阅读说明：本技术 一种烟花用防潮型无烟无硫发射药及其制备方法 (Moisture-proof smokeless sulfur-free propellant for fireworks and preparation method thereof ) 是由 刘吉平 刘克普 吉伟生 于保藏 李琪军 周耀明 于 2019-11-27 设计创作，主要内容包括：本发明涉及一种烟花用防潮型无烟无硫发射药及其制备方法,属于环保烟火药领域。组分包括：硝化竹纤维素、聚叠氮缩水甘油醚、硝基胍、组分A、组分B、组分C、改性铁粉、对苯二胺、膨润土、六偏磷酸钠、介孔二氧化硅和吡丙醚-D1；本发明提供的一种烟花用防潮型无烟无硫发射药,燃放时发射高度高、无烟、无残渣,符合环保型烟火剂要求。具有良好的防潮、抗氧化、防腐性能,可广泛应用于各类烟花制品。且制备工艺简单、原料易得、适合大规模生产。(The invention relates to a moisture-proof smokeless sulfur-free propellant for fireworks and a preparation method thereof, belonging to the field of environment-friendly pyrotechnic compositions. The components comprise: nitrated bamboo cellulose, poly nitrogen glycidyl ether, nitroguanidine, a component A, a component B, a component C, modified iron powder, p-phenylenediamine, bentonite, sodium hexametaphosphate, mesoporous silica and pyriproxyfen-D1; the moisture-proof smokeless sulfur-free propellant for fireworks provided by the invention has high launching height during setting off, is smokeless and residue-free, and meets the requirements of environment-friendly pyrotechnic compositions. Has good moisture-proof, oxidation-resistant and corrosion-resistant properties, and can be widely applied to various firework products. And the preparation process is simple, the raw materials are easy to obtain, and the method is suitable for large-scale production.)

1. The moisture-proof smokeless sulfur-free propellant for fireworks is characterized in that: the mass percentage of each component is as follows:

2. the moisture-proof smokeless and sulfur-free propellant for fireworks according to claim 1, characterized in that: the component A is ammonium nitrate or lithium nitrate; the component B is magnesium stearate, stearic acid file or aluminum stearate; the component C is aluminum powder, magnesium powder or boron powder.

3. The moisture-proof smokeless and sulfur-free propellant for fireworks according to claim 1, characterized in that: the nitrogen content of the nitrified bamboo cellulose is 12.4 percent; m of the GAP_n3380, hydroxyl number 0.646 mmol/g^-1(ii) a The specification of the bentonite is as follows: the particle size was 600 mesh, and the density was 0.9 (g/cm)³) The content of montmorillonite is more than or equal to 89 (%); the specification of the mesoporous silica is as follows: the average particle diameter is less than or equal to 3(um), and the specific surface area is more than or equal to 150-200 (m)²/g)，SiO₂The content is more than or equal to 99.9 percent and the whiteness is more than or equal to 95 percent.

4. A method of preparing a propellant charge as claimed in claim 1, 2 or 3, characterized in that: the method comprises the following steps:

the method comprises the following steps: mixing (0.01-0.03) the nitrified bamboo cellulose: (0.02-0.06): (0.2-0.6): 8 into a group I, a group II, a group III and a group IV; the pyriproxyfen-D1 is prepared by mixing the following components in a mass ratio of 1: (3-5) dividing the mixture into a group I and a group II; adding the group I of the nitrated bamboo cellulose into ethyl acetate, stirring at room temperature until the nitrated bamboo cellulose is dissolved to obtain a nitrated bamboo cellulose solution with the concentration of 0.02-0.1%, and marking as a solution I;

step two, adding the group II of the nitrated bamboo cellulose into ethyl acetate, stirring at room temperature until the nitrated bamboo cellulose is dissolved to obtain a nitrated bamboo cellulose solution with the concentration of 0.02-0.1%, adding the group I pyriproxyfen-D1 into the nitrated bamboo cellulose solution, and continuously stirring until the nitrated bamboo cellulose is dissolved to obtain a solution II;

adding III groups of nitrated bamboo cellulose into ethyl acetate, stirring at room temperature until swelling to obtain nitrated bamboo cellulose sol with the concentration of 2-6%, adding the component A, p-phenylenediamine and II groups of pyriproxyfen-D1, and continuously stirring until dissolving to obtain sol III;

step four, uniformly mixing the IV group of nitrated bamboo cellulose with GAP, nitroguanidine, the component B, the component C and modified iron powder to obtain a mixture A;

step five, uniformly mixing bentonite, sodium hexametaphosphate and mesoporous silica to obtain a mixture B;

step six, adding the mixture B obtained in the step five into the sol III obtained in the step three under the stirring state, stirring for 20-60 minutes, adding the mixture A obtained in the step four, uniformly stirring, kneading, and adding a proper amount of ethyl acetate in the kneading process until the mixture is kneaded into a uniform micelle with moderate hardness;

step seven, granulating the uniform micelle with moderate hardness obtained in the step six by using a 60-mesh copper sieve, transferring the uniform micelle into a blast oven after the uniform micelle is dried to be semi-dry in a fume hood, drying the uniform micelle for 8 hours at the temperature of 60 ℃, taking out the uniform micelle, crushing the uniform micelle by light pressure, sieving the uniform micelle by using a 120-mesh copper sieve, removing screen wastes with too small particles, then sieving the uniform micelle by using a 60-mesh copper sieve, and taking the screen wastes of the 60-mesh copper sieve to obtain a uniform-particle moisture-proof smokeless sulfur-free propellant powder intermediate I for fireworks;

step eight, in a blast drying environment, keeping a stirring state, continuously spraying the solution II obtained in the step two on the surface of the moisture-proof smokeless and sulfur-free propellant powder intermediate I for fireworks obtained in the step seven, and continuously stirring for 10-30 minutes after spraying is finished to obtain the moisture-proof smokeless and sulfur-free propellant powder intermediate II for fireworks; and (3) continuously spraying the solution I obtained in the step (I) on the surface of the moisture-proof smokeless sulfur-free propellant intermediate II for fireworks, and continuously stirring for 20-40 minutes after spraying to obtain the moisture-proof smokeless sulfur-free propellant for fireworks.

5. The method of claim 4, wherein: the preparation method of the modified iron powder in the step four comprises the following steps: according to the mass ratio (1-3): weighing shellac and iron powder (350 meshes) in 50-100, dissolving shellac in n-amyl alcohol solvent to obtain shellac solution with concentration of 0.2-1%, adding iron powder, carrying out ultrasonic treatment in an ultrasonic water bath kettle at room temperature for 0.5-2 hours, transferring the shellac solution to an oil bath kettle at 30-50 ℃, stirring for 2-4 hours, and dropwise adding a precipitator cyclohexane, wherein the volume ratio of cyclohexane to n-amyl alcohol is (1.2-1.6): (0.3-0.4), controlling the dropping time to be 10-30 minutes, continuing stirring for 20-60 minutes after the dropping is finished, stopping, standing to room temperature, filtering, washing filter residues with cyclohexane for 3-5 times, transferring to a blast oven, and drying at 80 ℃ for 6 hours to obtain the modified iron powder.

6. The method of claim 4, wherein: the method for judging the moderate hardness in the sixth step comprises the following steps: after the paste is extruded through a 20-mesh copper sieve, the paste is formed into continuous thin strips which are not adhered to each other.

Technical Field

The invention relates to a moisture-proof smokeless sulfur-free propellant for fireworks and a preparation method thereof, belonging to the field of environment-friendly pyrotechnic compositions.

Background

China has a long history of developing and using fireworks, and the demand of fireworks is increasing along with the continuous improvement of the living standard of people. Although fireworks are colorful when being set off and have sound like thunder, the fireworks have a plurality of potential safety hazards in preparation and storage.

The propellant commonly used in the firework industry at present takes military niter as a main component, and comprises potassium nitrate, charcoal, sulfur, metal powder and the like. A large amount of smoke and metal oxide dust are generated during the ignition of the coal, so that the serious environmental pollution is caused, and the human health is also harmed; meanwhile, the lift-off characteristic and the setting-off effect of the fireworks are also seriously influenced; after the combustion, a large amount of carbon, sulfur, potassium oxides and solid residues remain. These all severely restrict the use of fireworks and other series products. Moreover, the existing propellant has the problem of easy moisture absorption, so that the propellant is likely to absorb moisture and deteriorate in the production, transportation and storage processes, and serious economic loss is caused in serious cases.

Patent CN2102493U discloses a smokeless firework, the propellant of which is single nitrocellulose or various effect medicines mainly based on nitrocellulose, although the propellant is less smoke than black powder, but the propellant is not ideal. Patent CN101215211A discloses a smokeless firework agent, the main component of the smokeless firework agent is nickel hydrazine nitrate, which is a complex initiating explosive with potential safety hazards, and the potential safety hazards can be caused by improper use. Patent CN102924193A discloses a safe, environment-friendly and porous micro-smoke propellant powder for fireworks, which has good ignition capability and good moisture absorption performance by virtue of a porous structure, but contains perchlorate in the components, and can generate hydrogen chloride in the setting-off process to pollute the environment. Patent CN104557352A discloses a no sulphur environmental protection propellant powder, this dampproof agent has the security height, environmental protection etc. has some, but contains the component that easily absorbs moisture in this propellant powder component, reduces its storage stability, uses under difficult satisfied complex environment.

Comprehensively considering, on the premise of ensuring the normal performance of the propellant powder for fireworks, the moistureproof capability of the propellant powder for fireworks is enhanced, zero smoke release is realized, the propellant powder is a key problem and a hot spot problem to be solved urgently in the current and future fireworks industry, and a direction is pointed out for the development of the propellant powder for fireworks. Therefore, the prepared moisture-proof smokeless and sulfur-free propellant for fireworks has great social significance and economic value.

Disclosure of Invention

The invention aims to solve some dangerous problems existing in the production and storage processes of the existing firecracker propellant powder, ensure the normal performance of the firework propellant powder and improve the moisture absorption performance of the firework propellant powder, and provides a moisture-proof smokeless and sulfur-free propellant powder for fireworks and a preparation method thereof.

The purpose of the invention patent is realized by the following technical scheme:

a moisture-proof smokeless sulfur-free propellant for fireworks comprises the following components in percentage by mass:

the component A is ammonium nitrate or lithium nitrate;

the component B is magnesium stearate, stearic acid file or aluminum stearate;

the component C is aluminum powder, magnesium powder or boron powder;

the nitrogen content of the nitrified bamboo cellulose is 12.4 percent;

m of the GAP_n3380, hydroxyl number 0.646 mmol/g^-1；

The specification of the bentonite is as follows: the particle size was 600 mesh, and the density was 0.9 (g/cm)³) The content of montmorillonite is more than or equal to 89 (%);

the specification of the mesoporous silica is as follows: the average particle diameter is less than or equal to 3(um), and the specific surface area is more than or equal to 150-200 (m)²/g)，SiO₂The content is more than or equal to 99.9 (%), and the whiteness is more than or equal to 95;

a preparation method of a moisture-proof smokeless sulfur-free propellant for fireworks comprises the following steps:

the method comprises the following steps: mixing (0.01-0.03) the nitrified bamboo cellulose: (0.02-0.06): (0.2-0.6): 8 into a group I, a group II, a group III and a group IV; the pyriproxyfen-D1 is prepared by mixing the following components in a mass ratio of 1: (3-5) dividing the mixture into a group I and a group II; adding the group I of the nitrated bamboo cellulose into ethyl acetate, stirring at room temperature until the nitrated bamboo cellulose is dissolved to obtain a nitrated bamboo cellulose solution with the concentration of 0.02-0.1%, and marking as a solution I;

step two, adding the group II of the nitrated bamboo cellulose into ethyl acetate, stirring at room temperature until the nitrated bamboo cellulose is dissolved to obtain a nitrated bamboo cellulose solution with the concentration of 0.02-0.1%, adding the group I pyriproxyfen-D1 into the nitrated bamboo cellulose solution, and continuously stirring until the nitrated bamboo cellulose is dissolved to obtain a solution II;

adding III group of nitrated bamboo cellulose into ethyl acetate, stirring at room temperature until swelling to obtain nitrated bamboo cellulose sol with the concentration of 2-6%, adding the component A, p-phenylenediamine and II group of pyriproxyfen-D1, and continuously stirring until dissolving to obtain sol III;

step four, uniformly mixing the IV group of nitrated bamboo cellulose with GAP, nitroguanidine, the component B, the component C and modified iron powder to obtain a mixture A;

the preparation method of the modified iron powder in the step four comprises the following steps: according to the mass ratio (1-3): weighing shellac and iron powder (350 meshes) in 50-100, dissolving shellac in n-amyl alcohol solvent to obtain shellac solution with concentration of 0.2-1%, adding iron powder, carrying out ultrasonic treatment in an ultrasonic water bath kettle at room temperature for 0.5-2 hours, transferring the shellac solution to an oil bath kettle at 30-50 ℃, stirring for 2-4 hours, and dropwise adding a precipitator cyclohexane, wherein the volume ratio of cyclohexane to n-amyl alcohol is (1.2-1.6): (0.3-0.4), controlling the dropping time to be 10-30 minutes, continuing stirring for 20-60 minutes after the dropping is finished, stopping, standing to room temperature, filtering, washing filter residues with cyclohexane for 3-5 times, transferring to a blast oven, and drying at 80 ℃ for 6 hours to obtain the modified iron powder.

Step five, uniformly mixing bentonite, sodium hexametaphosphate and mesoporous silica to obtain a mixture B;

step six, adding the mixture B obtained in the step five into the sol III obtained in the step three under the stirring state, stirring for 20-60 minutes, adding the mixture A obtained in the step four, uniformly stirring, kneading, and adding a proper amount of ethyl acetate in the kneading process until the mixture is kneaded into a uniform micelle with moderate hardness;

step seven, granulating the uniform micelle with moderate hardness obtained in the step six by using a 60-mesh copper sieve, transferring the uniform micelle into a blast oven after the uniform micelle is dried to be semi-dry in a fume hood, drying the uniform micelle for 8 hours at the temperature of 60 ℃, taking out the uniform micelle, crushing the uniform micelle by light pressure, sieving the uniform micelle by using a 120-mesh copper sieve, removing screen wastes with too small particles, then sieving the uniform micelle by using a 60-mesh copper sieve, and taking the screen wastes of the 60-mesh copper sieve to obtain a uniform-particle moisture-proof smokeless sulfur-free propellant powder intermediate I for fireworks;

step eight, in a blast drying environment, keeping a stirring state, continuously spraying the solution II obtained in the step two on the surface of the moisture-proof smokeless and sulfur-free propellant powder intermediate I for fireworks obtained in the step seven, and continuously stirring for 10-30 minutes after spraying is finished to obtain the moisture-proof smokeless and sulfur-free propellant powder intermediate II for fireworks; and (3) continuously spraying the solution I obtained in the step (I) on the surface of the moisture-proof smokeless sulfur-free propellant intermediate II for fireworks, and continuously stirring for 20-40 minutes after spraying to obtain the moisture-proof smokeless sulfur-free propellant for fireworks.

The method for judging the moderate hardness in the sixth step comprises the following steps: extruding the paste-like substance through a 20-mesh copper sieve to form continuous thin strips which are not adhered to each other;

advantageous effects

1. The moisture-proof smokeless sulfur-free propellant for fireworks provided by the invention has high launching height during setting off, is smokeless and residue-free, and meets the requirements of environment-friendly pyrotechnic compositions.

2. The moisture-proof smokeless sulfur-free propellant for fireworks provided by the invention has good moisture-proof, oxidation-resistant and corrosion-resistant properties, and can be widely applied to various fireworks products.

3. The moisture-proof smokeless sulfur-free propellant for fireworks provided by the invention is simple in preparation process, easily available in raw materials and suitable for large-scale production

Detailed Description

The invention is further illustrated by the following examples.