammonium perchlorate, 0.0598 g of poly(vinyl ferrocene) and 1.0560 g of poly(vinyl ferrocene) / ammonium perchlorate / aluminum composite were dispersed in 0.4186 g of hydroxyl-terminated polybutadiene (type IV) to obtain the first product;

[0066] 2) Under stirring conditions, 0.0651 g of isophorone diisocyanate was added to the first product and mixed evenly to obtain the second product;

[0067] 3) Add the second product into the mold, and then cure it at a temperature of 50-80°C for 7-10 days to obtain a composite solid propellant.

[0068] Comparative Example

[0069] This comparative example prepared a composite solid propellant by simply mixing ammonium perchlorate, poly(vinyl ferrocene), aluminum powder, hydroxyl-terminated polybutadiene (type IV), and isophorone diisocyanate.

[0070] The amounts of each raw material are as follows: ammonium perchlorate 1.8913g, poly(vinyl ferrocene) 0.1510g, aluminum powder 0.4810g, hydroxyl-terminated polybutadiene 0.4256g, and isophorone diisocyanate 0.0677g.

[0071] The specific steps of this comparative example are as follows: ammonium perchlorate, poly(vinyl ferrocene) and aluminum powder are ground and mixed evenly using a mortar and pestle, and then added to hydroxyl-terminated polybutadiene to obtain the third product; under stirring conditions, 0.0677g of isophorone diisocyanate is added to the third product and mixed evenly to obtain the fourth product; the fourth product is added to a mold, and then cured for 7-10 days to obtain the composite solid propellant of the control group.

[0072] The curing temperature and time are the same as in Example 4.

[0073] The composite solid propellants prepared in Comparative Example (above) and Example 4 (below) were ignited using an electric arc, and the combustion time was recorded using a camera. Specific results are as follows: Figure 1 As shown, compared to the comparative example, the composite solid propellant designed in this invention has a shorter combustion rate and a more intense combustion flame.

[0074] It should be noted that the above embodiments are only used to explain and illustrate the present invention, and are not intended to limit the present invention. Any modifications and changes made to the present invention within the spirit and scope of the claims shall fall within the protection scope of the present invention.

Claims

1. A poly(vinyl ferrocene) / ammonium perchlorate / aluminum composite, characterized in that: The raw materials for the composite include poly(vinyl ferrocene), ammonium perchlorate, and polydopamine-modified aluminum powder; The composite has a core-shell structure, with the core layer being polydopamine-modified aluminum powder particles having a particle size of 0.1~30.0 μm; the shell layer includes an ammonium perchlorate layer and a poly(vinyl ferrocene) layer deposited sequentially from the inside out.

2. The poly(vinyl ferrocene) / ammonium perchlorate / aluminum composite according to claim 1, characterized in that: The mass ratio of the poly(vinyl ferrocene), ammonium perchlorate and polydopamine-modified aluminum powder is 0.02~0.2:0.2~2:

1.

3. A method for preparing the poly(vinyl ferrocene) / ammonium perchlorate / aluminum composite as described in any one of claims 1 to 2, characterized in that: The preparation method specifically includes the following steps: D1) Under a protective gas atmosphere, vinyl ferrocene and an initiator were dissolved in anhydrous toluene solvent and stirred at 60-80°C. After the reaction was completed, methanol was added to quench the reaction, and then the mixture was filtered, washed and dried to obtain poly(vinyl ferrocene). D2) Dopamine hydrochloride and aluminum powder were added to Tris-HCl buffer and stirred at room temperature. After the reaction was completed, the mixture was filtered, washed and vacuum dried to obtain polydopamine-modified aluminum powder. D3) The polydopamine-modified aluminum powder and ammonium perchlorate were added to deionized water, and the deionized water was removed by rotary evaporation to obtain the ammonium perchlorate / aluminum composite. D4) The ammonium perchlorate / aluminum complex and the poly(vinyl ferrocene) were added to toluene, and the toluene was removed by rotary evaporation to obtain the poly(vinyl ferrocene) / ammonium perchlorate / aluminum complex.

4. The method for preparing the poly(vinylferrocene) / ammonium perchlorate / aluminum composite according to claim 3, characterized in that: In step D1), the initiator is azobisisobutyronitrile or benzoyl peroxide, and the molar amount of the initiator is 0.02 to 0.20 times the molar amount of vinyl ferrocene; in step D2), the mass of dopamine hydrochloride is 0.5 to 2 times the mass of aluminum powder, and the particle size of aluminum powder is 0.1 to 30.0 μm.

5. The method for preparing the poly(vinylferrocene) / ammonium perchlorate / aluminum composite according to claim 3, characterized in that: In step D3), the mass of ammonium perchlorate is 0.2 to 2 times the mass of polydopamine-modified aluminum powder; in step D4), the mass of poly(vinyl ferrocene) is 0.02 to 0.1 times the mass of the ammonium perchlorate / aluminum composite.

6. A composite solid propellant, characterized in that: It comprises the poly(vinyl ferrocene) / ammonium perchlorate / aluminum composite as described in any one of claims 1 to 2 or the poly(vinyl ferrocene) / ammonium perchlorate / aluminum composite prepared by the preparation method described in any one of claims 3 to 5.

7. A method for preparing a composite solid propellant as described in claim 6, characterized in that: The preparation method, by weight, includes the following steps: S1) Disperse 40-50 parts of ammonium perchlorate, 1-5 parts of poly(vinyl ferrocene) and 30-40 parts of the poly(vinyl ferrocene) / ammonium perchlorate / aluminum composite in 10-30 parts of hydroxyl-terminated polybutadiene to obtain the first product; S2) Under stirring conditions, 1 to 10 parts of isophorone diisocyanate are added to the first product and mixed evenly to obtain the second product; S3) The second product is added into the mold and cured for 7-10 days to obtain a composite solid propellant.

8. A method for preparing a composite solid propellant as described in claim 7, characterized in that: In step S3), the curing temperature is 50~80℃.

9. The application of a poly(vinyl ferrocene) / ammonium perchlorate / aluminum composite as described in any one of claims 1 to 2, a poly(vinyl ferrocene) / ammonium perchlorate / aluminum composite obtained by the preparation method as described in any one of claims 3 to 5, a composite solid propellant as described in claim 6, or a composite solid propellant obtained by the preparation method as described in any one of claims 7 to 8 in the preparation of solid fuel.

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