1. The safe and environment-friendly explosive containing permanganate type explosion promoter is characterized in that: the composite material consists of a permanganate type explosion promoter, an active metal reducing agent modified by a silane coupling agent, a high-molecular fluoropolymer and an organic binder, wherein the organic binder is selected from one or more of polyvinyl alcohol, epoxy resin and phenolic resin.

2. The blasting explosive according to claim 1, wherein: the explosion promoter is selected from KMnO₄、Pb(MnO₄)₂、Co(MnO₄)₂、Zn(MnO₄)₂One or more of (a).

3. The blasting explosive according to claim 1, wherein: the high molecular fluorine polymer is one or more selected from perfluoropolyether, polyvinylidene fluoride, polyfluoroolefin and polyfluoroalkane.

4. The blasting explosive according to claim 3, wherein: the particle size of the high molecular fluorine polymer is 50-400 μm.

5. The blasting explosive according to claim 1, wherein: the particle size of the active metal reducing agent is 10-75 mu m.

6. The blasting explosive according to claim 6, wherein: the active metal reducing agent is selected from aluminum powder and magnesium powder.

7. The blasting explosive according to claim 1, wherein: the grain diameter of the explosion promoter is 10-120 mu m.

8. The blasting explosive according to claim 1, wherein: wherein the raw materials in parts by mass are as follows: 0.5-3 parts of silane coupling agent, 0.5-5 parts of binder, 10-100 parts of active metal reducing agent, 5-50 parts of explosion promoter and 20-75 parts of high-molecular fluoropolymer.

9. A process for the preparation of the blasting explosive according to any of claims 1 to 8, characterized in that: it includes:

(1) adding the active metal reducing agent into a silane coupling agent dispersion liquid, mixing, soaking for 1-6h, filtering, and drying to obtain a modified reducing agent;

(2) adding the modified reducing agent into a solution of the binder, mixing and soaking for 1-6h to obtain a dispersion liquid of the binder coated reducing agent;

(3) adding the explosion promoter and the high-molecular fluoropolymer into the dispersion liquid of the binder-coated reducing agent, and mixing to obtain mixed slurry;

(4) and granulating and drying the mixed slurry to obtain the explosive.

10. The method of claim 9, wherein: the solvent used for the silane coupling agent dispersion liquid and the solvent used for the binder solution are both selected from ethyl acetate.

Background

Black powder is one of the important raw materials in the production of traditional fireworks and crackers. The black powder is formed by mixing three components of potassium nitrate (oxidant), charcoal (reductant) and sulfur (combustible agent), is low in price and convenient to manufacture, but the black powder can generate a large amount of black smoke during combustion to influence the setting-off effect of fireworks, the combustion is incomplete, a large amount of carbon, sulfur and potassium oxides and solid residues can be generated in residues, the environment is seriously polluted, in addition, in the aspect of safety, the mechanical sensitivity of the black powder is high, and the black powder can be ignited or exploded when being subjected to strong impact or friction, so that the safety is low in the production and transportation processes, and great danger is brought to lives and properties of people.

In the existing explosive technology, the accelerators are potassium perchlorate, potassium chlorate and other oxidants, but the substances have high impact sensitivity and are easy to react violently under the condition of accidental impact, thereby bringing serious potential safety hazards to application, and the explosion accidents are frequent.

Disclosure of Invention

The invention aims to provide a safe and environment-friendly explosive without sulfur and nitrogen elements and a preparation method thereof, wherein the explosive is a fluoropolymer explosive and contains a reducing agent formed by metal or a mixture thereof, a permanganate type oxide explosion accelerator, a binder and fluoropolymer, so that the problems of high pollution, high mechanical sensitivity, high static and spark sensitivity, low safety in production and transportation processes and the like caused by using black powder for fireworks and crackers in the prior art can be solved, and the explosion efficiency can be improved while the impact sensitivity is further improved.

The invention firstly provides the following technical scheme:

the safe and environment-friendly explosive containing permanganate type explosion promoter consists of the permanganate type explosion promoter, an active metal reducing agent modified by a silane coupling agent, a high-molecular fluoropolymer and an organic binder, wherein the organic binder is selected from one or more of polyvinyl alcohol, epoxy resin and phenolic resin.

According to some preferred embodiments of the present invention, the high molecular weight fluoropolymer is selected from one or more of perfluoropolyether, polyvinylidene fluoride, polyfluoroolefin, polyfluoroalkane.

According to some preferred embodiments of the present invention, the polyfluoroalkene is selected from polytetrafluoroethylene and the polyfluoroalkane is selected from polyperfluoropentane.

According to some preferred embodiments of the present invention, the high molecular fluoropolymer has a particle size of 50 to 400 μm.

According to some preferred embodiments of the invention, the active metal reducing agent has a particle size of 10 to 75 μm.

According to some preferred embodiments of the invention, the active metal reducing agent is selected from the group consisting of spherical aluminum powder and magnesium powder.

According to some preferred embodiments of the invention, the enhancer is selected from KMnO₄、Pb(MnO₄)₂、Co(MnO₄)₂、Zn(MnO₄)₂One or more of (a).

According to some preferred embodiments of the invention, the particle size of the enhancer is 10 to 120 μm.

According to some preferred embodiments of the present invention, the raw materials comprise, in parts by mass: 0.5-3 parts of silane coupling agent, 0.5-5 parts of binder, 10-100 parts of active metal reducing agent, 5-50 parts of oxide explosion promoter and 20-75 parts of high-molecular fluoropolymer.

The invention further provides a preparation method of the explosive, which comprises the following steps:

(1) adding the active metal reducing agent into a silane coupling agent dispersion liquid, mixing, soaking for 1-6h, filtering, and drying to obtain a modified reducing agent;

(2) adding the modified reducing agent into a solution of the binder, mixing and soaking for 1-6h to obtain a dispersion liquid of the binder coated reducing agent;

(3) adding the explosion promoter and the high-molecular fluoropolymer into the dispersion liquid of the binder-coated reducing agent, and mixing to obtain mixed slurry;

(4) and granulating and drying the mixed slurry to obtain the explosive.

According to some preferred embodiments of the present invention, the solvent used for the silane coupling agent dispersion and the solvent used for the binder solution are both selected from ethyl acetate.

The invention has the following beneficial effects:

the invention uses the high molecular fluorine polymer as the raw material of the explosive, which has better thermal stability (the decomposition temperature is generally above 400 ℃), anti-aging performance and chemical stability, the heat of formation of the oxide is larger than that of the fluoride generated by the reaction of the metal powder, a large amount of heat can be released (the heat of explosion can reach 2150kcal/kg), and meanwhile, the invention has better compatibility with other components, excellent long-term storage performance and better formability. In addition, the combustion products of the high molecular fluorine polymer/active metal powder are carbon and fluoride particles, toxic and harmful gases such as sulfur oxides, nitrogen oxides and the like are not generated, the environment is protected, and in the aspect of safety, the high molecular fluorine polymer/active metal powder shows obvious insensitive to mechanical impact and thermal action, so that the safety is high in the production and transportation processes; based on the advantages, the black powder can completely replace the traditional black powder;

the permanganate type explosion promoter used in the invention has lower sensitivity compared with perchlorate and chlorate, has stable physical and chemical properties at normal temperature, has better thermal stability and mechanical stability, can generate violent redox reaction with reducing metal magnesium powder, aluminum powder, zinc powder and the like at higher temperature, and has higher explosion initiating efficiency.

In some specific embodiments, according to a test method of GJB 772A-1997 mechanical sensitivity, the impact sensitivity of the explosive prepared by the method is 6% -2%, the friction sensitivity is 0%, and the safety performance is obviously improved compared with that of the traditional fireworks explosive.

Detailed Description

The present invention is described in detail with reference to the following examples, but it should be understood that the examples are only for illustrative purposes and are not intended to limit the scope of the present invention. All reasonable variations and combinations that fall within the spirit of the invention are intended to be within the scope of the invention.

According to the technical scheme of the invention, the preparation method of the safe and environment-friendly explosion-initiating medicament containing the permanganate type explosion-promoting agent comprises the following steps:

(1) adding a silane coupling agent into ethyl acetate, uniformly stirring, dispersing an active metal reducing agent with the particle size of 10-75 mu m into the solution under the protection of inert atmosphere, stirring and soaking at the speed of 100-200rpm for 1-6h, filtering and drying to obtain a modified active reducing agent;

(2) adding the binder into ethyl acetate, and stirring at the speed of 100-200rpm for 1-6h until the binder is completely dissolved to obtain a binder solution;

(3) dispersing the modified active reducing agent into the binder solution, stirring and soaking at the speed of 100-200rpm for 1-6h to obtain a binder-coated reducing agent dispersion liquid;

(4) adding a permanganate type explosion promoter with the particle size of 10-120 mu m and a high polymer fluoropolymer with the particle size of 50-400 mu m into the dispersion, and stirring for a certain time to obtain mixed slurry;

(5) extruding and granulating the obtained mixed slurry through a granulator, and drying to obtain the explosive;

wherein, preferably, the soaking time in the step (3) is 1-3 h;

wherein the content of the first and second substances,

the binder can be selected from one or more of polyvinyl alcohol, epoxy resin and phenolic resin;

the active metal reducing agent can be selected from aluminum powder and/or magnesium powder;

the explosion promoter can be one or more of potassium permanganate, lead permanganate, zinc permanganate and cobalt permanganate;

the high molecular fluorine polymer is one or more selected from perfluoropolyether, polyvinylidene fluoride, polyfluoroolefin and polyfluoroalkane.

The raw materials in parts by mass can be as follows: 0.5-3 parts of silane coupling agent, 0.5-5 parts of binder, 10-100 parts of active reducing agent, 5-50 parts of explosion promoter and 20-75 parts of high-molecular fluorine polymer.

In the above specific embodiment, the present invention further provides the following examples, wherein the parts used in the examples all represent parts by mass:

example 1

The explosive is prepared by the following steps:

(1) modification of reducing agents

Weighing 0.5 part of silane coupling agent KH-550, adding into ethyl acetate, stirring for 0.5h, dispersing 10 parts of spherical aluminum powder and 32 parts of magnesium powder with the particle sizes of 10 mu m into the solution under the protection of inert atmosphere, soaking for 2h, filtering and drying to obtain a modified reducing agent;

(2) coating of

Weighing 1.5 parts of binder polyvinyl alcohol (with the molecular weight of 1000-3000) and adding into ethyl acetate, stirring until the binder polyvinyl alcohol is completely dissolved, dispersing the obtained modified reducing agent into the solution, and stirring for 2 hours to obtain a dispersion liquid of the binder coated reducing agent;

(3) mixed powder

Weighing 35 parts of polyvinylidene fluoride powder with the particle size of 160 mu m and 21 parts of explosion promoter KMnO₄Adding the mixture into a dispersion liquid obtained by coating a reducing agent with the binder, and stirring for 4 hours to obtain slurry;

(3) granulating

And extruding and granulating the obtained slurry through a granulator with a particle plate of 2mm, and drying the obtained particles at the drying temperature of 60 ℃ to obtain the final product.

Example 2

The explosive is prepared by the following steps:

(1) modification of reducing agents

Weighing 1 part of silane coupling agent KH-550, adding into ethyl acetate, stirring for 0.5h, dispersing 12 parts of spherical aluminum powder and 30 parts of magnesium powder with the particle sizes of 10 mu m into the solution under the protection of inert atmosphere, soaking for 2h, filtering and drying to obtain a modified reducing agent;

(2) coating of

Weighing 2 parts of binder epoxy resin (with the molecular weight of 1000-3000), adding the binder epoxy resin into ethyl acetate, stirring until the binder epoxy resin is completely dissolved, dispersing 32 parts of the obtained modified reducing agent into the solution, and stirring for 2 hours to obtain a dispersion liquid of the binder coated reducing agent;

(3) mixed powder

Weighing 30 parts of polytetrafluoroethylene with the particle size of 160 mu m and 35 parts of an explosion promoter Pb (MnO)₄)₂Adding into the above binder to coat and reduceStirring the dispersion liquid obtained by the agent for 4 hours to obtain slurry;

(3) granulating

And extruding and granulating the obtained slurry through a granulator with a particle plate of 2mm, and drying the obtained particles at the drying temperature of 60 ℃ to obtain the final product.

Example 3

The explosive is prepared by the following steps:

(1) modification of reducing agents

Weighing 1 part of silane coupling agent KH-550, adding into ethyl acetate, stirring for 0.5h, dispersing 8 parts of spherical aluminum powder and 22 parts of magnesium powder with particle sizes of 10 mu m into the solution under the protection of inert atmosphere, soaking for 2h, filtering and drying to obtain a modified reducing agent;

(2) coating of

Weighing 2 parts of binder phenolic resin (with the molecular weight of 1000-3000), adding the binder phenolic resin into ethyl acetate, stirring until the binder phenolic resin is completely dissolved, dispersing 30 parts of the obtained modified reducing agent into the solution, and stirring for 2 hours to obtain a binder-coated reducing agent dispersion liquid;

(3) mixed powder

50 parts of polytetrafluoroethylene with the particle size of 160 mu m and 17 parts of explosion promoter Zn (MnO)₄)₂Adding the mixture into a dispersion liquid obtained by coating a reducing agent with the binder, and stirring for 4 hours to obtain slurry;

(3) granulating

And extruding and granulating the obtained slurry through a granulator with a particle plate of 2mm, and drying the obtained particles at the drying temperature of 60 ℃ to obtain the final product.

According to the test method of GJB 772A-1997 mechanical sensitivity, the impact sensitivity of the explosive prepared by the embodiment is 6% -2% and the friction sensitivity is 0% by adopting a 10Kg drop hammer with a drop height of 25cm, and the safety performance is obviously improved compared with the traditional firework explosive.

The above examples are merely preferred embodiments of the present invention, and the scope of the present invention is not limited to the above examples. All technical schemes belonging to the idea of the invention belong to the protection scope of the invention. It should be noted that modifications and embellishments within the scope of the invention may be made by those skilled in the art without departing from the principle of the invention, and such modifications and embellishments should also be considered as within the scope of the invention.