CZ297751B6 - Propellant for gas producers and use thereof - Google Patents

Abstract

The present invention relates to a gas generator propellant comprising: (A) nitroguanidine, optionally nitroguanidine stabilized with 0.1 to 0.5 percent of nitroguanidinium hydrogen sulfate and nitroguanidinium nitrate as fuel; (B) an oxidizing agent selected from the group comprising alkali metal and alkaline earth metal nitrates, chlorates and perchlorates, ammonium nitrate and perchlorate, copper compounds with oxidizing properties and mixtures thereof; (C) a stabilizer selected from the group comprising hydrophobic silica dioxide SiOi2, inorganic and organic acids and mixtures thereof; and optionally (D) a combustion stabilizer or moderator and slag former or trap and mixtures thereof. The above gas generator propellants exhibit an improved shelf life under hot storage conditions at 110 degC.

Description

The propellant for the gas generators comprises (A) nitroguanidine or nitroguanidine stabilized by the addition of 0.1 to 0.5% nitroguanidinium hydrogen sulphate and nitroguanidine nitrate as fuel, (B) an oxidizing agent selected from the group consisting of alkali and earth alkali nitrates, chlorates and perchlorates, ammonium nitrate and perchlorate, oxidizing copper compounds and mixtures thereof, (C) a stabilizer selected from the group consisting of hydrophobic silica SiO ₂ and inorganic and organic acids and mixtures thereof, and optionally (D) a stabilizer or burn moderator and a means for forming or binding slags and mixtures thereof. Propellants for gas generators are characterized by improved long-term stability when stored hot at 110 ° C. This propellant is used for gas generators.

b * σ> CM

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Propellant for gas generators and its use

Technical field

The invention relates to a propellant for gas generators and to its use. The invention therefore relates to solid propellants, i.e. gas generating mixtures, in particular for gas generators for airbags and seat belt tensioners, wherein the propellant for gas generators is to have a very good long-term thermal stability.

BACKGROUND OF THE INVENTION

The airbag consists essentially of a gas generator housing which is filled with a propellant for generating gas, generally in the form of tablets, of a propellant for fueling the propellant, and of a gas bag. Suitable igniters are described, for example, in U.S. Pat. No. 4,931,111. The initially folded gas bag is filled, after the igniter has been detached, with gases generated by the combustion of the gas generating fuels and reaches its full volume in about 10 to 50 ms. Essentially, sparks, molten substances or solids from the gas generator must not be allowed to escape into the gas bag, as this could damage the gas bag or injure the occupants of the car. This is accomplished by binding and filtering the slag produced by the combustion of the fuel in the gas generator.

The existing fuel charges in gas generators for car airbags are sodium azide-based and have been known for a long time. However, the use of toxic sodium azide requires increased production costs for gas generators. In addition, the increasing number of non-burnt gas generators in discarded motor vehicles around the world is becoming a problem in terms of disposal and safety.

In recent years, therefore, attempts have been made to find suitable propellants for gas generators that contain no sodium azide or other toxic substances.

DE 44 35 790 A of the same Applicant discloses propellants for gas generators based on guanidine compounds on suitable supports, which have a substantially more favorable burnout and slag formation. DE 44 35 790 A discloses a propellant for gas generators comprising (A) at least one carbonate, bicarbonate or nitrate of guanidine, aminoguanidine, diaminoguanidine or triaminoguanidine in an amount of 20 to 55% by weight, based on the total amount of components (A) ) and (B), (B) at least one alkali metal nitrate or noble natural metal nitrate or ammonium nitrate as oxidizing agent in an amount of 80 to 45% by weight, based on the total amount of components (A) and (B), and at least one carrier (Cl) in an amount of 5 to 45% by weight, to moderate the combustion and to improve slag formation, based on the total amount of components (A) and (B), selected from the group consisting of Al2O3 alumina, alkali metal silicates or silicates or rare earth metals and / or (C2) at least one oxygen-releasing carrier selected from the group consisting of iron oxide, oxi d cobalt, manganese dioxide or copper oxide. However, this document does not address the problem of the long-term stability of propellant fuels at elevated temperatures. With respect to stability, this document DE 4435790 refers to the so-called Hollandtest, in which the propellant for gas generators is heated to 105 ° C for 72 hours.

The Holland test is a method that was developed in 1927 after determining the chemical durability of fuels. It shows the loss of weight that occurs after 72 hours of heating of propellants on several bases to 105 ° C or of propellants on one base to 110 ° C. The weight loss occurring, if subtracted during the first eight hours, may not exceed 2% (see J. Kohledr and R. Meyer, Explosivtoffe, 9th revised and supplemented 1998, Verlag Wiley-VCH 170).

- 1 GB 297751 B6

DE 19812372 A1, which also belongs to the same applicant, discloses propellants for gas generators comprising (A) at least one fuel selected from the group consisting of guanidinium nitrate, dicyanodiamide, ammonium dicyanodiamide, sodium dicyanodiamide, copper dicyanodiamide, tin dicyanodiamide, dicyanodiamide , guanidinedicyanodiamide, ammoniumguanidinedicarbonate, ammoniumguanidinium nitrate, triaminoguanidine nitrate, nitroguanidine, dicyandiamide, azodicarbonamide, as well as tetrazole, 5-aminotetrazole, 5-nitro-1,2,4-trizol-3-one, alkali salts and mixtures thereof, (B) a metal or a noble natural metal nitrate or ammonium nitrate, ammonium chlorate or ammonium perchlorate, (C) at least one high-melting, substantially chemically inert slag-binding agent selected from the group consisting of Al ₂ O ₃ , titanium dioxide TiO ₂ , and TiO ₂ zirconia ZrO _2, in highly disperse form, or mixtures thereof and optionally (D) at least one slag-forming agent selected from the group consisting of carbonates and oxides of alkali and rare earth metals, silicates, aluminates and aluminum silicates, ferric oxide and silicon nitride, which releases nitrogen and silicon dioxide upon combustion for further reactions and optionally (E) at least one water-soluble binder at room temperature.

The high melting, substantially chemically inert slag binding agent in highly dispersed form, i.e. produced by flame hydrolysis, serves as an inert filter, thereby largely preventing the formation and leakage of dust particles from the gas generator. Part of the slag binding agent in highly dispersed form can serve as a support for the catalytic metals. Thus, this document does not address the long-term stability of propellants for hot gas generators.

In view of the ever-increasing number of different airbag systems in motor vehicles, such as head airbags, passenger airbags and side airbags, and taking into account the ever-increasing technical lifetime of motor vehicles, the automotive industry is increasingly demanding the stability of fuels for gas generators. Experiments have shown that satisfactory stability results cannot be achieved with the existing propellant propellants with nitroguanidine as fuel.

Thus, the problem of long-term stability of propellants for hot gas generators has not been solved in the prior art.

SUMMARY OF THE INVENTION It is an object of the present invention to provide improved propellants for gas generators which meet the increasing requirements of the automotive industry for stability in the hot storage for at least 400 hours at a temperature of 110 ° C while maintaining their operability.

SUMMARY OF THE INVENTION

This task solves propellant for gas generators containing:

(A) nitroguanidine as a fuel stabilized by the addition of 0.1 to 0.5% nitrogaunidine hydrogen sulphate and nitroguanidinium nitrate, (B) an oxidizing agent selected from the group consisting of alkali and earth alkali nitrates, chlorates and perchlorates, ammonium nitrate and perchlorate mixtures, (C) a stabilizer selected from the group consisting of inorganic and organic acids and mixtures thereof, and optionally

(D) a burner stabilizer or moderator, and a means for forming or binding the slag and mixtures thereof.

This propellant for gas generators contains at least 400 hours at 100 ° C for hot storage and thus meets the increasing demand of the automotive industry for the stability of propellants for gas generators in air waste.

Further preferred is a propellant for gas generators comprising:

(A) nitroguanidine as a fuel, (B) an oxidizing agent selected from the group consisting of alkali and earth alkali nitrates, chlorates and perchlorates, ammonium nitrate and perchlorate, oxidizing copper compounds and mixtures thereof, (C) boric acid stabilizer, and optionally ( D) a burner stabilizer or moderator and a means for forming or binding the slag and mixtures thereof.

Surprisingly, propellants for nitroguanidine gas generators as fuel and said oxidizing agents, or mixtures thereof, in conjunction with one or more stabilizers of this kind can be surprisingly achieved by storage at 110 ° C for 400 hours, preferably 1000 hours, and in particular 3000 hours of weight loss of less than 1%, preferably less than 0.5% and in particular less than 0.2%, while maintaining the functionality of the propellant for the gas generators. The stability values achieved apply equally in both open and in practice closed systems.

The fuel is nitroguanidine. Nitroguanidine is practically non-toxic, non-hygroscopic, poorly water soluble, heat stable, low temperature, and low impact and friction sensitive. The combustion yield of the gases is high, with the flue gas being largely nitrogen.

Nitroguanidine containing 0.1 to 0.5% nitroguanidine hydrogen sulfate and nitroguanidine nitrate is particularly suitable according to the invention. Such acid stabilized nitroguanidine is hereinafter referred to as stabilized nitroguanidine. The pH of the aqueous extract, i.e. 5 g of nitroguanidine in 200 ml of water at 20 ° C, of this stabilized nitroguanidine is in the range of 3.5 to 4.4. Nitroguanidine thus stabilized is commercially available, for example, from NIGU CHEMIE GmbH, Waldkraiburg, Germany.

The present nitroguanidine has a pH in the range of 4.5 to 7.0 at a concentration of 5 g nitroguanidine in 200 ml of water at 20 ° C.

As the oxidizing agent, i.e. component (B), alkali and earth alkali metal nitrates such as lithium nitrate, sodium nitrate, potassium nitrate, magnesium nitrate, calcium nitrate, strontium nitrate or barium nitrate can be used. Similarly, ammonium nitrate and chlorates and perchlorates of alkali or earth alkali metals such as lithium chlorate, sodium chlorate, potassium chlorate, magnesium chlorate, calcium chlorate, strontium or barium chlorate, and lithium perchlorate, sodium perchlorate, potassium perchlorate, magnesium perchlorate , calcium perchlorate, strontium perchlorate or ammonium perchlorate and mixtures thereof. In addition, oxidizing copper compounds such as Cu (NO ₃ ) ₃ Cu (OH) ₂ and Cu ₂ (OH) ₃ NO ₃ , CuCO ₃ and CuO and mixtures thereof may also be used. Potassium nitrate, potassium perchlorate, strontium nitrate, ammonium nitrate, ammonium peerchlorate and Cu (NO ₃ ) ₂ Cu (OH) ₂ , (divalent copper trihydroxynitrate) are preferably used. Preference is also given to mixtures of alkaline and rare earth metal nitrates with ammonium perchlorate, in particular mixtures consisting of potassium nitrate or sodium nitrate with ammonium perchlorate.

-3 CZ 297751 B6

Inorganic and organic acids can be used as stabilizers, i.e. component (C). A particularly preferred inorganic acid is boric acid. Suitable organic acids are citric acid, tartaric acid, cyanuric acid, terephthalic acid and fumaric acid.

Another suitable stabilizer is hydrophobic silica SiO ₂ . marketed, for example, by Degussa AG, the hydrophobizing agent is hexamethyldisilazane when stabilized nitroguanidine is used as fuel. Silica SiO ₂ is a material that does not soak in water, ie it floats on the surface of the water - see infra, Schriftenreihe Pigmente, No. 11, p. 55 et seq. The silica SiO ₂ is preferably present in combination with another stabilizer.

The gaseous products resulting from the combustion of the propellants for the gas generators according to the invention consist essentially of carbon dioxide, nitrogen and water vapor. The concentrations of any toxic gaseous combustion products such as carbon monoxide CO, nitrogen oxide NO _X and ammonia (NH ₃ ) are below the required limit values.

Nitroguanidine, component (A), is present in the propellant for the gas generators according to the invention in an amount of 33 to 60% by weight, preferably 40 to 60% by weight, and in particular 45 to 55% by weight, oxidizing agent, component (B) ), in the presence of from 35 to 55% by weight, preferably from 38 to 52% by weight. and in particular 40 to 48% by weight, the stabilizer component (C) is present in an amount of up to 5% by weight, preferably up to 3% by weight. and in particular up to 1.6% by weight, and component (D) is present in an amount of up to 7% by weight, preferably up to 5% by weight. % and in particular 0.4 to 5 wt.

It is preferred that as component (C) in addition to hydrophobic silica SiO ₂ is present also inorganic or organic acid as stabilizer.

The propellant for the gas generators according to the invention optionally also comprises a stabilizer or a burner moderator, i.e. component (D), which can also act as a means for forming or binding the slag. This can be alumina Al ₂ O ₃ , in particular highly dispersed alumina Al ₂ O ₃ with a specific surface area according to DIN 66131 in the range of 100 ± 15 m ² / g, for example from the German company Dugessa AG. It may also be Fe ₂ O ₃ , SiO ₂ , iron (III) acetylacetonate and mixtures thereof, and mixtures of highly dispersed Al ₂ O ₃ alumina and highly dispersed silica SiO ₂ , for example a mixture consisting of 16% highly dispersed oxide Al ₂ O ₃ and 84% of the highly dispersed SiO ₂ silica marketed, for example, by the German company Duggessa AG - see schriftenreihe Pigmente, "Grundland von Aerosil ^(R) ", No. 11, 5th edition 1993, p. 38, Dugessa AG.

The advantageous effects of using highly dispersed Al ₂ O ₃ alumina in propellants for gas generators are described in DE 19812372 A1, to which reference is expressly made. The highly dispersed Al ₂ O ₃ alumina with a primary particle size of approximately 13 nm acts as a slag trap, i.e., as an inert filter within the propellant propellant propellant which binds the slag. These pyrogenic oxides are produced by high temperature hydrolysis - flame hydrolysis - gaseous metal chloride - A1C ₃ - under the influence of the water produced by the reaction of the gas, at the temperature characteristic of such reaction - 4 AlCl ₃ + 6 H ₂ + 3 O ₂ -> 2 AI ₂ O ₃ + 12 HCl - visa Schriftenreihe Pigmente, "Hochdisperse Metalloxide nach dem Aerosil" ^(R Verfahren), No. 56, 4th edition 1989, Degussa AG.

The stabilizers or burners moderators, component (D), induce a linear burn-out, i.e., an exponential increase in pressure and temperature during the burn-out is avoided. For example, iron oxide Fe ₂ O ₃ can also serve as an oxygen source under certain burn-out conditions. In addition, these compounds can be used to form slag to prevent the formation of pulverized combustion products.

The component (d) is present in the propellant for the gas generators in an amount of up to 7% by weight, preferably up to 5% by weight. % and in particular in an amount of 0.4 to 5 wt.

-4GB 297751 B6

The highly dispersed alumina Al ₂ O ₃ is present in the propellants for the gas generators according to the invention in an amount of up to 5% by weight, preferably in an amount of between 0.5 to 3% by weight. % and in particular in an amount of 2-3 wt. Due to this small proportion of Al ₂ O ₃ alumina, a high gas yield is ensured.

The propellants for the gas generators according to the invention may further comprise at least one binder as component (E). Examples of suitable binders are cellulose compounds, polymerizates of one or more polymerizable olefinic unsaturated monomers, water-insoluble room temperature metal stearic acid salts, and graphite. Graphite is particularly preferred.

Examples of cellulose compounds are cellulose ethers such as carboxymethylcellulose, methylcellulose ethers, especially methylhydroxyethylcellulose. A well-usable methylhydroxyethylcellulose is a product from Aquelon. Suitable binder-binding polymers are, for example, polyvinylpyrrolidone, polyvinyl acetate, polyvinyl alcohol and polycarbonates.

The binder (E) serves as a means for desensitizing and facilitating the processing of propellant for gas generators in the manufacture of granules or tablets. The binder also serves to reduce the hydrophilicity of propellants for gas generators.

Component (E) is present in an amount of up to 5% by weight, preferably in an amount of up to 3% by weight, in particular up to 1% by weight. % and especially in an amount of 0.2 to 0.5 wt.

A preferred variant of the propellant for gas generators according to the invention comprises as fuel (A) nitroguanidine, in particular nitroguanidine stabilized according to the invention by the addition of 0.1 to 0.5% nitroguanidine hydrogen sulphate and nitroguanidine nitrate, as oxidizing agent (B) Cu (NO ₃ ) ₂ . 3Cu (OH) ₂ . 3Cu (OH) ₂ , KNO ₃ , Sr (NO ₃ ) ₂ , KNO ₃ or a mixture of KNO _{3 and} NFUClCL, at least one stabilizer (C) selected from the group consisting of hydrophobic silica SiO ₂ , cyanuric acid, terephthalic acid, fumaric acid, optionally mixed with hydrophobic silica SiO ₂ , and as component (D) highly dispersed alumina Al ₂ O ₃ , optionally mixed with ferric oxide Fe ₂ O ₃ , and graphite as component (E).

In another embodiment, the propellant for the gas generators (A) comprises nitroguanidine stabilized by the addition of 0.1 to 0.5% nitroguanidine hydrogen sulphate and nitroguanidine nitrate as fuel, (B) Sr (NO ₃ ) ₂ or a mixture of KNO ₃ or and NaNO ₃ and NH 4 ClO 4 as an oxidizing agent, and optionally (D) at least one stabilizer or a burner moderator, and a means for forming or binding the slag.

Another embodiment is that the propellant for the gas generators comprises a component (D) selected from the group consisting of Al ₂ O ₃ , highly dispersed Al ₂ O ₃ , Fe ₂ O ₃ , SiO ₂ , acetylacetonate iron oxide and a mixture of highly dispersed Al ₂ O ₃ alumina and highly dispersed SiO ₂ .

In these cases, component (A) is present in the propellant for the gas generators in an amount of 33 to 60% by weight, preferably 40 to 60% by weight. and in particular 45 to 55% by weight, component (B) is present in an amount of 35 to 55% by weight, preferably 38 to 52% by weight. and in particular 40 to 48% by weight, component (D) is present in an amount of up to 7% by weight, preferably up to 5% by weight. % and in particular 0.4 to 5 wt.

It is also preferred that the propellant for the gas generators in these cases further comprises at least one binder as component (E).

In such cases, the binder is selected from the group consisting of cellulose compounds, polymerizates of one or more polymerizable olefinic unsaturated monomers, water-insoluble, at room temperature, metal stearic acid salt and graphite.

-5GB 297751 B6

The invention also relates to the use of the described propellant for gas generators as a means for generating gases in air waste and as an extinguishing agent or propellant.

Surprisingly, it has been shown that a propellant for gas generators which contains stabilized nitroguanidine nitrate as fuel and Sr (NO3) ₂ , or a mixture of NaNO ₃ or KNO _{3 with} NH ₄ C10 ₄ as an oxidizing agent, even in the presence of stabilizers or burners moderators and agents for the formation or binding of slag, it has good or excellent long-term stability when stored under heat at 110 ° C. A stabilizer additive (component (C)) is not required to stabilize the propellant for the gas generators.

The excellent long-term stability of the gas generator propellants according to the invention can be explained by the acid environment in the gas generator propellants.

Examples

Manufacturing code

Generally, the production of propellants and propellants for gas generators was carried out according to the following procedure:

A) Wet process:

The starting components (A), (B), (C) and optionally (D) were mixed and ground and optionally pre-thickened using a ball mill. Granulated propellant blends for gas generators were made by mixing in a vertical mixer with an additive of about 20 wt. water at a temperature increased to approximately 40 ° C. After briefly venting or pre-drying, the obtained mixed mass was rubbed in a friction machine with a sieve size of 1 mm. The granulate thus obtained was dried for about 2 hours in a drying oven at about 80 ° C.

The finished propellant granulate for gas generators with a grain size of 0 to 1 mm was then compressed into a tablet by means of a rotary disk press. These gas generator pellets or fuel pellets were dried in a drying oven at 80 ° C.

B) Dry process:

The starting components (A), (B), (C) and optionally (D) and (E) were dry blended and then compressed under pressure, for example by means of a gear compactor. The compress was then broken into granules and compressed into tablets using a rotary disk press.

The fuel tablets used in the gas granulators can be prepared by known methods, for example by extrusion by means of the aforementioned rotary disk press or by tabletting machines. The size of the tablets or pellets depends on the burning time required in the application.

The propellant for the gas generators according to the invention consists of non-toxic, easy-to-manufacture and cost-effective components whose processing is problem-free. Mixtures can be well ignited. The mixtures then burn rapidly and achieve a high yield of gas with a low content of carbon monoxide (CO), nitrogen oxides (Νθχ) and ammonia (NH ₃ ), which is below the permissible maximum levels. The compositions of the invention are therefore particularly suitable for use as gas generators in various airbag systems and have very good stability when stored hot at 110 ° C for more than 400 hours. The mixtures are also suitable as extinguishing agents or as propellants.

The invention is further illustrated by the following Examples 1 to 24 (Table II), but are not limited thereto. In Table 1, Examples 1 to 11 are comparative examples.

-6GB 297751 B6

The data in the tables have the following meanings:

aluminum oxide iron oxide aerosil COK 84 aerosil R 812 S

Explanation of fuel structure

T4x2 tablets with a diameter of 4 mm and a height of 2 mm

T3xl, 5 tablets with a diameter of 3 mm and a height of 1.5 mm

T3x0.8 tablets with a diameter of 3 mm and a height of 0.8 mm

T6x2 tablets with a diameter of 6 mm and a height of 2 mm

The granulate produced by the wet process described above.

The percentages are in% by weight.

GuNO ₃ stands for guanidinium nitrate and serves as an auxiliary fuel with less energy.

In the following examples, the abbreviation NIG (Stabilized) means nitroguanidine which is stabilized with nitroguanidinium hydrogen sulfate and nitroguanidine dimenate in a total amount of 0.2%.

Table I x>

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-8EN 297751 B6 continued Table I

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-9EN 297751 B6 continued Table I thermal stability propellant structure mm T4x2 T4x2 T4x2 T4x2 T3xl, 5 T4x2 T4x2 T3xl, 5 T4x2 Shelf life 400 h.% -0.19 -1.47 -3.76 -0.49 -0, 62-1.45 -0.86 -0.84 ro iio

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- 10GB 297751 B6 continued Table I o

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- Table I continued

P MU r-4

CM <£> O r- <T> cr » O <T> 0> 5—1 r-4 what r-4

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P MU rp □ T <M

r-4 00 cn w k £> C what tn kO «5 TO what CN cn WHAT P O CM CN r-4 "and* CM Cn 1 1

P MU rp

3 kO r-4 kO 00 what uo kO C CM xr * » SKK TO O <u • b kŮ cn CN m <U · P O r-4 CM r ~ 4 n * CM Cn 1 1

p mú r-4

3 cn cn kO CM cn "and· r- 3 xr CM SKK «» * » kO flj * » kO MO iH WHAT O P O cn CM r-4 cn xr CM Cn 1 1

I r — I 0 £ XJ O <*> -ro XJ O dP Ό XJ O 0 *> Stí <0 CU in £ <*> Λ O O <#> her about o o <# » • n o o lD <*> j3 O o o «M O • φ • sr r — I r-4 WHAT P O r4 « 3 0 3 O * P 3 »4 —4 m-4 —4 C 3 what iD -rp O 3 3 3 3 Ό '> 1 \WITH CM WHAT r-4 • 3 HIM HIM HIM HIM O r-4 P X rP • <4 O > > > > jC £ L -r-4 HER I and O O O O XJ <U AT <0 T5 T5 Ό Ό <0) P • -r4 P P <0 <U m <u <U J »C tn P r-4 CM HIM tn P r — i rp r-4 r-4 υ O w .3 OF CL <u 3 Λ £ Λ! Λί Ή 3 3 3 P him P tn tn tn « • P > N O Λ! m-4 O and X (d) XI) A4 T5 »4 C r — 1 r-4 5 Jtí <U <u (AT flj P P II • r4 tn Ό Cu 0) P P Λ Λ XI XJ O '> > O <D and P HIM 0 O O O Φ > O Ό > P <p 0) r-4 σ Ό Ό Ό -P P

- 12GB 297751 B6

Table II

O V0 what «» what i m i V 1 1 1 1 1 II I 1 o

lD O In £> (N CX1 »» <N1 i m i Vlili II Η 1 1 o

X3 CM O ·. WHAT «5 i <r> i

dP dP dP dP dP dP dP dP dP dP dP dP dP

XJ ϋ <0

Ή

Λ a

dP dP dP

c 05> Ή 0 C N Ό • H > -H 03 / J3 »» 03 / 0 + J 3 W O D l *> O 0 0 of n M 3 OF OF 0

'03> O

4-> Ή υ * “p

X o m

*

CSl Csí

<n o <n o O <—1 <r of of O O O O »-» 0 O w <-1 of 3 3 3 X 0 ω 0 AT 0 of

<o β -Η <—I <υ ω tartaric acid

SiO ₂ , hydrophob ⁴ cyano acid fumaric acid terephthalic acid ιι

- Table II r-4 tO *>

Ol O

OJ o

O MO XT r * X X rH CM r * cn r-4 Ol rH xT cn CM

boric acid

MO LD

OJ o I mo tn

OJ O I

OJ o

OJ

K o

O Ch he 00 u> *. rH K0 CM MO cn r-4 OJ rH XT what CM

σ \ m what MO cn «H i.e m Ol Γ * σ> r4 OJ rH XT WHAT OJ

σ » <#> dP <* » dP dP 44 • rn • • x; \ Λ • n •O r-4 O JQ YEAH O O O £ dP <*> <*> 03 / 0 CU CN λ «Π XT P 'Φ > 1 <M O 00 '03 +4 44 O r4 P C -r4 O 3 υ ♦ • H & 0 N C C O m N O 44 Φ Ό > 1 '> 4 CN what Φ O Φ r-4 0 rd 44 OF v-i r-4 0 Φ -C 0 < • r4 II Φ r-4 m > N .—. oj Steed ♦ H > N • H r-4 44 'φ P * -r4 M CD 3 Ή 44 m P r-4 CN Ό3 <*> zS Ό O P Ό M-1 υ 0 m OF and oj VJ CM -r4 M Φ • H <0 • r4 C C 3 44 Φ O X P > N O 44 m-4 O O <0 O Cn Φ ►Φ 44 τ » M-J C r-4 M P II * r4 w Ό nu || II O > X 5 O φ Φ > O T5 > 44 Q ω P

- 14GB 297751 B6 continued Table II r «« I

Ol m i i

OJ mj ·

Ol Ol O O X *. O sr O * » 1 O

MS σ> CM O O X X. O O 1 1

cn co i cn i £ i

OJ X ’Τ it as to *, O AND r * · * · O cn 1 1 1 1 CU «. as what it it 'O' X x. what O O it 1 1 dp dp OP dp Op OP OP OP o »P OP OP <*> <# « • X X X G jd it C fc O O O G <u O O O O HIM > O O uo O > it O · * "* HIM Ό * f — 1 it what O C N <0 C O I.E it O P C xH xrM Ή it <u <u it ***** it O C C C C P > it 3 it x HIM HIM HIM HIM 44 <u £ t CJ it O > > > > O what <u cn X and O O O O and O X «XI * »0 T5 •O T> Ό Ό tn CM P <0 <0 íU IU <U i-i • · * - * <*> <*) 0 WHAT at it <—1 «—1 it m > o <* » O O m , —1 3 44 44 44 44 O D O O of sz O at in HIM P 0) WHAT WHAT tn Φ Ό O O OF O O O α 44 > 1 44 Φ it it 3 OF P 3 3 X it 5 .X <0 <u <u <u it it of OF O w O O AT of Φ P P X X X X 3 44 and P him 0 O 0 O X) it II II <u what r ~ 4 Ό T5 Ό Ό rU > P P H and what

- 15 CZ 297751 B6 continued Table II o

I r-H

O

CN

». 10

About CM rM

<0 M? M? in X X X *. kD O 1 1 1 1 o CM O 1 1 1 CM

<* » dP dP c *> dP dP dP dP dP dP dP dP dP MB MB MB O > > MB * - < O 0 > m fn O C P O P MB Cl jC O MB X) 3 P Um > TT 4-> Φ $ M C O C <B Φ 0 '5n what MB P P β <8 έ sm P p β • H • H • H O > Ί 5 Φ O • H Her O N O > M Ad Um P Λ N O P Φ «5 Φ O Φ <H <0 ra <8 <B <B <0 <-4 O Φ C C C β β β Φ <B KM • H «Η Ή • H • H • H r ·· KM • H P r-4 r-l rH r-4 rP rH <0 > 1 3 -r4 O φ Φ 0) Φ Φ Φ O Ό O P Ό Um r-H what W O <0 WHAT WHAT what <N • <H P Φ • rl <B O > 1 > 1 • H > 1 >! > 1 r4 X Φ O X p bd Ad ω Ad Ad Ad O <B O O>

II

II

II theoretical values gas yield mol / kg (V = const.)

- 16GB 297751 B6 continued Table II

r ~ ro ro in O WHAT <X> CN O O «. κ cn X O · » CN r- what O N * - O rH ro CN O 1

ro ro r- O ro CN O O O r-l ro X · » M sr O O O H 1 1 1 1 O CN CN CN O O O X TO. NT •and· O O O TO. E-i 1 1 1 1 ro cn ro 00 O O CN O r-l r4 X with. <^> Ν ' O O O H 1 1 1 1

what O N? * » rM CN r- O tH r— ( * 3 * CN

ro co ro i

ro r4 ro ro CN O O O O X "it. •it with" • X O O O O 1 1 t 1

«A · ro

ro r-1 X ro .O O ro o O co O O cn O «To o r- ro i 1 • 1 1 1 1 • r-> -ΓΊ -r-> X3 XI r * O O O G CN dP dfi dP of G dP dP dP dP <x> ro 1 1 dP dP « • x x x: x C C O O O him dP <0 'In cu O O O O > > > n O O O O O vr4 O O HIM N * r-d ro ro KJ G N O r-l <0 c <u X3 • H CJ ♦ Bye M- | M-1 M-1 P <0 r — t and ro • rl O C C and C Although > Ή '>> VA ro r-1 X MtJ MO m0 HIM O Π3 X) P Λ r — 1 -H 0 > J> > ř> and WHAT <0 -H II X> Ot. O O O O O P > υ <0 and <0 Ό • 0 Ό • 0 what * rl P P <13 <0 <0 <0 <u M • w i — 1 CM HIM to p r — 1 r-l r-4 r-l M > 0 r> X OF {X <0 3 Although Although Although Although D P O 0 4J MU P « it W <0 <U • 0 0 0 of Although M-1 0 C -X AČ <0 1—1 M 0 Ό * r ~ 4 C r-f r-1 5 Although WHAT «3 <13 <0 r-M r-l OF OF 0 -rl it 0 and <U P P X) XI XI xi 3 Although X 3 O Φ and p HIM 0 O O 0 XI M-1 II 0 T3 > P and> co r-l -0 • 0 • 0 Ό <0 • P P and <c

- 17GB 297751 B6 continued Table II r — t ©

«4 · lili

O I I co

AND" K0 kD kD © 04 / in *. · 1 1 1 1 II 1 1 O 1 1 O 1 04 / O

Ό »lili

MS MS M> © O 1 i o i i 1 04 O

© xr uo

M? © · »

O

- o © w x κ

I.E* 1 1 1 1 1 1 1 r-4 1 1 1 1 1 04 / r-4 1 <#> 40 «*> <*> > O 40 dP 0 dP dP <*> <*> <*> <*> <#> > dP <#> > 40 r-4 <*> <*> <* » dP CM 0 *** O > <0 <· » »··» ,C M O + -> 40 CM Um NO O 3 M > vU M C 0 C « Φ O 1> 1 as r «t 4J <s Ψ4 <0 G M M 4-> iU -r4 -r4 O 3 and> O Ή X O O > M Λί 4J O N O V i I.E Φ O CM CM <0 <0 <0 <0 <0 <0 r-4 C C X C and and and Φ rH m <* » O -H • r4 Ή * r4 • H • H r-t * 4 • H O O Λ r-l nr r-4 r-4 r-4 r-4 r-4 rM tn of of O Q O O <P CM ® Φ <υ 01 O Ί3 O O * - * O O in «-4 »» « O W tn tn tn IN CM • H M & M 3 5 3 X O >> -r4 > 4 > 1 > > 4 X O & tn O AT O of X Λ! Λί ω Λί Whatever •C O

ferric oxide acetylacetonate ca

- 18GB 297751 B6 continued Table II o r-

O r ~ l σι r * · rd OJ i — 4 rH r-l X * » US CM r- σι rH US O O Ol r ~ H «5Γ ro (XI E-I 1 1

O iD O

Ol m CM CB (0 OJ rM O rH *. "to rH X *> *> US CM r- WHAT r-4 US O O O O) r ~ 4 m (XI 1 1 1 1 t

US (Ό what rH r ~ m US Ol r-4 rH v-'1 •to *to rH X % "to X. kO Ol Γ- σι r-l US O O O (XI r-M * ζΓ m Ol 1 1 1 1 1

LO Ol -and* r-4 kD r ~ Γ- ko OJ r-4 Ol Ol tk · » r- < X "to *to to US CXI r- σ \ rH US C5 O O OJ rH «Θ’ m CM E- < 1 1 1 1 1

Graphite

II ω

Ο · » US οι σ »44 \ <—1 0 ε US * » OJ <—1 • ΓΊ JQ Ο θ ¥> «K r * «’ ΓΊ Λ Ο Ο *> σ> m -ΓΊ η 0 <Ό Ο γΗ CM X φ CU οι X «Η 00 ο * ► ο 1 <#> SW ο ο C0 OJ ο AND <#> JC ο ο ο 1 <*> X ο ο ο 1 <*> X ο ο ιη > 1 « dt> <* · Ο 'Φ > 9 · r-l rH <η P ο γΗ Φ C G 0 3 ο * Ρ C G Ή Ή -Η μΗ and C ο LO -Η Ο C C C C Ό >> '> CM WHAT Ή JC. «Φ 'φ -Φ -φ O r-l Ρ X Γ ~ ί • Η 0 > > > > r; £ Χ II jQ CX Ο ο 0 0 > υ «5 (X Φ τι • σ τ> Ό -Φ Ρ · <Η Μ - Ρ Φ φ φ φ Φ 44 « Ρ <-Η ÍM -Φ »Μ r-l rH r-J r-l O ο <0 χ: 2 α «5 3 44 44 44 44 -i — 1 C C 3 Ρ -Φ Ρ \ what <0 0) C0 4-1 > Ν Ο 44 Ή ο C 44 Φ > φ 44 Ό Ή C »—1 r-l 3 & φ Φ Φ φ Μ ρ II Η « Ό α Φ Ρ 4Μ 4) Λ XJ XI Ο > X 3 0 φ α, ρ MTJ Ο Ο Ο Ο Φ > ο Ό > Ρ Φ W γ-Η Ό Ό τ> Ό Ρ Ρ

- 19GB 297751 B6 continued Table II

r-i O CD • w TO Lf) cn CN O r-i | i cn CN CN 1 1 O O TO CN r-4 r ~ 1 1 cD 1 CN 1 1 tn 1 » AFTER cn she knows r-l i m 1 CN 1 1 m % » CM r-i i tn 1 1 1 1 m lT> ·. r-4 what Γ- r-i i * ^ r 1 • r i i

rH · » 1 CM 1 lil TO sr 1 CM 1 III cn 1 CM 1 III 0 <>. 0 1 1 N · III 1 1 1 lit

<*>

<*> <* »<#> <*> <#>« # »<*» <*> <* »

<*> 0 *>

c <Ú> «4 0 C N Ό • H r — 1 > Ή rtJ Λ what <TJ 0 4-> • 0 WHAT * »· _ ·· > υ O 0 Ό 0 0 m M M r-4 OF OF AJ II > 1-4 Q.

<*>

O (*> 0 3 of 0

II £ 0

C4 • f f c · c c c c c c

CM CM

* —Fc. r> 0 0 <n of of 0 · - · at S-4 3 3 IN) AT AT

O

r-4 O in 0 O r-4 3 X at AT of X.

II

O

whose

0) CM <n O> · M AC W cyanuric acid fumaric acid

-20EN 297751 B6 continued Table II co o

oo * »ID m <*> c *>

terephthalic acid boric acid y? tn

O o tn i

I H C4 (N <*> <#> <*>)

tn

TO

CO cn <x>

cn m

cn

O

Ol Λ • y P 41) > 1 00 40 -P • P 4J C r4 O 5 • H X O and C N O P Φ Ό > 1 Φ AT Φ •-AND 0 rHI <—T O Φ I CU Φ <—1 <0 44 w > N Ή rH P 0 P m O tn 3 Ή «X tn Ό O P I.E M O 0 CM • H Φ Ή <0 Ή C r-H X Φ O X P 44 < O <0 O cn Φ > Φ P P H 11 0 '> 1 Φ > Q ω P

(V = const.) Carbon dioxide CO3% vol 13,7 19,1 15,0 14,9 14,2 nitrogen N ₂ % vol 46,3 35,4 36,1 36,0 34,3 water vapor H ₂ 0% vol 39,3 35,4 42,3 42,2 45,2 temperature (p = 135 * 10 ⁵ Pa) K 2100 2797 2716 2666 2589

-21 CZ 297751 B6 continued Table II

OJ rH O X X X O H O 1

o Ol i ko

X what in i oo

X what I I

Ch Ol O rH X O *. T X O H O 1

r ~ ·> τ i m i rX

T l - = r

04 / r-4 OJ O O X r-4 O X *> X 00 <CJ * O O 1 1 r-4 1 <D t 1

AND

4-> 'here

C (0

Γv-t I k £>

X co <cr i kO

CO i m i

LD O o I o <0 kD o ·

00 r4 I 1 1 1 uo I 1 1 X. r · O O X X what O »» 1 1 £ -4 1 «*> <*> <*> dP <*> <* » <*> <*> <*> OP <*> • * X « x x: X Ή G x: C C O O O HIM <* » here O O O O > > CM O O in O O Ή O <r-x »r <u '<D r — t r-t what C N □ m + j and <U I.E • rl O -H C Ή Ή M m <—I r — t 0 C C C 0 JX > • H P f \ Ή of HIM HIM HIM HIM O here jQ /IN\ -Q 0 i> > > > Ol <0 here C’l <0 Ol O O O O · - O 4J CM TO CM + J •and I.E i.e I.E I.E W W fU <u <U nj <u M • <n m O M r-4 «—1 «- < «- < M KJ n O O <O HIM 3 JX JX JX JX O D O of of O Q £ · 4-> w m m <n <u I.E E O of O - · - ' O O MF -X JX here M H 3 of 3 3 3 OF Φ 3 here nj here <u H r- $ OF OF O s < CQ AT O AT of Ol AT X> Λ XJ Λ XI 3 Φ 4J Ή3 0 0 O 0 Λ Ή II II 4J <0 r — 1 • 3 i.e I.E I.E (AT fM (X < CQ

-22EN 297751 B6 continued Table II cn tn i <n

AND

AND

UJ i o

CN I

UJ

I o o

CN i

UJ

I o o

CN I

UJ

I o lili

citric acid tartaric acid

II o xr

UJ

I CN m

LO

I CN o

UJ

I CN

I CN σ '

dP <*> dP <#> dP dP dP dP dP dP Whatever M0 r4 > 0 MO 0 ε > MO r-4 O > <0 O XP M O p M0 Λ O 5 P M-4 > XT P MO π and <0 Φ O what M0 +> p v <μ | <0 E P H + J and Ή O 3 O 3 <0 O • H O N C C In m M-t P Λ N O 4-J <0 σ >> 7í <U O <0 «-Η O pH <0 io (0 rp υ <0 X CL r? C and C C Φ r-1 <0 > N —- • H Ή • H • H > N • rl r-1 P M0 P • r- | * “4 i — 1 r-1 <0 > 1 3 • H Whatever « -P CM 0) and> <0 <0 O τ » O 4-> Ό M-1 υ O tn O tn <n <n CM • H P 0) • H <0 -H and C -H >, > 1 X <0 υ X P • P > N 0 ω Whatever Whatever Whatever Whatever O < <0 O σ> <0 HIM Whatever P 4J II II II 0 > <0 > - Q ω • P

-23EN 297751 B6 continued Table II

X rP

2 what O <n cn cn cn ID 3 O rM O WHAT 0 ·. * » O what what what M O O O <—I «Σρ what CN cn F 1 1

X him

3 what cn cn O CM CN CN C O O O sr *. O 0 *. *> I — i * sT Γ- r ~ M O O O cn rH XT ΓΟ CN Cn 1 1 1 1 CM I co

X him

3 m rH CD O r ~ 4 what in 3 0 CM fO <3 * X. cn CU * » «. rH <3 · LP m 0 0 O what cn rH what CN Cn 1 1 1 1 CN 1 CM

x

MU rp cn o

CN γ-4 m tn 3 0 0 CN * » <u 0 *to * what tn what r “4 S-4 0 0 CN cn r-M WHAT »3 » CM cn 0 1 1 1 CN 1 '

x MU

5 «3 · r- cn 0 · T ~ i rH <cr xr C 0 0 0 CN CN %. TO Γ— fU TO H. TO * 0 WHAT tn 00 <-— 1 X 0 0 0 0 1—1 0 r-H m CM tn 1 1 1 1 CN 1 1 cn

-n X • m x> ♦ “(“ Ί x E? <*> dP dP dP dP dP dP O 0 0 OF • X • X X Ή "of*·*. '> dP dP dP 0 CU> A X O 0 O c MU dP 3 0 0 O 0 O > > what O m O 0 In m O CM 0 Ml) «3 · tP rp WHAT KJ C N O rp <U 3 0 I.E Ή O ♦ X 3 Ή Ή mH Ή 14 cu rp O CM m ♦ H 0 3 C C C 44 > -rl what ““ “j X HIM HIM HIM HIM O (0 X X OF tP • H 0 > > > > CL 0 0 II X CL O 0 0 0 '—R 0 X 0 and <U i.e I.E I.E I.E I.E 0 Ή X X 0 *at 0 <U <u IP * ' '-r * —1 CM HIM 0 M <p rp rp rp Μ > u « x OF α <0 5 44 44 44 44 O D O m 3 X HIM 4- » 0 0 0 0 <u TJ O O of O 44 Ή 0 3 44 > 1 44 φ IP μ 3 53 I.E Ή 3 r-1 «—1 3 44 <U here <U ip rp Z OF (JJ Ή <0 I.E CL φ X X X X X 3 44 TO X 3 O Φ CL X HIM 0 0 O 0 X Ή II 0 I.E > X Φ 0 I.E I.E I.E I.E <U > $ 4 CQ X CL <

-24EN 297751 B6 continued Table II o o v v

CM CM o Γ - I

p. *.

v v <N CM d I dP dP dP dP dP lP o

I r7 I kD

I dP dP dP dP dP dP dP o

CM I lili * <*> #> * • OJ>

0 Ό5 C > O O J-t Ό5 CM * T * + J • Ή in >5> O 05 / 4-> OJ CM <n Whose at • 05 0 M <W > IN C O C m Φ O •> I 00 n 05 / Hive m G M P ry C • H 0 >, 3 Φ O • H Xw / WHAT Ή > M áí M P Λ N O CM * CM rH Φ 05 / Ό X «5 OJ m Λ cn O Φ rH O —X W C £ C C G C CM Φ rH r> O Ή • <4 • H • H • H rH > N Ή O O r-1 in and: r — 1 rH rH <—1 «—1 < <Λ of of O CJ O Φ CM Φ φ Φ Φ Ό O ‘R cj O • r r ~ —4 II 0) O W n m WHAT H • H M □ 3 □ X O > 1 • H >, > 1 > 4 X Φ ω O AT cj of S4 cj Aí OT Ai Aí Aí Ad O 0 <

ferric oxide acetylacetonate

-25GB 297751 B6 continued Table II

4J MO

2 r- 00 rd 00 00 CN ko C O O w r4 nj % *. cn cn σ> O r4 P O O r-H rH what «Φ CM cn 1 1

4-J < 0 rH

5 CN CN cn <P 00 C rH r-J «. 00 <0 cn CM 00 00 P O O rH <3 · CM CM rH cn 1 1

P MO dp graphite

II ω

sr l> ro * » * » XT CD 00 rH οο CN rH * 9 · CM

m WHAT r-4 O CN Μ » WHAT CD 00 CM ST ΜΓ CN rH CN

3 in r— r- C O O <0 - * w M O O O tn 1 1 1

P MO

3 uo O C O O CN <0 O *. P O O cn 1 O 1

cn -VC r ~ H o ε r ~ i Λ O dp • m 43 O dP • ΓΊ A 0 dP X « X · "* (0 (X <n dp jŽ O dP XJ O O dP x: O O dP • x: o o > » fM O O O tn O P O rH rO XU «Τ r — 4 r-4 m O □ O · * 4- » C C C m -H C Ή Ή Ή Ή •O >. '> 1 CN what r ~ 1 O C C C C O r ~ H P X r — 4 -P x: M0 M0 M0 MO x: CX Ή II JQ O > > > > *** »» > o <0 <x <o cx O O O O 'CU P • Ή P > - P I.E T> Ό I.E AC w P <—1 <S | 'WHAT it <o <0 <0 <0 (0 O O m x: of and P i-4 <-4 · - < r-t -rl C C 5 • P XO Aí Aí P > N O Xí Ή O C -P m <0 <n w IN xu I.E M-1 C Ή «—L Aí >, P P II • rl m I.E íX Φ D Φ <0 <0 <0 0 '> 1 > X 5 O Φ <x P P Λ XI XJ XI φ > O I.E > P Φ -P M0 O O O O P P m <-4 Ό I.E Ό I.E

-26GB 297751 B6

Comparative Examples 1 to 5 demonstrate the usual fuel stability for gas generators based on prior nitroguanidine fuel.

Comparative Examples 1 to 3 show increasing instability with increasing content of highly dispersed Al ₂ O ₃ alumina. According to Example 1, the propellant for the gas generators does not contain the proper alumina Al ₂ O ₃ and exhibits satisfactory long-term storage stability for 400 hours or 1000 hours. Such a propellant for gas generators is nevertheless unsuitable for practical use, since its burning out is not suitable. Along with the increasing content of Al ₂ O ₃ alumina, this burn-out improves, but at the same time the stability of the propellant for gas generators decreases rapidly. According to Comparative Example 2, a weight loss of 1.47% and an alumina content of Al ₂ O _{3 of} 5.0% by weight were already observed for 400 hours after storage. the weight loss after storage for 400 hours is already 3.76%. These values are unacceptable for practical use.

Comparative Example 4 shows a significant increase in stability due to the addition of hydrophobic silica SiO ₂ . Compared to the formulation of Comparative Example 5, a tablet with a diameter of 4 mm and a height of 2 mm after storage for 400 hours has a weight loss of only 0.62%, whereas the formulation of Comparative Example 5 is 1.45%. Both formulations according to Comparative Example 4 and Comparative Example 5 contain a sufficient amount of 2.6% by weight. of aluminum oxide A1 ₂ O ₃ . However, this stability improvement is not sufficient to meet the requirements of the automotive industry.

In the case of the formulation according to Comparative Example 6, stabilized nitroguanidine was used for the first time according to the invention. Here too, there is a marked increase in stability compared to the formulation of Comparative Example 5. However, this stability improvement is not sufficient to achieve satisfactory stability. The receptors of Comparative Example 6 are not prior art receptors. Based on the results of Comparative Example 6, it has been found by further experiments that an acidic environment is required to stabilize the propellants for nitroguanidine gas generators.

Comparative Example 7 shows the instability of a propellant for gas generators which contains stabilized nitroguanidine in the presence of Cu (NO ₃ ) ₂ * ₃ Cu (OH) ₂ . In Comparative Examples 8 and 9, an oxidation mixture of Sr (NO ₃ ) ₂ and Cu (NO ₃ ) ₂ * ₃ Cu (OH) _{2 was used} . Al ₂ O ₃ additionally present in the formulation according to Comparative Example 9 again causes a decrease in stability. In Comparative Examples 10 and 11, the stability of stabilized nitroguanidine was finally investigated in the presence of CuCO ₃ and CuO, respectively.

According to Example 1 of the present invention - Table II - a very good stabilization was achieved for the gas generator propellant containing component Al (D) Al ₂ O _{3 by} combining stabilized nitroguanidine as fuel and hydrophobic silica SiO ₂ as stabilizer - see Comparison of Example 1 with Comparative Examples 4 and 6.

An even greater improvement in stability is achieved by the presence of another stabilizer selected from the group consisting of inorganic and organic acids - see comparison with Examples 2-4.

Very good stability is also achieved with propellants for gas generators which contain existing nitroguanidine as fuel and Al ₂ O ₃ alumina as component (D) and use stabilizers selected from the group consisting of inorganic and organic acids - see comparison with example 5 to 10.

In Examples 1 to 10, KNO ₃ was used as the oxidizing agent, i.e. component (B), in combination with alumina Al ₂ O ₃ in highly dispersed form and ferric oxide acetylacetonate as component (D).

-27GB 297751 B6

According to Example 11, very good stability was also achieved in combination with COK 84 aerosol and ferric oxide acetylacetonate as component (D).

The receptor of Example 12 contains KClO ₄ as an oxidizing agent, i.e. component (B), and aerosol COK 84 as component (D). Here too, very good stability has been achieved with the granulate.

Finally, Examples 13 to 15 show that stable propellants for gas generators can be achieved even in the presence of Al2O3 - compare to Example 14 - without the addition of a stabilizer when a mixture of KNO3 and NH4CIO4 is used in combination with stabilized nitroguanidine as fuel . Comparison with Comparative Example 5 shows that such good stability cannot be achieved with the existing nitroguanidine as fuel and KNO ₃ as oxidizing agent in the presence of Al ₂ O ₃ alumina.

Finally, Example 15 demonstrates good fuel stability for gas generators which, in addition to nitroguanidine as fuel, also contain guanidine nitrate as an energy-poor auxiliary fuel.

According to Examples 16 and 17, very good stability, even in the presence of Al ₂ O _{3, is} achieved using Cu (NO ₃ ) ₂ * ₃ Cu (OH) ₂ as the oxidizing agent and boric acid as the stabilizer.

In Examples 18 to 20, Sr (NO ₃ ) ₂ was used as the oxidizing agent. The stability of stabilized nitroguanidine in the presence of Sr (NO ₃ ) ₂ and alumina Al ₂ O ₃ has been demonstrated. By adding boric acid as a stabilizer, this stability is further improved.

Examples 21 and 22 demonstrate the stabilizing effect of boric acid in mixtures containing Sr (NO ₃ ) ₂ and Cu (NO ₃ ) ₂ * ₃ Cu (OH) ₂ as oxidizing agents - see Comparative Examples 8 and 9.

Finally, Examples 23 and 24 show the stabilizing effect of boric acid in mixtures containing CuCO ₃ and / or CuO as oxidizing agent - see Comparative Examples 10 and 11.

PATENT CLAIMS

Claims (21)

1. Propellant for gas generators, comprising: (A) nitroguanidine as a fuel stabilized by the addition of 0.1 to 0.5% nitrogaunidine hydrogen sulphate and nitroguanidinium nitrate, (B) an oxidizing agent selected from the group consisting of alkali and earth alkali nitrates, chlorates and perchlorates, ammonium nitrate and perchlorate mixtures thereof, (C) a stabilizer selected from the group consisting of inorganic and organic acids and mixtures thereof, and optionally (D) a stabilizer or a fire moderator and a means for forming or binding the slag and mixtures thereof. 2. Propellants for gas generators shall comprise: (A) nitroguanidine as a fuel, (B) an oxidizing agent selected from the group consisting of alkali and earth alkali nitrates, chlorates and perchlorates, ammonium nitrate and perchlorate, oxidizing copper compounds and mixtures thereof, (C) boric acid stabilizer, and optionally (D) a flame retardant or moderator, and a means for forming or binding the slag and mixtures thereof. Propellant for gas generators according to claim 1 or 2, characterized in that component (A) is present in an amount of 33 to 60% by weight, preferably 40 to 60% by weight. and in particular 45 to 55% by weight, component (B) is present in an amount of 35 to 55% by weight, preferably 38 to 52% by weight. and in particular 40 to 48% by weight, component (C) is present in an amount of up to 5% by weight, preferably up to 3% by weight. and in particular up to 1.6% by weight, and component (D) is present in an amount of up to 7% by weight, preferably up to 5% by weight. % and in particular 0.4 to 5 wt. Propellant for gas generators according to one of Claims 1 to 3, characterized in that component (C) additionally contains hydrophobic silica SiO ₂ as a stabilizer. Propellant for gas generators according to one of claims 1 to 4, characterized in that component (B) is selected from the group consisting of sodium nitrate, potassium nitrate, strontium nitrate, ammonium perchlorate, potassium perchlorate, trivalent copper trihydroxy nitrate and mixtures thereof . 6. The propellant for gas generators according to claim 1, wherein component (B) is a mixture of potassium nitrate and ammonium perchlorate. 7. The propellant for gas generators according to claim 1, wherein component (C) is selected from the group consisting of boric acid, citric acid, tartaric acid, cyanoic acid, terephthalic acid and fumaric acid. Propellant for gas generators according to one of Claims 1 to 7, characterized in that, as component (C), in addition to the hydrophobic silica SiO _2, an inorganic or organic acid is also present as a stabilizer. 9th Propellant for gas generators according to any one of claims 1-8, characterized in that component (D) is selected from the group consisting of aluminum oxide A1 ₂ O ₃ and iron oxide Fe ₂ O _3, silica SiO _2, iron oxide acetylacetonate and a mixture of highly dispersed Al ₂ O ₃ alumina and highly dispersed SiO ₂ . 10th Propellant for gas generators according to claim 9, characterized in that the aluminum oxide A1 ₂ O ₃ is present in highly dispersed form. Propellant for gas generators according to claim 9, characterized in that component (D) is a mixture consisting essentially of 16% highly dispersed Al ₂ O ₃ alumina and 84% highly dispersed SiO ₂ . Propellant for gas generators according to one of Claims 1 to 11, characterized in that it further comprises at least one binder as component (E). 13. The propellant for gas generators according to claim 12, wherein component (E) is selected from the group consisting of cellulose compounds, polymerizates of one or more polymerizable olefinic unsaturated monomers, water-insoluble, at room temperature, metal stearic acid salt and graphite. . Propellant for gas generators according to claim 12 or 13, characterized in that component (E) is present in an amount of up to 5% by weight, preferably in an amount of up to 3% by weight, in particular up to 1% by weight. . % and especially in an amount of 0.2 to 0.5 wt. A propellant for gas generators according to any one of claims 1 to 14, characterized in that it comprises: (A) nitroguanidine stabilized by the addition of 0.1 to 0.5% nitroguanidine hydrogen sulphate and nitroguanidinium nitrate as fuel, (B) KNO ₃ or a mixture of KNO ₃ and NH 4 ClO 4 as an oxidizing agent, (C) a stabilizer selected from hydrophobic silica SiO ₂ , boric acid, citric acid, tartaric acid, cyanoic acid, teraftalic acid, fumaric acid and mixtures thereof, (D) highly dispersed alumina Al ₂ O ₃ , optionally mixed with ferric oxide Fe ₂ O ₃ , and (E ) graphite. 16. A propellant for gas generators comprising (A) nitroguanidine stabilized by the addition of 0.1 to 0.5% nitroguanidine hydrogen sulphate and nitroguanidine nitrate as fuel, (B) Sr (NO ₃ ) ₂ or a mixture of KNO _3, or NaNO ₃ and NH 4 ClO 4 as the sole oxidizing agent, and optionally (D) at least one stabilizer or burn moderator, and means for forming or binding the slag. 17th Propellant for gas generators according to claim 16, characterized mares d c d in that the component (D) is selected from the group consisting of aluminum oxide A1 ₂ O ₃ and highly dispersed aluminum oxide A1 ₂ O ₃ and iron oxide Fe ₂ O ₃ , silica SiO ₂ , ferric oxide acetylacetonate and a mixture of highly dispersed Al ₂ O ₃ alumina and highly dispersed SiO ₂ . Propellant for gas generators according to claim 16 or 17, characterized in that component (A) is present in an amount of 33 to 60% by weight, preferably 40 to 60% by weight. and in particular 45 to 55% by weight, component (B) is present in an amount of 35 to 55% by weight, preferably 38 to 52% by weight, and in particular 40 to 48% by weight, and component (D) is present in % up to 7 wt.%, preferably up to 5 wt. % and in particular 0.4 to 5 wt. Propellant for gas generators according to one of Claims 16 to 18, characterized in that it further comprises at least one binder as component (E). 20. The propellant for gas generators according to claim 19, characterized in that the binder is selected from the group consisting of cellulose compounds, polymerizates of one or more polymerizable olefinic unsaturated monomers, water-insoluble metal salts of acid at room temperature. stear and graphite. Use of a propellant for gas generators according to any one of claims 1 to 20 as a means for generating gases in air waste and as an extinguishing agent or propellant.