DE102005011563A1 - Preparation of dihydrazinium compounds of 5,5'-azotetrazolate type, used in propellant, pyrotechnic formulation, rocket fuel or gas-generating composition, involves reacting alkali metal azotetrazole and hydrazinium salt in aqueous medium - Google Patents

Abstract

Preparation of a compound (I) of the dihydrazinium series of the 5,5'-azotetrazolate type with 0-2 hydrazinate and 0-1 hydrate groups comprises reacting alkali metal 5,5'-azotetrazolate (II) and hydrazinium salt (III) in an aqueous reaction medium.

Description

The This invention relates to the production of high-explosives Nitrogen content.

The salts of the series Dihydrazinium 5,5'-azotetrazolate · x · y Hydrazinat hydrate ([N ₂ H _{5] 2} ⁺ [N ₄ CN = N-CN _{4] 2} ^- · x N ₂ H ₄ · yH ₂ O, where: 0 ≦ x ≦ 2, 0 ≦ y ≦ 1) represent nitrogen-rich energetic compounds that can be used in combination with various oxidizing agents for the production of blowing agents with a substantially residue-free burnup.

Out a technical paper (A. Hammerl, T. M. Klapötke, H. Nöth, M. Warchhold, Inorg. Chem. 2001, 40, 3570-3575) is a process for the preparation of compounds of the foregoing Series dihydrazinium 5,5'-azotetrazolate · x-hydrazinate · y-hydrate (0 ≤ x ≤ 2, 0 ≤ y ≤ 1) become.

The technical reference states that the compounds in question are obtained as the product of the reaction of the two educts barium 5,5'-azotetrazolate and hydrazinium sulfate (page 3571, column 1, paragraph "Synthesis and Properties of Dihydrazinium 5,5 Furthermore, it is stated that the hydrazine sulfate ([N ₂ H ₅ ] ⁺ ₂ [SO ₄ ] ^2- ) is formed from the commercially available [N ₂ H ₆ ] ²⁺ [SO ₄ ] ^2- and one equivalent of N ₂ H ₄ .H ₂ O (hydrazine hydrate) in water.

• • HZT, ebenso Dihydrazinium 5,5'-Azotetrazolat, ebenso [N₂H₅]₂ ⁺[N₄C-N=N-CN₄]₂ ^-, ebenso [N₂H₅]₂ ⁺[N₄C-N=N-CN₄]₂ ^-·xN₂H₄·yH₂O mit x = 0 und y = 0: – HZT erhält man durch eine thermische Behandlung von HZTH.
• • HZTH, ebenso Dihydrazinium 5,5'-Azotetrazolat·Monohydrat, ebenso [N₂H₅]₂ ⁺[N₄C-N=N-CN₄]₂ ^-·1H₂O, ebenso [N₂H₅]₂ ⁺[N₄C-N=N-CN₄]₂ ^-·xN₂H₄ yH₂O mit x = 0 und y = 1: – Erhalt von HZTH aus Barium 5,5'-Azotetrazolat und [N₂H₆]₂ ⁺[SO₄]₂ ^- in Wasser mit einem Equivalent Hydraziniumhydrat. – Im Fachaufsatz wird das HZTH als Dihydrat vorgestellt (x = 0, y = 2); dabei handelt es sich allerdings um einen Fehler. Der richtige Wassergehalt dieser Verbindung entspricht dem eines Monohydrates, was durch Kristallstrukturanalyse, TGA und Elementaranalyse bestätigt werden konnte.
• • DAD, ebenso Dihydrazinium 5,5'-Azotetrazolat·Dihydrazinat, ebenso ([N₂H₅]₂ ⁺[N₄C-N=N-CN₄]₂ ^-·2N₂H₄, ebenso [N₂H₅]₂ ⁺[N₄C-N=N-CN₄]₂ ^-·xN₂H₄·yH₂O mit x = 2 und y = 0: – DAD erhält man aus Barium 5,5'-Azotetrazolat und [N₂H₆]₂ ⁺[SO₄]₂ ^- in wasserfreiem Hydrazin.

The technical paper further sets forth (page 3575, second column) that, depending on the reaction procedure, the following 3 compounds, which are referred to in this application as HZT, HZTH and DAD, are obtained:

• • HZT, as well as dihydrazinium 5,5'-azotetrazolate, also [N ₂ H ₅ ] ₂ ⁺ [N ₄ CN = N-CN ₄ ] ₂ ^- , as well as [N ₂ H ₅ ] ₂ ⁺ [N ₄ CN = N-] CN _{4] 2} ^- · x N ₂ H ₄ · yH ₂ O with x = 0 and y = 0: - HZT is obtained by a thermal treatment of HZTH.
• • HZTH, as well as dihydrazinium 5,5'-azotetrazolate · monohydrate, also [N ₂ H ₅ ] ₂ ⁺ [N ₄ CN = N-CN ₄ ] ₂ ^- · 1H ₂ O, also [N ₂ H ₅ ] ₂ ⁺ [ N ₄ CN = N-CN _{4] 2} ^- · x N ₂ H ₄ yH ₂ O where x = 0 and y = 1: - obtaining HZTH of barium 5,5'-azotetrazolate, and [N ₂ H _{6] 2} ⁺ [ SO ₄ ] ₂ ^- in water with one equivalent of hydrazinium hydrate. - The paper presents the HZTH as a dihydrate (x = 0, y = 2); but this is a mistake. The correct water content of this compound corresponds to that of a monohydrate, which could be confirmed by crystal structure analysis, TGA and elemental analysis.
• • DAD, as well as dihydrazinium 5,5'-azotetrazolate · dihydrazinate, also ([N ₂ H ₅ ] ₂ ⁺ [N ₄ CN = N-CN ₄ ] ₂ ^- · 2N ₂ H ₄ , as well as [N ₂ H ₅ ] ₂ ⁺ [N ₄ CN = N-CN _{4] 2} ^- · x N ₂ H ₄ · yH ₂ O with x = 2 and y = 0: - DAD obtained from barium 5,5'-azotetrazolate, and [N ₂ H _{6] 2} ⁺ [SO ₄ ] ₂ ^- in anhydrous hydrazine.

in the Trap of the DAD must, as stated above, in highly explosive, anhydrous Hydrazine be worked, which for the purpose of product isolation distilled off after difficult separation of the precipitated barium sulfate must become.

at The reactions presented in the paper are one Precipitation reaction, in by reaction of anhydrous barium 5,5'-azotetrazolate with a hydrazinium sulfate by precipitation of the sparingly soluble Barium sulfate, the dihydrazinium 5,5'-azotetrazolate is obtained in solution. The representation of barium 5,5'-azotetrazolate takes place in an upstream reaction, which is not described in detail in the technical paper is. The anhydrous barium 5,5'-azotetrazolate Reacts extremely sensitive on friction, impact and temperature and is therefore extremely explosive.

The known, very complicated procedure is based on the implementation of corresponding barium 5,5'-azotetrazolate. Barium is an alkaline earth metal which belongs to the Counting heavy metals is. Barium is in the form of its soluble Salts highly toxic and therefore to avoid in large-scale syntheses. In addition, barium is very expensive compared to sodium. at the precipitation reaction, starting from the barium salt, barium sulfate is formed as a by-product, which is a problem in terms of disposal.

The invention has for its object to provide a further process for the preparation of nitrogen-rich explosives, which works efficiently and economically and in which such reactants used which enable a large-scale, safe synthesis.

These Task is achieved by the features of claim 1 solved.

The synthesis of a compound of number [N ₂ H _{5] 2} ⁺ [N ₄ CN = N-CN _{4] 2} ^- · x N ₂ H ₄ · yH ₂ O (0 ≤ x ≤ 2, 0 ≤ y ≤ 1) is performed by Metathesis reaction of an alkali metal 5,5'-azotetrazolate (preferably the disodium 5,5'-azotetrazolate pentahydrate) and a hydrazinium salt (preferably NO ₃ ^- or Cl ^- ). In comparison to the precipitation reaction described in the technical essay, the new process is a fractional crystallization. Both starting materials are also easy to handle on an industrial scale.

One greater Advantage lies in the efficient design of the method.

In In a first step, an alkali metal 5,5'-azotetrazolate · x-hydrate (preferably the Disodium 5,5'-azotetrazolate x-hydrate (x ≤ 5)) obtained from an upstream stage (for example, according to a subclaim).

In in a second step, the resulting alkali metal is 5,5'-azotetrazolate · x hydrate (Preferably, the disodium 5,5'-azotetrazolate x-hydrate (x ≤ 5)) in a corresponding solvent mixture reacted, the corresponding product from the reaction solution at cooling down crystallized. The product can be purified by simple filtration of Be separated reaction mixture. It is available in high yields and obtained a high degree of purity. The by-products are depending on the hydrazine salt used, it is sodium chloride or sodium nitrate, which poses no problems in terms of disposal represent.

The Two-stage procedure is possible because as one of the two Starting materials an alkali metal 5,5'-azotetrazolate is used. The advantage of the alkali metal 5,5'-azotetrazolate salts across from The alkaline earth metal salts is their better solubility in aqueous or hyrdazine-aqueous Solutions. In contrast, the hydrazinium azotetrazolates also a worse solubility what allows fractional crystallization. The acquaintance leads one same reaction of hydrazinium salts with barium 5,5'-azotetrazolate in aqueous or hyrdazine-aqueous solutions to a mixed crystallization of corresponding barium and hydrazinium salts, and therefore does not provide phase-pure products.

A complicated separation of by-products, such as the BaSO ₄ in the known method is avoided. In addition, a further advantage lies in the very high yield and the possibility for economical, industrial production of hydrazine-free compounds, eg of dihydrazinium 5,5'-azotetrazolate · monohydrate (HZTH, x = 0, y = 1) and dihydrazinium 5,5 ' Azotetrazolate (HZT, x = 0, y = 0). Because with regard to the toxicological classification, the salts with varying hydrazine content pose a safety problem, which is due to the health hazards of hydrazine solutions in the synthesis step. Therefore, the aforementioned hydrazine-free compounds HZT and HZTH are of particular technical interest.

A load of possibly delivered hydrazine from DAD and other hydrazine-containing salts of the series [N ₂ H ₅ ] ₂ ⁺ [N ₄ CN = N-CN ₄ ] ₂ ^- · xN ₂ H ₄ · yH ₂ O (0 ≤ x ≤ 2, 0 ≤ y ≤ 1) is not given since stability and compressive stress tests confirm that even under extreme pressures and temperatures near the decomposition point, hydrazine release does not occur.

The Reaction of the two starting materials alkali metal 5,5'-azotetrazolate · x-hydrate (x ≤ 5) and hydrazine salt is in an aqueous Reaction medium carried out. This increases security in a large-scale process.

According to one Embodiment of the invention is the starting material alkali metal 5,5'-azotetrazolate · x hydrate (x ≤ 5) Disodium 5,5'-azotetrazolate x-hydrate (x ≤ 5). Preferably, the disodium 5,5'-azotetrazolate · x-hydrate (x ≤ 5) is the compound Disodium 5,5'-Azotetrazolate · Pentahydrate used.

According to one In a further embodiment of the invention, the disodium 5,5'-azotetrazolate · x-hydrate (x ≦ 5) from a obtained upstream step, wherein the 5-amino-1H-tetrazole x-hydrate (x ≤ 1) with sodium hydroxide and Potassium permanganate is implemented.

According to one In another embodiment of the invention, the aqueous reaction medium has no Hydrazine on. This is for the production of HZTH.

According to one Another embodiment of the invention comprises the reaction medium a hydrazine / water mixture. This reaction medium is certainly too handle (hydrazine content ≤ 64 Vol%) and can be used in closed equipment, what kind of the corresponding operator does not pose a health burden.

According to one Another embodiment of the invention can by adjusting the Hydrazine content advantageously the water content of the products can be adjusted (see the following Table 1). Leave it Products containing up to 7% vary.

According to a further embodiment, dehydrating salts can be added to the reaction medium during the reaction. In question, the salts such. B. NaCl or NaNO ₃ . The hydration of the corresponding cation (eg [Na (H ₂ O) ₆ ] ⁺ ) allows the use of dilute hydrazine / water solutions. In addition, this forces the crystallization of the less soluble salt, here the corresponding hydrazinium salts, since the system is supersaturated with another species (displacement principle).

According to one Another embodiment of the invention, the by-products, such as also the water and the hydrazine, removed by sublimation in vacuo, to achieve the required purities.

The Invention will now be described with reference to several, in the drawings illustrated embodiments explained in more detail. there demonstrate:

1 successive reaction equations which show how, starting from the 5-amino-1H-tetrazole x-hydrate (x ≦ 1), compounds of the series dihydrazinium 5,5'-azotetrazolate · x-hydrazinate · y-hydrate (0 ≤ x ≤ 2, 0 ≤ y ≤ 1);

2 a reaction equation which sets out how to proceed from the series dihydrazinium 5,5'-azotetrazolate · x-hydrazinate · y-hydrate (0 ≦ x ≦ 2, 0 ≦ y ≦ 1) to the compound HZT;

3 is a graph showing the nitrogen content of the compounds as a function of hydrazine to water ratio in the reaction medium.

The 1 shows a process for preparing a compound of the series dihydrazinium 5,5'-azotetrazolate · x-hydrazinate · y-hydrate (0 ≦ x ≦ 2, 0 ≦ y ≦ 1), which is obtained as the product of the reaction of the two reactants alkali metal 5, 5'-azotetrazolate (for example disodium 5,5'-azotetrazolate x-hydrate (x≤5)) and hydrazinium salt.

The The above series has various borderline cases because, as stated previously in the formula, the variable x values from 0 to 2 and the variable y values from 0 to 1 may have.

If x takes the value of 2 and y the value of 0, is the connection (I) before. The compound (I) has the chemical name dihydrazinium 5,5'-azotetrazolate Dihydrazinate (DAD) on.

The Compound (II) concerns the limiting case where x is 0 and y takes the value 1. The second compound represents dihydrazinium 5,5'-azotetrazolate Monohydrate (HZTH).

at of compound (III) assumes both x and y the value of 0. The third compound is designated dihydrazinium 5,5'-azotetrazolate (HZT).

As reaction medium water (HZTH) or a hydrazine / water may mixture (salts of the series [N ₂ H _{5] 2} + [N ₄ CN = N-CN _{4] 2} ^- · x N ₂ H ₄ · yH ₂ O (x ≤ 2, y ≤ 1)). This reaction medium is safe to handle (hydrazine content ≤ 64 vol .-%) and can be used in closed equipment, which represents no health burden for the corresponding operator. Depending on the requirement, the content of hydrazine in the desired product can be adjusted. 3 shows the crystallization behavior of the various phases as a function of the ratio of hydrazine to water in the reaction medium. If the reactions are carried out in water as the sole reaction medium, the product HZTH (II) (N: 79.0%) is obtained, and from anhydrous hydrazine DAD (I) (N: 85.7%) is obtained. Reactions in anhydrous hydrazine are omitted because of concentrated, supersaturated hydrazine hydrate solutions also DAD (Reaction Example 5).

Depending on the concentration of the educts used for the reaction medium, for example of the hydrazine hydrate (N ₂ H ₄ : 64.0%), the hydrazine / water content in the products of the general composition [N ₂ H ₅ ] ₂ ⁺ [N ₄ CN = N-CN ₄ ] ₂ ^- xN ₂ H ₄ .yH ₂ O (0 ≤ x ≤ 2, 0 ≤ y ≤ 1).

Is working in water as solvent, so receives in the reaction of a corresponding alkali metal azotetrazolate (preferably the sodium salt) and a corresponding hydrazinium salt (preferably the chloride) at temperatures between 80 and 90 ° C, the HZTH (Synthesis Example 1).

Is working one in a supersaturated one solution a corresponding alkali metal azotetrazolate (preferably the sodium salt) and a corresponding hydrazinium salt (preferably the chloride) at temperatures between 50 and 90 ° C in hydrazine hydrate (hydrazine / water mixture?), thus, DAD is obtained (Synthesis Example 5).

The Table 1 below gives synthesis examples with the corresponding Elementary analysis of the products obtained here again.

Tabelle 1

Table 1

hydrazinium is commercially available and faces Hydrazinium nitrate, which is highly hygroscopic, a better Handling on.

Dehydrating salts (eg NaCl, NaNO ₃ ) can be added to the reaction medium in order to carry out the reaction also in dilute water / hydrazine solutions. However, one then observes a slightly lower yield.

The crystallization temperature of the products depends on the concentration of the hydrazine content and is at 5 ° C in pure water and decreases with increasing hydrazine content to -20 ° C. The products thus obtained crystallize in the form of fine yellow crystals. In any case, the products are obtained in very high yields (depending on the reaction medium between 70 and 90%) and purities of more than 98%. The products are separated by simple suction filtration from the reaction medium and freed with alcohol (preferably EtOH) of adherent reaction medium. For further drying, treatment with ethers or other aprotic solvents is possible (preferably diethyl ether). The byproduct is the corresponding alkali metal salt (preferably NaCl or NaNO ₃ ), which remains in the reaction medium. Contamination of the products with this alkali metal salt is low (<1%), it is more likely to be contaminated by the corresponding hydrazine salts (N ₂ H ₅ NO ₃ or N ₂ H ₅ Cl), with sufficient purity for most applications.

The educt of alkali metal azotetrazolate is a disodium azotetrazolate · x-hydrate (x ≤ 5) obtained from an upstream stage, in which 5-amino-1H-tetrazole · hydrate is reacted with caustic soda and potassium permanganate. The disodium azotetrazolate · x hydrate (x ≦ 5) used is preferably the compound disodium 5,5'-azotetrazolate pentane hydrate. 5-amino-1H-tetrazole monohydrate is commercially available. Based on the 5-amino-1H-tetrazole monohydrate, an overall yield of disodium 5,5'-azotetrazolate pentahydrate of up to 75% is obtained. The 1 shows reaction equations demonstrate how, starting from 5-amino-1H-tetrazole monohydrate to give the compounds of the type [N ₂ H _{5] 2} ⁺ [N ₄ CN = N-CN _{4] 2} ^- · x N ₂ H ₄ · yH ₂ O (0 ≤ x ≤ 2, 0 ≤ y ≤ 1).

As well may differ from the illustrated embodiment, the disodium azotetrazolate x-hydrate (x ≤ 5) in any form of its hydrates can be used (x ≤ 5).

The by-products, as well as the water and the hydrazine, are removed by sublimation under reduced pressure (preferably 105 ° C. at a pressure of about 5 × 10 ^-3 bar; N ₂ H ₅ NO ₃ , mp 70.7 ° C., N ₂ H ₅ Cl, mp 89 ° C). This gives the solvent-free HZT (III), as in 2 is illustrated (Synthesis Example 6).

Tabelle 2

Table 2

In Table 2 above are the elemental analyzes of all dried ones Products summarized following the synthesis examples given above were obtained.

following the production of various compounds is explained:

Concerning example 1 HZTH (II) (N: 85.2%):

To a hot (80-90 ° C) solution of di (sodium) 5,5'-azotetrazolate (5.80 g, 20 mmol) in 35 mL H ₂ O is added a hot (60-70 ° C) solution of hydrazinium monochloride (2.740 g, 40 mmol) in 5 ml of water. After 5 minutes, the product begins to crystallize out of the solution. To complete the crystallization, the reaction is allowed to stand for about ₂ hours at 5 ° C, the product is separated from the mother liquor and washed with EtOH and Et ₂ O (4.871 g, 19.6 mmol, 98% yield). The product thus obtained has a high purity (> 98%) but can be further purified (> 99%) by recrystallization from water (4.528, 18.2 mmol, 91% yield).

Example 2 concerning [N ₂ H ₅ ] ₂ ⁺ [N ₄ CN = N-CN ₄ ] ₂ ^- * N ₂ H ₄ • H ₂ O (N: 80.0%):

Disodium 5,5'-azotetrazole · 5H ₂ O (5.803, 20 mmol) is added to a solution of 25 mL of hydrazine hydrate (hydrazine content 64%) and 7.5 mL of water and heated to 50 ° C to 70 ° C. To this solution are added all at once hydrazinium chloride (2.748, 40 mmol) and the resulting mixture is stirred at about 75 ° C until a clear, red-orange solution is formed. The crystallization of the product takes place in the form of fine yellow needles at -18 ° C usually within 2h. The crystals are separated by suction filtration of the mother liquor and freed by EtOH of adhering solvent residues. Washing with Et ₂ O and drying yields [N ₂ H ₅ ] ₂ ⁺ [N ₄ CN = N-CN ₄ ] ₂ ^- . N ₂ H ₄ .H ₂ O in 98% purity (3.47 g, 70% yield ).

Example 3 concerning [N ₂ H ₅ ] ₂ ⁺ [N ₄ CN = N-CN ₄ ] ₂ ^- * 0.5N ₂ H ₄ • 0.5H ₂ O (N: 82.4%):

Disodium 5,5'-Azotetrazole · 5H ₂ O (4.353, 15 mmol) is added to a solution of 20 mL of hydrazine hydrate (hydrazine content 64%) and 2.5 mL of water and heated to 50 ° C to 70 ° C. To this solution is added all at once hydrazinium chloride (2.0558, 30 mmol) and the resulting mixture is stirred until a clear, red-orange solution is formed. The crystallization of the product occurs in the form of fine yellow needles at -18 ° C usually within 2 hours. The crystals are separated by suction filtration from the mother liquor (3.32 g, 13.5 mmol) and recrystallized from hydrazinium hydrate. By suction filtration and washing with EtOH and Et ₂ O gives [N ₂ H ₅ ] ₂ ⁺ [N ₄ CN = N-CN ₄ ] ₂ ^- · 0.5N ₂ H ₄ · 0.5H ₂ O in 99% purity ( 2.12 g, 55% yield). From the mother liquors can continue to win product fractions, however, vary in content of hydrazine / water.

Example 4 concerning [N ₂ H ₅ ] ₂ ⁺ [N ₄ CN = N-CN ₄ ] ₂ ^- * 1.5 N ₂ H ₄ · 0.5H ₂ O (N: 82.9%):

Disodium 5,5'-azotetrazole · 5H ₂ O (4.353, 15 mmol) is added to a solution of 25 mL of hydrazine hydrate (hydrazine content 64%) and 1.5 mL of water and heated to 50 ° C to 70 ° C. To this solution are added all at once hydrazinium chloride (2.055 g, 30 mmol) and the resulting mixture is stirred at 75 ° C until a clear, red-orange solution is formed. The crystallization of the product takes place in the form of fine yellow needles at -18 ° C usually within 2h. The crystals are separated from the mother liquor by suction filtration (3.32 g, 90% yield).

Concerning example 5 DAD (I) (N: 85.7%):

To 15 mL of hydrazine hydrate (hydrazine content 64%) is added disodium 5,5'-azotetrazole · 5H ₂ O (5.803, 20 mmol) and heated to 50 ° C to 70 ° C. To this solution are added all at once hydrazinium chloride (2.74 g, 40 mmol) and the resulting mixture is stirred at 75 ° C until a clear, red-orange solution is formed. The crystallization of the product takes place in the form of fine yellow needles at - 18 ° C within 2h. The crystals are separated by suction filtration of the mother liquor and freed by EtOH of adhering solvent residues. Washing with Et ₂ O and drying gives [N ₂ H ₅ ] ₂ ⁺ [N ₄ CN = N-CN ₄ ] ₂ ^- * 2H ₂ H ₄ in 99% purity (4.21 g, 85% yield).

Concerning example 6 HZT (III):

HZT (III) is quantitatively prepared by baking in vacuo at temperatures between 80 and 110 ° C of the salts prepared by the above method of the type [N ₂ H ₅ ] ₂ ⁺ [N ₄ CN = N-CN ₄ ] ₂ ^- xN ₂ H ₄ * yH ₂ O (0 ≦ x ≦ 2.0 ≦ y ≦ 1). HZT (III) can be triturated and pressed with oxidizers (eg ADN).

Concerning example 7 DAD (I):

DAD (I) is obtained in 75% yield by recrystallization of HZT (III) hydrazine hydrate (> 64%) receive. A mixture of 10 g HZT and 15 g hydrazine hydrate is added warmed up for so long (70-90 ° C) until one clear, yellow-orange solution originated. On cooling (-5 ° C) crystallized the DAD as fine yellow needles.

in the Contrary to the traditional energetic materials (e.g. TNT, RDX or HMX) owe the compounds in question [Nitrogen content varies between 79.0% (III) and 85.7% (I)] of theirs high energy content mainly their high positive enthalpies of formation ((I), 288 kcal / mol; (III), 205 kcal / mol) and not the oxidation of the underlying hydrocarbon backbone. additional uses are given as an additive for pyrotechnic formulations and rocket propellants (hydrazine, MMH, UDMH) and as a gas-generating component in formulations for gas generators. DAD (I), HZTH (II) and HZT (III) show in comparison to most oxidators good resistance.

The oxidizing agents used may be nitrates, perchlorates, dinitramides of ammonium, sodium, potassium, magnesium, calcium or iron, and others, preferably ammonium dinitramide (ADN) or peroxides of zinc, calcium, strontium or magnesium. With respect to propellants, peroxides are used with an oxygen value; how it can be obtained from stable compounds. For zinc peroxide this is about 11 to 14 wt .-%. The corresponding molar ratio is adjusted according to the oxygen requirement of the particular compound (I), (II) or (III) and is in the range from 1: 2 to 5.5. Calcium peroxide can have an active oxygen value of, for example, 18.62% by weight and is advantageously used in the molar ratio HEDM / peroxide of 1: 3. In general, the abovementioned peroxides can be used in a molar ratio of 1: 1 to 20. There may be mixtures of the peroxides with one another or those be used with other oxidizing agents. Other oxidizing agents are, for example, those mentioned above. In the case of DAD (I) and HZTH (II) it may come in combination with various oxidizers for temporary liquefaction due to the hydrazine (I) or water (II) contained in the crystal. Certain mixtures solidify again after a certain time (eg ADN as oxidizer) or can be dried without problems at temperatures of preferably between 60 and 110 ° C. In this case, escapes hydrazine or water and it remains essentially HZT (III) acting as a fuel component. In addition, there seems to be more appropriate for certain applications, the salts of the series [N ₂ H _{5] 2} ⁺ [N ₄ CN = N-CN _{4] 2} ^- · x N ₂ H ₄ · y H ₂ O (0 <x ≤ 2 , 0 <y ≤ 1), since HZT (III) has a slightly increased impact sensitivity.

at Use of acidic oxidizers (rarely reacting with basic) or other acidic (rarely reacting with basic) reacting additives it may lead to reactions with the compounds (I), (II) or (III) come. Here is a coating of the corresponding components with inorganic or organic materials according to known Method expedient.

Due to the high nitrogen content of the compounds (I), (II) and (III) arise in the mixture, with or without oxidizer, in the thermal / chemical conversion mainly N ₂ and H ₂ O, in addition to low CO ₂ (poorly detectable signature). The emissions of energetic substances, in particular those of hazardous gases, must not exceed certain limit values of the most diverse national and international regulations. High nitrogen compounds, such as compound (I), (II) or (III), can contribute significantly to this.

Claims (8)

Process for the preparation of a compound of Series dihydrazinium 5,5'-azotetrazolate · x-hydrazinate · y-hydrate (0 ≦ x ≦ 2, 0 ≦ y ≦ 1), that the compound as the product of the reaction of the two reactants alkali metal 5,5'-azotetrazolate and Hydrazinium salt is obtained and that this reaction in an aqueous reaction medium duch out becomes. Process according to claim 1, wherein the educt is alkali metal 5,5'-azotetrazolate a disodium 5,5'-azotetrazolate x-hydrate (x ≤ 5). The method of claim 2, wherein the disodium 5,5'-azotetrazolate .x hydrate (x ≤ 5) an upstream step, wherein the 5-amino-1H-tetrazole x-hydrate (x ≤ 1) with Sodium hydroxide solution and potassium permanganate is reacted. Method according to one of claims 1 to 3, wherein the im Claim 1 mentioned aqueous Reaction medium has no hydrazine. Method according to one of claims 1 to 3, wherein the im Claim 1 reaction medium called a hydrazine / water mixture includes. Method according to claim 5, wherein during the Reaction of hydrazine content can be adjusted. Method according to claim 5 or 6, wherein during the in claim 1 said reaction dehydrating the reaction medium Salts are added. Method according to one of claims 1 to 7, wherein upon receipt of the compounds from the series dihydrazinium 5,5'-azotetrazolate · x-hydrazinate · y-hydrate (0 ≤ x ≤ 2, 0 ≤ y ≤ 1) the by-products be removed by sublimation in vacuo.