CN110845286A - Moisture-proof smokeless sulfur-free propellant for fireworks and preparation method thereof - Google Patents
Moisture-proof smokeless sulfur-free propellant for fireworks and preparation method thereof Download PDFInfo
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- CN110845286A CN110845286A CN201911177804.8A CN201911177804A CN110845286A CN 110845286 A CN110845286 A CN 110845286A CN 201911177804 A CN201911177804 A CN 201911177804A CN 110845286 A CN110845286 A CN 110845286A
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- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B33/00—Compositions containing particulate metal, alloy, boron, silicon, selenium or tellurium with at least one oxygen supplying material which is either a metal oxide or a salt, organic or inorganic, capable of yielding a metal oxide
- C06B33/08—Compositions containing particulate metal, alloy, boron, silicon, selenium or tellurium with at least one oxygen supplying material which is either a metal oxide or a salt, organic or inorganic, capable of yielding a metal oxide with a nitrated organic compound
Abstract
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.
Description
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 GAPn3380, 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.
Examples 1,
A moisture-proof smokeless sulfur-free propellant for fireworks comprises the following formula:
a preparation method of a moisture-proof smokeless sulfur-free propellant for fireworks comprises the following steps:
step one, according to the mass ratio of 1: 50 weighing 0.3g of shellac and 15g of iron powder (350 meshes), dissolving the shellac in 80mL of n-amyl alcohol solvent to obtain a shellac solution with the concentration of 0.47%, adding the iron powder into the shellac solution, carrying out ultrasonic treatment in an ultrasonic water bath kettle at room temperature for 1 hour, transferring the shellac solution into an oil bath kettle at 40 ℃, stirring for 3 hours, dropwise adding 320mL of precipitator cyclohexane, continuing stirring for 40 minutes, stopping stirring, standing to room temperature, filtering, washing filter residues with cyclohexane for 3 times, transferring the filter residues into a blast oven, and drying at 80 ℃ for 6 hours to obtain modified iron powder;
weighing 8.2g of nitrobamboo cellulose, 0.4g of GAP, 0.4g of nitroguanidine, 0.3g of lithium nitrate, 0.05g of stearic acid file, 0.3g of boron powder, 0.1g of modified iron powder, 0.1g of p-phenylenediamine, 0.05g of bentonite, 0.025g of sodium hexametaphosphate, 0.05g of mesoporous silicon dioxide and 0.025g of pyriproxyfen-D1 according to the formula proportion;
step three: mixing the nitrified bamboo cellulose according to the weight ratio of 0.01: 0.02: 0.2: 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: 4, dividing the mixture into a group I and a group II; adding 0.010g of group I nitrobamboo cellulose into 20mL of ethyl acetate, and stirring at room temperature until the nitrobamboo cellulose is dissolved to obtain a nitrobamboo cellulose solution with the concentration of 0.06%, which is marked as solution I;
step four, adding 0.020g of group II nitrobamboo cellulose into 40mL of ethyl acetate, stirring at room temperature until the nitrobamboo cellulose is dissolved to obtain a nitrobamboo cellulose solution with the concentration of 0.06%, adding 0.005g of group I pyriproxyfen-D1 into the solution, and continuously stirring until the nitrobamboo cellulose solution is dissolved to obtain a solution II;
step five, adding 0.199g of III group nitrified bamboo cellulose into 10mL of ethyl acetate, stirring at room temperature until swelling is achieved, obtaining 2.16% nitrified bamboo cellulose sol, adding lithium nitrate, p-phenylenediamine and II group pyriproxyfen-D1, and continuously stirring until dissolving, so as to obtain sol III;
step six, uniformly mixing the IV group of nitrated bamboo cellulose with GAP, nitroguanidine, stearic acid file, boron powder and modified iron powder to obtain a mixture A;
seventhly, uniformly mixing bentonite, sodium hexametaphosphate and mesoporous silica to obtain a mixture B;
step eight, adding the mixture B obtained in the step seven into the sol III obtained in the step five under the stirring state, stirring for 40 minutes, adding the mixture A obtained in the step six, uniformly stirring, and kneading, wherein 2.5mL of ethyl acetate is used in the kneading process until the mixture is kneaded into a uniform micelle with moderate hardness;
step nine, granulating the uniform micelle with moderate hardness obtained in the step eight by using a 60-mesh copper sieve, transferring the uniform micelle into a blast oven after the micelle is dried to be semi-dry in a fume hood, drying the micelle for 8 hours at the temperature of 60 ℃, taking out the micelle, crushing the micelle by light pressure, sieving the micelle by using a 120-mesh copper sieve, removing screen wastes with too small particles, then sieving by using a 60-mesh copper sieve, and taking the screen wastes of the 60-mesh copper sieve to obtain the moisture-proof smokeless sulfur-free propellant powder intermediate I for the fireworks with uniform particles;
step ten, in a blast drying environment, keeping a stirring state, continuously spraying the solution II obtained in the step four onto the surface of the moisture-proof smokeless sulfur-free propellant powder intermediate I for the fireworks obtained in the step nine, and continuously stirring for 20 minutes after spraying to obtain a moisture-proof smokeless sulfur-free propellant powder intermediate II for the fireworks; continuously spraying the solution I obtained in the step three on the surface of the moisture-proof smokeless sulfur-free propellant intermediate II for fireworks, and continuously stirring for 30 minutes after spraying to obtain the moisture-proof smokeless sulfur-free propellant for fireworks.
The moisture-proof smokeless sulfur-free propellant for fireworks prepared by the invention is determined under certain experimental conditions: good moisture-proof effect, no moisture regain, stable thermal stability at 78 ℃ for 72 hours, and meeting the environmental protection requirement of no smoke and sulfur. In addition, the propellant powder has 3% of impact sensitivity (the drop height is 250 +/-1 mm, the drop weight mass is 10.0 +/-0.1 kg), 0% of friction sensitivity (the gauge pressure is 3.92MPa, the sample mass is 31mg, and the swing angle is 90 degrees), is filled into a powder cover, and has the firework emission height of 25.3 +/-3 m in the setting-off process, so that the firework setting-off requirement is met.
Examples 2,
A moisture-proof smokeless sulfur-free propellant for fireworks comprises the following formula:
a preparation method of a moisture-proof smokeless sulfur-free propellant for fireworks comprises the following steps:
step one, according to the mass ratio of 1: 60 weighing 1g of shellac and 60g of iron powder (350 meshes), dissolving the shellac in 250mL of n-amyl alcohol solvent to obtain a shellac solution with the concentration of 0.50%, adding the iron powder into the shellac solution, carrying out ultrasonic treatment in an ultrasonic water bath kettle at room temperature for 1 hour, transferring the shellac solution into an oil bath kettle at 40 ℃, stirring for 3 hours, dropwise adding 1L of precipitator cyclohexane, continuing stirring for 40 minutes after dropwise adding for 25 minutes, stopping stirring, standing to room temperature, filtering, washing filter residues for 3 times by using cyclohexane, transferring the filter residues into a blast oven, and drying at 80 ℃ for 6 hours to obtain modified iron powder;
weighing 43g of nitrobamboo cellulose, 1g of GAP, 1g of nitroguanidine, 1.5g of ammonium nitrate, 0.25g of stearic acid file, 1.5g of magnesium powder, 0.5g of modified iron powder, 0.5g of p-phenylenediamine, 0.25g of bentonite, 0.125g of sodium hexametaphosphate, 0.25g of mesoporous silica and 0.125g of pyriproxyfen-D1 according to the formula proportion;
step three: mixing the nitrified bamboo cellulose according to the weight ratio of 0.02: 0.04: 0.3: 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: 4, dividing the mixture into a group I and a group II; adding 0.103g of group I nitrobamboo cellulose into 150mL of ethyl acetate, and stirring at room temperature until the nitrobamboo cellulose is dissolved to obtain a nitrobamboo cellulose solution with the concentration of 0.08%, which is marked as solution I;
step four, adding 0.206g of group II nitrobamboo cellulose into 260mL of ethyl acetate, stirring at room temperature until the nitrobamboo cellulose is dissolved to obtain a nitrobamboo cellulose solution with the concentration of 0.09%, adding 0.025g of group I pyriproxyfen-D1 into the nitrobamboo cellulose solution, and continuously stirring until the nitrobamboo cellulose solution is dissolved to obtain a solution II;
step five, adding 1.543g of group III nitrobamboo cellulose into 80mL of ethyl acetate, stirring at room temperature until swelling to obtain nitrobamboo cellulose sol with the concentration of 2.09%, adding ammonium nitrate, p-phenylenediamine and group II pyriproxyfen-D1, and continuously stirring until dissolving to obtain sol III;
step six, uniformly mixing the IV group of nitrated bamboo cellulose with GAP, nitroguanidine, stearic acid file, magnesium powder and modified iron powder to obtain a mixture A;
seventhly, uniformly mixing bentonite, sodium hexametaphosphate and mesoporous silica to obtain a mixture B;
step eight, adding the mixture B obtained in the step seven into the sol III obtained in the step five under the stirring state, stirring for 40 minutes, adding the mixture A obtained in the step six, uniformly stirring, kneading, and adding 23.5mL of ethyl acetate in the kneading process until the mixture is kneaded into a uniform micelle with moderate hardness;
step nine, granulating the uniform micelle with moderate hardness obtained in the step eight by using a 60-mesh copper sieve, transferring the uniform micelle into a blast oven after the micelle is dried to be semi-dry in a fume hood, drying the micelle for 8 hours at the temperature of 60 ℃, taking out the micelle, crushing the micelle by light pressure, sieving the micelle by using a 120-mesh copper sieve, removing screen wastes with too small particles, then sieving by using a 60-mesh copper sieve, and taking the screen wastes of the 60-mesh copper sieve to obtain the moisture-proof smokeless sulfur-free propellant powder intermediate I for the fireworks with uniform particles;
step ten, in a blast drying environment, keeping a stirring state, continuously spraying the solution II obtained in the step four onto the surface of the moisture-proof smokeless sulfur-free propellant powder intermediate I for the fireworks obtained in the step nine, and continuously stirring for 25 minutes after spraying to obtain a moisture-proof smokeless sulfur-free propellant powder intermediate II for the fireworks; and (4) continuously spraying the solution I obtained in the step three on the surface of the moisture-proof smokeless sulfur-free propellant intermediate II for fireworks, and continuously stirring for 35 minutes after spraying is finished to obtain the moisture-proof smokeless sulfur-free propellant for fireworks.
The moisture-proof smokeless sulfur-free propellant for fireworks prepared by the invention is determined under certain experimental conditions: good moisture-proof effect, no moisture regain, stable thermal stability at 78 ℃ for 72 hours, and meeting the environmental protection requirement of no smoke and sulfur. In addition, the propellant powder has 3% of impact sensitivity (the drop height is 250 +/-1 mm, the drop weight mass is 10.0 +/-0.1 kg), 0% of friction sensitivity (the gauge pressure is 3.91MPa, the sample mass is 30mg, and the swing angle is 90 degrees), is filled into a powder cover, and has the firework emission height of 24.5 +/-3 m in the setting-off process, so that the firework setting-off requirement is met.
Examples 3,
A moisture-proof smokeless sulfur-free propellant for fireworks comprises the following formula:
a preparation method of a moisture-proof smokeless sulfur-free propellant for fireworks comprises the following steps:
step one, according to the mass ratio of 2: 75 weighing 0.2g of shellac and 7.5g of iron powder (350 meshes), dissolving shellac in 80mL of n-amyl alcohol solvent to obtain shellac solution with the concentration of 0.31%, adding iron powder into the shellac solution, carrying out ultrasonic treatment in an ultrasonic water bath kettle at room temperature for 1 hour, transferring the shellac solution into an oil bath kettle at 40 ℃, stirring for 3 hours, dropwise adding 350mL of precipitator cyclohexane, continuing stirring for 40 minutes, stopping stirring, standing to room temperature, filtering, washing filter residue with cyclohexane for 3 times, transferring the filter residue into a blast oven, and drying at 80 ℃ for 6 hours to obtain modified iron powder;
weighing 17g of nitrobamboo cellulose, 0.4g of GAP, 0.6g of nitroguanidine, 0.6g of lithium nitrate, 0.1g of stearic acid file, 0.8g of aluminum powder, 0.1g of modified iron powder, 0.1g of p-phenylenediamine, 0.1g of bentonite, 0.1g of sodium hexametaphosphate, 0.05g of mesoporous silica and 0.05g of pyriproxyfen-D1 according to the formula proportion;
step three: mixing the nitrified bamboo cellulose according to the weight ratio of 0.01: 0.04: 0.3: 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: 4, dividing the mixture into a group I and a group II; adding 0.020g of group I nitrobamboo cellulose into 80mL of ethyl acetate, stirring at room temperature until the nitrobamboo cellulose is dissolved to obtain a nitrobamboo cellulose solution with the concentration of 0.03%, and marking as a solution I;
adding 0.081g of group II nitrobamboo cellulose into 200mL of ethyl acetate, stirring at room temperature until the mixture is dissolved to obtain a nitrobamboo cellulose solution with the concentration of 0.04%, adding 0.01g of group I pyriproxyfen-D1 into the solution, and continuously stirring until the mixture is dissolved to obtain a solution II;
step five, adding 0.611g of group III nitrobamboo cellulose into 30mL of ethyl acetate, stirring at room temperature until swelling is achieved, obtaining nitrobamboo cellulose sol with the concentration of 2.21%, adding lithium nitrate, p-phenylenediamine and group II pyriproxyfen-D1, and continuously stirring until dissolving, thus obtaining sol III;
step six, uniformly mixing the IV groups of the bamboo cellulose nitrate with GAP, nitroguanidine, stearic acid file, aluminum powder and modified iron powder to obtain a mixture A;
seventhly, uniformly mixing bentonite, sodium hexametaphosphate and mesoporous silica to obtain a mixture B;
step eight, adding the mixture B obtained in the step seven into the sol III obtained in the step five under the stirring state, stirring for 40 minutes, adding the mixture A obtained in the step six, uniformly stirring, kneading, and adding 1.5mL of ethyl acetate in the kneading process until the mixture is kneaded into a uniform micelle with moderate hardness;
step nine, granulating the uniform micelle with moderate hardness obtained in the step eight by using a 60-mesh copper sieve, transferring the uniform micelle into a blast oven after the micelle is dried to be semi-dry in a fume hood, drying the micelle for 8 hours at the temperature of 60 ℃, taking out the micelle, crushing the micelle by light pressure, sieving the micelle by using a 120-mesh copper sieve, removing screen wastes with too small particles, then sieving by using a 60-mesh copper sieve, and taking the screen wastes of the 60-mesh copper sieve to obtain the moisture-proof smokeless sulfur-free propellant powder intermediate I for the fireworks with uniform particles;
step ten, in a blast drying environment, keeping a stirring state, continuously spraying the solution II obtained in the step four onto the surface of the moisture-proof smokeless sulfur-free propellant powder intermediate I for the fireworks obtained in the step nine, and continuously stirring for 15 minutes after spraying to obtain a moisture-proof smokeless sulfur-free propellant powder intermediate II for the fireworks; continuously spraying the solution I obtained in the step three on the surface of the moisture-proof smokeless sulfur-free propellant intermediate II for fireworks, and continuously stirring for 30 minutes after spraying to obtain the moisture-proof smokeless sulfur-free propellant for fireworks.
The moisture-proof smokeless sulfur-free propellant for fireworks prepared by the invention is determined under certain experimental conditions: good moisture-proof effect, no moisture regain, stable thermal stability at 78 ℃ for 72 hours, and meeting the environmental protection requirement of no smoke and sulfur. In addition, the propellant powder has the impact sensitivity (the drop height is 250 +/-1 mm, the drop weight mass is 10.0 +/-0.1 kg) of 2 percent, the friction sensitivity (the gauge pressure is 3.91MPa, the sample mass is 30mg, and the swing angle is 90 degrees) of 0 percent, and is filled into a powder cover, the firework launching height is 24.9 +/-3 m in the process of setting off, and the firework setting off requirement is met.
The above detailed description is intended to illustrate the objects, aspects and advantages of the present invention, and it should be understood that the above detailed description is only exemplary of the present invention and is not intended to limit the scope of the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (6)
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 GAPn3380, 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.
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