Dual perovskite structure primary explosive and its synthesis method

Abstract

The application provides a double perovskite structure primary explosive and a synthesis method, and the synthesis method specifically comprises the following steps: step one, a certain amount of triethylenediamine dihydrochloride solid and a certain amount of ammonium chloride powder are dissolved in a certain amount of water to prepare a mixed solution of triethylenediamine dihydrochloride and ammonium chloride; step two, a certain amount of sodium periodate powder is dissolved in a certain amount of water to prepare a sodium periodate aqueous solution; step three, the sodium periodate aqueous solution is added into the mixed solution of triethylenediamine dihydrochloride and ammonium chloride at a certain rotating speed under room temperature, and mixing is carried out for a period of time; step four, after continuous stirring for a period of time, colorless transparent to white or off-white crystals are obtained through filtration; step five, the white or off-white crystals are washed by ice water or 95% volume fraction of anhydrous ethanol or acetonitrile, and then dried, so that the primary explosive is obtained.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of primary explosive, in particular to a primary explosive with double perovskite structure and a synthesis method thereof. BACKGROUND

[0002] Primary explosive is a kind of sensitive explosive that can rapidly combust and transform into detonation under weak stimulation (such as light, electricity, heat, force, magnetism, etc.). The rapid transformation of primary explosive into detonation can ensure the reliability of various civil and military pyrotechnics, and thus it is widely filled in various pyrotechnics to ensure the smooth completion of various predetermined actions such as delay, separation, projection, cutting, transmission, instantaneous heat supply, opening and closing of remote switch and remote control, decoy projection, seat ejection and self-destruction of missile weapons. So far, the development of primary explosive has a history of nearly 400 years, and nearly 100 kinds of primary explosives have been reported. Overall, it can be divided into four categories: metal salt, complex, perchlorate ion salt and organic matter. Since mercury fulminate was used as a primary explosive in 1628, lead azide (LA), lead styphnate (LS), tetrazene, dinitro-diazophenol (DDNP) and other elemental primary explosives have been developed for use in military pyrotechnics and civilian explosive materials. In recent years, in order to promote the safety and high-quality development of the industry, two new types of primary explosives, nickel hydrazine nitrate (NHN) and zinc bis (trifluorocarbonate) hydrazinium perchlorate (GTX), have been developed for use in the civilian explosive industry.

[0003] The civilian explosive industry is known as the "energy of energy industry and the basis of basic industry", which includes industrial explosives, seismic explosive columns, primary explosive columns, industrial detonators, plastic booster tubes, fuses, detonating cords and shaped charge perforators, etc. 400 kinds of products are widely used in coal, metallurgy, mining, building material mining, mechanical processing, water and electricity engineering, rural infrastructure and urban construction and national defense construction, etc. Among them, the industrial detonator used for detonating explosive has a basic product position in the field of civilian explosive materials in terms of functionality and product quantity (10 billion times per year). In the structure of industrial detonator, the primary explosive is the front-end agent in the firing sequence structure. In the early days, mercury fulminate (MF) agent was mainly used in China, but it was gradually replaced by lead azide (LA) with better comprehensive performance due to its weak initiation ability, high toxicity and low intrinsic safety. However, with the increasing pressure of environment, health, cost, safety and other aspects, the development has gradually developed to the use of organic primary explosive dinitro-diazophenol (DDNP) with low cost, good initiation ability and mature technology. However, due to the shortage of initial raw material picric acid supply chain and the extremely serious wastewater pollution problem, DDNP has been required to be stopped production by the industry in recent years. Before this period, Beijing University of Technology and Nanjing University of Technology have developed DDNP replacement agents GTX and NHN respectively.

[0004] The molecular structure of GTX is [Zn(CHZ)3]ClO4, wherein the perchlorate ion will produce HCl after detonation, and the HCl molecule will aggravate the harm of acid rain, cause pollution of soil and water, and directly threaten the health of living beings; on the other hand, from the preparation process point of view, perchloric acid will be used to prepare zinc perchlorate in the synthesis process of GTX, and the strong acidity and oxidizability of perchloric acid bring great safety risks to the process; in addition, a large amount of gas is generated in the synthesis process of zinc perchlorate, which is also a risk factor that is not easy to control; and the synthesis of GTX must be carried out at a high temperature of about 60 DEG C, and the material mixing speed needs to be strictly controlled, which causes large energy consumption, high operation difficulty and great safety risk of the process.

[0005] In addition, the molecular structure of NHN is Ni(N2H4)3(NO3)2, wherein the nickel ion (divalent) belongs to heavy metal ion, and the residue after use will cause serious pollution to soil and air, and enter living beings through air, water and other ways, which will cause great harm to the health of living beings; at the same time, from the preparation process point of view, high concentration of hydrazine hydrate solution will be used in the synthesis process of NHN, and the hydrazine hydrate has strong volatility, flammability and high biological toxicity, which brings great safety risk and health ethics risk to the process; on the other hand, the synthesis of NHN also needs to be carried out at a high temperature of about 60 DEG C, and the material mixing speed needs to be strictly controlled, which causes large energy consumption, high operation difficulty and great safety risk of the corresponding process. SUMMARY

[0006] The main purpose of the present application is to provide a dual perovskite structure of initiating explosive and a synthesis method, which has excellent initiation ability and is safe and environmentally friendly.

[0007] To achieve the above purpose, the technical scheme adopted by the present application is as follows: a dual perovskite structure of initiating explosive, the chemical formula is as follows:

[0008]

[0009] The present application also provides a synthesis method of the dual perovskite structure of initiating explosive, which specifically comprises the following steps:

[0010] Step one, a certain amount of triethylenediamine dihydrochloride solid and a certain amount of ammonium chloride powder are dissolved in a certain amount of water to prepare a mixed solution of triethylenediamine dihydrochloride and ammonium chloride;

[0011] Step two, a certain amount of sodium periodate powder is dissolved in a certain amount of water to prepare a sodium periodate aqueous solution;

[0012] Step three, under certain rotation speed, add sodium periodate aqueous solution into the mixed solution of triethylenediamine dihydrochloride and ammonium chloride at room temperature, and mix for a period of time;

[0013] Step four, after continuous stirring for a period of time, filter to obtain colorless transparent to white or off-white crystals;

[0014] Step five, after washing the white or off-white crystals with ice water or 95% volume fraction of anhydrous ethanol or acetonitrile, and drying, the primary explosive is obtained.

[0015] Compared with the prior art, the present application has the following beneficial effects:

[0016] The molecular structure of DPPE-1 is a new compound synthesized, the structure of DPPE-1 belongs to double perovskite type, and the general structure formula is "A2BB'C6" type, four different components are contained in the structure, and the components are connected through non-covalent interaction, and there is no complex uncontrollable skeleton reorganization and group introduction, and by means of the self-assembly type reaction mechanism, the reaction substrate can accurately construct the target molecule at a very fast speed at room temperature;

[0017] (2) The DPPE-1 molecule has the intrinsic safety based on the structure of the substance, the DPPE-1 structure does not contain heavy metal ions and perchlorate ions, and the periodate ions are finally converted into non-toxic and harmless iodine element, and the molecular structure has the intrinsic green environmental protection;

[0018] (3) The DPPE-1 molecular structure is the result of accurate design after scientific summary, which directly leads to the excellent performance, the space size of the double perovskite structure skeleton composed of sodium ions, ammonium ions and periodate ions is about And the molecular space diameter of the triethylenediamine divalent cation is about Can be matched with the space to the greatest extent, so that the atomic packing efficiency reaches 80.7%, the high atomic packing efficiency can give the structure high density, and the high pore filling rate is more conducive to improving the stability of the whole structure; and the oxidizing property of periodate ions is stronger than that of perchlorate ions, and the oxidation-reduction reaction speed is faster, which is more conducive to promoting the change from combustion to detonation of the propellant in a short time and a short distance;

[0019] (4) The limit primary explosive amount of DPPE-1 is 5mg, which is lower than 120mg of NHN and 50mg of GTX, therefore, DPPE-1 is a primary explosive with extremely excellent primary explosive ability. BRIEF DESCRIPTION OF DRAWINGS

[0020] Figure 1 is the flow chart of the synthesis method according to the present application. DETAILED DESCRIPTION

[0021] The following description is provided to enable any person skilled in the art to practice the present application. The preferred embodiments described herein are only examples of the present application and various modifications can be made by those skilled in the art.

[0022] Embodiment one

[0023] A dual perovskite structure primary explosive, the chemical formula of which is as follows:

[0024]

[0025] The code of the primary explosive is DPPE-1.

[0026] Embodiment two

[0027] The embodiment is a method for synthesizing the primary explosive of embodiment one, specifically comprising the following steps:

[0028] Step one, 0.037g-3.7kg of triethylenediamine dihydrochloride solid and 0.0054g-540g of ammonium chloride powder are dissolved in 0.5mL-5L of water to prepare a mixed solution of triethylenediamine dihydrochloride and ammonium chloride;

[0029] Step two, 0.128g-12.8kg of sodium periodate powder is dissolved in 0.5mL-5L of water to prepare a sodium periodate aqueous solution;

[0030] Step three, the sodium periodate aqueous solution is added to the mixed solution of triethylenediamine dihydrochloride and ammonium chloride at a rotation speed of 50-1800 revolutions per minute at room temperature, and the mixing is completed within 1min-1h;

[0031] Step four, the stirring is continued for 5 seconds-1 hour, and then the stirring is stopped after the reaction is completed, and a colorless transparent to white or off-white crystal is obtained by filtration;

[0032] Step five, the white or off-white crystal is washed with ice water or 95% volume fraction of anhydrous ethanol or acetonitrile for 2-5 times, and then dried, to obtain the primary explosive, and the yield is 75%-85%.

[0033] The reaction chemical formula of the above steps is as follows:

[0034]

[0035] Experimental example one

[0036] The booster of Example One was tested, including: infrared absorption spectrum test, nuclear magnetic resonance spectrometer test, elemental analysis test, powder x-ray diffraction test, single crystal x-ray diffraction test, thermal stability test, mechanical sensitivity test and initiation performance test. Infrared absorption spectrum test: a German Bruker EQUINO X55 advanced research Fourier infrared spectrometer was used, the test sample was made into a potassium bromide tablet for absorption spectrum test, and the absorption intensity in the range of 400-4000 cm -1 was recorded; nuclear magnetic resonance spectrometer test: the sample was dissolved in DMSO-d6 solvent, and then placed in a German Bruker AVANCE III HD 600 type 600MHz nuclear magnetic resonance spectrometer for 1 H NMR and 13 CNMR spectrum test and recording; elemental analysis test: the percentage content of C, H, N, O and other elements in the structure of the compound was measured by a German ELEMENTAR company vario MICRO cube elemental analyzer; powder x-ray diffraction test: a German D8 Advance powder x-ray single crystal diffraction tester was used, working at 60kV, 300mA, with Cu Kα ray source at 5 0 ·min -1 , 0.02 0 step working condition, 2θ angle diffraction data scanning was carried out; single crystal x-ray diffraction test: single crystal x-ray diffraction data collection was carried out on a Rigaku AFC-10 / Saturn 724+CCD diffractometer, graphite monochromatic, with Mo Kα ray source scanning, the crystal structure was measured by direct method, the SHELXL-97 program in SHELXS-97 was used for refinement on F2 by full matrix least squares program, all non-hydrogen atoms were obtained from the difference Fourier map, and further refined by anisotropy refinement on F2 by full matrix least squares. Organic hydrogen atoms were obtained by theoretical hydrogenation method; thermal stability test: a Shanghai Precision Scientific Instrument Co., Ltd. CDR 4 type simultaneous thermal analyzer was used, with a temperature rising rate of 5℃·min -1 , under a dry nitrogen atmosphere of 20·mLmin -1 , the thermal decomposition data of the compound at 40℃-350℃ was recorded; mechanical sensitivity test: according to the BAM test method, the drop hammer sensitivity instrument and the friction sensitivity instrument were used to test the impact sensitivity and friction sensitivity of the compound respectively; initiation performance test: according to the method of GJB 5891.19-2006, the limit booster amount of the compound was evaluated.

[0037] The test results are as follows:

[0038] Table of physicochemical performance parameters of Table DPPE-1

[0039]

[0040] Experimental Example Two

[0041] A mixture solution of triethylenediamine dihydrochloride and ammonium chloride was prepared by weighing 0.37 g (2 mmol) of triethylenediamine dihydrochloride powder and 0.0535 g (1 mmol) of ammonium chloride powder into 5 mL of water.

[0042] Then, a sodium periodate aqueous solution was prepared by weighing 1.28 g (6 mmol) of sodium periodate powder into 8 mL of water.

[0043] The mixture solution of triethylenediamine dihydrochloride and ammonium chloride was stirred at a speed of 600 revolutions per minute at room temperature, and then the prepared sodium periodate aqueous solution was added dropwise at a rate of 4 mL·min -1 -1 into the mixture solution, and stirring was continued. After 5 minutes of reaction, the stirring was stopped, and the white crystals were filtered. After being washed with 6 mL of ice water twice and dried, the target product was weighed to be 1.1 g, and the yield was 78.1%. The characterization test results of the obtained product are as follows:

[0044] Thermal decomposition temperature (5 ℃·min -1 -1, ℃): 161.3 (decomposition);

[0045] Infrared absorption spectrum (KBr pressed tablet, cm -1 ): 3122 (m), 3034 (w), 1475 (m), 1419 (s), 91328 (w), 1214 (m), 1056 (s), 830 (s);

[0046] 1H NMR (600 MHz, DMSO-d6, ppm, 25 ℃): δ = 7.06 (1H, NH), 3.36 (2H, CH2);

[0047] 13C NMR (150 MHz, DMSO-d6, ppm, 25 ℃): δ = 43.90;

[0048] Elemental analysis: C 12 H 32 I6N5NaO 24 (1414.82 g mol -1 , %), the theoretical value: C 10.19, H 2.28, N 4.95; the measured value: C 10.30, H 2.69, N 5.80.

[0049] Experimental Example Three

[0050] A mixture solution of triethylenediamine dihydrochloride and ammonium chloride was prepared by dissolving 15.17 g (82 mmol) of triethylenediamine dihydrochloride powder and 2.19 g (41 mmol) of ammonium chloride powder in 170 mL of water.

[0051] Then, a sodium periodate aqueous solution was prepared by dissolving 51.22 g (246 mmol) of sodium periodate powder in 170 mL of water.

[0052] The mixture solution of triethylenediamine dihydrochloride and ammonium chloride was stirred at a speed of 800 rpm at room temperature, and then the prepared sodium periodate aqueous solution was added dropwise into the mixture solution at a speed of 12 mL·min -1 -1, and the stirring was continued. After 10 min of reaction, the stirring was stopped, and the white crystals were obtained by filtration. The crystals were washed with 40 mL of ice water in three times and then with 10 mL of anhydrous ethanol once, and then dried and weighed. The weight of the target product was 47.4 g, and the yield was 82.2%. The characterization test results of the obtained product were as follows:

[0053] Thermal decomposition temperature (5 ℃·min -1 -1, ℃): 161.2 (decomposition);

[0054] Infrared absorption spectrum (KBr pressed tablet, cm -1 -1): 3122 (m), 3034 (w), 1475 (m), 1419 (s), 91328 (w), 1214 (m), 1056 (s), 830 (s);

[0055] 1H NMR (600 MHz, DMSO-d6, 25 ℃): δ = 7.06 (1H, NH), 3.36 (2H, CH2);

[0056] 13C NMR (150 MHz, DMSO-d6, 25 ℃): δ = 43.91;

[0057] Elemental analysis: C 12 H 32 I6N5NaO 24 (1414.82 g mol -1 , %), the theoretical value: C 10.19, H 2.28, N 4.95; the measured value: C 10.34, H 2.77, N 5.12.

[0058] The above shows and describes the basic principles, main features and advantages of the present application. Those skilled in the art should understand that the present application is not limited to the above-mentioned embodiments, and the above-mentioned embodiments and descriptions in the specification are only the principles of the present application. Various changes and improvements can be made without departing from the spirit and scope of the present application, and these changes and improvements all fall within the scope of the claimed present application. The scope of protection of the present application is defined by the appended claims and their equivalents.

Claims

1. A primary explosive of a double perovskite structure, characterized in that, The chemical formula is as follows: 。 2. A method for synthesizing a double perovskite structure primary explosive, the double perovskite structure primary explosive being the double perovskite structure primary explosive according to claim 1, characterized in that, Specifically comprising the following steps: Step one, a certain amount of triethylenediamine dihydrochloride solid and a certain amount of ammonium chloride powder are dissolved in a certain amount of water to prepare a mixed solution of triethylenediamine dihydrochloride and ammonium chloride; Step two, a certain amount of sodium periodate powder is dissolved in a certain amount of water to prepare a sodium periodate aqueous solution; Step three, at room temperature, the sodium periodate aqueous solution is added to the mixed solution of triethylenediamine dihydrochloride and ammonium chloride at a certain rotating speed, and mixed for a period of time; Step four, after continuous stirring for a period of time, a colorless transparent to white or off-white crystal is obtained by filtration; Step five, the white or off-white crystal is washed with ice water or 95% volume fraction of anhydrous ethanol or acetonitrile, and then dried, to obtain the primary explosive.

Images