Preparation method of micro-smoke and less-dust firework medicament based on metastable-state energetic material

Abstract

The invention discloses a preparation method of a micro-smoke and less-dust firework powder based on a metastable-state energetic material, the micro-smoke and less-dust firework powder is composed of a macromolecule-based safe and environment-friendly metastable-state basic formula and a dust reducing agent, and solid particle emission of the material is adjusted by adjusting the type and the particle size of the dust reducing agent. The preparation method comprises the following steps: carrying out chemical modification, coating, powder mixing, drying and other processes to obtain a metastable-state basic formula A of the high-molecular fluoropolymer / active component; the metastable state basic formula A and a dust reducing agent are subjected to a series of processes such as powder mixing and granulation, and the safe and environment-friendly firework medicament with the adjustable burning speed is obtained. The solid particle discharge amount of the firework powder is reduced by adjusting the type and the particle size of the dust reducing agent. The material source is wide, the cost is controllable, the preparation process is simple, and the method is suitable for batch industrial production. The product prepared by the invention not only has the advantages of safety and environmental protection of a polymer-based metastable-state energetic material, but also can reduce the emission of solid particles generated by reaction through the dust reducing agent.

Description

Technical Field

[0001] This invention relates to a method for preparing a low-smoke, low-dust fireworks agent based on metastable energetic materials, belonging to the field of fireworks and firecrackers. Background Technology

[0002] In response to the prominent safety hazards in the production, transportation, and use of fireworks, the smoke and dust pollution and ground litter pollution generated during the setting off of fireworks systems, and the fact that fireworks cannot meet the entertainment and consumption needs of the people due to the current ban on fireworks, it is of great significance to design and develop a safe and environmentally friendly pyrotechnic agent for fireworks and firecrackers.

[0003] In the development of energetic materials, metastable energetic materials have attracted much attention due to their unique properties. Among them, polymer-based metastable energetic materials have great potential in the development of safe and environmentally friendly pyrotechnic agents for fireworks and firecrackers because they can undergo violent self-sustaining redox reactions without the participation of external oxygen and the raw materials are free of sulfur and nitrogen. Summary of the Invention

[0004] The purpose of this invention is to provide a method for preparing a low-smoke, low-dust fireworks agent based on metastable energetic materials. The material is widely available, cost is controllable, and the preparation process is simple, making it suitable for mass industrial production. The product prepared by this invention not only possesses the safety and environmental benefits of polymer-based metastable energetic materials, but also reduces the emission of solid particles generated during the reaction through a dust-reducing agent.

[0005] The objective of this invention is achieved through the following technical solution.

[0006] This invention discloses a method for preparing a low-smoke, low-dust fireworks agent based on metastable energetic materials. The low-smoke, low-dust fireworks agent based on metastable energetic materials consists of a polymer-based safe and environmentally friendly metastable basic formula and a dust-reducing agent. The solid particle emission of the material is adjusted by adjusting the type and particle size of the dust-reducing agent.

[0007] This invention first discloses a low-smoke, low-dust fireworks agent based on metastable energetic materials, comprising:

[0008] Basic formulations and dust reducers for metastable energetic polymeric materials with a mass ratio of 85~95:15~5; wherein:

[0009] The basic formulation of the polymer-based metastable energetic material includes:

[0010] 30-60 parts of high molecular weight fluorinated polymer; 20-50 parts of active non-metallic powder; 1-3 parts of silane coupling agent; 1-5 parts of binder.

[0011] The polymeric fluoropolymer is selected from any one of the following: ethylene-tetrafluoroethylene copolymer, fluorinated ethylene propylene copolymer, and polyvinylidene fluoride;

[0012] The active nonmetal is selected from either boron powder or silicon powder.

[0013] The silane coupling agent is an aminosilane coupling agent;

[0014] The adhesive is selected from either polyvinyl alcohol or polyurethane elastomer.

[0015] Furthermore, the particle size of the polymeric fluorinated polymer is 50~200μm, and the particle size of the active non-metallic powder is 10~50μm.

[0016] Furthermore, the aminosilane coupling agent is selected from KH-550 or KH-570.

[0017] Furthermore, the dust reducing agent is a non-metallic oxide or an inorganic salt.

[0018] Furthermore, the dust reducing agent is selected from: B2O3, SiO2, CaSiO3, CaCO3, Na2CO3, and NaHCO3.

[0019] This invention also discloses a method for preparing a low-smoke, low-dust fireworks agent based on any of the above-mentioned metastable energetic materials, comprising the following steps:

[0020] (1) Surface modification: Weigh the silane coupling agent and add it to 50 mL of ethyl acetate. Stir for 0.5 h and disperse the active non-metallic powder into the solution under an inert atmosphere. Soak for 6 h, filter and dry to obtain modified non-metallic powder.

[0021] (2) Coating: Weigh the binder and add it to 50 mL of ethyl acetate. Stir until completely dissolved, and then disperse the modified non-metallic powder into the solution and stir to obtain a dispersion of non-metallic powder coated with binder.

[0022] (3) Mixing powder: Weigh out the high molecular weight fluorine polymer and dust reducing agent and add them to the dispersion of the above binder-coated non-metallic powder and stir to obtain slurry;

[0023] (4) Granulation: The slurry is extruded and granulated through a granulator with a 2mm granule plate, and the resulting granules are dried to obtain a low-smoke and low-dust fireworks agent.

[0024] Furthermore, the stirring speed in step (2) is 200 rpm / min, and the stirring time is 2 h.

[0025] Furthermore, the stirring speed in step (3) is 200 rpm / min, and the stirring time is 4 h.

[0026] Furthermore, the drying temperature in step (4) is 60°C.

[0027] The present invention also discloses a low-smoke, low-dust fireworks agent prepared according to any of the above preparation methods.

[0028] The beneficial effects of this invention are as follows:

[0029] 1. The present invention discloses a method for preparing a low-smoke and low-dust fireworks agent based on metastable energetic materials. The method employs processes such as chemical modification, coating, powder mixing, granulation, and drying. The preparation process is simple and suitable for mass industrial production.

[0030] 2. The present invention discloses a method for preparing a low-smoke and low-dust fireworks agent based on metastable energetic materials. It consists of a polymer-based safe and environmentally friendly metastable basic formula and a dust reducer. It uses conventional polymeric fluorinated polymers, active non-metallic powders, binders and dust reducers as raw materials, and has the advantages of wide availability of materials and controllable cost.

[0031] 3. This invention discloses a method for preparing a low-smoke, low-dust fireworks agent based on metastable energetic materials. The prepared low-smoke, low-dust fireworks agent reduces solid particle emissions by adjusting the type and particle size of the dust-reducing agent. The resulting product has advantages such as being sulfur-free, nitrogen-free, producing minimal smoke, and exhibiting high safety. It is beneficial for reducing solid particle emissions during the combustion of fireworks and firecracker pyrotechnic agents, thus reducing dust pollution to the environment. It is a novel environmentally friendly fireworks agent. Detailed Implementation

[0032] The present invention will be further described in detail below with reference to specific embodiments, but these embodiments do not limit the present invention in any way. Unless otherwise specified, all raw materials used in the embodiments of the present invention can be obtained through conventional commercial purchases or prepared according to conventional methods in the art, and the equipment used is commonly used experimental equipment. Unless otherwise defined or stated, all technical and scientific terms used herein have the same meaning as those skilled in the art.

[0033] Example 1

[0034] A method for preparing a low-smoke, low-dust fireworks agent based on metastable energetic materials, the specific steps of which are as follows:

[0035] (1) Modified coating

[0036] Surface modification: Weigh 1 part of silane coupling agent KH-550 and add it to 50 mL of ethyl acetate. Stir for 0.5 h, and under inert atmosphere protection, disperse 35 parts of boron powder into the solution, soak for 6 h, filter and dry to obtain modified boron powder; wherein the boron powder particle size is 10 μm;

[0037] Coating: Weigh 2 parts of polyurethane elastomer (molecular weight 1000~3000) and add them to 50 mL of ethyl acetate. Stir until completely dissolved, and disperse the above 35 parts of modified boron powder into the solution. Stir for 2 hours at a speed of 200 rpm / min to obtain a dispersion of polyurethane elastomer coated with boron powder.

[0038] (2) Molding and preparation

[0039] Mixing powder: Weigh 57 parts of polyvinylidene fluoride and 5 parts of dust-reducing agent SiO2 and add them to the dispersion obtained by coating boron powder with polyurethane elastomer above. Stir for 4 hours at a speed of 200 rpm / min to obtain a slurry; wherein, the particle size of polyvinylidene fluoride is 160 μm.

[0040] Granulation: The slurry obtained above is extruded and granulated through a granulator with a 2mm granule plate, and the resulting granules are dried at a drying temperature of 60℃ to obtain the final product.

[0041] DSC-TG testing and weighing of the reaction residue showed that the reaction residue per unit mass of metastable energetic polymeric material reduced by 38% after the addition of dust-reducing agent.

[0042] Example 2

[0043] A method for preparing a low-smoke, low-dust fireworks agent based on metastable energetic materials, the specific steps of which are as follows:

[0044] (1) Modified coating

[0045] Surface modification: Weigh 1 part of silane coupling agent KH-550 and add it to 50 mL of ethyl acetate. Stir for 0.5 h, and under inert atmosphere protection, disperse 40 parts of boron powder into the solution, soak for 6 h, filter and dry to obtain modified boron powder; wherein the boron powder particle size is 10 μm;

[0046] Coating: Weigh 2 parts of polyvinyl alcohol and add them to 50 mL of ethyl acetate. Stir until completely dissolved, and disperse the above 40 parts of modified boron powder into the solution. Stir for 2 hours at a speed of 200 rpm / min to obtain a dispersion of polyvinyl alcohol coated boron powder.

[0047] (2) Molding and preparation

[0048] Mixing: Weigh 47 parts of ethylene-tetrafluoroethylene copolymer and 10 parts of dust reducing agent Na2CO3 and add them to the dispersion obtained by the above polyvinyl alcohol coated boron powder. Stir for 4 hours at a speed of 200 rpm / min to obtain a slurry; wherein, the particle size of ethylene-tetrafluoroethylene copolymer is 160 μm.

[0049] Granulation: The slurry obtained above is extruded and granulated through a granulator with a 2mm granule plate, and the resulting granules are dried at a drying temperature of 60℃ to obtain the final product.

[0050] DSC-TG testing and weighing of the reaction residue showed that the reaction residue per unit mass of metastable energetic polymeric material reduced by 52% after the addition of dust-reducing agent.

[0051] Example 3

[0052] A method for preparing a low-smoke, low-dust fireworks agent based on metastable energetic materials, the specific steps of which are as follows:

[0053] (1) Modified coating

[0054] Surface modification: Weigh 1 part of silane coupling agent KH-570 and add it to 50 mL of ethyl acetate. Stir for 0.5 h and disperse 45 parts of silicon powder into the solution under an inert atmosphere. Soak for 6 h, filter and dry to obtain modified boron powder; wherein the silicon powder particle size is 10 μm.

[0055] Coating: Weigh 2 parts of polyurethane elastomer (molecular weight 1000~3000) and add them to 50 mL of ethyl acetate. Stir until completely dissolved, and disperse the above 45 parts of modified silica powder into the solution. Stir for 2 hours at a speed of 200 rpm / min to obtain a dispersion of polyurethane elastomer coated with silica powder.

[0056] (2) Molding and preparation

[0057] Mixing: Weigh 44 parts of fluorinated ethylene propylene copolymer and 8 parts of dust reducing agent CaCO3 and add them to the dispersion obtained by coating boron powder with polyurethane elastomer above. Stir for 4 hours at a speed of 200 rpm / min to obtain a slurry; wherein, the particle size of fluorinated ethylene propylene copolymer is 160 μm.

[0058] Granulation: The slurry obtained above is extruded and granulated through a granulator with a 2mm granule plate, and the resulting granules are dried at a drying temperature of 60℃ to obtain the final product.

[0059] DSC-TG testing was conducted, and the reaction residue was weighed. It was found that the reaction residue per unit mass of metastable energetic material reduced by 22% after the addition of dust-reducing agent.

[0060] The above detailed description further illustrates the purpose, technical solution, and beneficial effects of the invention. It should be understood that the above description is only a specific embodiment of the present invention and is not intended to limit the scope of protection of the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1.A micro-smoke and low-dust pyrotechnic composition based on metastable energetic material, comprising: a high-molecular metastable energetic material base formula and a dust-reducing agent in a mass ratio of 85-95:15-5; wherein: the high-molecular metastable energetic material base formula comprises: 30-60 parts of a high-molecular fluoropolymer; 20-50 parts of an active non-metallic powder; 1-3 parts of a silane coupling agent; and 1-5 parts of a binder; the high-molecular fluoropolymer is selected from any one of ethylene-tetrafluoroethylene copolymer, fluorinated ethylene propylene copolymer, and polyvinylidene fluoride; the active non-metal is selected from any one of boron powder and silicon powder; the silane coupling agent is an amino silane coupling agent; the binder is selected from any one of polyvinyl alcohol and polyurethane elastomer. 2.The micro-smoke and low-dust pyrotechnic composition according to claim 1, wherein: the high-molecular fluoropolymer has a particle size of 50-200 μm, and the active non-metallic powder has a particle size of 10-50 μm. 3.The micro-smoke and low-dust pyrotechnic composition according to claim 1, wherein: the amino silane coupling agent is selected from KH-550 or KH-570. 4.The micro-smoke and low-dust pyrotechnic composition according to claim 1, wherein: the dust-reducing agent is a non-metallic oxide or an inorganic salt. 5.The micro-smoke and low-dust pyrotechnic composition according to claim 4, wherein: the dust-reducing agent is selected from B2O3, SiO2, CaSiO3, CaCO3, Na2CO3, and NaHCO3. 6.A preparation method of the micro-smoke and low-dust pyrotechnic composition based on metastable energetic material according to any one of claims 1-5, comprising the following steps: (1) surface modification: a silane coupling agent is weighed and added into 50 mL of ethyl acetate, stirred for 0.5 h, and under the protection of an inert atmosphere, an active non-metallic powder is dispersed into the solution, soaked for 6 h, filtered and dried to obtain a modified non-metallic powder; (2) coating: a binder is weighed and added into 50 mL of ethyl acetate, stirred until completely dissolved, and the modified non-metallic powder is dispersed into the solution and stirred to obtain a dispersion of the binder-coated non-metallic powder; (3) powder mixing: a high-molecular fluoropolymer and a dust-reducing agent are weighed and added into the dispersion of the binder-coated non-metallic powder and stirred to obtain a slurry; (4) granulation: the slurry is extruded by a granulator with a 2 mm granule plate, and the obtained granules are dried to obtain a micro-smoke and low-dust pyrotechnic composition. 7.The micro-smoke and low-dust pyrotechnic composition prepared by the preparation method according to claim 6. In step (2), the stirring speed is 200 rpm / min, and the stirring time is 2 h. 8.The micro-smoke and low-dust pyrotechnic composition prepared by the preparation method according to claim 6. In step (3), the stirring speed is 200 rpm / min, and the stirring time is 4 h. 9.The micro-smoke and low-dust pyrotechnic composition prepared by the preparation method according to claim 6. In step (4), the drying temperature is 60℃. 10.A micro-smoke and low-dust pyrotechnic composition prepared by any one of the preparation methods according to claims 6-9.