CN115466155A - LLM-105/AP energetic composite material and preparation method thereof - Google Patents

LLM-105/AP energetic composite material and preparation method thereof Download PDF

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CN115466155A
CN115466155A CN202211055467.7A CN202211055467A CN115466155A CN 115466155 A CN115466155 A CN 115466155A CN 202211055467 A CN202211055467 A CN 202211055467A CN 115466155 A CN115466155 A CN 115466155A
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llm
neck flask
dmf
dichloromethane
composite material
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成健
张霁月
许响生
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Zhejiang University of Technology ZJUT
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    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B29/00—Compositions containing an inorganic oxygen-halogen salt, e.g. chlorate, perchlorate
    • C06B29/22—Compositions containing an inorganic oxygen-halogen salt, e.g. chlorate, perchlorate the salt being ammonium perchlorate
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B21/00—Apparatus or methods for working-up explosives, e.g. forming, cutting, drying
    • C06B21/0008—Compounding the ingredient
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B23/00—Compositions characterised by non-explosive or non-thermic constituents
    • C06B23/007—Ballistic modifiers, burning rate catalysts, burning rate depressing agents, e.g. for gas generating
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06D—MEANS FOR GENERATING SMOKE OR MIST; GAS-ATTACK COMPOSITIONS; GENERATION OF GAS FOR BLASTING OR PROPULSION (CHEMICAL PART)
    • C06D5/00—Generation of pressure gas, e.g. for blasting cartridges, starting cartridges, rockets
    • C06D5/06—Generation of pressure gas, e.g. for blasting cartridges, starting cartridges, rockets by reaction of two or more solids

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention discloses an LLM-105/AP energetic composite material and a preparation method thereof, wherein the preparation method comprises the following operation processes: weighing a DMF three-neck flask, weighing LLM-105 and AP to dissolve the LLM-105 and AP in the DMF three-neck flask, putting the sealed three-neck flask into a magnetic stirrer to be heated until the LLM-105 and AP are completely dissolved, cooling the magnetic stirrer to room temperature, weighing 100ml dichloromethane by using a measuring cylinder, and slowly dropping the dichloromethane into the three-neck flask at a constant speed by using a dropping funnel. After all dichloromethane enters the three-neck flask, the three-neck flask is hermetically stirred for 24 hours. And then, carrying out suction filtration by using a vacuum pump and a sand core funnel, and drying the filter residue in a drying box. The thermal decomposition characteristics were analyzed by TG-DTG. The LLM-105/AP energetic composite material prepared by the solvent-nonsolvent method is used as an energetic insensitive material and a insensitive agent to adjust the safety of a propellant and adjust the combustion behavior of the propellant, and has the excellent characteristics of high energy, environmental friendliness, low characteristic signal and the like.

Description

LLM-105/AP energetic composite material and preparation method thereof
Technical Field
The invention belongs to the technical field of energetic material preparation, and particularly relates to an LLM-105/AP energetic composite material and a preparation method thereof.
Background
The propellant is the power source of missiles, rockets and carrier rockets. The propellant components may be solid or liquid. The liquid propellant has more energy than solid in terms of energy, but is difficult to be used in practice because the equipment structure of the liquid propellant is very complicated. The equipment structure of the solid propellant is simple, the cost is low, the use is very safe, and the instant explosive thrust is huge, so the solid propellant can be applied in various aspects. Ammonium Perchlorate (AP) is the most commonly used oxidizer in composite propellants, modified biradical propellants and propellants, and generally accounts for more than 70% of the total propellant.
Because the combustion performance of pure AP can not completely meet the use requirements of the compound propellant rocket engine, a certain proportion of combustion catalyst is added in the use process to adjust the thermal decomposition activation energy, the thermal decomposition rate and the high-temperature decomposition temperature of AP so as to adjust the combustion performance of the compound propellant. The traditional catalyst of the solid propellant reduces the energy level of the solid propellant and contains heavy metal, while the energetic salt and the energetic complex do not reduce the energy level but contain heavy metal. The energetic catalyst has the dual advantages of both energetic and nano-catalyst from the viewpoint of a catalytic mechanism.
Therefore, a non-metal energetic catalyst-LLM-105 was developed. LLM-105 was applied to AP-based composite solid propellants as a catalyst to regulate the combustion behavior of AP. LLM-105 acts as an energetic desensitizing material and as a desensitizing agent to regulate the safety of the propellant. The method has the excellent characteristics of high energy, environmental friendliness, low characteristic signal and the like. The application prospect is good.
Disclosure of Invention
In view of the above problems, the present invention aims to provide an energetic material, a preparation method and applications thereof.
In order to achieve the purpose, the following technical scheme is provided:
a preparation method of LLM-105/AP energetic composite material comprises the following steps: measuring DMF (dimethyl formamide) in a three-neck flask, weighing a certain amount of LLM-105 and AP (ammonium hydroxide) to dissolve the LLM-105 and the AP in the three-neck flask, putting the sealed three-neck flask into a magnetic stirrer, heating the sealed three-neck flask until the LLM-105 and the AP are completely dissolved, cooling the magnetic stirrer to room temperature, measuring dichloromethane by using a measuring cylinder, and slowly dropping the dichloromethane into the three-neck flask at a constant speed by using a dropping funnel. And after all dichloromethane enters the three-neck flask, hermetically stirring the three-neck flask for 24 hours, and performing post-treatment to obtain the LLM-105/AP solvent non-solvent preparation product.
LLM-105 has a structural formula shown in formula (I)
Figure DEST_PATH_IMAGE001
（I）
And further, performing suction filtration on the product through a vacuum pump and a sand core funnel, and drying the filter residue in a drying box.
Further, the volume ratio of the DMF to the dichloromethane solvent added is 1:5-1.
Further, the mass of the AP feed accounts for 50 to 90 percent of the total mass of the LLM-10 and the AP feed.
Further, the mass ratio of the LLM-105 to the AP is 1:1. 1: 2. 1:4, 1:9, preferably 1:1.
further, the heating temperature in the magnetic stirrer is 70-80 ℃, and the time for hermetically stirring the three-neck flask before post-treatment is 12-24h.
The invention also discloses the LLM-105/AP energetic composite material prepared by the preparation method.
The thermal weight loss test of the crystal form of the prepared LLM-105/AP energetic composite material comprises the following steps: placing the prepared LLM-105/AP in a thermal analyzer, and carrying out a thermal weight loss test under the atmosphere test condition of a nitrogen flow of 20ml with a heating rate of 10 ℃/min.
The invention has the beneficial effects that: the LLM-105/AP energetic composite material prepared by a solvent-nonsolvent method is used as an energetic insensitive material and a insensitive agent to adjust the safety of a propellant and the combustion behavior of the propellant, and has the excellent characteristics of high energy, environmental friendliness, low characteristic signal and the like.
Drawings
FIG. 1 is an XRD of solvent nonsolvent method of LLM-105, AP and LLM-105/AP in examples 1-4 of the present invention;
FIG. 2 is a TG-DTG graph in nitrogen atmosphere at a temperature rise rate of 10 ℃/min for comparison of example 1 of the present invention and comparative example 5 (left is example 1);
FIG. 3 is a TG-DTG graph of example 2 of the present invention and comparative example 6 in a nitrogen atmosphere at a temperature rise rate of 10 ℃/min (left is example 2);
FIG. 4 is a TG-DTG graph of example 3 of the present invention compared with comparative example 7 under a nitrogen atmosphere at a temperature rise rate of 10 ℃/min (left is example 3);
FIG. 5 is a TG-DTG graph of inventive example 4 and comparative example 8 in a nitrogen atmosphere at a temperature rise rate of 10 ℃/min (left is example 4).
Detailed Description
The technical solutions of the present invention are described clearly and completely by the following specific embodiments, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 11:1LLM-105/AP solvent nonsolvent synthesis
Measuring 20mL of DMF, transferring to a 250mL three-neck flask, weighing and dissolving 0.28g of LLM-105 and 0.28g of gAP in the DMF, sealing the three-neck flask, putting into a magnetic stirrer, heating to 80 ℃, cooling the magnetic stirrer to 20 ℃ after the three-neck flask is completely dissolved, measuring 200mL of dichloromethane by using a measuring cylinder, and slowly and uniformly dropping into the three-neck flask by using a dropping funnel. After all dichloromethane enters the three-neck flask, the three-neck flask is hermetically stirred for 24 hours. And then, carrying out suction filtration by using a vacuum pump and a sand core funnel, and drying the filter residue in a drying box.
Example 21: synthesis of 2LLM-105/AP solvent non-solvent method
The synthesis method is the same as example 1, except that 20ml of DMF is measured, and 0.28g of LLM-105 and 0.56gAP are weighed and dissolved.
Example 31: synthesis of 4LLM-105/AP solvent non-solvent method
The synthesis method is the same as example 1, except that 20ml DMF is measured, 0.14g LLM-105 and 0.56gAP are weighed and dissolved in
Example 41: synthesis of 9LLM-105/AP solvent non-solvent method
The synthesis method is the same as example 1, except that 20ml of DMF is measured, 0.24g of LLM-105 and 2.16g of gAP are weighed and dissolved, 100ml of dichloromethane is measured by a measuring cylinder, and the dichloromethane is slowly dripped into a three-neck flask at a constant speed by using a dropping funnel.
Comparative examples 5-8, as comparative examples, were prepared by mechanical mixing of LLM-105 and AP, specifically:
comparative example 51:1LLM-105/AP mechanical mixture preparation
0.28g of LLM-105 and 0.28gAP were weighed into a milling vessel and mixed for milling.
Comparative example 61:2LLM-105/AP mechanical mixture preparation
The preparation method is the same as that of comparative example 5, except that 0.28g of LLM-105 and 0.56gAP are weighed in the grinding container
Comparative example 71: preparation of 4LLM-105/AP mechanical mixture
The preparation method is the same as that of comparative example 5, except that 0.14g of LLM-105 and 0.56gAP are weighed in the grinding container
Comparative example 81:9LLM-105/AP mechanical mixture preparation
The procedure is as in comparative example 5, except that 0.24g of LLM-105 and 2.16g of gAP are weighed into the milling vessel.
Example 91:1LLM-105/AP thermogravimetric testing
The thermogravimetric process of the TG-DTG chart of example 1 has only one stage, which is a severe weight loss process, and the starting decomposition temperature is 275.31 ℃. The maximum weight loss occurs at 285.21 ℃ at which stage the material is completely decomposed.
Comparative example 5 TG-DTG thermogravimetric weight loss process can be divided into two stages, starting with a decomposition temperature of 273 ℃. Wherein the first stage is a severe weight loss process with a weight loss rate of 67.89%. The second stage is a slow weight loss process, the weight loss rate is 28.51 percent, and the maximum weight loss rate occurs in 287.47.
Example 101: 2LLM-105/AP thermogravimetric testing
Example 2 TG-DTG the thermogravimetric weight loss process can be divided into two stages, starting with a decomposition temperature of 262.78 ℃. Wherein the first stage is a severe weight loss process, the weight loss rate is 87 percent, and the maximum weight loss rate occurs at 285.21 ℃. The second stage is a slow weight loss process, and the weight loss rate is 11%.
Comparative example 6 TG-DTG the thermogravimetric weight loss process can be divided into two stages, starting with a decomposition temperature of 276.81 ℃. Wherein the first stage is a severe weight loss process, the weight loss rate is 39.28 percent, and the maximum weight loss rate occurs in 289.84. The second stage is a slow weight loss process, the weight loss rate is 56.01%, and the maximum weight loss rate occurs at 331.82.
Example 111: 4LLM-105/AP thermogravimetric testing
Example 3 TG-DTG the thermogravimetric weight loss process can be divided into two stages, starting with a decomposition temperature of 264.09 ℃. Wherein the first stage is a severe weight loss process, the weight loss rate is 78.19 percent, and the maximum weight loss rate occurs at 275.31 ℃. The second stage is a slow weight loss process, and the weight loss rate is 23.81%.
Comparative example 7 TG-DTG the thermogravimetric weight loss process can be divided into two stages, starting with a decomposition temperature of 269.3 ℃. Wherein the first stage is a severe weight loss process, the weight loss rate is 30.29 percent, and the maximum weight loss rate occurs in 288.35. The second stage is a slow weight loss process, the weight loss rate is 65.71 percent, and the maximum weight loss rate occurs in 321.05.
Example 121: 9LLM-105/AP thermogravimetric testing
Example 4 TG-DTG the thermogravimetric weight loss process can be divided into three stages, starting with a decomposition temperature of 270.36 ℃. Wherein the first stage is a severe weight loss process, and the weight loss rate is 16.75 percent. The second stage is a slow weight loss process, the weight loss rate is 74.6 percent, the maximum weight loss rate occurs in 288.34 ℃, and the third stage is a slow weight loss process, the weight loss rate is 9 percent.
Comparative example 8 TG-DTG the thermogravimetric weight loss process can be divided into two stages with an onset decomposition temperature of 270.36 ℃. Wherein the first stage is a severe weight loss process, the weight loss rate is 16.75 percent, and the maximum weight loss rate occurs at 275.31 ℃. The second stage is a slow weight loss process, the weight loss rate is 74.6 percent, and the maximum weight loss rate occurs at 288.34 ℃. The third stage is a slow weight loss process, the weight loss rate is 9 percent, and the maximum weight loss rate occurs at 376.06 ℃.
The solvent nonsolvent method 1 is characterized in that the temperature of the decomposition peak of the 1LLM-105/AP is advanced, and the low-temperature decomposition peak and the high-temperature decomposition peak coincide, thus proving that the catalytic effect is good. The initial decomposition temperature is relatively high and the thermal stability is relatively high.

Claims (7)

1. A preparation method of an LLM-105/AP energetic composite material is characterized by comprising the following steps: weighing a certain amount of DMF (dimethyl formamide) into a three-neck flask, weighing LLM-105 and AP (ammonium nitrate) to dissolve the DMF into the DMF, putting the three-neck flask into a magnetic stirrer for sealing, heating the three-neck flask until the DMF is completely dissolved, cooling the magnetic stirrer to room temperature, weighing a certain proportion of dichloromethane by using a measuring cylinder, slowly and uniformly dripping the dichloromethane into the three-neck flask by using a dropping funnel, hermetically stirring the three-neck flask after all the dichloromethane enters the three-neck flask, and performing post-treatment to obtain the LLM-105/AP solvent non-solvent method preparation product.
2. The method of claim 1, wherein the solvent volume ratio of DMF to dichloromethane added is 1:5-1.
3. The method of claim 1, wherein the mass of the AP feed is 50-90% of the total mass of the LLM-10 and the AP feed.
4. The method of claim 3, wherein the LLM-105/AP energetic composite material is prepared from the LLM-105 and the AP in a mass ratio of 1:1. 1: 2. 1:4 and 1:9, preferably 1:1.
5. the method of claim 1, wherein the heating temperature in the magnetic stirrer is 70-80 ℃; the time for hermetically stirring the three-neck flask before the post-treatment is 12-24h.
6. The method of claim 1, wherein the post-treatment process comprises: and (3) carrying out suction filtration on the product after sealed stirring in the three-neck flask by using a vacuum pump and a sand core funnel, and putting the filter residue into a drying box for drying.
7. An LLM-105/AP energetic composite material prepared by the method of any one of claims 1-6 for preparing an LLM-105/AP energetic composite material.
CN202211055467.7A 2022-08-30 2022-08-30 LLM-105/AP energetic composite material and preparation method thereof Withdrawn CN115466155A (en)

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Application publication date: 20221213