CN115819164A - High-energy micro-smoke type firework propellant and preparation method thereof - Google Patents

Abstract

The present invention provides a high-energy micro-smoke type fireworks propellant, which is characterized in that: in parts by weight, the propellant includes 1-10 parts of binder, 30-50 parts of reducing agent, and 45-65 parts of oxidizing agent. The binder is nitrocellulose or polyazide glycidyl ether, the reducing agent is aluminum-magnesium alloy, and the oxidizing agent is an organic polymer skeleton type oxidizing agent. The present invention also provides the preparation method of the propellant, which is characterized in that: the following steps are adopted: step A: glue compounding: mixing the adhesive with acetone or ethanol; step B: preparing an organic polymer skeleton type oxidant; step C : raw material mixing; step D: granulation; step E: screening; step F: drying. The invention provides an ideal propellant used in civil launch products such as fireworks and a preparation method thereof. The propellant has high explosion temperature, high emission force, low pressure index, good stability, safety and reliability, and the preparation method is simple, which is beneficial to Promote production.

Description

High-energy micro-smoke type fireworks propellant and preparation method thereof

technical field

The invention relates to the fields of formula design and production of fireworks and firecrackers, in particular to a high-energy micro-smoke type fireworks propellant and a preparation method thereof.

Background technique

For the field of fireworks and firecrackers, the disadvantages of general-purpose black powder-based propellants in terms of environmental protection, and the continuation of its low-pressure exponential launch reliability advantages. Starting from the combustion reaction mechanism of the components of the existing fireworks propellant (universal black powder-based propellant), select the micro-smoke oxidizer, combustible agent and additives that can replace the fireworks propellant, and then design the formula of the micro-smoke agent.

This technical solution aims to provide a low-cost, easy-to-use fireworks propellant based on chemical energy. Other firework launch technologies based on physical technology and more complex launch structures are not within the scope of elaboration, as described in the patent document CN201910356177.8. An environmentally friendly Firework launcher. Understandably, to reduce the amount of smoke exiting the launch port during the launch of fireworks, the first approach is to design a propellant whose reaction product is as gas as possible and has low hygroscopicity. Capsule single-base propellant, as described in the patent document CN201010178424.9, a microporous smokeless fireworks anther and its preparation method; the second approach is to explore the possibility of a micro-smoke pyrotechnic powder applied to fireworks, such as widely used in the fireworks industry The explosive effect produced by the magnesium-aluminum alloy and copper oxide-based pyrotechnic agent is a representative application of using chemical energy to do work, and a carbon nanotube micro-pyrotechnic composition and its production method described in the patent document CN202110992406.2. The principle is to use a group of high-energy compound agents to achieve reliable launch work.

The above two approaches have been conceived in the initial research process, especially the first approach is still the mainstream design idea of the fireworks industry, and the second approach is only a concept in the early stage and there is no ideal and feasible plan; the assumptions of these two approaches represent The application and innovation of the two mainstream pyrotechnic agents, single-base drug and micro-gas pyrotechnic drug. The design idea of fireworks propellant based on single-base drug is to meet the requirements of fireworks launch by adjusting the formula and model parameters of the propellant. Combining the basically formed and self-made single-base drug system propellant, it can basically meet the requirements of fireworks launch. The propellant is divided into two types: type a is a porous surface-increasing combustion type, such as a smokeless propellant and its preparation method described in the patent document CN201910175173. The sensitization method of fireworks and fireworks; type b is a composite single-base gunpowder type with an ultra-high linear burning rate, such as a firecracker propellant described in the patent document CN201911177721. Smoke-free sulfur firecracker propellant and preparation method thereof. Compared with the general-purpose black powder-based propellants, both types a and b have a narrow range of emission force adjustment, and are prone to fluctuating highs and lows or sudden strengths and weaknesses. That is, the emission force can be adjusted to be suitable for fireworks through the formula and type system. When the charge is slightly uneven, the phenomenon of poor launch consistency will appear, which is directly related to the fact that the combustion pressure index of single-base powder series propellants is higher than that of general-purpose black powder-based propellants. In addition, due to old problems such as sensitivity and moisture absorption and deterioration of single-base drug series propellants, it is difficult to apply fireworks propellants based on single-base drug design.

The micro-smoke propellant that stayed in the concept in the early stage has been found in practice to have a much higher combustion heat than other types of propellant, the product is mainly solid large particles, and the linear burning rate is high and extremely stable; the application of this type of pyrotechnic powder to In the propellant, the observed launch effect is stable and reproducible. Through the regulation of formula, powder charge and preparation process, a kind of propellant propellant scheme of low-smoke high-energy fireworks has been mastered, and the evaluation of parameters such as sensitivity, smoke volume at the exit and launch port, launch consistency, storage stability and application economic value are well established. have good performance.

Contents of the invention

The high-energy micro-smoke type fireworks propellant is characterized in that, in parts by weight, the propellant includes 1-10 parts of binder, 30-50 parts of reducing agent and 45-65 parts of oxidizing agent.

Further, the binder is nitrocellulose or polyazide glycidyl ether.

Further, the reducing agent is an aluminum-magnesium alloy.

Further, the oxidizing agent is an organic polymer skeleton type oxidizing agent.

Further, the aluminum-magnesium alloy is Mg ₄ Al ₃ .

Further, the organic polymer skeleton type oxidant is composed of an oxidant and an organic polymer skeleton, wherein the mass of the organic polymer skeleton accounts for 3 to 10% of the total mass of the organic polymer skeleton type oxidant, and the oxidant is MnO ₂ , KClO ₄ , KIO ₄ , KNO ₃ or Fe ₂ O ₃ ; the organic polymer skeleton is PVB resin or FKM rubber.

Further, the organic polymer skeleton type oxidant is a particle with a particle diameter of 50 μm-400 μm and a bulk density of 1-2 g/cm ³ .

The preparation method of the above-mentioned high-energy micro-smoke type fireworks propellant is characterized in that: the following steps are adopted:

Step A: glue compounding: mixing the adhesive with acetone or ethanol, so that the adhesive is fully dissolved in acetone or ethanol to prepare a mixed solution of the adhesive and acetone or ethanol;

Step B: Preparation of organic polymer skeleton-type oxidant: use a high-speed homogenizer to carry out wet compounding of the oxidant and organic polymer skeleton, and then spray granulate to make a particle size of 50 μm to 400 μm and a bulk density of 1-2 g /cm ³ particles, the organic polymer skeleton type oxidant is obtained;

Step C: raw material mixing: thoroughly mix the reducing agent and the oxidizing agent prepared in step B through a sieve to prepare mixture 1; mix the mixture 1 and the mixed solution prepared in step A evenly to prepare to obtain mixture 2;

Step D: granulation: the mixture 2 prepared in step C is passed through a standard sieve to make granules by rolling;

Step E: screening: sieve the granules prepared in step D, take the granules with a particle size between 8 and 20 mesh and transfer them to the drying process, and return the particles with a particle size smaller than 8 mesh to the mixture 1 prepared in step C , returning the particles with a particle size larger than 20 mesh to step D;

Step F: Drying: drying the granules between 8 and 20 meshes obtained in step E to prepare a high-energy micro-smoke type fireworks propellant.

The beneficial effects of the present invention are as follows: the present invention provides an ideal propellant for civilian launch products such as fireworks and a preparation method thereof. Good performance, safe and reliable, the charge is only 20-30% by mass of general-purpose black powder-based propellant, and has good performance in economy and environmental protection. The measured ignition sensitivity is about 330°C (black powder is 290°C), reaching the index range of 280-350°C in the TCSTM00361-2021 standard for civil black powder design, and the preparation method is simple, which is conducive to popularization and production.

Detailed ways

Example 1

The high-energy micro-smoke type fireworks propellant consists of: (1) The composition of the organic polymer skeleton type oxidant is: in parts by weight, 45 parts of KClO ₄ ball mill pulverized and ultrafine for 24 hours, 5 parts of PVB resin dissolved in 50 parts of ethanol solvent . (2) The composition of the high-energy micro-smoke type fireworks propellant is as follows: in parts by weight, 5 parts of nitrocellulose are dissolved in 50 parts of acetone, 45 parts of Mg ₄ Al ₃ , and 50 parts of organic polymer skeleton type oxidant.

The preparation method for preparing the above-mentioned high-energy micro-smoke type fireworks propellant adopts the following steps:

Step A: glue compounding: in parts by weight, 5 parts of nitrocellulose are dissolved in 50 parts of acetone, and the nitrocellulose is fully dissolved in the acetone to obtain a mixed solution of the adhesive and acetone;

Step B: Preparation of organic polymer skeleton type oxidant: in parts by weight, take 45 parts of KClO ₄ , use a ball mill to pulverize the ultrafine KClO 4 for 24H to obtain ultrafine KClO ₄ ; weigh 5 parts of PVB resin and dissolve it in 50 parts of ethanol solvent Prepare PVB solution; mix ultra-fine KClO ₄ into PVB solution, fully stir and disperse KClO ₄ under the action of a high-speed homogenizer to obtain a dispersion liquid, dry the dispersion liquid in a spray granulator to form a composite powder, and spray Granulation The composite powder is made into particles with a particle size of 50 μm to 400 μm and a bulk density of 1-2 g/cm ³ to obtain an organic polymer skeleton type oxidant;

Step C: Mixing of raw materials: in parts by weight, 45 parts of Mg ₄ Al ₃ and 50 parts of the organic polymer skeleton type oxidant prepared in step B are fully mixed through a sieve and a method to obtain a mixture 1; the mixture 1 Mix evenly with the mixed solution prepared in step A to prepare mixture 2;

Step D: granulation: the mixture 2 prepared in step C is passed through a standard sieve to make granules by rolling;

Step E: screening: sieve the granules prepared in step D, take the granules with a particle size between 8 and 20 mesh and transfer them to the drying process, and return the particles with a particle size smaller than 8 mesh to the mixture 1 prepared in step C , returning the particles with a particle size greater than 20 mesh to step D.

Step F: Drying: drying the granules between 8 and 20 meshes obtained in step E to prepare a high-energy micro-smoke type fireworks propellant.

Example 2

The high-energy micro-smoke type fireworks propellant consists of: (1) The composition of the organic polymer skeleton type oxidant is: in parts by weight, 45 parts of _MnO2 ball mill pulverized and ultra-fine 24H, 5 parts of FKM rubber dissolved in 50 parts of ethyl acetate ester solvent. (2) The composition of the high-energy micro-smoke type fireworks propellant is: in parts by weight, 10 parts of polyazide glycidyl ether dissolved in 50 parts of ethanol, 40 parts of Mg ₄ Al ₃ , and 50 parts of organic polymer skeleton type oxidant.

The preparation method for preparing the above-mentioned high-energy micro-smoke type fireworks propellant adopts the following steps:

Step A: glue compounding: in parts by weight, dissolve 10 parts of polyazide glycidyl ether in 50 parts of ethanol, fully dissolve polyazide glycidyl ether in ethanol, and prepare a mixed solution of adhesive and ethanol ;

Step B: Preparation of organic polymer skeleton type oxidant: in parts by weight, take 45 parts of MnO ₂ , use a ball mill to pulverize ultra-fine MnO 2 for 24H to obtain ultra-fine MnO ₂ ; weigh 5 parts of FKM rubber and dissolve in 50 parts of ethyl acetate The FKM rubber solution is prepared in the solvent; the ultra-fine _MnO2 is mixed into the FKM rubber solution, and the _MnO2 is fully stirred and dispersed under the action of a high-speed homogenizer to obtain a dispersion liquid, and the dispersion liquid is dried in a spray granulator to form a compound Powder, the composite powder is made into particles with a particle size of 50 μm to 400 μm and a bulk density of 1-2 g/cm ³ by spray granulation to obtain an organic polymer skeleton type oxidant;

Step C: mixing of raw materials: in parts by weight, 40 parts of Mg ₄ Al ₃ and 50 parts of the organic polymer skeleton type oxidant prepared in step B are fully mixed through a sieve and a method to obtain a mixture 1; the mixture 1 Mix evenly with the mixed solution prepared in step A to prepare mixture 2;

Step D: granulation: the mixture 2 prepared in step C is passed through a standard sieve to make granules by rolling;

Step E: screening: sieve the granules prepared in step D, take the granules with a particle size between 8 and 20 mesh and transfer them to the drying process, and return the particles with a particle size smaller than 8 mesh to the mixture 1 prepared in step C , returning the particles with a particle size greater than 20 mesh to step D.

Step F: Drying: drying the granules between 8 and 20 meshes obtained in step E to prepare a high-energy micro-smoke type fireworks propellant.

Claims (8)

1. High-energy micro-smoke type firework propellant is characterized in that: the propellant comprises, by weight, 1-10 parts of an adhesive, 30-50 parts of a reducing agent and 45-65 parts of an oxidizing agent.

2. The high-energy micro-smoke type firework propellant as claimed in claim 1, wherein: the adhesive is nitrocellulose or polyaziridine glycidyl ether.

3. The high-energy micro-smoke type firework propellant as claimed in claim 1, wherein: the reducing agent is aluminum magnesium alloy.

4. The high-energy micro-smoke type firework propellant as claimed in claim 1, wherein: the oxidant is an organic polymer skeleton type oxidant.

5. The high-energy micro-smoke type firework propellant as claimed in claim 3, wherein: the aluminum-magnesium alloy is Mg ₄ Al ₃ 。

6. The high-energy micro-smoke type firework propellant as claimed in claim 4, wherein: the organic polymer framework type oxidant consists of an oxidant and an organic polymer framework, wherein the mass of the organic polymer framework accounts for 3-10% of the total mass of the organic polymer framework type oxidant, and the oxidant is MnO ₂ 、KClO ₄ 、KIO ₄ 、KNO ₃ Or Fe ₂ O ₃ (ii) a The organic polymer framework is PVB resin or FKM rubber.

7. The high-energy micro-smoke type firework propellant as claimed in claim 4, wherein: the organic polymer framework type oxidant has the particle size of 50-400 mu m and the bulk density of 1-2g/cm ³ The particles of (1).

8. The preparation method of the high-energy micro-smoke type firework propellant as claimed in claims 1 to 7, which is characterized in that: the method comprises the following steps:

step A: preparing glue: mixing the adhesive with acetone or ethanol to fully dissolve the adhesive in the acetone or ethanol to prepare a mixed solution of the adhesive and the acetone or ethanol;

and B, step B: preparation of organic polymer matrix-type oxidizing agent: wet compounding the oxidant and the organic polymer skeleton in a high speed homogenizer, and spray pelletizing to obtain the product with grain size of 50-400 micron and bulk density of 1-2g/cm ³ To produce an organic polymer matrix-type oxidizing agent;

and C: mixing raw materials: b, fully and uniformly mixing the reducing agent and the oxidizing agent prepared in the step B through a sieving mode to prepare a mixture 1; uniformly mixing the mixture 1 with the mixed solution prepared in the step A to prepare a mixture 2;

step D: and (3) granulation: c, preparing the mixture 2 prepared in the step C into particles through a standard screen in a rolling mode;

and E, step E: screening: d, screening the particles prepared in the step D, transferring the particles with the particle size of 8-20 meshes into a drying process, returning the particles with the particle size of less than 8 meshes to the mixture 1 prepared in the step C, and returning the particles with the particle size of more than 20 meshes to the step D;

step F: drying: and E, drying the particles of 8-20 meshes prepared in the step E to prepare the high-energy micro-smoke type firework propellant.