CN103319426A - Preparation method of temperature-resisting lead-free and barium-free primary explosive 5-nitramino tetrazole calcium - Google Patents

Abstract

The invention provides a preparation method of a temperature-resisting lead-free and barium-free primary explosive 5-nitramino tetrazole calcium. The method comprises the following steps of: mixing nitrosonitric acid and concentrated sulfuric acid by a ratio of 1:1, adding 5-amino tetrazole powder under a stirring condition, heating to 50-70 DEG C to react for 4-6 hours, cooling to room temperature and adding anhydrous Na2CO3 till pH value is neutral; extracting by absolute ethyl alcohol, spirally evaporating a filtrate, adding ethyl acetate to generate a white precipitate, filtering a solid product, and drying at 55-65 DEG C to obtain 5-nitramino tetrazole calcium; adding 5-nitramino tetrazole calcium and distilled water to a reaction bottle, stirring, adding solid powder Ca(OH)2 and heating to 75-85 DEG C to react for 1-2 hours, separating out white crystals, cooling to room temperature, filtering the solid product, washing by absolute ethyl alcohol, and drying at 55-65 DEG C to obtain CaNAT. In the synthesizing process, no toxic and harmful gases are generated, so that the primary explosive has very good thermal stability.

Description

The unleaded preparation method without barium priming explosive 5-nitramino tetrazolium calcium of a kind of heatproof

Technical field

The present invention relates to a kind of priming explosive 5-nitramino tetrazolium calcium (II) preparation method of (being called for short CaNAT).

Background technology

The priming explosive that loads in the domestic and international project detonator at present is generally coprecipitation compounds or the inclusion compounds of nitrogen lead or DDNP.The weakness of last class medicament is that mechanical sensitivity is higher, and the waste water of generation needs to discharge through chemical treatment; Although the production of DDNP, use safety many, the wastewater flow rate that produces is large, dyeability is strong and be difficult to process, the performance of medicament itself also exists deficiency, and is little such as apparent density, resistance to pressure is poor, free-running property is poor etc.

Many novel priming explosives are widely studied in recent years.In United States Patent (USP) 22,066 and 3,965, just reported the research of mercuric 5-nitrotetrazole (II) in 951, it has the superior character of detonating, but makes to use and be restricted because containing poisonous heavy metal Hg.Use the 5-nitro tetrazolium copper (II) of mentioning in the patent 2006/0030715 and have good heat-resistant quality, have good impact sensitivity and friction sensitivity with the lead azoimide ratio, acting is fast, the output energy is high, but because its solid is cotton-shaped crystal, free-running property is bad, in preparation process, be difficult for filtering, not easy to operate in the filling in later stage, and its application is affected.

Summary of the invention

In order to overcome the deficiencies in the prior art, the invention provides a kind of Novel detonating medicine---the preparation method of 5-nitramino tetrazolium calcium (II) does not produce toxic and harmful, easily preparation in the building-up process.

The technical solution adopted for the present invention to solve the technical problems may further comprise the steps:

(1) adding mass concentration in reaction flask is 98% nitrosonitric acid, and the ice bath cooling drips mass concentration and be 98% the vitriol oil, and the mass ratio of nitrosonitric acid and the vitriol oil is 1:1; Add 5-amino tetrazole powder under agitation condition, the mass ratio of 5-amino tetrazole and nitrosonitric acid is 0.43:1; Be warming up to 50-70 ℃ of reaction 4-6 hour, be cooled to room temperature and add anhydrous Na ₂CO ₃Neutral to the pH value; Use dehydrated alcohol extraction, the mass ratio of dehydrated alcohol and nitrosonitric acid is 8:1, and rotary evaporation filtrate adds ethyl acetate to producing white precipitate, filters out solid product, 60 ± 5 ℃ of lower oven dry, obtains 5-nitramino tetrazolium;

(2) add 5-nitramino tetrazolium and distilled water in reaction flask, the mass ratio of 5-nitramino tetrazolium and distilled water is 1.3:10, stirs, and adds pressed powder Ca (OH) ₂Be warming up to 80 ± 5 ℃, 5-nitramino tetrazolium: Ca (OH) ₂Molar mass than for 1:1, reacted 1-2 hour, separate out white crystals, be cooled to room temperature, filter out solid product, use absolute ethanol washing, 60 ± 5 ℃ of oven dry, obtain CaNAT.

The invention has the beneficial effects as follows: not containing heavy metal and the perchlorates such as lead, barium in the molecule of CaNAT, do not produce toxic and harmful in the building-up process, is the Novel detonating medicine that meets environmental requirement.Its heat decomposition temperature is higher than any priming explosive of active service, shows that CaNAT has extraordinary thermostability.

Description of drawings

Fig. 1 is the infrared spectrogram of 5-NAT;

Fig. 2 is 5-NAT ¹H NMR spectrogram;

Fig. 3 is ¹³C NMR spectrogram;

Fig. 4 adopts the DSC204F1 tester to the analytical results figure of 5-NAT sample;

Fig. 5 adopts the infrared spectrum analyser of Magna-760 model of U.S. Nicolet company to the analytical results figure of CaNAT sample;

Fig. 6 adopts VEGA TS5136XM type scanning electronic microscope and INCA300 type energy dispersive spectrometry, to the analytical results figure of CaNAT sample;

Fig. 7 is CaNAT ¹H NMR spectrogram;

Fig. 8 adopts the DSC204F1 tester to the analytical results figure of CaNAT sample.

Embodiment

The invention provides a kind of Novel detonating medicine---the preparation method of 5-nitramino tetrazolium calcium (II), preparation process was divided into for two steps:

(1) preparation 5-nitramino tetrazolium:

(2) preparation 5-nitramino tetrazolium calcium:

The technical solution adopted for the present invention to solve the technical problems is:

(1) adding mass concentration in reaction flask is 98% nitrosonitric acid, and the ice bath cooling drips mass concentration and be 98% the vitriol oil, HNO ₃: H ₂SO ₄Mass ratio be 1:1.Under agitation add 5-amino tetrazole powder.Be warming up to 50-70 ℃ of reaction 4-6 hour, be cooled to room temperature and add anhydrous Na ₂CO ₃Neutral to the pH value.Use dehydrated alcohol extraction, rotary evaporation filtrate adds ethyl acetate and produces white precipitate, filters out solid product, 60 ± 5 ℃ of lower oven dry, obtains 5-nitramino tetrazolium.

(2) in reaction flask, add 5-nitramino tetrazolium and distilled water, stir, add pressed powder Ca (OH) ₂Be warming up to 80 ± 5 ℃, 5-nitramino tetrazolium: Ca (OH) ₂Molar mass than for 1:1, reacted 1-2 hour, separate out white crystals, be cooled to room temperature, filter out solid product, use absolute ethanol washing, 60 ± 5 ℃ of oven dry, obtain CaNAT.

The present invention is further described below in conjunction with drawings and Examples, and technical scheme of the present invention includes but are not limited to following embodiment.

1, the preparation of 5-nitramino tetrazolium

Add the 10g nitrosonitric acid in the there-necked flask, the ice bath cooling drips the 10g vitriol oil (98%), under agitation adds 4.3g(0.05mol) 5-AT.Be cooled to room temperature behind the reaction 6h in 60 ℃ of water-baths, add anhydrous sodium carbonate (at every turn adding 1-2g) to neutral in batches.With the extraction of 100mL dehydrated alcohol, rotary evaporation filtrate, add the 20mL ethyl acetate and produce precipitation, to filter, oven dry obtains product 5-NAT3.5g.

2, the preparation of 5-nitramino tetrazolium calcium

Add 20ml distilled water in the there-necked flask, add 2.6g(0.2mol) 5-NAT, stir and make it dissolving, add 1.48g(0.2mol) Ca (OH) ₂Powder, oil bath are warming up to 80 ℃ of reactions 2 hours, filter, and recrystallization obtains products C aNAT1.8g.

The infrared spectrogram of 5-NAT is seen Fig. 1, wherein 3538cm ^-1, 3463cm ^-1Be the stretching vibration of N-H, 1597cm ^-1Be the antisymmetric stretching vibration of NO2,1321cm ^-1Be the symmetrical stretching vibration of NO2,757cm ^-1Be the outer formation vibration of the face of tetrazole ring.Show and contain nitro and tetrazolium functional group in the synthetic compound.

5-NAT's ¹Be presented in the H NMR spectrogram 11.896 places have one unimodal, this shows that sample only has a kind of H of environment, sees Fig. 2. ¹³Show 1 peak δ C153.107 in the C NMR collection of illustrative plates, this shows that sample only has a kind of carbon, sees Fig. 3.

Adopt the DSC204F1 tester that the 5-NAT sample is analyzed, the results are shown in Figure 4.The decomposition temperature of 5-NAT is 125 ℃.

Adopt the infrared spectrum analyser of the Magna-760 model of U.S. Nicolet company that the CaNAT sample is analyzed, the results are shown in Figure 5.As can be seen from Figure 5: wherein 1503,1475cm ^-1Be NO ₂Antisymmetric stretching vibration, 1408,1297cm ^-1Be NO ₂Symmetrical stretching vibration, 868cm ^-1Be the stretching vibration of C-N key, 604cm ^-1The outer formation vibration of the face of tetrazole ring.

Adopt VEGA TS5136XM type scanning electronic microscope and INCA300 type energy dispersive spectrometry, the CaNAT sample is carried out energy spectrum analysis, the results are shown in Figure 6.The EDAX results of CaNAT shows: contain C, N, O, Ca element in the synthetic medicament, conform to the molecular formula of target product.

CaNAT's ¹Be presented in the H NMR spectrogram 3.33 places have one unimodal, this is the peak of hydrogen atom in the crystal water, sees Fig. 7.

Adopt Vario EL III type elemental analyser, C, N, H element in the CaNAT sample are analyzed, test-results sees the following form.By data in the table as can be known, the trial value of 3 kinds of elements is all coincide better with theoretical value in the CaNAT sample.

The results of elemental analyses of CaNAT

Adopt the DSC204F1 tester that the CaNAT sample is analyzed, the results are shown in Figure 8.As can be seen from Figure 8: CaNAT has an obvious endotherm(ic)peak at 85 ℃, and this is a process of sloughing crystal water; Violent decomposition reaction then occurs near 402 ℃, and peak shape is sharp-pointed, has the notable feature of priming explosive.The decomposition temperature of CaNAT and other several priming explosives such as following table, the heat decomposition temperature of CaNAT is all higher than CuNT, MNT, BNCP, LA, shows that CaNAT has extraordinary thermostability.

The heat decomposition temperature of CaNAT and related agents thereof (10 ℃/min)

Claims (1)

1. the unleaded preparation method without barium priming explosive 5-nitramino tetrazolium calcium of heatproof is characterized in that comprising the steps:

(1) adding mass concentration in reaction flask is 98% nitrosonitric acid, and the ice bath cooling drips mass concentration and be 98% the vitriol oil, and the mass ratio of nitrosonitric acid and the vitriol oil is 1:1; Add 5-amino tetrazole powder under agitation condition, the mass ratio of 5-amino tetrazole and nitrosonitric acid is 0.43:1; Be warming up to 50-70 ℃ of reaction 4-6 hour, be cooled to room temperature and add anhydrous Na ₂CO ₃Neutral to the pH value; Use dehydrated alcohol extraction, the mass ratio of dehydrated alcohol and nitrosonitric acid is 8:1, and rotary evaporation filtrate adds ethyl acetate to producing white precipitate, filters out solid product, 60 ± 5 ℃ of lower oven dry, obtains 5-nitramino tetrazolium;

(2) add 5-nitramino tetrazolium and distilled water in reaction flask, the mass ratio of 5-nitramino tetrazolium and distilled water is 1.3:10, stirs, and adds pressed powder Ca (OH) ₂Be warming up to 80 ± 5 ℃, 5-nitramino tetrazolium: Ca (OH) ₂Molar mass than for 1:1, reacted 1-2 hour, separate out white crystals, be cooled to room temperature, filter out solid product, use absolute ethanol washing, 60 ± 5 ℃ of oven dry, obtain CaNAT.

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