阅读说明：本技术 一种无硫无氮耐高温环保烟花发射药及其制备方法 (Sulfur-free nitrogen-free high-temperature-resistant environment-friendly firework propellant and preparation method thereof ) 是由 束庆海 赵帅 吕席卷 吴启才 于 2021-02-09 设计创作，主要内容包括：本发明涉及一种无硫无氮耐高温环保烟花发射药及其制备方法,属于烟花爆竹技术领域。该无硫微烟耐高温烟花发射药由以下重量份配比和粒径的组分组成：聚四氟乙烯55～75份,粒径50～300μm；铝粉5～25份,粒径5～75μm；锌粉5～25份,铜粉5～15份,粒径5～75μm；硅酸钙,2～10份,粒径20～150μm；硅烷偶联剂0.5～5份；含能粘结剂1～5份。该制备方法采用化学改性、包覆、混粉、造粒、干燥等工艺,过程简单,无特殊工艺要求,成本低,便于批量生产。所得产品具有无硫、微烟、不污染环境、冲击或摩擦感度低、耐高温、防静电、安全性高等优势,可广泛应用于烟花爆竹用发射药生产中。(The invention relates to a sulfur-free nitrogen-free high-temperature-resistant environment-friendly firework propellant and a preparation method thereof, belonging to the technical field of fireworks and crackers. The sulfur-free micro-smoke high-temperature-resistant firework propellant consists of the following components in parts by weight and particle size: 55-75 parts of polytetrafluoroethylene with the particle size of 50-300 mu m; 5-25 parts of aluminum powder with the particle size of 5-75 mu m; 5-25 parts of zinc powder, 5-15 parts of copper powder and 5-75 mu m of particle size; 2-10 parts of calcium silicate, and the particle size is 20-150 mu m; 0.5-5 parts of a silane coupling agent; 1-5 parts of energy-containing binder. The preparation method adopts the processes of chemical modification, coating, powder mixing, granulation, drying and the like, has simple process, no special process requirement and low cost, and is convenient for batch production. The obtained product has the advantages of no sulfur, little smoke, no environmental pollution, low impact or friction sensitivity, high temperature resistance, static resistance, high safety and the like, and can be widely applied to the production of propellant for fireworks and crackers.)

1. The sulfur-free nitrogen-free high-temperature-resistant environment-friendly firework propellant is characterized in that: the paint comprises the following components in parts by weight: 55-75 parts of polytetrafluoroethylene with the particle size of 50-300 mu m; 5-25 parts of aluminum powder with the particle size of 5-75 mu m; 5-25 parts of zinc powder, 5-15 parts of copper powder and 5-75 mu m of particle size; 2-10 parts of calcium silicate, and the particle size is 20-150 mu m; 0.5-5 parts of a silane coupling agent; 1-5 parts of energy-containing binder.

2. The sulfur-free nitrogen-free high-temperature-resistant environment-friendly firework propellant as claimed in claim 1, wherein: the particle size of the polytetrafluoroethylene is 50-300 mu m; the particle size of the aluminum powder is 5-75 mu m; the particle sizes of the zinc powder and the copper powder are 5-75 mu m; the particle size of the calcium silicate is 20 to 150 μm.

3. The sulfur-free nitrogen-free high-temperature-resistant environment-friendly firework propellant as claimed in claim 1 or 2, wherein: 47 parts of polytetrafluoroethylene with the particle size of 300 mu m; 20 parts of aluminum powder with the particle size of 10 microns; 5 parts of zinc powder with the particle size of 10 mu m; 10 parts of copper powder with the particle size of 20 microns; 10 parts of calcium silicate, and the particle size is 150 mu m; KH-5503 parts of a silane coupling agent; 5 parts of energy-containing binder.

4. The preparation method for preparing the sulfur-free nitrogen-free high-temperature-resistant environment-friendly firework propellant as claimed in claim 1, 2 or 3, is characterized in that: the method comprises the following steps:

the method comprises the following steps: adding a silane coupling agent KH-550 into ethanol, uniformly stirring, sequentially dispersing aluminum powder, copper powder and zinc powder into a solution under the protection of inert atmosphere, soaking for a certain time, and adsorbing the silane coupling agent KH-550 on the surface of metal powder through chemical bonds to modify metals; filtering and drying to obtain modified metal powder;

step two: adding the energy-containing binder into ethyl acetate, stirring until the energy-containing binder is completely dissolved, adding the modified metal powder obtained in the step one, and uniformly stirring to obtain a dispersion liquid of elastomer-coated metal powder;

step three: sequentially adding polytetrafluoroethylene powder and calcium silicate into the dispersion liquid obtained in the second step, and uniformly stirring to obtain slurry;

step four: and E, extruding and granulating the slurry obtained in the step three through a granulator, and drying the granules to obtain the final product.

5. The method of claim 4, wherein: the stirring time from the first step to the third step is 1-6 h, and the stirring speed is 100-200 rpm/min.

6. The method of claim 4, wherein: the soaking time in the step one is 6-12 hours.

7. The method of claim 4, wherein: and fourthly, the grain size of the granules is 1-3 mm.

Technical Field

The invention relates to a sulfur-free nitrogen-free high-temperature-resistant environment-friendly firework propellant and a preparation method thereof, in particular to a preparation method of a sulfur-free nitrogen-free micro-smoke, anti-static and high-temperature-resistant firework propellant, and belongs to the technical field of fireworks and crackers.

Background

Black powder is one of the important raw materials in the production of fireworks and crackers. The black powder is made up by mixing three components of potassium nitrate (oxidant), charcoal (reductant) and sulfur (combustible), and has the advantages of low cost, safe operation and convenient production. However, the black powder can generate a large amount of black smoke during combustion, which affects the setting off effect of fireworks, and the combustion is incomplete, and the residue contains a large amount of oxides of carbon, sulfur and potassium and solid residues, which seriously pollutes the environment. In the aspect of safety, the black powder has high mechanical sensitivity, and 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.

The application research of high molecular polymer in pyrotechnic composition has been long, and many basic theories and application researches are continuously carried out at home and abroad, mainly comprising the combustion mechanism, the thermal stability, the radiation characteristic and the like of polytetrafluoroethylene, polytetrafluoroethylene/metal and the like. The high molecular polymer has better thermal stability (the decomposition temperature is more than 400 ℃), ageing resistance and chemical stability, and compared with the heat of formation of fluoride generated by the reaction of metal powder, the oxide is larger, and a large amount of heat can be released (the explosion heat can reach 2150 kcal/kg). Meanwhile, the high molecular polymer has better compatibility with substances such as common combustible agents, additives and the like of pyrotechnic compositions, has excellent long-term storage performance, and has better formability when applied to energetic materials such as pyrotechnic compositions and the like. In addition, most of combustion products of the high molecular polymer/metal powder are carbon and fluoride particles, weak smoke is generated, and sulfur oxide and nitrogen oxide cannot be generated, so that environmental pollution is avoided. In terms of safety, the high molecular polymer/metal powder shows a remarkable insensitivity to mechanical impact and thermal action, and therefore is highly safe during production and transportation. Based on the characteristics and advantages, the application of the high molecular polymer/metal powder in the field of fireworks and crackers can obviously improve the safety performance and the environmental protection performance of the fireworks and crackers.

Disclosure of Invention

The invention aims to overcome the defects of large smoke, more residues, large product pollution, high mechanical sensitivity and low safety in the production and transportation processes of the current black powder for fireworks and crackers during combustion, and provides a sulfur-free nitrogen-free high-temperature-resistant environment-friendly firework propellant and a preparation method thereof.

The invention relates to a sulfur-free nitrogen-free high-temperature-resistant environment-friendly firework propellant and a preparation method thereof, wherein the firework propellant takes a high-molecular polymer/active metal/energy-containing binder as a component, has the characteristics and advantages of no sulfur, little smoke, no environmental pollution, low impact or friction sensitivity, high temperature resistance, high safety, low cost and the like, and can be widely applied to the production of the propellant for fireworks and crackers. In addition, the energy-containing binder coating layer is adsorbed on the surface of the active metal powder through chemical bonds, so that the thermal stability of the micron metal powder can be enhanced, and the heat release characteristic of the micron metal powder is obviously improved; can prevent the oxidation and agglomeration of active metal powder, and the energy property of the energy-containing binder can also improve the energy release of the system.

A sulfur-free nitrogen-free high-temperature-resistant environment-friendly firework propellant is composed of the following components in parts by weight and particle size:

55-75 parts of polytetrafluoroethylene with the particle size of 50-300 mu m; 5-25 parts of aluminum powder with the particle size of 5-75 mu m; 5-25 parts of zinc powder, 5-15 parts of copper powder and 5-75 mu m of particle size; 2-10 parts of calcium silicate, and the particle size is 20-150 mu m; 0.5-5 parts of a silane coupling agent; 1-5 parts of energy-containing binder.

Preferably, the composition consists of the following components in parts by weight and particle size:

47 parts of polytetrafluoroethylene with the particle size of 300 mu m; 20 parts of aluminum powder with the particle size of 10 microns; 5 parts of zinc powder with the particle size of 10 mu m; 10 parts of copper powder with the particle size of 20 microns; 10 parts of calcium silicate, and the particle size is 150 mu m; KH-5503 parts of a silane coupling agent; 5 parts of energy-containing binder.

A preparation method of a sulfur-free nitrogen-free high-temperature-resistant environment-friendly firework propellant comprises the following steps:

the method comprises the following steps: adding a silane coupling agent KH-550 into ethanol, uniformly stirring, sequentially dispersing aluminum powder, copper powder and zinc powder into a solution under the protection of inert atmosphere, soaking for a certain time, and adsorbing the silane coupling agent KH-550 on the surface of metal powder through chemical bonds to modify metals; filtering and drying to obtain modified metal powder;

step two: adding the energy-containing binder into ethyl acetate, stirring until the energy-containing binder is completely dissolved, adding the modified metal powder obtained in the step one, and uniformly stirring to obtain a dispersion liquid of elastomer-coated metal powder;

step three: sequentially adding polytetrafluoroethylene powder and calcium silicate into the dispersion liquid obtained in the second step, and uniformly stirring to obtain slurry;

step four: and E, extruding and granulating the slurry obtained in the step three through a granulator, and drying the granules to obtain the final product.

The stirring time from the first step to the third step is 1-6 h, and the stirring speed is 100-200 rpm/min.

The soaking time in the step one is 6-12 hours.

And fourthly, the grain size of the granules is 1-3 mm.

Advantageous effects

1. A sulfur-free nitrogen-free high-temperature resistant environment-friendly firework propellant and a preparation method thereof adopt conventional metal powder, polytetrafluoroethylene powder, an elastomer and calcium silicate as raw materials; the process of chemical modification, coating, powder mixing, granulation, drying and the like is adopted, the process is simple, no special process requirement exists, the cost is low, and the batch production is convenient.

2. Compared with the traditional black powder, the sulfur-free nitrogen-free high-temperature-resistant environment-friendly firework propellant and the preparation method thereof have the advantages of no sulfur, little smoke, no environmental pollution, low impact or friction sensitivity, high temperature resistance, high safety and the like, and can be widely applied to the production of the propellant for firework explosion. In addition, the elastomer coating layer is adsorbed on the surface of the active metal powder through chemical bonds, so that the thermal stability of the micron metal powder can be enhanced, and the heat release characteristic of the micron metal powder is obviously improved; the oxidation and agglomeration of the active metal powder can be prevented, and the energy property of the elastomer can also improve the energy release of the system.

Detailed Description

The present invention will be described in further detail with reference to specific examples, which are not intended to limit the present invention in any manner. Unless otherwise indicated, the various starting materials used in the examples of the present invention are either conventionally available commercially or prepared according to conventional methods in the art using equipment commonly used in the laboratory. Unless defined or stated otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.

Example 1

A sulfur-free nitrogen-free high-temperature-resistant environment-friendly firework propellant and a preparation method thereof comprise the following specific steps:

(1) firstly, metal powder is modified and coated

Surface modification: weighing 3 parts of silane coupling agent KH-550, adding into 50mL of ethanol, stirring for 0.5h, sequentially dispersing 8 parts of aluminum powder, 6 parts of zinc powder and 12 parts of copper powder into the solution under the protection of inert atmosphere, soaking for 6h, filtering and drying to obtain modified metal powder; wherein the particle size of the aluminum powder is 10 mu m, the particle size of the zinc powder is 10 mu m, and the particle size of the copper powder is 30 mu m;

coating: weighing 2 parts of elastomer, adding the elastomer into 50mL of ethyl acetate, stirring until the elastomer is completely dissolved, dispersing the 26 parts of modified metal powder into the solution, stirring for 2 hours at the rotating speed of 200rpm/min, and obtaining the dispersion liquid of the elastomer coated metal powder.

(2) Preparation of fireworks propellant powder particles

Mixing powder: weighing 65 parts of polytetrafluoroethylene powder and 4 parts of calcium silicate, sequentially adding the polytetrafluoroethylene powder and the calcium silicate into the dispersion liquid obtained by coating the metal powder with the elastomer, and stirring for 4 hours at the rotating speed of 200rpm/min to obtain slurry; wherein, the particle size of the polytetrafluoroethylene powder is 50 μm, and the particle size of the calcium silicate is 50 μm;

and (3) granulation: 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.

The final product obtained in the embodiment can stably react after 3g of firework propellant powder is ignited, the quality consistency is good, and the internal throwing height of the filled display shell reaches more than 50 meters.

Example 2

A sulfur-free nitrogen-free high-temperature-resistant environment-friendly firework propellant and a preparation method thereof comprise the following specific steps:

(1) firstly, metal powder is modified and coated

Surface modification: weighing 1 part of silane coupling agent KH-550, adding into 50mL of ethanol, stirring for 0.5h, sequentially dispersing 10 parts of aluminum powder, 5 parts of zinc powder and 20 parts of copper powder into the solution under the protection of inert atmosphere, soaking for 6h, filtering and drying to obtain modified metal powder; wherein the particle size of the aluminum powder is 10 mu m, the particle size of the zinc powder is 10 mu m, and the particle size of the copper powder is 10 mu m;

coating: weighing 4 parts of elastomer, adding the elastomer into 50mL of ethyl acetate, stirring until the elastomer is completely dissolved, dispersing the 35 parts of modified metal powder into the solution, stirring for 2 hours at the rotating speed of 200rpm/min, and obtaining the dispersion liquid of the elastomer coated metal powder.

(2) Preparation of fireworks propellant powder particles

Mixing powder: weighing 58 parts of polytetrafluoroethylene powder and 2 parts of calcium silicate, sequentially adding the polytetrafluoroethylene powder and the calcium silicate into the dispersion liquid obtained by coating the metal powder on the elastomer, and stirring for 6 hours at the rotating speed of 200rpm/min to obtain slurry; wherein, the grain diameter of the polytetrafluoroethylene powder is 160 μm, and the grain diameter of the calcium silicate is 10 μm;

and (3) granulation: and extruding and granulating the obtained slurry through a granulator with a particle plate of 3mm, and drying the obtained particles at the drying temperature of 60 ℃ to obtain the final product.

The final product obtained in the embodiment can stably react after 3g of firework propellant powder is ignited, the quality consistency is good, and the internal throwing height of the filled display shell reaches more than 50 meters.

Example 3

A sulfur-free nitrogen-free high-temperature-resistant environment-friendly firework propellant and a preparation method thereof comprise the following specific steps:

(1) firstly, metal powder is modified and coated

Surface modification: weighing 2 parts of silane coupling agent KH-550, adding into 50mL of ethanol, stirring for 0.5h, sequentially dispersing 22 parts of aluminum powder, 8 parts of zinc powder and 5 parts of copper powder into the solution under the protection of inert atmosphere, soaking for 6h, filtering and drying to obtain modified metal powder; wherein the particle size of the aluminum powder is 40 mu m, the particle size of the zinc powder is 10 mu m, and the particle size of the copper powder is 10 mu m;

coating: weighing 5 parts of elastomer, adding the elastomer into 50mL of ethyl acetate, stirring until the elastomer is completely dissolved, dispersing the 35 parts of modified metal powder into the solution, stirring for 2 hours at the rotating speed of 200rpm/min, and obtaining the dispersion liquid of the elastomer coated metal powder.

(2) Preparation of fireworks propellant powder particles

Mixing powder: weighing 56 parts of polytetrafluoroethylene powder and 2 parts of calcium silicate, sequentially adding the polytetrafluoroethylene powder and the calcium silicate into the dispersion liquid obtained by coating the metal powder on the elastomer, and stirring for 4 hours at the rotating speed of 200rpm/min to obtain slurry; wherein, the grain diameter of the polytetrafluoroethylene powder is 160 μm, and the grain diameter of the calcium silicate is 10 μm;

and (3) granulation: 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.

The final product obtained in the embodiment can stably react after 3g of firework propellant powder is ignited, the quality consistency is good, and the internal throwing height of the filled display shell reaches more than 50 meters.

Example 4

A sulfur-free nitrogen-free high-temperature-resistant environment-friendly firework propellant and a preparation method thereof comprise the following specific steps:

(1) firstly, metal powder is modified and coated

Surface modification: weighing 5 parts of silane coupling agent KH-550, adding into 50mL of ethanol, stirring for 0.5h, sequentially dispersing 25 parts of aluminum powder, 5 parts of zinc powder and 10 parts of copper powder into the solution under the protection of inert atmosphere, soaking for 6h, filtering and drying to obtain modified metal powder; wherein the particle size of the aluminum powder is 10 mu m, the particle size of the zinc powder is 10 mu m, and the particle size of the copper powder is 10 mu m;

coating: weighing 5 parts of elastomer, adding the elastomer into 50mL of ethyl acetate, stirring until the elastomer is completely dissolved, dispersing 40 parts of modified metal powder into the solution, stirring for 2 hours at the rotating speed of 200rpm/min, and obtaining the dispersion liquid of the elastomer coated metal powder.

(2) Preparation of pyrotechnic propellant particles

Mixing powder: weighing 45 parts of polytetrafluoroethylene powder and 5 parts of calcium silicate, sequentially adding the polytetrafluoroethylene powder and the calcium silicate into the dispersion liquid obtained by coating the metal powder on the elastomer, and stirring for 6 hours at the rotating speed of 200rpm/min to obtain slurry; wherein, the grain diameter of the polytetrafluoroethylene powder is 160 μm, and the grain diameter of the calcium silicate is 10 μm;

and (3) granulation: and extruding and granulating the obtained slurry through a granulator with a particle plate of 3mm, and drying the obtained particles at the drying temperature of 60 ℃ to obtain the final product.

The final product obtained in the embodiment can stably react after 3g of firework propellant powder is ignited, the quality consistency is good, and the internal throwing height of the filled display shell reaches more than 50 meters.

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.