CN110845283A - Smokeless sulfur-free moisture-proof auxiliary agent for fireworks and firecrackers and preparation method thereof - Google Patents
Smokeless sulfur-free moisture-proof auxiliary agent for fireworks and firecrackers and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
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- C06B23/00—Compositions characterised by non-explosive or non-thermic constituents
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Abstract
The invention relates to a smokeless sulfur-free moisture-proof auxiliary agent for fireworks and a preparation method thereof, belonging to the field of environment-friendly pyrotechnic compositions. The components comprise: nitrated bamboo cellulose, nitroguanidine, a component A, a component B, fluorosilicone resin, modified activated carbon, potassium sorbate, 2-hydroxy-4-n-octoxy benzophenone, ethoxylated lauramide and salicylic acid; the smokeless and sulfur-free moisture-proof auxiliary agent for fireworks and firecrackers provided by the invention has a good moisture absorption effect, is excellent in moisture-proof performance and has a certain hydrophobic performance. Has the advantages of antistatic and antioxidant performance, etc. The preparation method has the advantages of simple preparation process, easily controlled reaction conditions, low cost, suitability for large-scale production and realization of industrialization.
Description
Technical Field
The invention relates to a smokeless sulfur-free moisture-proof auxiliary agent for fireworks and a preparation method thereof, belonging to the field of environment-friendly pyrotechnic compositions.
Background
The fireworks and firecrackers are inexplicable with the ancient folk custom of China, and people just contend for putting firecrackers and fireworks to show festivals every time the folk custom festivals or various celebration evening parties, and the fireworks are novel in structure, attractive in decoration, bright and colorful when being set off, and are colorful and sounding, so that fresh, comfortable and lively feelings can be brought to people. Particularly, the golden flower is burnt at night, the golden flower splashes, the five colors are colorful, or the golden flower jumps over the ground in a rotating way, or the golden flower shines in the sky in a flying way, so that people cannot catch the golden flower with the golden flower.
In every holiday of major festivals in China, fireworks are used for celebration in many places, the phenomenon that the best possibility of putting the fireworks is that the fireworks are dumb ammunition occurs, and the reasons for the situation are many, wherein the damp is the main reason, and once the fireworks are damped, the charcoal and the potassium nitrate in the black powder are diluted and increased, so that the ignition is difficult and the burning speed is slow; failure of the ignition feature, misfire, etc. It also causes the propellant to draw in too much moisture, resulting in unacceptable propellant ballistic performance.
The moisture-proof agent for fireworks is mainly a sulfur-containing and antimony-containing substance, although the moisture-proof agent belongs to low-toxicity dangerous chemicals, the steam and sulfur-containing and antimony-containing compounds generated after combustion of the moisture-containing and antimony-containing substances have high toxicity, and can generate toxic action on organisms after being inhaled, eaten or absorbed by skin. The generated hydrogen sulfide is a strong nerve poison, has obvious stimulation effect on gastrointestinal mucosa and respiratory tract, can be combined with ferric iron in oxidative cytochrome oxidase in organisms so as to inhibit the activity of the enzyme, and the higher the concentration is, the higher the possibility of causing central nervous system symptoms and suffocation symptoms is. Therefore, the research of replacing sulfur-containing and antimony-containing firework moisture-proof agents attracts extensive research of scholars.
Patent CN108211681A discloses a high-efficiency mildew-proof moisture-proof agent, but the moisture-proof agent contains sulfur-containing substance isothiazolinone, and the sulfur-containing substance is released in the process of matching with fireworks, so that air pollution is caused. Patent CN1341583A discloses a firework moisture-proof agent, which is simple to prepare, is sulfur-free and antimony-free, but uses a large amount of toxic volatile solvents in the preparation process, and celluloid in the components is accompanied by black smoke when burning, so that environmental pollution is brought, and the environment-friendly requirements of no smoke and sulfur are not met.
Aiming at the problems, the improvement research for enhancing the integration performance of the moistureproof agent for fireworks and firecrackers develops a smokeless sulfur-free moistureproof auxiliary agent for fireworks and firecrackers for improving the hydrophobic, antistatic and antioxidant performances of the firecracker and has important research significance for improving the safety, the stability during storage, the safety during setting off, the long-term storage time of fireworks and the like in the production process of fireworks.
Disclosure of Invention
The invention aims to solve the potential safety hazard problem of the existing firecracker moisture-proof agent in the production and storage processes, and provides a smokeless sulfur-free moisture-proof auxiliary agent for fireworks and firecrackers and a preparation method thereof.
The purpose of the invention is realized by the following technical scheme:
a smokeless and sulfur-free moisture-proof auxiliary agent for fireworks and firecrackers comprises the following components in percentage by mass:
the nitrogen content of the nitrified bamboo cellulose is 12 to 12.5 percent;
the component A is any one of melamine, dicyandiamide, p-phenylenediamine and benzoguanamine;
the component B is one of zinc stearate, sodium stearate and potassium stearate;
a smokeless and sulfur-free moisture-proof auxiliary agent for fireworks and firecrackers and a preparation method thereof comprise the following steps:
the method comprises the following steps: according to the formula (0.05-0.5): (0.5-2): (9.5-11.5) dividing the nitrified bamboo cellulose into a group I, a group II and a group III according to the mass ratio; dissolving the group I of the nitrated bamboo cellulose in ethyl acetate to obtain a nitrated bamboo cellulose solution with the concentration of 0.3-1.2%, sequentially adding potassium sorbate, salicylic acid and ethoxylated lauramide into the nitrated bamboo cellulose solution, stirring until the potassium sorbate, the salicylic acid and the ethoxylated lauramide are dissolved to obtain a solution I, and transferring the solution I into a spray gun;
adding the group II of the nitrated bamboo cellulose obtained in the step I into ethyl acetate, stirring until the nitrated bamboo cellulose is completely swelled to obtain nitrated bamboo cellulose sol with the concentration of 5-20%, continuously adding the fluorosilicone resin, the 2-hydroxy-4-n-octoxy benzophenone and the component A into the nitrated bamboo cellulose sol in sequence under the stirring state, and uniformly stirring to obtain sol II;
step three, uniformly mixing the group III nitro bamboo cellulose obtained in the step one with nitroguanidine, modified activated carbon and the component B, adding the mixture into the sol II obtained in the step two under a stirring state, 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;
the preparation method of the modified activated carbon in the third step comprises the following steps: according to the mol ratio of 1: (3-4): (6-20) weighing hexachlorocyclotriphosphazene, bisphenol AF and triethylamine, and weighing activated carbon, wherein the mass of the activated carbon is 0.5-10% of that of the hexachlorocyclotriphosphazene. Dissolving hexachlorocyclotriphosphazene in tetrahydrofuran to obtain a hexachlorocyclotriphosphazene solution with the concentration of 0.1-5%; dissolving bisphenol AF and triethylamine in tetrahydrofuran in sequence to obtain a mixed solution A with the content of the bisphenol AF of 5-40%, and placing the mixed solution A in a dropping funnel. Under the protection of nitrogen, putting a hexachlorocyclotriphosphazene solution into an ultrasonic water bath, performing ultrasonic treatment at 30 ℃ for 3-10 minutes, adding activated carbon, keeping the temperature at 30 ℃, continuing the ultrasonic treatment for 10-60 minutes, dropwise adding the mixed solution A into the mixed solution A, after 5-30 minutes of dropwise adding, heating to 40-50 ℃, continuing the ultrasonic treatment for 2-12 hours, transferring the mixed solution A into a centrifuge tube, centrifuging at the rotating speed of 3000-10000 rad/min, alternately washing the centrifuged product with acetone and deionized water for 3 times, transferring the washed product into a vacuum oven, and drying at the temperature of 60-105 ℃ for 8 hours to obtain the modified activated carbon.
The method for judging the moderate hardness in the step three 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;
granulating the uniform micelle-like substance with moderate hardness obtained in the step three by using a 20-mesh copper sieve, after airing in a fume hood to be half-dry, transferring the uniform micelle-like substance to a blast oven at 40-80 ℃ for drying for 12 hours, crushing the uniform micelle-like substance by light pressure, sieving the uniform micelle-like substance by using a 100-mesh copper sieve, removing screen remnants with too small particles, then sieving the crushed uniform micelle-like substance by using a 20-mesh copper sieve, and taking the screen remnants of the 20-mesh copper sieve to obtain a smoke-free sulfur-free moisture-proof auxiliary agent intermediate with uniform particles for fireworks;
and step five, keeping the stirring state in a blast drying environment, continuously spraying the solution I obtained in the step one on the surface of the smokeless sulfur-free moisture-proof auxiliary agent intermediate for fireworks and firecrackers with uniform particles obtained in the step four, and continuously stirring for 10-60 minutes after spraying, and taking out the solution I to obtain the smokeless sulfur-free moisture-proof auxiliary agent for fireworks and firecrackers with uniform particles.
Advantageous effects
1. The smokeless and sulfur-free moisture-proof auxiliary agent for fireworks and firecrackers provided by the invention has a good moisture absorption effect, is excellent in moisture-proof performance and has a certain hydrophobic performance.
2. The smokeless and sulfur-free moisture-proof auxiliary agent for fireworks and firecrackers provided by the invention has the advantages of antistatic property, oxidation resistance and the like.
3. The smokeless and sulfur-free moisture-proof auxiliary agent for fireworks and firecrackers provided by the invention is simple in preparation process, easy to control reaction conditions and lower in cost.
4. The smokeless and sulfur-free moisture-proof auxiliary agent for fireworks and firecrackers, provided by the invention, is suitable for large-scale production and can realize industrialization.
Detailed description of the preferred embodiments
The purpose of the invention patent is realized by the following technical scheme:
example 1:
a smokeless and sulfur-free moisture-proof auxiliary agent for fireworks and firecrackers comprises the following components in percentage by mass:
the nitrogen content of the nitrated bamboo cellulose in the components is 12 to 12.5 percent;
a smokeless and sulfur-free moisture-proof auxiliary agent for fireworks and firecrackers and a preparation method thereof comprise the following steps:
step one, according to a molar ratio of 1: 3: 4.1g (11.79mmol) of hexachlorocyclotriphosphazene, 11.89g (35.37mmol) of bisphenol AF and 7.16g (70.74mmol) of triethylamine are weighed 6 and 0.205g of activated carbon is weighed based on 5% by mass of hexachlorocyclotriphosphazene. Dissolving hexachlorocyclotriphosphazene in 200mL tetrahydrofuran to obtain a hexachlorocyclotriphosphazene solution with the concentration of 2.25%; dissolving bisphenol AF and triethylamine in 200mL of tetrahydrofuran in sequence to obtain a mixed solution A with the content of the bisphenol AF being 6.03%, and placing the mixed solution A in a dropping funnel;
and step two, installing a thermometer, a condenser pipe, an air inlet pipe and a tail gas absorption device. Under the protection of nitrogen, putting a hexachlorocyclotriphosphazene solution into an ultrasonic water bath, performing ultrasonic treatment at 30 ℃ for 5 minutes, adding the activated carbon weighed in the first step, keeping the temperature at 30 ℃ for continuing ultrasonic treatment for 30 minutes, dropwise adding the mixed solution A into the mixed solution A, heating to 50 ℃ after the dropwise adding is completed for 30 minutes, continuing ultrasonic treatment for 8 hours, transferring the mixed solution A into a centrifuge tube, centrifuging at the rotating speed of 3000rad/min, alternately washing the centrifugal product with acetone and deionized water for 3 times, and transferring the centrifugal product into a vacuum oven to dry the centrifugal product for 8 hours at 80 ℃ to obtain modified activated carbon;
step three: weighing 9g, 2.75g, 0.125g, 0.0625g and 0.0625g of each of nitrated bamboo cellulose, nitroguanidine, melamine, zinc stearate, fluorosilicone resin, modified activated carbon, potassium sorbate, 2-hydroxy-4-n-octoxybenzophenone, ethoxylated lauramide and salicylic acid;
step four, according to the proportion of 0.1: 0.6: 10, dividing the nitrified bamboo cellulose into a group I, a group II and a group III; dissolving 0.08g of group I nitrated bamboo cellulose in 8.78mL ethyl acetate to obtain a 1% nitrated bamboo cellulose solution, sequentially adding potassium sorbate, salicylic acid and ethoxylated lauramide into the solution, stirring until the potassium sorbate, the salicylic acid and the ethoxylated lauramide are dissolved to obtain a solution I, and transferring the solution I into a spray gun;
step five, adding 0.50g of II-group nitrobamboo cellulose obtained in the step four into 6.37mL of ethyl acetate, stirring until the nitrobamboo cellulose is completely swelled to obtain 8% nitrobamboo cellulose sol, continuously adding fluorosilicone resin, 2-hydroxy-4-n-octoxy benzophenone and melamine into the nitrobamboo cellulose sol in a stirring state, and uniformly stirring to obtain sol II;
step six, uniformly mixing the III group nitrified bamboo cellulose in the step four with nitroguanidine, modified activated carbon and zinc stearate, adding the mixture into the sol II obtained in the step five under a stirring state, kneading, and adding 3.5mL of ethyl acetate in the kneading process until the mixture is kneaded to form uniform micelle with moderate hardness;
step seven, granulating the uniform micelle with moderate hardness obtained in the step six by using a 20-mesh copper sieve, after airing to be half-dry in a fume hood, transferring the uniform micelle into a 60-DEG C blast oven for drying for 12 hours, crushing the uniform micelle by light pressure, sieving the uniform micelle by using a 100-mesh copper sieve, removing screen remnants with too small particles, then sieving the screen remnants by using a 20-mesh copper sieve, and taking the screen remnants of the 20-mesh copper sieve to obtain the smoke-free sulfur-free moisture-proof auxiliary agent intermediate for fireworks with uniform particles;
and step eight, in a forced air drying environment, keeping a stirring state, continuously spraying the solution I obtained in the step four onto the surface of the smokeless sulfur-free moisture-proof auxiliary agent intermediate for fireworks and firecrackers, which is obtained in the step seven, and continuously stirring for 60 minutes after spraying, and then taking out the solution I to obtain the smokeless sulfur-free moisture-proof auxiliary agent for fireworks and firecrackers, which is obtained in a uniform particle manner.
The smokeless and sulfur-free moisture-proof auxiliary agent for fireworks and firecrackers, which is prepared by the invention, is determined under certain experimental conditions: good moisture-proof effect, no moisture regain, and surface resistance of 0.2 × 104Omega, the thermal stability is stable at 78 ℃ for 72 hours, the temperature is 98 ℃, the environmental protection requirement of no smoke and no sulfur is met, and the comprehensive performances of hydrophobicity, oxidation resistance, antistatic property and the like of the moisture-proof auxiliary agent are improved while the normal performance of the moisture-proof auxiliary agent is ensured.
Example 2:
a smokeless and sulfur-free moisture-proof auxiliary agent for fireworks and firecrackers comprises the following components in percentage by mass:
the nitrogen content of the nitrated bamboo cellulose in the components is 12 to 12.5 percent;
a smokeless and sulfur-free moisture-proof auxiliary agent for fireworks and firecrackers and a preparation method thereof comprise the following steps:
step one, according to a molar ratio of 1: 3.2: 3.6g (10.35mmol) of hexachlorocyclotriphosphazene, 11.14g (33.12mmol) of bisphenol AF and 8.38g (82.8mmol) of triethylamine are weighed into 8g, and 0.216g of activated carbon is weighed out at 6% by mass of hexachlorocyclotriphosphazene. Dissolving hexachlorocyclotriphosphazene in 200mL tetrahydrofuran to obtain a hexachlorocyclotriphosphazene solution with the concentration of 1.98%; dissolving bisphenol AF and triethylamine in 200mL of tetrahydrofuran in sequence to obtain a mixed solution A with the content of the bisphenol AF of 5.64 percent, and placing the mixed solution A in a dropping funnel;
and step two, installing a thermometer, a condenser pipe, an air inlet pipe and a tail gas absorption device. Under the protection of nitrogen, putting a hexachlorocyclotriphosphazene solution into an ultrasonic water bath, performing ultrasonic treatment at 30 ℃ for 5 minutes, adding the activated carbon weighed in the first step, keeping the temperature at 30 ℃ for continuing ultrasonic treatment for 30 minutes, dropwise adding the mixed solution A into the mixed solution A, heating to 50 ℃ after the dropwise adding is completed for 30 minutes, continuing ultrasonic treatment for 8 hours, transferring the mixed solution A into a centrifugal tube, centrifuging at the rotating speed of 4000rad/min, alternately washing the centrifugal product with acetone and deionized water for 3 times, and transferring the centrifugal product into a vacuum oven to dry the centrifugal product for 8 hours at 80 ℃ to obtain modified activated carbon;
step three: weighing 38g, 9g, 0.375g, 0.5g, 0.25g, 0.375g and 0.25g of nitrified bamboo cellulose, nitroguanidine, melamine, zinc stearate, fluorosilicone resin, modified activated carbon, potassium sorbate, 2-hydroxy-4-n-octoxy benzophenone, ethoxylated lauramide and salicylic acid respectively;
step four, according to the proportion of 0.2: 0.9: 10, dividing the nitrified bamboo cellulose into a group I, a group II and a group III; dissolving 0.68g of group I nitrobamboo cellulose in 100mL of ethyl acetate to obtain a nitrobamboo cellulose solution with the concentration of 0.75%, sequentially adding potassium sorbate, salicylic acid and ethoxylated lauramide, stirring until the potassium sorbate, the salicylic acid and the ethoxylated lauramide are dissolved to obtain a solution I, and transferring the solution I into a spray gun;
step five, adding 3.08g of II-group nitrated bamboo cellulose obtained in the step four into 40mL ethyl acetate, stirring until the nitrated bamboo cellulose is completely swelled to obtain 7.87% nitrated bamboo cellulose sol, continuously adding fluorosilicone resin, 2-hydroxy-4-n-octoxy benzophenone and melamine into the nitrated bamboo cellulose sol in a stirring state, and uniformly stirring to obtain sol II;
step six, uniformly mixing the III group nitrified bamboo cellulose in the step four with nitroguanidine, modified activated carbon and zinc stearate, adding the mixture into the sol II obtained in the step five under a stirring state, kneading, and adding 6.8mL of ethyl acetate in the kneading process until the mixture is kneaded to form uniform micelle with moderate hardness;
step seven, granulating the uniform micelle with moderate hardness obtained in the step six by using a 20-mesh copper sieve, after airing to be half-dry in a fume hood, transferring the uniform micelle into a 60-DEG C blast oven for drying for 12 hours, crushing the uniform micelle by light pressure, sieving the uniform micelle by using a 100-mesh copper sieve, removing screen remnants with too small particles, then sieving the screen remnants by using a 20-mesh copper sieve, and taking the screen remnants of the 20-mesh copper sieve to obtain the smoke-free sulfur-free moisture-proof auxiliary agent intermediate for fireworks with uniform particles;
and step eight, in a forced air drying environment, keeping a stirring state, continuously spraying the solution I obtained in the step four onto the surface of the smokeless sulfur-free moisture-proof auxiliary agent intermediate for fireworks and firecrackers, which is obtained in the step seven, and continuously stirring for 60 minutes after spraying, and then taking out the solution I to obtain the smokeless sulfur-free moisture-proof auxiliary agent for fireworks and firecrackers, which is obtained in a uniform particle manner.
The smokeless and sulfur-free moisture-proof auxiliary agent for fireworks and firecrackers, which is prepared by the invention, is determined under certain experimental conditions: good moisture-proof effect, no moisture regain, and surface resistance of 0.2 × 104Omega, the thermal stability is stable at 78 ℃ for 72 hours, the temperature is 98 ℃, the environmental protection requirement of no smoke and no sulfur is met, and the comprehensive performances of hydrophobicity, oxidation resistance, antistatic property and the like of the moisture-proof auxiliary agent are improved while the normal performance of the moisture-proof auxiliary agent is ensured.
Example 3:
a smokeless and sulfur-free moisture-proof auxiliary agent for fireworks and firecrackers comprises the following components in percentage by mass:
the nitrogen content of the nitrated bamboo cellulose in the components is 12 to 12.5 percent;
a smokeless and sulfur-free moisture-proof auxiliary agent for fireworks and firecrackers and a preparation method thereof comprise the following steps:
step one, according to a molar ratio of 1: 3.4: 5.2g (14.96mmol) of hexachlorocyclotriphosphazene, 17.10g (50.86mmol) of bisphenol AF and 12.11g (119.68mmol) of triethylamine are weighed in 8, and 0.364g of activated carbon is weighed in relation to 7% by mass of hexachlorocyclotriphosphazene. Dissolving hexachlorocyclotriphosphazene in 200mL tetrahydrofuran to obtain a hexachlorocyclotriphosphazene solution with the concentration of 2.84%; dissolving bisphenol AF and triethylamine in 300mL of tetrahydrofuran in sequence to obtain a mixed solution A with the content of the bisphenol AF of 5.77 percent, and placing the mixed solution A in a dropping funnel;
and step two, installing a thermometer, a condenser pipe, an air inlet pipe and a tail gas absorption device. Under the protection of nitrogen, putting a hexachlorocyclotriphosphazene solution into an ultrasonic water bath, performing ultrasonic treatment at 30 ℃ for 5 minutes, adding the activated carbon weighed in the first step, keeping the temperature at 30 ℃ for continuing ultrasonic treatment for 30 minutes, dropwise adding the mixed solution A into the mixed solution A, heating to 50 ℃ after the dropwise adding is completed for 30 minutes, continuing ultrasonic treatment for 8 hours, transferring the mixed solution A into a centrifugal tube, centrifuging at the rotating speed of 4000rad/min, alternately washing the centrifugal product with acetone and deionized water for 3 times, and transferring the centrifugal product into a vacuum oven to dry the centrifugal product for 8 hours at 80 ℃ to obtain modified activated carbon;
step three: weighing 78g, 16g, 0.5g, 1g, 0.5g, 1.25g, 1g, 0.5g and 0.75g of nitrified bamboo cellulose, nitroguanidine, p-phenylenediamine, zinc stearate, fluorosilicone resin, modified activated carbon, potassium sorbate, 2-hydroxy-4-n-octoxy benzophenone, ethoxylated lauramide and salicylic acid respectively;
step four, according to the proportion of 0.3: 1.4: 10, dividing the nitrified bamboo cellulose into a group I, a group II and a group III; dissolving 2g of group I nitrated bamboo cellulose in 250mL ethyl acetate to obtain a nitrated bamboo cellulose solution with the concentration of 0.88%, sequentially adding potassium sorbate, salicylic acid and ethoxylated lauramide into the nitrated bamboo cellulose solution, stirring until the potassium sorbate, the salicylic acid and the ethoxylated lauramide are dissolved to obtain a solution I, and transferring the solution I into a spray gun;
step five, adding 9.33g of II-group nitrobamboo cellulose obtained in the step four into 100mL of ethyl acetate, stirring until the nitrobamboo cellulose is completely swelled to obtain 9.37% nitrobamboo cellulose sol, continuously adding fluorosilicone resin, 2-hydroxy-4-n-octoxy benzophenone and p-phenylenediamine into the mixture in a stirring state, and uniformly stirring to obtain sol II;
step six, uniformly mixing the III group nitrified bamboo cellulose in the step four with nitroguanidine, modified activated carbon and zinc stearate, adding the mixture into the sol II obtained in the step five under a stirring state, kneading, and adding 3.5mL of ethyl acetate in the kneading process until the mixture is kneaded to form uniform micelle with moderate hardness;
step seven, granulating the uniform micelle with moderate hardness obtained in the step six by using a 20-mesh copper sieve, after airing to be half-dry in a fume hood, transferring the uniform micelle into a 60-DEG C blast oven for drying for 12 hours, crushing the uniform micelle by light pressure, sieving the uniform micelle by using a 100-mesh copper sieve, removing screen remnants with too small particles, then sieving the screen remnants by using a 20-mesh copper sieve, and taking the screen remnants of the 20-mesh copper sieve to obtain the smoke-free sulfur-free moisture-proof auxiliary agent intermediate for fireworks with uniform particles;
and step eight, in a forced air drying environment, keeping a stirring state, continuously spraying the solution I obtained in the step four onto the surface of the smokeless sulfur-free moisture-proof auxiliary agent intermediate for fireworks and firecrackers, which is obtained in the step seven, and continuously stirring for 60 minutes after spraying, and then taking out the solution I to obtain the smokeless sulfur-free moisture-proof auxiliary agent for fireworks and firecrackers, which is obtained in a uniform particle manner.
The smokeless and sulfur-free moisture-proof auxiliary agent for fireworks and firecrackers, which is prepared by the invention, is determined under certain experimental conditions: good moisture-proof effect, no moisture regain, and surface resistance of 0.2 × 104Omega, the thermal stability is stable at 78 ℃ for 72 hours, the temperature is 98 ℃, the environmental protection requirement of no smoke and no sulfur is met, and the comprehensive performances of hydrophobicity, oxidation resistance, antistatic property and the like of the moisture-proof auxiliary agent are improved while the normal performance of the moisture-proof auxiliary agent is ensured.
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 (7)
1. The smokeless and sulfur-free moisture-proof auxiliary agent for fireworks and firecrackers is characterized in that: the mass percentage of each component is as follows:
2. the smokeless and sulfur-free moisture-proof auxiliary agent for fireworks and firecrackers as claimed in claim 1, wherein: the component A is any one of melamine, dicyandiamide, p-phenylenediamine and benzoguanamine; the component B is one of zinc stearate, sodium stearate and potassium stearate.
3. The smokeless and sulfur-free moisture-proof auxiliary agent for fireworks and firecrackers as claimed in claim 1, wherein: the nitrogen content of the nitrified bamboo cellulose is 12-12.5%.
4. The smokeless and sulfur-free moisture-proof auxiliary agent for fireworks and firecrackers as claimed in claim 1, wherein: the preparation method of the modified activated carbon comprises the following steps: according to the mol ratio of 1: (3-4): (6-20) weighing hexachlorocyclotriphosphazene, bisphenol AF and triethylamine, and weighing activated carbon, wherein the mass of the activated carbon is 0.5-10% of that of the hexachlorocyclotriphosphazene; dissolving hexachlorocyclotriphosphazene in tetrahydrofuran to obtain a hexachlorocyclotriphosphazene solution with the concentration of 0.1-5%; dissolving bisphenol AF and triethylamine in tetrahydrofuran in sequence to obtain a mixed solution A with the content of the bisphenol AF of 5-40%, and placing the mixed solution A in a dropping funnel; under the protection of nitrogen, putting a hexachlorocyclotriphosphazene solution into an ultrasonic water bath, performing ultrasonic treatment at 30 ℃ for 3-10 minutes, adding activated carbon, keeping the temperature at 30 ℃, continuing the ultrasonic treatment for 10-60 minutes, dropwise adding the mixed solution A into the mixed solution A, after 5-30 minutes of dropwise adding, heating to 40-50 ℃, continuing the ultrasonic treatment for 2-12 hours, transferring the mixed solution A into a centrifuge tube, centrifuging at the rotating speed of 3000-10000 rad/min, alternately washing the centrifuged product with acetone and deionized water for 3 times, transferring the washed product into a vacuum oven, and drying at the temperature of 60-105 ℃ for 8 hours to obtain the modified activated carbon.
5. A process for preparing a moisture resistance aid according to claim 1, 2 or 3 wherein: the method comprises the following steps:
the method comprises the following steps: according to the formula (0.05-0.5): (0.5-2): (9.5-11.5) dividing the nitrified bamboo cellulose into a group I, a group II and a group III according to the mass ratio; dissolving the group I of the nitrated bamboo cellulose in ethyl acetate to obtain a nitrated bamboo cellulose solution with the concentration of 0.3-1.2%, sequentially adding potassium sorbate, salicylic acid and ethoxylated lauramide into the nitrated bamboo cellulose solution, stirring until the potassium sorbate, the salicylic acid and the ethoxylated lauramide are dissolved to obtain a solution I, and transferring the solution I into a spray gun;
adding the group II of the nitrated bamboo cellulose obtained in the step I into ethyl acetate, stirring until the nitrated bamboo cellulose is completely swelled to obtain nitrated bamboo cellulose sol with the concentration of 5-20%, continuously adding the fluorosilicone resin, the 2-hydroxy-4-n-octoxy benzophenone and the component A into the nitrated bamboo cellulose sol in sequence under the stirring state, and uniformly stirring to obtain sol II;
step three, uniformly mixing the group III nitro bamboo cellulose obtained in the step one with nitroguanidine, modified activated carbon and the component B, adding the mixture into the sol II obtained in the step two under a stirring state, 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;
granulating the uniform micelle-like substance with moderate hardness obtained in the step three by using a 20-mesh copper sieve, after airing in a fume hood to be half-dry, transferring the uniform micelle-like substance to a blast oven at 40-80 ℃ for drying for 12 hours, crushing the uniform micelle-like substance by light pressure, sieving the uniform micelle-like substance by using a 100-mesh copper sieve, removing screen remnants with too small particles, then sieving the crushed uniform micelle-like substance by using a 20-mesh copper sieve, and taking the screen remnants of the 20-mesh copper sieve to obtain a smoke-free sulfur-free moisture-proof auxiliary agent intermediate with uniform particles for fireworks;
and step five, keeping the stirring state in a blast drying environment, continuously spraying the solution I obtained in the step one on the surface of the smokeless sulfur-free moisture-proof auxiliary agent intermediate for fireworks and firecrackers with uniform particles obtained in the step four, and continuously stirring for 10-60 minutes after spraying, and taking out the solution I to obtain the smokeless sulfur-free moisture-proof auxiliary agent for fireworks and firecrackers with uniform particles.
6. The method of claim 5, wherein: the preparation method of the modified activated carbon in the third step comprises the following steps: according to the mol ratio of 1: (3-4): (6-20) weighing hexachlorocyclotriphosphazene, bisphenol AF and triethylamine, and weighing activated carbon, wherein the mass of the activated carbon is 0.5-10% of that of the hexachlorocyclotriphosphazene; dissolving hexachlorocyclotriphosphazene in tetrahydrofuran to obtain a hexachlorocyclotriphosphazene solution with the concentration of 0.1-5%; dissolving bisphenol AF and triethylamine in tetrahydrofuran in sequence to obtain a mixed solution A with the content of the bisphenol AF of 5-40%, and placing the mixed solution A in a dropping funnel; under the protection of nitrogen, putting a hexachlorocyclotriphosphazene solution into an ultrasonic water bath, performing ultrasonic treatment at 30 ℃ for 3-10 minutes, adding activated carbon, keeping the temperature at 30 ℃, continuing the ultrasonic treatment for 10-60 minutes, dropwise adding the mixed solution A into the mixed solution A, after 5-30 minutes of dropwise adding, heating to 40-50 ℃, continuing the ultrasonic treatment for 2-12 hours, transferring the mixed solution A into a centrifuge tube, centrifuging at the rotating speed of 3000-10000 rad/min, alternately washing the centrifuged product with acetone and deionized water for 3 times, transferring the washed product into a vacuum oven, and drying at the temperature of 60-105 ℃ for 8 hours to obtain the modified activated carbon.
7. The method of claim 5, wherein: the method for judging the moderate hardness in the step three 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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