CN111018633A - Environment-friendly smokeless sulfur-free moisture-proof agent and preparation method thereof - Google Patents
Environment-friendly smokeless sulfur-free moisture-proof agent and preparation method thereof Download PDFInfo
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Abstract
The invention relates to an environment-friendly smokeless and sulfur-free moisture-proof agent and a preparation method thereof, belonging to the field of environment-friendly pyrotechnic compositions. The components comprise: the composite material comprises nitrocellulose, nitroguanidine, dinitrotoluene, a component A, salicylic acid, 2-hydroxy-4-n-octoxy benzophenone, nitrilotrimethylene phosphoric acid, natural vitamin E, methyl silicone oil, sodium citrate, modified mesoporous silica, 3-amino-1, 2, 4-triazole, cobalt nitrate hexahydrate and anhydrous lithium chloride. The environment-friendly smokeless and sulfur-free moisture-proof agent provided by the invention contains an organic metal framework component in the structure, and the porous channel structure has a good moisture absorption effect. Has the advantages of moisture resistance, corrosion prevention, bacteriostasis and corrosion inhibition, no smoke and sulfur, environmental protection and long storage period of more than 3 years. The preparation process is simple, the reaction conditions are easy to control, the raw materials are easy to obtain, the cost is low, the method is suitable for large-scale production, and industrialization can be realized.
Description
Technical Field
The invention relates to an environment-friendly smokeless and sulfur-free moisture-proof agent and a preparation method thereof, belonging to the field of environment-friendly pyrotechnic compositions.
Background
China is always famous for producing fireworks and firecrackers. The fireworks and firecrackers are inexplicable with the ancient folk custom of China, and people can contend for the firecrackers and the fireworks to show festivals whenever the folk custom festivals or various celebration evening meetings. The firework has novel structure, attractive decoration, and is colorful, glorious, colorful, or rotating to jump over the ground, or flying to twinkle in the sky, thereby giving people fresh, comfortable and rapid feeling.
With the continuous improvement of living standard of people, the demand of fireworks is increasing day by day. 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.
The patent CN108184916A discloses a multipurpose mildew-proof moisture-proof agent, and the invention provides a mildew-proof technology with good effect aiming at the problem of mildew protection of products in real life. However, the moisture-proof agent has high contents of phenols and acids in the components, which hardly meets the use requirements of fireworks and crackers and influences the stability of the fireworks and crackers. Patent CN108211681A discloses a high-efficiency mildew-proof moisture-proof agent, but the cost of isothiazolinone in the moisture-proof agent is high, and the moisture-proof agent is a sulfur-containing compound and can cause environmental pollution when being matched with fireworks. Patent CN1341583A discloses a firework moisture-proof agent, which is simple to prepare, but uses a large amount of toxic volatile solvents in the preparation process, and has single function, so that the current requirements are difficult to meet.
Aiming at the problems, the improvement research of the moistureproof agent for fireworks is enhanced, and the environment-friendly smokeless and sulfur-free moistureproof agent is developed, which has important research significance for improving the safety, the stability during storage, the environmental protection 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 problem of certain biological toxicity of the existing sulfur-containing and antimony-containing firecracker moisture-proof agent, and provides an environment-friendly smokeless and sulfur-free moisture-proof agent and a preparation method thereof. The moisture-proof agent is light purple micro powder, has the advantages of moisture resistance, corrosion prevention, bacteriostasis and corrosion inhibition, is smokeless and sulfur-free, and is green and environment-friendly.
The purpose of the invention is realized by the following technical scheme:
an environment-friendly smokeless and sulfur-free moisture-proof agent 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 one of melamine, dicyandiamide, p-phenylenediamine and dimethyl diphenylurea;
a preparation method of an environment-friendly smokeless and sulfur-free moisture-proof agent comprises the following steps:
the method comprises the following steps: according to the formula (0.01-0.2): (0.1-2): 10, dividing the nitrified bamboo cellulose into a group I, a group II and a group III; according to the following steps: (2-6) dividing anhydrous lithium chloride into a group I and a group II according to the mass ratio; sequentially adding the group I of nitrated bamboo cellulose and the group I of anhydrous lithium chloride into acetone, stirring until the nitrated bamboo cellulose and the anhydrous lithium chloride are dissolved to obtain a mixed solution with the content of the nitrated bamboo cellulose of 0.3-1.2%, standing at room temperature for 30-90 minutes, sequentially adding salicylic acid, 2-hydroxy-4-n-octoxy benzophenone and nitrilotrimethylene phosphate into the mixed solution, continuously stirring until the mixed solution is dissolved to obtain a solution I, and transferring the solution I into a spray gun;
secondly, sequentially adding the group II of the nitrated bamboo cellulose obtained in the step one and the group II of anhydrous lithium chloride into acetone, stirring until the nitrated bamboo cellulose is completely swelled to obtain a mixed sol with the nitrated bamboo cellulose content of 3-12%, continuously adding the component A, nitroguanidine, dinitrotoluene and natural vitamin E in sequence under a stirring state, and stirring uniformly to obtain a sol II;
step three, uniformly mixing the group III nitro-bamboo cellulose in the step one with methyl silicone oil, sodium citrate and modified mesoporous silica, adding the mixture into the sol II obtained in the step two, stirring the mixture until the mixture is uniformly mixed, kneading the mixture, and adding a proper amount of acetone in the kneading process until the mixture is kneaded into a uniform micelle with moderate hardness;
the preparation method of the modified mesoporous silica in the third step comprises the following steps: according to the mass ratio of 1: (5-10) placing the mesoporous silica in an aqueous solution with 0.5-3% of kasugamycin concentration, performing ultrasonic treatment at 30-40 ℃ for 1-5 hours, transferring the solution to a centrifugal machine, centrifuging the solution at a centrifugal speed of 3000-10000 rad/min, washing the centrifuged product with anhydrous methanol for 3-5 times, and transferring the product to a forced air oven for drying at 80-105 ℃ for 8 hours to obtain modified mesoporous silica;
the method for judging the moderate hardness in the step three comprises the following steps: extruding the paste-like substance through a 40-mesh copper sieve to form continuous thin strips which are not adhered to each other;
step four, granulating the uniform micelle with moderate hardness obtained in the step three by using a 40-mesh copper sieve, after airing to be half-dry in a fume hood, transferring the uniform micelle into a blast oven at 40-80 ℃ for drying for 8 hours, crushing the uniform micelle by light pressure, sieving the uniform micelle by using a 200-mesh copper sieve, removing screen wastes with too small particles, then sieving by using a 100-mesh copper sieve, and taking the screen wastes of the 100-mesh copper sieve to obtain an environment-friendly smokeless sulfur-free moisture-proof agent intermediate I with uniform particles;
dissolving 3-amino-1, 2, 4-triazole in anhydrous methanol to obtain a 3-amino-1, 2, 4-triazole solution with the concentration of 0.2-2%; dissolving cobalt nitrate hexahydrate in absolute methanol to obtain a cobalt nitrate hexahydrate solution with the concentration of 0.1-1%;
step six, adding the environment-friendly smokeless sulfur-free moisture-proof agent intermediate I with uniform particles obtained in the step four into the cobalt nitrate hexahydrate solution obtained in the step five, stirring the mixture at room temperature for 10-30 minutes, dropwise adding a 3-amino-1, 2, 4-triazole solution into the mixture, controlling the dropwise adding time to be 5-40 minutes, heating the mixture to 30-40 ℃ after the dropwise adding is finished, continuously stirring the mixture for 0.5-3 hours, transferring the mixture to a centrifugal machine, centrifuging the mixture at a centrifugal speed of 3000-8000 rad/min, washing the centrifuged product with anhydrous methanol for 3-5 times, and airing the centrifuged product in a fume hood to be semi-dry to obtain an environment-friendly smokeless sulfur-free moisture-proof agent intermediate II;
step seven, granulating the environment-friendly smokeless and sulfur-free moisture-proof agent intermediate II obtained in the step six by using a 40-mesh copper sieve, transferring the obtained product into a blast oven at 40-80 ℃ for drying for 8 hours, crushing the product by light pressure, sieving the crushed product by using the 80-mesh copper sieve, removing the residue of the sieve with too small particles, then sieving the crushed product by using the 40-mesh copper sieve, and taking the residue of the 40-mesh copper sieve to obtain an environment-friendly smokeless and sulfur-free moisture-proof agent intermediate III 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 one on the surface of the environment-friendly smokeless sulfur-free moisture-proof agent intermediate III with uniform particles obtained in the step seven, and continuously stirring for 10-60 minutes after spraying, and taking out the solution I to obtain the environment-friendly smokeless sulfur-free moisture-proof agent with uniform particles.
Advantageous effects
1. The environment-friendly smokeless and sulfur-free moisture-proof agent provided by the invention has the advantages of moisture resistance, corrosion prevention, bacteriostasis and corrosion inhibition, is smokeless and sulfur-free, is environment-friendly, and has a storage period of more than 3 years.
2. The environment-friendly smokeless and sulfur-free moisture-proof agent provided by the invention has the advantages of simple preparation process, easily controlled reaction conditions, easily obtained raw materials and lower cost.
3. The environment-friendly smokeless and sulfur-free moisture-proof agent provided by the invention contains an organic metal framework component in the structure, and the porous channel structure has a good moisture absorption effect.
4. The environment-friendly smokeless and sulfur-free moisture-proof agent provided by the invention is suitable for large-scale production and can realize industrialization.
Detailed description of the preferred embodiments
The invention is further illustrated by the following examples
Example 1:
a preparation method of an environment-friendly smokeless and sulfur-free moisture-proof agent comprises the following specific steps:
a preparation method of an environment-friendly smokeless and sulfur-free moisture-proof agent comprises the following steps:
step one, according to the mass ratio of 1: 8, placing 5g of mesoporous silica in 40g of aqueous solution with kasugamycin concentration of 1%, performing ultrasonic treatment at 40 ℃ for 3 hours, transferring the solution to a centrifuge, centrifuging the solution at a centrifugal speed of 4000rad/min, washing the centrifuged product with absolute methanol for 3 times, and transferring the product to a blast oven for drying at 85 ℃ for 8 hours to obtain modified mesoporous silica;
weighing 76g of nitrified bamboo cellulose, 16g of nitroguanidine, 1g of dinitrotoluene, 1g of p-phenylenediamine, 0.5g of salicylic acid, 0.5g of 2-hydroxy-4-n-octoxybenzophenone, 0.5g of nitrilotrimethylene phosphate, 0.5g of natural vitamin E, 0.5g of methyl silicone oil, 0.5g of sodium citrate, 1g of modified mesoporous silica, 1g of 3-amino-1, 2, 4-triazole, 0.5g of cobalt nitrate hexahydrate and 0.5g of anhydrous lithium chloride according to the formula proportion;
step three: according to the weight ratio of 0.05: 0.3: 10, dividing the nitrified bamboo cellulose into a group I, a group II and a group III; according to the following steps: 3, dividing anhydrous lithium chloride into a group I and a group II according to the mass ratio; sequentially adding 0.37g of group I nitrobamboo cellulose and 0.125g of group I anhydrous lithium chloride into 55mL of acetone, stirring until the mixture is dissolved to obtain a mixed solution with the nitrobamboo cellulose content of 0.84%, standing at room temperature for 40 minutes, sequentially adding salicylic acid, 2-hydroxy-4-n-octyloxy benzophenone and nitrilotrimethylene phosphate into the mixed solution, continuously stirring until the mixed solution is dissolved to obtain a solution I, and transferring the solution I into a spray gun;
step four, sequentially adding 2.20g of II-group nitrified bamboo cellulose obtained in the step three and 0.375g of II-group anhydrous lithium chloride into 80mL of acetone, stirring until the nitrified bamboo cellulose is completely swelled to obtain mixed sol with the content of the nitrified bamboo cellulose of 3.35%, sequentially adding p-phenylenediamine, nitroguanidine, dinitrotoluene and natural vitamin E under the stirring state, and stirring uniformly to obtain sol II;
step five, uniformly mixing the III group nitrobamboo cellulose in the step three with methyl silicone oil, sodium citrate and modified mesoporous silica, adding the mixture into the sol II obtained in the step four, stirring the mixture until the mixture is uniformly mixed, kneading the mixture, and adding 20.5mL of acetone in the kneading process until the mixture is kneaded into a uniform micelle with moderate hardness;
step six, granulating the uniform micelle with moderate hardness obtained in the step five by using a 40-mesh copper sieve, after airing to be half-dry in a fume hood, transferring the uniform micelle into a 50-DEG C blast oven to dry for 8 hours, crushing the uniform micelle by light pressure, sieving the uniform micelle by using a 200-mesh copper sieve, removing screen remnants with too small particles, then sieving the crushed micelle by using a 100-mesh copper sieve, and taking screen remnants of the 100-mesh copper sieve to obtain an environment-friendly smokeless sulfur-free moisture-proof agent intermediate I with uniform particles;
step seven, dissolving 3-amino-1, 2, 4-triazole in 251.33mL of anhydrous methanol to obtain a 0.5% 3-amino-1, 2, 4-triazole solution; dissolving cobalt nitrate hexahydrate in 157.24mL of anhydrous methanol to obtain a 0.4% cobalt nitrate hexahydrate solution;
step eight, adding the environment-friendly smokeless and sulfur-free moisture-proof agent intermediate I with uniform particles obtained in the step six into the cobalt nitrate hexahydrate solution obtained in the step seven, stirring the mixture for 10 minutes at room temperature, dropwise adding a 3-amino-1, 2, 4-triazole solution into the mixture, heating the mixture to 40 ℃ after the dropwise adding is completed for 10 minutes, continuously stirring the mixture for 2 hours, transferring the mixture to a centrifugal machine, centrifuging the mixture at a centrifugal speed of 3000rad/min, washing the centrifugal product for 3 times by using anhydrous methanol, and airing the product in a fume hood to be semi-dry to obtain an environment-friendly smokeless and sulfur-free moisture-proof agent intermediate II;
step nine, granulating the environment-friendly smokeless and sulfur-free moisture-proof agent intermediate II obtained in the step eight by using a 40-mesh copper sieve, transferring the obtained product into a 40-DEG C blast oven to dry for 8 hours, crushing the product by light pressure, sieving the crushed product by using an 80-mesh copper sieve, removing screen wastes with too small particles, then sieving the crushed product by using a 40-mesh copper sieve, and taking the screen wastes of the 40-mesh copper sieve to obtain an environment-friendly smokeless and sulfur-free moisture-proof agent intermediate III with uniform particles;
step ten, in a forced air drying environment, keeping a stirring state, continuously spraying the solution I obtained in the step three on the surface of the environment-friendly smokeless sulfur-free moisture-proof agent intermediate III with uniform particles obtained in the step nine, continuously stirring for 15 minutes after spraying, and taking out to obtain the environment-friendly smokeless sulfur-free moisture-proof agent with uniform particles.
Tests prove that the environment-friendly smokeless and sulfur-free moisture-proof agent has the advantages of 2 percent of water, 6.5 of PH value, good moisture-proof effect, no moisture regain phenomenon, stable thermal stability for 72 hours at 78 ℃, 90 ℃ resistance, 1-grade mildew grade measured by a plate counting method, good storage stability and capability of meeting the environment-friendly requirements of no smoke and sulfur.
Example 2:
a preparation method of an environment-friendly smokeless and sulfur-free moisture-proof agent comprises the following specific steps:
a preparation method of an environment-friendly smokeless and sulfur-free moisture-proof agent comprises the following steps:
step one, according to the mass ratio of 1: 9 placing 5g of mesoporous silica in 45g of aqueous solution with kasugamycin concentration of 1.2%, performing ultrasonic treatment at 40 ℃ for 3 hours, transferring the solution to a centrifuge, centrifuging the solution at a centrifugal speed of 4000rad/min, washing the centrifuged product with absolute methanol for 3 times, and transferring the product to a blast oven for drying at 85 ℃ for 8 hours to obtain modified mesoporous silica;
weighing 74g of nitrified bamboo cellulose, 16g of nitroguanidine, 1.25g of dinitrotoluene, 1.25g of dimethyl diphenyl urea, 0.75g of salicylic acid, 0.75g of 2-hydroxy-4-n-octoxy benzophenone, 0.75g of nitrilo trimethylene phosphoric acid, 0.75g of natural vitamin E, 0.75g of methyl silicone oil, 0.75g of sodium citrate, 1g of modified mesoporous silica, 1g of 3-amino-1, 2, 4-triazole, 0.5g of cobalt nitrate hexahydrate and 0.5g of anhydrous lithium chloride according to the formula proportion;
step three: according to the weight ratio of 0.08: 1.5: 10, dividing the nitrified bamboo cellulose into a group I, a group II and a group III; according to the following steps: 4, dividing anhydrous lithium chloride into a group I and a group II according to the mass ratio; sequentially adding 0.51g of group I nitrobamboo cellulose and 0.1g of group I anhydrous lithium chloride into 80mL of acetone, stirring until the mixture is dissolved to obtain a mixed solution with the nitrobamboo cellulose content of 0.8%, standing at room temperature for 40 minutes, sequentially adding salicylic acid, 2-hydroxy-4-n-octyloxy benzophenone and nitrilotrimethylene phosphate into the mixed solution, continuously stirring until the mixed solution is dissolved to obtain a solution I, and transferring the solution I into a spray gun;
step four, adding 9.59g of II-group nitrified bamboo cellulose obtained in the step three and 0.4g of II-group anhydrous lithium chloride into 90mL of acetone in sequence, stirring until the nitrified bamboo cellulose is completely swelled to obtain mixed sol with the content of the nitrified bamboo cellulose of 11.85%, continuously adding dimethyldiphenylurea, nitroguanidine, dinitrotoluene and natural vitamin E in sequence under a stirring state, and stirring uniformly to obtain sol II;
step five, uniformly mixing the III group nitrobamboo cellulose in the step three with methyl silicone oil, sodium citrate and modified mesoporous silica, adding the mixture into the sol II obtained in the step four, stirring the mixture until the mixture is uniformly mixed, kneading the mixture, and adding 12.5mL of acetone in the kneading process until the mixture is kneaded into a uniform micelle with moderate hardness;
step six, granulating the uniform micelle with moderate hardness obtained in the step five by using a 40-mesh copper sieve, after airing to be half-dry in a fume hood, transferring the uniform micelle into a 50-DEG C blast oven to dry for 8 hours, crushing the uniform micelle by light pressure, sieving the uniform micelle by using a 200-mesh copper sieve, removing screen remnants with too small particles, then sieving the crushed micelle by using a 100-mesh copper sieve, and taking screen remnants of the 100-mesh copper sieve to obtain an environment-friendly smokeless sulfur-free moisture-proof agent intermediate I with uniform particles;
step seven, dissolving 3-amino-1, 2, 4-triazole in 250mL of anhydrous methanol to obtain a 0.5% 3-amino-1, 2, 4-triazole solution; dissolving cobalt nitrate hexahydrate in 150mL of anhydrous methanol to obtain a 0.42% cobalt nitrate hexahydrate solution;
step eight, adding the environment-friendly smokeless and sulfur-free moisture-proof agent intermediate I with uniform particles obtained in the step six into the cobalt nitrate hexahydrate solution obtained in the step seven, stirring the mixture for 10 minutes at room temperature, dropwise adding a 3-amino-1, 2, 4-triazole solution into the mixture, heating the mixture to 40 ℃ after the dropwise adding is completed for 10 minutes, continuously stirring the mixture for 2 hours, transferring the mixture to a centrifugal machine, centrifuging the mixture at a centrifugal speed of 3000rad/min, washing the centrifugal product for 3 times by using anhydrous methanol, and airing the product in a fume hood to be semi-dry to obtain an environment-friendly smokeless and sulfur-free moisture-proof agent intermediate II;
step nine, granulating the environment-friendly smokeless and sulfur-free moisture-proof agent intermediate II obtained in the step eight by using a 40-mesh copper sieve, transferring the obtained product into a 40-DEG C blast oven to dry for 8 hours, crushing the product by light pressure, sieving the crushed product by using an 80-mesh copper sieve, removing screen wastes with too small particles, then sieving the crushed product by using a 40-mesh copper sieve, and taking the screen wastes of the 40-mesh copper sieve to obtain an environment-friendly smokeless and sulfur-free moisture-proof agent intermediate III with uniform particles;
step ten, in a forced air drying environment, keeping a stirring state, continuously spraying the solution I obtained in the step three on the surface of the environment-friendly smokeless sulfur-free moisture-proof agent intermediate III with uniform particles obtained in the step nine, continuously stirring for 15 minutes after spraying, and taking out to obtain the environment-friendly smokeless sulfur-free moisture-proof agent with uniform particles.
Tests prove that the environment-friendly smokeless and sulfur-free moisture-proof agent has the water content of 2.2 percent, the pH value of 6.6, good moisture-proof effect and no moisture regain phenomenon, has stable thermal stability at 78 ℃ for 72 hours, can resist the temperature of 91 ℃, has the mould growth grade of 1 grade as measured by a plate counting method, has good storage stability and meets the environment-friendly requirements of smokeless and sulfur-free.
Example 3:
a preparation method of an environment-friendly smokeless and sulfur-free moisture-proof agent comprises the following specific steps:
a preparation method of an environment-friendly smokeless and sulfur-free moisture-proof agent comprises the following steps:
step one, according to the mass ratio of 1: 10, placing 5g of mesoporous silica in 50g of aqueous solution with kasugamycin concentration of 1.6%, performing ultrasonic treatment at 40 ℃ for 4 hours, transferring the solution to a centrifugal machine, centrifuging the solution at the centrifugal speed of 5000rad/min, washing the centrifuged product with absolute methanol for 3 times, and transferring the product to a blast oven for drying at 85 ℃ for 8 hours to obtain modified mesoporous silica;
weighing 142g of nitrified bamboo cellulose, 38g of nitroguanidine, 4g of dinitrotoluene, 2g of dimethyl diphenyl urea, 1g of salicylic acid, 1g of 2-hydroxy-4-n-octoxy benzophenone, 1g of nitrilo trimethylene phosphoric acid, 1.5g of natural vitamin E, 1g of methyl silicone oil, 1.5g of sodium citrate, 3g of modified mesoporous silica, 2g of 3-amino-1, 2, 4-triazole, 1g of cobalt nitrate hexahydrate and 1g of anhydrous lithium chloride according to the formula proportion;
step three: according to the weight ratio of 0.1: 0.5: 10, dividing the nitrified bamboo cellulose into a group I, a group II and a group III; according to the following steps: 4, dividing anhydrous lithium chloride into a group I and a group II according to the mass ratio; sequentially adding 1.34g of group I nitrobamboo cellulose and 0.2g of group I anhydrous lithium chloride into 150mL of acetone, stirring until the mixture is dissolved to obtain a mixed solution with the nitrobamboo cellulose content of 1.12%, standing at room temperature for 50 minutes, sequentially adding salicylic acid, 2-hydroxy-4-n-octyloxy benzophenone and nitrilotrimethylene phosphate into the mixed solution, continuously stirring until the mixed solution is dissolved to obtain a solution I, and transferring the solution I into a spray gun;
step four, sequentially adding 6.7g of II-group nitrified bamboo cellulose obtained in the step three and 0.8g of II-group anhydrous lithium chloride into 70mL of acetone, stirring until the nitrified bamboo cellulose is completely swelled to obtain a mixed sol with the content of the nitrified bamboo cellulose of 10.69%, sequentially adding dimethyldiphenylurea, nitroguanidine, dinitrotoluene and natural vitamin E under the stirring state, and stirring uniformly to obtain a sol II;
step five, uniformly mixing the III group nitrobamboo cellulose in the step three with methyl silicone oil, sodium citrate and modified mesoporous silica, adding the mixture into the sol II obtained in the step four, stirring the mixture until the mixture is uniformly mixed, kneading the mixture, and adding 28mL of acetone in the kneading process until the mixture is kneaded into a uniform micelle with moderate hardness;
step six, granulating the uniform micelle with moderate hardness obtained in the step five by using a 40-mesh copper sieve, after airing to be half-dry in a fume hood, transferring the uniform micelle into a 50-DEG C blast oven to dry for 8 hours, crushing the uniform micelle by light pressure, sieving the uniform micelle by using a 200-mesh copper sieve, removing screen remnants with too small particles, then sieving the crushed micelle by using a 100-mesh copper sieve, and taking screen remnants of the 100-mesh copper sieve to obtain an environment-friendly smokeless sulfur-free moisture-proof agent intermediate I with uniform particles;
step seven, dissolving 3-amino-1, 2, 4-triazole in 500mL of anhydrous methanol to obtain a 0.5% 3-amino-1, 2, 4-triazole solution; dissolving cobalt nitrate hexahydrate in 300mL of anhydrous methanol to obtain a 0.42% cobalt nitrate hexahydrate solution;
step eight, adding the environment-friendly smokeless and sulfur-free moisture-proof agent intermediate I with uniform particles obtained in the step six into the cobalt nitrate hexahydrate solution obtained in the step seven, stirring the mixture for 10 minutes at room temperature, dropwise adding a 3-amino-1, 2, 4-triazole solution into the mixture, heating the mixture to 40 ℃ after the dropwise adding is completed for 10 minutes, continuously stirring the mixture for 2 hours, transferring the mixture to a centrifugal machine, centrifuging the mixture at a centrifugal speed of 3000rad/min, washing the centrifugal product for 3 times by using anhydrous methanol, and airing the product in a fume hood to be semi-dry to obtain an environment-friendly smokeless and sulfur-free moisture-proof agent intermediate II;
step nine, granulating the environment-friendly smokeless and sulfur-free moisture-proof agent intermediate II obtained in the step eight by using a 40-mesh copper sieve, transferring the obtained product into a 40-DEG C blast oven to dry for 8 hours, crushing the product by light pressure, sieving the crushed product by using an 80-mesh copper sieve, removing screen wastes with too small particles, then sieving the crushed product by using a 40-mesh copper sieve, and taking the screen wastes of the 40-mesh copper sieve to obtain an environment-friendly smokeless and sulfur-free moisture-proof agent intermediate III with uniform particles;
step ten, in a forced air drying environment, keeping a stirring state, continuously spraying the solution I obtained in the step three on the surface of the environment-friendly smokeless sulfur-free moisture-proof agent intermediate III with uniform particles obtained in the step nine, continuously stirring for 15 minutes after spraying, and taking out to obtain the environment-friendly smokeless sulfur-free moisture-proof agent with uniform particles.
Tests prove that the environment-friendly smokeless and sulfur-free moisture-proof agent has the water content of 2.1 percent, the pH value of 6.4, good moisture-proof effect and no moisture regain phenomenon, has stable thermal stability at 78 ℃ for 72 hours, can resist the temperature of 90 ℃, has the mould growth grade of 1 grade as measured by a plate counting method, has good storage stability and meets the environment-friendly requirements of smokeless and sulfur-free.
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. An environment-friendly smokeless and sulfur-free moisture-proof agent is characterized in that: the mass percentage of each component is as follows:
2. the environment-friendly smokeless and sulfur-free moisture-proof agent as claimed in claim 1, wherein: the component A is one of melamine, dicyandiamide, p-phenylenediamine and dimethyldiphenylurea.
3. The environment-friendly smokeless and sulfur-free moisture-proof agent as claimed in claim 1, wherein: the nitrogen content of the nitrified bamboo cellulose is 12-12.5%.
4. The environment-friendly smokeless and sulfur-free moisture-proof agent as claimed in claim 1, wherein: the preparation method of the modified mesoporous silica comprises the following steps: according to the mass ratio of 1: (5-10) placing the mesoporous silica in an aqueous solution with 0.5-3% of kasugamycin concentration, performing ultrasonic treatment at 30-40 ℃ for 1-5 hours, transferring the solution to a centrifugal machine, centrifuging the solution at a centrifugal speed of 3000-10000 rad/min, washing the centrifuged product with anhydrous methanol for 3-5 times, and transferring the product to a forced air oven for drying at 80-105 ℃ for 8 hours to obtain the modified mesoporous silica.
5. A process for preparing a moisture barrier as defined in claim 1 or 2 or 3 or 4 wherein: the method comprises the following steps:
the method comprises the following steps: according to the formula (0.01-0.2): (0.1-2): 10, dividing the nitrified bamboo cellulose into a group I, a group II and a group III; according to the following steps: (2-6) dividing anhydrous lithium chloride into a group I and a group II according to the mass ratio; sequentially adding the group I of nitrated bamboo cellulose and the group I of anhydrous lithium chloride into acetone, stirring until the nitrated bamboo cellulose and the anhydrous lithium chloride are dissolved to obtain a mixed solution with the content of the nitrated bamboo cellulose of 0.3-1.2%, standing at room temperature for 30-90 minutes, sequentially adding salicylic acid, 2-hydroxy-4-n-octoxy benzophenone and nitrilotrimethylene phosphate into the mixed solution, continuously stirring until the mixed solution is dissolved to obtain a solution I, and transferring the solution I into a spray gun;
secondly, sequentially adding the group II of the nitrated bamboo cellulose obtained in the step one and the group II of anhydrous lithium chloride into acetone, stirring until the nitrated bamboo cellulose is completely swelled to obtain a mixed sol with the nitrated bamboo cellulose content of 3-12%, continuously adding the component A, nitroguanidine, dinitrotoluene and natural vitamin E in sequence under a stirring state, and stirring uniformly to obtain a sol II;
step three, uniformly mixing the group III nitro-bamboo cellulose in the step one with methyl silicone oil, sodium citrate and modified mesoporous silica, adding the mixture into the sol II obtained in the step two, stirring the mixture until the mixture is uniformly mixed, kneading the mixture, and adding a proper amount of acetone in the kneading process until the mixture is kneaded into a uniform micelle with moderate hardness;
step four, granulating the uniform micelle with moderate hardness obtained in the step three by using a 40-mesh copper sieve, after airing to be half-dry in a fume hood, transferring the uniform micelle into a blast oven at 40-80 ℃ for drying for 8 hours, crushing the uniform micelle by light pressure, sieving the uniform micelle by using a 200-mesh copper sieve, removing screen wastes with too small particles, then sieving by using a 100-mesh copper sieve, and taking the screen wastes of the 100-mesh copper sieve to obtain an environment-friendly smokeless sulfur-free moisture-proof agent intermediate I with uniform particles;
dissolving 3-amino-1, 2, 4-triazole in anhydrous methanol to obtain a 3-amino-1, 2, 4-triazole solution with the concentration of 0.2-2%; dissolving cobalt nitrate hexahydrate in absolute methanol to obtain a cobalt nitrate hexahydrate solution with the concentration of 0.1-1%;
step six, adding the environment-friendly smokeless sulfur-free moisture-proof agent intermediate I with uniform particles obtained in the step four into the cobalt nitrate hexahydrate solution obtained in the step five, stirring the mixture at room temperature for 10-30 minutes, dropwise adding a 3-amino-1, 2, 4-triazole solution into the mixture, controlling the dropwise adding time to be 5-40 minutes, heating the mixture to 30-40 ℃ after the dropwise adding is finished, continuously stirring the mixture for 0.5-3 hours, transferring the mixture to a centrifugal machine, centrifuging the mixture at a centrifugal speed of 3000-8000 rad/min, washing the centrifuged product with anhydrous methanol for 3-5 times, and airing the centrifuged product in a fume hood to be semi-dry to obtain an environment-friendly smokeless sulfur-free moisture-proof agent intermediate II;
step seven, granulating the environment-friendly smokeless and sulfur-free moisture-proof agent intermediate II obtained in the step six by using a 40-mesh copper sieve, transferring the obtained product into a blast oven at 40-80 ℃ for drying for 8 hours, crushing the product by light pressure, sieving the crushed product by using the 80-mesh copper sieve, removing the residue of the sieve with too small particles, then sieving the crushed product by using the 40-mesh copper sieve, and taking the residue of the 40-mesh copper sieve to obtain an environment-friendly smokeless and sulfur-free moisture-proof agent intermediate III 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 one on the surface of the environment-friendly smokeless sulfur-free moisture-proof agent intermediate III with uniform particles obtained in the step seven, and continuously stirring for 10-60 minutes after spraying, and taking out the solution I to obtain the environment-friendly smokeless sulfur-free moisture-proof agent with uniform particles.
6. The method of claim 5, wherein: the preparation method of the modified mesoporous silica in the third step comprises the following steps: according to the mass ratio of 1: (5-10) placing the mesoporous silica in an aqueous solution with 0.5-3% of kasugamycin concentration, performing ultrasonic treatment at 30-40 ℃ for 1-5 hours, transferring the solution to a centrifugal machine, centrifuging the solution at a centrifugal speed of 3000-10000 rad/min, washing the centrifuged product with anhydrous methanol for 3-5 times, and transferring the product to a forced air oven for drying at 80-105 ℃ for 8 hours to obtain the modified mesoporous silica.
7. The method of claim 5, wherein: the method for judging the moderate hardness in the step three comprises the following steps: the paste is extruded through a 40-mesh copper screen to form continuous thin strips which are not adhered to each other.
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