Friction type safe and environment-friendly pyrotechnic composition and application thereof

Abstract

The invention relates to a friction type safe and environment-friendly pyrotechnic composition and application thereof, and belongs to the technical field of fireworks and crackers. The safe and environment-friendly friction type pyrotechnic composition is formed by mixing the high-nitrogen energetic complex which does not contain precious metal, toxic heavy metal and highly toxic azide, sand, metal powder and a binder, and the pyrotechnic composition is safe and easy to prepare, low in cost, free of pollution and suitable for industrial production. The finished product is high in ignition rate, good in sound and light effect, stable in property, long in quality guarantee period and suitable for fireworks and crackers. According to the preparation method and application of the friction-type safe and environment-friendly pyrotechnic composition, the friction-type safe and environment-friendly pyrotechnic composition is low in manufacturing cost, safe in production process, simple in process, good in stability, capable of being stored for a long time without deterioration and free of highly toxic azide agents; friction type fireworks and crackers prepared from the friction type pyrotechnic composition are high in explosion rate, large in loudness, better in set-off effect, good in environmental protection property and long in quality guarantee period.

Description

Technical Field

[0001] The invention relates to a friction type pyrotechnic agent and a preparation method and application thereof, belonging to the technical field of fireworks and firecrackers. Background Art

[0002] Firecracker toys that are triggered by friction are popular both at home and abroad due to their novelty, uniqueness, fun and safety. Such firecracker toys, such as sand cannons and pull firecrackers, are very convenient to play with. They do not need to be ignited. They can be made into crisp "crackling" sounds and bright lights just by letting them fall freely from a height or stepping on them or throwing them casually. They are great entertainment products during festivals.

[0003] The core of friction-type firecracker toys is friction-type pyrotechnic agents, which are required to have sufficient sensitivity, reliable safety, sufficiently high ignition rate and long-term storage stability, and be compatible with other materials in contact. In the prior art, friction-type pyrotechnic agents mainly use highly sensitive pyrotechnic agents mixed with inert granular sand, which are wrapped together in gauze, paper or foil. The collision and friction between the sand and the sensitive agent explode, thereby triggering the pyrotechnic agent to form a "crackling" explosion effect. The detonating agent in traditional friction-type pyrotechnic agents is mainly nitric acid, silver nitrate, and alcohol as raw materials, which are mixed and reacted to form silver fulminate. However, silver fulminate is easily decomposed by light and has a short shelf life. The products made are prone to low explosion loudness or no explosion, which affects the firing effect. In addition, silver is a precious metal, which leads to excessively high production costs for such friction-type pyrotechnic agents. Summary of the invention

[0004] In view of this, the purpose of the present invention is to provide a type and preparation method of friction-type pyrotechnic compositions which are cheap, safe, environmentally friendly, have simple production processes, good stability and are pollution-free, so as to produce such new friction-type pyrotechnic compositions and obtain friction-type sound and light toys with high ignition rate, crisp sound, better flame effect and longer shelf life.

[0005] To achieve the above object, the technical solution of the present invention is as follows:

[0006] A friction type pyrotechnic composition, the friction type pyrotechnic composition comprising sand particles, a halogen acid high nitrogen complex, metal powder and a binder;

[0007] The total mass of the sand and the pyrotechnic agent is 100%, wherein the mass percentage of the sand is 92%-99%, and the mass percentage of the pyrotechnic agent is 0.1%-8%;

[0008] The mass of the metal powder is 0.05%-5% of the total mass of the sand and the pyrotechnic agent;

[0009] The mass of the binder is 0.01%-5% of the total mass of the sand and the pyrotechnic agent;

[0010] The sand is clean and dry, with a particle size range of 10-200 mesh;

[0011] The halogen acid high nitrogen complex is at least one of halogen acid (4,4-diazo-1,2,4-triazole) copper, halogen acid (1-methyl-1H-tetrazole) copper, halogen acid (2-methyl-2H-tetrazole) copper, halogen acid (2-methyl-5-aminotetrazole) copper, halogen acid (4-amino-1,2,4-triazole) copper, and halogen acid (1-amino-1,2,3-triazole) copper;

[0012] Halogen acid (4,4-diazo-1,2,4-triazole) copper complexes include chloric acid (4,4-diazo-1,2,4-triazole) copper complexes, bromic acid (4,4-diazo-1,2,4-triazole) copper complexes, and iodic acid (4,4-diazo-1,2,4-triazole) copper complexes;

[0013] Halogen acid (1-methyl-1H-tetrazolyl) copper complexes include chloric acid (1-methyl-1H-tetrazolyl) copper complexes, bromic acid (1-methyl-1H-tetrazolyl) copper complexes, and iodic acid (1-methyl-1H-tetrazolyl) copper complexes;

[0014] Halogen acid (2-methyl-2H-tetrazolyl) copper complexes include chloric acid (2-methyl-2H-tetrazolyl) copper complexes, bromic acid (2-methyl-2H-tetrazolyl) copper complexes, and iodic acid (2-methyl-2H-tetrazolyl) copper complexes;

[0015] Halogen acid (2-methyl-5-aminotetrazolyl) copper complexes include chloric acid (2-methyl-5-aminotetrazolyl) copper complexes, bromic acid (2-methyl-5-aminotetrazolyl) copper complexes, and iodic acid (2-methyl-5-aminotetrazolyl) copper complexes;

[0016] Halogen acid (4-amino-1,2,4-triazole) copper complexes include chloric acid (4-amino-1,2,4-triazole) copper complexes, bromic acid (4-amino-1,2,4-triazole) copper complexes, and iodic acid (4-amino-1,2,4-triazole) copper complexes;

[0017] Halogen acid (1-amino-1,2,3-triazole) copper complex includes chloric acid (1-amino-1,2,3-triazole) copper complex, bromic acid (1-amino-1,2,3-triazole) copper complex, and iodic acid (1-amino-1,2,3-triazole);

[0018] The metal powder is at least one of titanium powder, zirconium powder, aluminum powder and copper powder;

[0019] The binder is at least one of phenolic resin, nitrocellulose, polyvinyl alcohol, polyvinyl butyral, shellac, gelatin aqueous solution, ethanol solution, glycerol solution, ethyl acetate solution, and butyl acetate solution;

[0020] The preparation method of halogen acid (4,4-diazo-1,2,4-triazole) copper complex is as follows: dissolving 4,4-diazo-1,2,4-triazole in water, adding a mixed aqueous solution of a halogen acid salt and a copper salt thereto, reacting for 5-120 minutes, cooling naturally to room temperature, filtering by suction, and taking out a filter cake, which is halogen acid (4,4-diazo-1,2,4-triazole) copper complex;

[0021] The halogen acid salt is at least one of sodium chlorate, potassium chlorate, sodium bromate, potassium bromate, sodium iodate and potassium iodate;

[0022] The copper salt is at least one of copper nitrate, copper sulfate and copper chloride;

[0023] The molar ratio of the copper salt, the halogen acid salt and the 4,4-diazo-1,2,4-triazole is 1:2-10:1-5;

[0024] The preparation method of halogen acid (1-methyl-1H-tetrazole) copper complex is as follows: 1-methyl-1H-tetrazole is dissolved in water, a mixed aqueous solution of a soluble halogen acid salt and a copper salt is added thereto, the mixture is reacted for 5-120 minutes, the mixture is naturally cooled to room temperature, and the mixture is filtered and a filter cake is taken out, which is halogen acid (1-methyl-1H-tetrazole) copper complex;

[0025] The molar ratio of the copper salt, the halogen acid salt and 1-methyl-1H-tetrazole is 1:2-10:1-5;

[0026] The preparation method of halogen acid (2-methyl-2H-tetrazole) copper complex is as follows: 2-methyl-2H-tetrazole is dissolved in water, a mixed aqueous solution of a soluble halogen acid salt and a copper salt is added thereto, the mixture is reacted for 5-120 minutes, the mixture is naturally cooled to room temperature, and the mixture is filtered and a filter cake is taken out, which is halogen acid (2-methyl-2H-tetrazole) copper complex;

[0027] The molar ratio of the copper salt, the halogen acid salt and the 2-methyl-2H-tetrazole is 1:2-10:1-5;

[0028] The preparation method of halogen acid (2-methyl-5-aminotetrazole) copper complex is as follows: 2-methyl-5-aminotetrazole is dissolved in water, a mixed aqueous solution of a soluble halogen acid salt and a copper salt is added thereto, the mixture is reacted for 5-120 minutes, the mixture is naturally cooled to room temperature, and the mixture is filtered by suction to obtain a filter cake, which is halogen acid (2-methyl-5-aminotetrazole) copper complex;

[0029] The molar ratio of the copper salt, the halogen acid salt and the 2-methyl-5-aminotetrazole is 1:2-10:1-5;

[0030] The preparation method of halogen acid (4-amino-1,2,4-triazole) copper complex is as follows: 4-amino-1,2,4-triazole is dissolved in water, a mixed aqueous solution of a soluble halogen acid salt and a copper salt is added thereto, the mixture is reacted for 5-120 minutes, the mixture is naturally cooled to room temperature, and the mixture is filtered and a filter cake is taken out, which is halogen acid (4-amino-1,2,4-triazole) copper complex;

[0031] The molar ratio of the copper salt, the halogen acid salt and 4-amino-1,2,4-triazole is 1:2-10:1-5;

[0032] The preparation method of halogen acid (1-amino-1,2,3-triazole) copper complex is as follows: 1-amino-1,2,3-triazole is dissolved in water, a mixed aqueous solution of a soluble halogen acid salt and a copper salt is added thereto, the mixture is reacted for 5-120 minutes, the mixture is naturally cooled to room temperature, and the mixture is filtered and a filter cake is taken out, which is halogen acid (1-amino-1,2,3-triazole) copper complex;

[0033] The molar ratio of the copper salt, the halogen acid salt and 1-amino-1,2,3-triazole is 1:2-10:1-5.

[0034] A method for preparing a friction type pyrotechnic agent comprises the following steps: mixing sand particles, a halogen acid high nitrogen complex and metal powder, and then adding a binder and mixing the mixture evenly to obtain the friction type pyrotechnic agent.

[0035] The invention discloses an application of a friction type pyrotechnic agent. The prepared friction type pyrotechnic agent is wrapped with diamond-shaped copy paper, pinched into a tadpole shape, and dried to obtain a shattering type firecracker toy.

[0036] Beneficial Effects

[0037] The safe and environmentally friendly friction-type pyrotechnic agent of the present invention is based on a high nitrogen energetic complex that does not contain precious metals, toxic heavy metals, or highly toxic azides, and is mixed with sand, metal powder, and a binder. The preparation process of the pyrotechnic agent is safe, easy, low-cost, and pollution-free. The finished product has a high ignition rate, good sound and light effects, stable properties, and a long shelf life, and is suitable for use in fireworks and firecrackers. The present invention provides a preparation method and application of a friction-type safe and environmentally friendly pyrotechnic agent. The friction-type pyrotechnic agent has low manufacturing cost, a safe production process, a simple process, good agent stability, can be stored for a long time without deterioration, and does not contain highly toxic azide-type agents. The finished friction-type fireworks and firecrackers prepared by the friction-type pyrotechnic agent have a high explosion rate, a large loudness, a better firing effect, good environmental protection, and a long shelf life.

[0038] The invention discloses a safe, friction-impact ignitable pyrotechnic agent based on a halogen acid complex, which is a single-substance pyrotechnic material synthesized from oxygen-containing halogen acid radicals, high-nitrogen organic compounds and copper central ions. The single-substance crystalline material obtained through a chemical process is directly used for mixing and charging pyrotechnic agents in a wet state after the agent crystals are separated by filtration. The metal powder is used to adjust the sound and light effects during firing, and the metal used is a mixture formed by any one or more metal powders of titanium powder, zirconium powder, aluminum powder and copper powder. The mixture is mixed with a binder glue liquid to form a mixture with a firm structure, and the amount of the binder is (0.01-5.00)% of the added mass ratio. The binder used is an aqueous solution of phenolic resin, nitrocellulose, polyvinyl alcohol, polyvinyl butyral, shellac, gelatin, or an ethanol solution, or a glycerol solution, or an ethyl acetate solution, or a butyl acetate solution. DETAILED DESCRIPTION

[0039] The present invention will be further described in detail below in conjunction with specific embodiments.

[0040] Example 1

[0041] In the first step, 16 g of 4,4-diazo-1,2,4-triazole was dissolved in 1 L of water, and the temperature was raised to 70°C to completely dissolve it. Then, 50 ml of an aqueous solution containing 24 g of copper nitrate and 50 g of sodium chlorate was added thereto. After reacting for 10 minutes, the temperature was naturally lowered to room temperature, and the filter cake was transferred to a beaker, and 10 ml of water was added as a trigger.

[0042] Step 2: Weigh 200g of sand with a particle size of 20-30 mesh and moisten it with a small amount of water;

[0043] The third step is to weigh 10 g of titanium powder with a particle size of 200 mesh and mix it evenly with the mixture obtained in the second step;

[0044] Step 4: weigh 1 g of the sound-generating agent obtained in the first step and mix it evenly with the mixture obtained in the third step;

[0045] The fifth step is to weigh 1 g of phenolic resin and dissolve it in a small amount of alcohol, and then mix it evenly with the mixture obtained in the fourth step to obtain a friction type pyrotechnic composition.

[0046] The sixth step is to wrap the friction type pyrotechnic agent prepared in the fifth step with diamond-shaped copy paper, pinch it into a tadpole shape, and then dry it to obtain a bursting type firecracker toy.

[0047] Step 7: Let the explosive firecracker toy obtained in step 6 fall freely from a height of 2.5 meters and ignite normally.

[0048] Example 2

[0049] In the first step, 16 g of 4,4-diazo-1,2,4-triazole was dissolved in 1 L of water, and the temperature was raised to 70°C to completely dissolve it. Then, 50 ml of an aqueous solution containing 13.5 g of copper chloride and 50 g of potassium bromate was added thereto. After reacting for 10 minutes, the temperature was naturally lowered to room temperature, and the filter cake was transferred to a beaker, and 10 ml of water was added as a trigger.

[0050] Step 2: Weigh 200g of sand with a particle size of 20-30 mesh and moisten it with a small amount of water;

[0051] Step 3: weigh 2 g of the sound-generating agent obtained in the first step and mix it evenly with the mixture obtained in the third step;

[0052] The fourth step is to weigh 1 g of phenolic resin and dissolve it in a small amount of alcohol, and then mix it evenly with the mixture obtained in the fourth step to obtain a friction type pyrotechnic composition.

[0053] The fifth step is to wrap the friction type pyrotechnic agent prepared in the fifth step with diamond-shaped copy paper, pinch it into a tadpole shape, and then dry it to obtain a bursting type firecracker toy.

[0054] Step 6. Let the explosive firecracker toy obtained in step 6 fall freely from a height of 2.5 meters and ignite normally.

[0055] Example 3

[0056] In the first step, 84 g of 4-amino-1,2,4-triazole was dissolved in 500 ml of water, and the temperature was raised to 50°C to completely dissolve it. Then, 300 ml of an aqueous solution containing 72 g of copper nitrate and 90 g of sodium bromate was added thereto. After reacting for 30 minutes, the temperature was naturally lowered to room temperature, and the filter cake was transferred to a beaker, and 15 ml of water was added as a trigger.

[0057] Step 2: Weigh 200g of sand with a particle size of 50-60 mesh and moisten it with a small amount of water;

[0058] In the third step, 10 g of aluminum powder with a particle size of 200 mesh is weighed and mixed evenly with the mixture obtained in the second step;

[0059] Step 4: weigh 2 g of the sound-generating agent obtained in the first step and mix it evenly with the mixture obtained in the third step;

[0060] In the fifth step, 2 g of polyvinyl alcohol is weighed and dissolved in a small amount of glycerin, and the mixture obtained in the fourth step is mixed evenly to obtain a friction type pyrotechnic composition.

[0061] The sixth step is to wrap the friction type pyrotechnic agent prepared in the fifth step with diamond-shaped copy paper, pinch it into a tadpole shape, and then dry it to obtain a bursting type firecracker toy.

[0062] Step 7: Let the explosive firecracker toy obtained in step 6 fall freely from a height of 2.5 meters and ignite normally.

[0063] Example 4

[0064] In the first step, 84 g of 1-methyl-1H-tetrazole was dissolved in 800 ml of water, and the temperature was raised to 50°C to completely dissolve it. Then, 700 ml of an aqueous solution containing 125 g of copper sulfate and 150 g of sodium bromate was added thereto. After reacting for 30 minutes, the temperature was naturally lowered to room temperature, and the filter cake was transferred to a beaker, and 20 ml of water was added as a trigger.

[0065] Step 2: Weigh 500g of sand with a particle size of 60-70 mesh and moisten it with a small amount of water;

[0066] In the third step, 25 g of aluminum powder with a particle size of 300 mesh was weighed and mixed evenly with the mixture obtained in the second step;

[0067] Step 4: weigh 40 g of the sound-generating agent obtained in the first step and mix it evenly with the mixture obtained in the third step;

[0068] The fifth step is to weigh 5 g of nitrocellulose and dissolve it in a small amount of alcohol, and then mix it evenly with the mixture obtained in the fourth step to obtain the friction type pyrotechnic agent.

[0069] The sixth step is to wrap the friction type pyrotechnic agent prepared in the fifth step with diamond-shaped copy paper, pinch it into a tadpole shape, and then dry it to obtain a bursting type firecracker toy.

[0070] Step 7: Let the explosive firecracker toy obtained in step 6 fall freely from a height of 2.5 meters and ignite normally.

[0071] Example 5

[0072] In the first step, 99 g of 2-methyl-5-amino-tetrazole was dissolved in 2 L of water, and the temperature was raised to 60 ° C to completely dissolve it. Then, 800 ml of an aqueous solution containing 62.5 g of copper sulfate and 100 g of sodium iodate was added thereto. After reacting for 30 minutes, the temperature was naturally lowered to room temperature, and the filter cake was transferred to a beaker, and 20 ml of water was added as a trigger.

[0073] The second step is to weigh 1000g of sand with a particle size of 80-90 mesh and moisten it with a small amount of water;

[0074] In the third step, 30 g of aluminum powder with a particle size of 300 mesh was weighed and mixed evenly with the mixture obtained in the second step;

[0075] Step 4: weigh 50 g of the sound-generating agent obtained in the first step and mix it evenly with the mixture obtained in the third step;

[0076] In the fifth step, 8 g of polyvinyl butyral is weighed and dissolved in a small amount of ethyl acetate, and the mixture obtained in the fourth step is mixed evenly to obtain a friction type pyrotechnic composition.

[0077] The sixth step is to wrap the friction type pyrotechnic agent prepared in the fifth step with diamond-shaped copy paper, pinch it into a tadpole shape, and then dry it to obtain a bursting type firecracker toy.

[0078] Step 7: Let the explosive firecracker toy obtained in step 6 fall freely from a height of 2.5 meters and ignite normally.

[0079] Example 6

[0080] In the first step, 84 g of 4-amino-1,2,4-triazole was dissolved in 200 ml of water, and the temperature was raised to 50°C to completely dissolve it. Then, 500 ml of an aqueous solution containing 50 g of copper chloride and 80 g of potassium chlorate was added thereto. After reacting for 10 minutes, the temperature was naturally lowered to room temperature, and the filter cake was transferred to a beaker, and 20 ml of water was added as a trigger.

[0081] Step 2: Weigh 500g of sand with a particle size of 60-70 mesh and moisten it with a small amount of water;

[0082] In the third step, 25 g of aluminum powder with a particle size of 300 mesh was weighed and mixed evenly with the mixture obtained in the second step;

[0083] Step 4: weigh 40 g of the sound-generating agent obtained in the first step and mix it evenly with the mixture obtained in the third step;

[0084] Step 5: weigh 5 g of nitrocellulose and dissolve it in a small amount of alcohol. Mix it evenly with the mixture obtained in step 4 to obtain friction pyrotechnic agent.

[0085] The sixth step is to wrap the friction type pyrotechnic agent prepared in the fifth step with diamond-shaped copy paper, pinch it into a tadpole shape, and then dry it to obtain a bursting type firecracker toy.

[0086] Step 7: Let the explosive firecracker toy obtained in step 6 fall freely from a height of 2.5 meters and ignite normally.

[0087] Example 7

[0088] In the first step, 84 g of 4-amino-1,2,4-triazole was dissolved in 200 ml of water, and the temperature was raised to 50°C to completely dissolve it. Then, 800 ml of an aqueous solution containing 50 g of copper chloride and 100 g of potassium bromate was added thereto. After reacting for 20 minutes, the temperature was naturally lowered to room temperature, and the filter cake was transferred to a beaker, and 20 ml of water was added as a trigger.

[0089] Step 2: Weigh 500g of sand with a particle size of 60-70 mesh and moisten it with a small amount of water;

[0090] In the third step, 25 g of titanium powder with a particle size of 100 mesh was weighed and mixed evenly with the mixture obtained in the second step;

[0091] Step 4: weigh 40 g of the sound-generating agent obtained in the first step and mix it evenly with the mixture obtained in the third step;

[0092] Step 5: Weigh 10 g of nitrocellulose and dissolve it in a small amount of alcohol. Mix it evenly with the mixture obtained in step 4 to obtain friction pyrotechnic composition.

[0093] The sixth step is to wrap the friction type pyrotechnic agent prepared in the fifth step with diamond-shaped copy paper, pinch it into a tadpole shape, and then dry it to obtain a bursting type firecracker toy.

[0094] Step 7: Let the explosive firecracker toy obtained in step 6 fall freely from a height of 2.5 meters and ignite normally.

[0095] In summary, the above are only preferred embodiments of the present invention and are not intended to limit the protection scope of the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the protection scope of the present invention.

Claims

1. A friction type pyrotechnic composition, characterized in that: The friction type pyrotechnic composition comprises sand particles, halogen acid high nitrogen complex, metal powder and binder; The total mass of the sand and the pyrotechnic agent is 100%, wherein the mass percentage of the sand is 92%-99%, and the mass percentage of the pyrotechnic agent is 0.1%-8%; The mass of the metal powder is 0.05%-5% of the total mass of the sand and the pyrotechnic agent; The mass of the binder is 0.01%-5% of the total mass of the sand and the pyrotechnic agent.

2. A friction type pyrotechnic composition according to claim 1, characterized in that: The sand is clean and dry, and has a particle size range of 10-200 meshes.

3. A friction type pyrotechnic composition according to claim 1, characterized in that: The halogen acid high nitrogen complex is at least one of halogen acid (4,4-diazo-1,2,4-triazole) copper, halogen acid (1-methyl-1H-tetrazole) copper, halogen acid (2-methyl-2H-tetrazole) copper, halogen acid (2-methyl-5-aminotetrazole) copper, halogen acid (4-amino-1,2,4-triazole) copper, and halogen acid (1-amino-1,2,3-triazole) copper.

4. A friction type pyrotechnic composition according to claim 3, characterized in that: The halogen acid (4,4-diazo-1,2,4-triazole) copper complex includes chloric acid (4,4-diazo-1,2,4-triazole) copper complex, bromic acid (4,4-diazo-1,2,4-triazole) copper complex, and iodic acid (4,4-diazo-1,2,4-triazole) copper complex; The halogen acid (1-methyl-1H-tetrazole) copper complex includes chloric acid (1-methyl-1H-tetrazole) copper complex, bromic acid (1-methyl-1H-tetrazole) copper complex, and iodic acid (1-methyl-1H-tetrazole) copper complex; The halogen acid (2-methyl-2H-tetrazolyl) copper complex includes chloric acid (2-methyl-2H-tetrazolyl) copper complex, bromic acid (2-methyl-2H-tetrazolyl) copper complex, and iodic acid (2-methyl-2H-tetrazolyl) copper complex; The halogen acid (2-methyl-5-aminotetrazolyl) copper complex includes chloric acid (2-methyl-5-aminotetrazolyl) copper complex, bromic acid (2-methyl-5-aminotetrazolyl) copper complex, and iodic acid (2-methyl-5-aminotetrazolyl) copper complex; The halogen acid (4-amino-1,2,4-triazole) copper complex includes chloric acid (4-amino-1,2,4-triazole) copper complex, bromic acid (4-amino-1,2,4-triazole) copper complex, and iodic acid (4-amino-1,2,4-triazole) copper complex; The halogen acid (1-amino-1,2,3-triazole) copper complex includes chloric acid (1-amino-1,2,3-triazole) copper complex, bromic acid (1-amino-1,2,3-triazole) copper complex, and iodic acid (1-amino-1,2,3-triazole) copper complex.

5. A friction type pyrotechnic composition according to claim 4, characterized in that: The preparation method of the halogen acid (4,4-diazo-1,2,4-triazole) copper complex is as follows: 4,4-diazo-1,2,4-triazole is dissolved in water, a mixed aqueous solution of a halogen acid salt and a copper salt is added thereto, the mixture is reacted for 5-120 minutes, the mixture is naturally cooled to room temperature, and the mixture is filtered and a filter cake is taken out, which is the halogen acid (4,4-diazo-1,2,4-triazole) copper complex; The halogen acid salt is at least one of sodium chlorate, potassium chlorate, sodium bromate, potassium bromate, sodium iodate and potassium iodate; The copper salt is at least one of copper nitrate, copper sulfate and copper chloride; The molar ratio of the copper salt, the halogen acid salt and the 4,4-diazo-1,2,4-triazole is 1:2-10:1-5; The preparation method of the halogen acid (1-methyl-1H-tetrazole) copper complex is as follows: 1-methyl-1H-tetrazole is dissolved in water, a mixed aqueous solution of a soluble halogen acid salt and a copper salt is added thereto, the mixture is reacted for 5-120 minutes, the mixture is naturally cooled to room temperature, and the mixture is filtered by suction to obtain a filter cake, which is the halogen acid (1-methyl-1H-tetrazole) copper complex; The molar ratio of the copper salt, the halogen acid salt and 1-methyl-1H-tetrazole is 1:2-10:1-5; The preparation method of the halogen acid (2-methyl-2H-tetrazole) copper complex is as follows: 2-methyl-2H-tetrazole is dissolved in water, a mixed aqueous solution of a soluble halogen acid salt and a copper salt is added thereto, the mixture is reacted for 5-120 minutes, the mixture is naturally cooled to room temperature, and the mixture is filtered and a filter cake is taken out, which is the halogen acid (2-methyl-2H-tetrazole) copper complex; The molar ratio of the copper salt, the halogen acid salt and the 2-methyl-2H-tetrazole is 1:2-10:1-5.

6. A friction type pyrotechnic composition according to claim 5, characterized in that: The preparation method of the halogen acid (2-methyl-5-aminotetrazole) copper complex is as follows: 2-methyl-5-aminotetrazole is dissolved in water, a mixed aqueous solution of a soluble halogen acid salt and a copper salt is added thereto, the mixture is reacted for 5-120 minutes, the mixture is naturally cooled to room temperature, and the mixture is filtered by suction to obtain a filter cake, which is the halogen acid (2-methyl-5-aminotetrazole) copper complex; The molar ratio of the copper salt, the halogen acid salt and the 2-methyl-5-aminotetrazole is 1:2-10:1-5; The preparation method of the halogen acid (4-amino-1,2,4-triazole) copper complex is as follows: 4-amino-1,2,4-triazole is dissolved in water, a mixed aqueous solution of a soluble halogen acid salt and a copper salt is added thereto, the mixture is reacted for 5-120 minutes, the mixture is naturally cooled to room temperature, and the mixture is filtered and a filter cake is taken out to obtain the halogen acid (4-amino-1,2,4-triazole) copper complex; The molar ratio of the copper salt, the halogen acid salt and 4-amino-1,2,4-triazole is 1:2-10:1-5; The preparation method of the halogen acid (1-amino-1,2,3-triazole) copper complex is as follows: 1-amino-1,2,3-triazole is dissolved in water, a mixed aqueous solution of a soluble halogen acid salt and a copper salt is added thereto, the mixture is reacted for 5-120 minutes, the mixture is naturally cooled to room temperature, and the mixture is filtered and a filter cake is taken out to obtain the halogen acid (1-amino-1,2,3-triazole) copper complex; The molar ratio of the copper salt, the halogen acid salt and 1-amino-1,2,3-triazole is 1:2-10:1-5.

7. A friction type pyrotechnic composition according to claim 1, characterized in that: The metal powder is at least one of titanium powder, zirconium powder, aluminum powder and copper powder.

8. A friction type pyrotechnic composition according to claim 1, characterized in that: The binder is at least one of phenolic resin, nitrocellulose, polyvinyl alcohol, polyvinyl butyral, shellac, gelatin aqueous solution, ethanol solution, glycerol solution, ethyl acetate solution, and butyl acetate solution.

9. A method for preparing a friction type pyrotechnic composition, characterized in that: Sand particles, halogen acid high nitrogen complex and metal powder are mixed, and then a binder is added and mixed evenly to obtain a friction type pyrotechnic agent.

10. An application of a friction type pyrotechnic composition, characterized in that: The prepared friction type pyrotechnic agent is wrapped with paper, and after drying, a bursting type firecracker toy is obtained.