JP2002519278A - Ignitable gas generating composition comprising high oxygen balance fuel - Google Patents

Abstract

  (57) [Summary] The ignitable gas generating composition comprises a high oxygen balance compound (fuel), preferably azodiformamidine dinitrate. Azodiformamidine dinitrate is a reaction product obtained by reacting an aminoguanidine salt with nitric acid. More specifically, the high oxygen balance compound (fuel) according to the present invention is a reaction product obtained by reacting aminoguanidine nitrate, aminoguanidine bicarbonate, or aminoguanidine sulfate, which is an aminoguanidine salt, with nitric acid. is there. Preferred as the aminoguanidine salt is aminoguanidine bicarbonate. The resulting reaction product is a yellow precipitate which can be used alone to cause self-deflagration or can be used with oxidizing agents and other additives. In each case, the gas generating composition exhibits high gas production and low production of solid combustion products. Furthermore, the precipitate is relatively non-hygroscopic and exhibits a high burn rate. This gas generating composition is used as a gas generating source for airbags, gun propellants, inflating / discharging devices, levitation devices, pyrotechnics, fire suppression devices, which are occupant restraint devices for automobiles. Is useful as a gas source for rocket propellants with no smoke or reduced smoke and smoke.

Description

DETAILED DESCRIPTION OF THE INVENTION

Background of the Invention 1. TECHNICAL FIELD The present invention relates to a material used for an ignition type (pyrotechnic) gas generating composition, specifically,
It relates to high oxygen balance fuel. This gas generating composition is used for a gas generating propellant, a gun propellant, an inflation / discharge device, a flotation device, an ignition material, a fireworks, a flame suppression device, a smokeless or smokeless rocket used in an automobile airbag occupant restraint device and the like. It can be used as propelling fuel.

[0001] 2. BACKGROUND OF THE INVENTION Ignition-type gas generation that produces an acceptable flammability rate during combustion, generates substantial non-toxic gases at relatively low combustion temperatures, and generates only small amounts of solid particulate matter that can generate smoke. There is a growing demand for compositions. It is also important that the solid by-products remaining when the gas generating composition is burned are minimized, and that the gaseous products generated by the burning are substantially non-toxic and non-corrosive. In the past, gas-generating substances having various compositions have been used in order to obtain the above-mentioned preferable characteristics.

[0002] 1-Azido-N, N, N-N, N, useful as propellant compositions with highly specific impulses
N, -trifluoroformamidine is disclosed in U.S. Patent No. 3,405,144. The above materials have been disclosed as being useful as rocket fuel compositions.

[0003] Gas generating compositions have also evolved by adding regulators to achieve lower combustion temperatures and to increase gas production. Other raw materials that enhance various features of the underlying propellant, such as binders, ignition aids, slag formers, scavengers, and catalysts, may be added. However, the above-mentioned modifier and additive materials are
Often, while improving one property of the propellant composition, it may also play a role in the production of unwanted by-products and may increase corrosivity. This is especially negative in an automotive airbag environment.

[0004] One of the main gas generating compositions having favorable properties is one containing strontium nitrate or 5-aminotetrazole (SrN / 5ATZ) as a main constituent.
This formulation is relatively non-toxic and superior in resilience compared to the sodium azide system, and most solid combustion products are slag or slag, e.g., for combustion in automotive airbag systems. It is held in the area or filter area. Also, in these formulations, the allowable combustion temperature is from 2250 ° K to 2750 ° K depending on the stoichiometry of the formulation and the oxygen-fuel ratio. In addition, strontium nitrate or 5
The aminotetrazole formulation has a relatively low hygroscopicity and, furthermore, its raw material does not undergo a phase inversion of the crystals within the operating temperature range of the airbag device.

[0005] However, such formulations have problems with regard to gas generation, especially in a volumetrically limited system of a driver side airbag. This is because high concentrations of strontium nitrate must maintain a neutral oxygen to fuel (O / F) balance. Inflators have become increasingly smaller in size, and consequently
Due to the more stringent volume limitations, the propellant is required to generate more gas while at the same time maintaining the preferred attributes of the strontium nitrate / 5-aminotetrazole system. is there.

[0006] Various means have been adopted for imparting suitable characteristics to the propellant, and various attempts have been made to solve the problem of low gas output. As a result, propellants based on mixtures of potassium perchlorate and oxidizing fuels such as guanidine nitrate and aminoguanidine nitrate have been developed. These propellants also have relatively low hygroscopicity, excellent gas generation, high combustion rates, and the amount of solid combustion products depends on the strontium nitrate and 5-aminotetrasol. Propellant 2
/ 3 only. Unfortunately, the solid combustion products do not accumulate in the combustion area or filter area as slag or slag, but are formed as extremely fine particulate matter in the gas flow, so that the exhaust And garbage.

[0007] Smoke or dusty exhaust combustion products are not commercially desirable and, in particular,
When an automobile airbag device produces such a product, it is not preferable in that it may cause excessive anxiety to a driver or an occupant involved in a car accident in which the airbag is deployed. As a result, there is a need for a propellant material or gas generating material that has high gas production during combustion, but does not produce unwanted by-products.

SUMMARY OF THE INVENTION The present invention is directed to improving the above prior art and overcoming its disadvantages, and provides an ignitable gas generating composition which produces a substantially non-hygroscopic and non-toxic gas. It is still another object of the present invention to provide an ignitable gas-generating composition which exhibits a high gas production amount and a high combustion rate during combustion and suppresses the production of non-gaseous combustion products.

The present invention further provides azodiform dinitrate, which produces a high oxygen balance fuel, preferably a high gas output at low combustion temperatures, and reduces the production of non-gaseous combustion products. It is intended to provide an ignitable gas generating composition containing amidine.

Another object of the present invention is to provide an ignitable gas generating composition comprising azodiformamidine dinitrate, capable of self-deflagration similar to a high oxygen balance fuel, preferably a solid monopropellant. And

[0011] The present invention further provides a high oxygen balance fuel which is automatically ignited in the expander at an allowable temperature and at such a low temperature that the expander does not become a small piece at the time of an ignition test, but ruptures reliably. It is an object of the present invention to provide an ignitable gas generating composition comprising:

Another object of the present invention is to provide a gas-generating composition which is used as a propellant for an airbag for an automobile and is capable of producing extremely high gas upon combustion. on the other hand,
The composition of the present invention is used when inflating an inflatable raft or a passenger evacuation chute of an airplane, and also for a gun propellant, a pyrotechnic, an ignition mixture, a flame suppression device and a rocket propellant. Good. From a practical standpoint, the compositions of the present invention also include an oxidizing agent,
Gas conversion catalyst, ballistic modifier, slag former, ignition aid, energetic plasticizer (e
nergetic plasticizer), binders and non-energetic binders
It may contain additives conventionally used in combination with other gas generating compositions, such as r) and a synthesis auxiliary.

The above objects are generally achieved by an ignitable gas generating composition comprising a high oxygen compound (fuel), preferably formed by the reaction of aminoguanidine nitrate with nitric acid, using potassium permanganate. This is achieved with azodiformamidine dinitrate, prepared with or without the use. That is, the product of the above reaction ignites itself without an oxidizing agent or other additives, is a usable yellow precipitate, and is used for spontaneous deflagration, which is extremely rapid and produces little smoke. In addition, it burns by the oxidizing agent alone or in combination with other additives. In any case, the gas generating composition produces a large amount of gas and a small amount of solid decomposition products upon combustion.
Further, the precipitate is relatively non-hygroscopic and has a high burning rate. for that reason,
Unlike the gas generating composition of the prior art, the cartridge for storing the gas generating composition need not have a very high pressure resistance. Also, prior art gas generating compositions, such as ammonium nitrate based compositions, while exhibiting low productivity of solid combustion products close to the gas generating composition of the present invention, the burning rate is low,
Generally has hygroscopicity.

From the general physical properties of the reaction product according to the present invention, the product is considered to be 1,1′-azodiformamidine dinitrate. However, the ignitable gas generating composition according to the present invention refers to both a yellow reaction product obtained by the reaction of aminoguanidine nitrate and nitric acid, and 1,1′-azodiformamidine dinitrate, respectively. It is.

The azodiformamidine dinitrate also includes nitric acid and other aminoguanidine salts,
For example, it may be formed as a reaction product by reaction with aminoguanidine bicarbonate, aminoguanidine sulfate, or any combination thereof. Preferably, the aminoguanidine salt is aminoguanidine bicarbonate. By using such a material, it is possible to provide a method for efficiently producing the azodiformamidine dinitrate of the present invention at a low cost.

The gas generating composition of the present invention is usually prepared by a method which has heretofore been employed for the production of a conventional composition, and generally, but not necessarily, pulverized according to a combination of raw materials. Raw materials are prepared by dry or wet blending and compression. In view of the advantageous features of the gas generating composition of the present invention, i.e., high gas output, low solid combustion product output, and high burn rate, the generating material may be an automotive airbag device, an inflatable It can be applied to rafts and passenger evacuation chutes, gun propellants, fireworks manufacturing, ignition mixtures, flame suppression equipment and rocket propelled fuel.

For the purposes of the present invention, these two terms propellant and gas generant are used interchangeably. Also, for the purposes of the present invention, the above reaction is with an anhydrous component. However, the use of non-anhydrous components is also being considered.

[0018] DETAILED DESCRIPTION The present invention of the preferred embodiment is intended to provide the ignitability (pyrotechnic) material that generates expected. The gas generating material is preferably azodiformamidine dinitrate (azodifo
It contains rmamidine dinitrate) and produces a large amount of gas and a trace amount of solid combustion products when burned, and is useful for various purposes. When the high oxygen balance fuel of the present invention is reacted in the presence of an oxidizing agent, a large amount of gas is generated, but the amount of solid combustion products is very small. In addition, the fuel, preferably azodiformamidine dinitrate, exhibits a high burn rate and is a self-deflagrating monopropellant (monop
ropellant). Accordingly, the gas generating composition of the present invention can be used as a single component auto-igniting agent (AIP), a solid type monopropellant, a high oxygen balance fuel used in various ignition systems, and an additive for improving the combustion rate. It can also be used as a component for use in a hybrid expansion system of a conventional system and an oxygen supply system. The gas generating material of the present invention is particularly useful when used as a propellant for an air bag of an automobile, but gun powder, a gas generating material for a levitation device, a propellant, a pyrotechnic, a gas generating source,
It will be appreciated that the invention is also applicable to ignition mixtures, fire suppression systems, and propellants for rockets.

Other objects and advantages of the present invention will become apparent to those skilled in the art from the following detailed description. In the following description, the best mode that can be considered when practicing the present invention will be described, and thereby a preferred embodiment of the present invention will be presented. Therefore, it should be apparent from the following description that embodiments of the present invention are not limited to the following, and details can be changed in various aspects without departing from the gist of the present invention. In other words, the drawings and the description provide an explanation of the gist of the present invention, and do not limit the scope of the present invention.

Specifically, the gas generating composition of the present invention is a high oxygen balanced formamidine type fuel, and is produced by the reaction of nitric acid and aminoguanidine nitrate. The inventor of the present invention claims that this fuel is azodiformamidine dinitrate (also referred to as azodicarbamidine dinitrate, azobicarbamidine dinitrate, or azobisformamidine dinitrate) having the following structural formula: thinking.

[0021]

Embedded image

However, the present invention is not limited to only the crystallized or recrystallized azodiformamidine dinitrate. As will be described in detail below, other reaction products of nitric acid and aminoguanidine nitrate may be used. Is also targeted.

The gas generating composition of the present invention may be formed by reacting nitric acid with an aminoguanidine salt other than those described above (for example, aminoguanidine hydrogen carbonate (AGB) or aminoguanidine sulfate (AGS)). . A preferred aminoguanidine salt is AGB.
When these salts are reacted with nitric acid, a light yellow solid is obtained which is likely to be azodiformamidine dinitrate, similar to the reaction between nitric acid and aminoguanidine nitrate described above.

For azodiformamidine dinitrate, see J. Thiele, Ann 270, 39 (1892), this compound is azodicarbon amidine nitrate.
idinnitrat). The previous synthesis was conducted in connection with research on materials that could be used as wool dyes or pigments.

Further, in the above conventional synthesis method, the oxidizable metal compound (potassium permanganate)
Was added to give a yellow reactant, during which no heating was performed using an external heat source. The advantage of the method of the present invention, which will be described below, over these conventional methods is that the reaction occurs rapidly by heating without the need of adding an oxidizing metal compound. By avoiding the use of an oxidizing metal compound during the preparation of the yellow reaction product, the highly oxygen-fueled gas generating substance of the present invention does not include solid fine particles which are foreign substances during the preparation. In addition, there is no possibility that a granular metal oxide is formed during the preparation. In this way, the gas generating substance using the high oxygen balance fuel of the present invention can be produced without containing metal-containing impurities.

According to the present invention, if the digestion time between nitric acid and aminoguanidine nitrate is made longer, the reaction for producing azodiformamidine dinitrate can be carried out without using potassium permanganate. Also at room temperature without external heat supply. This method is also applicable when using the above-mentioned additive salts (specifically, aminoguanidine hydrogen carbonate (AGB) and aminoguanidine sulfate (AGS)).

Furthermore, other high oxygen balance fuels such as hydrazodicarbonamidine, diazoguanidine, formamidine, bisformamidine, azobisformamidine, guanyl azide nitrate, diazoguanidine nitrate, azobisnitroforme Derivative fuels such as amidine and 1,1′-azodiformamidine dipicrate are also useful as the gas generating component according to the present invention. Also, (N
Formamidines, guanyl azides, diazoguanidines or hydrazodicarbonamidines having one or more oxidizing groups such as O ₂ ), (NO ₃ ), (ClO ₄ ) and (ClO ₃ ). Other derivatives and fuels comprising, in addition, hydrazodicarbonamidine compounds, guanyl azides, diazoguanidine compounds, formamidine compounds, bisformamidine compounds or azobisformamidine compounds containing an appropriate amount of an oxidizing group in advance Are also useful as propellant compositions.

Conventional propellants, including propellants containing ammonium nitrate, produce very little solid product during combustion, but are less desirable given other properties. For example, ammonium nitrate is hygroscopic. Further, when used in a gas generating composition or a propellant composition, the burning rate is reduced, and
At operating pressures from si to 2000 psi, the pressure index increases. Therefore, a propellant composition containing mainly ammonium nitrate as an oxidizing agent is, for example, 4000 psi.
It must be burned at a high pressure, such as from 6000 psi to 6000 psi, and must be sealed to prevent contact of the propellant composition with moisture. In addition, ammonium nitrate usually needs to be used with a phase stabilizer such as a potassium compound, but burning it produces solid products.

With the high oxygen balance fuel of the present invention, the above undesirable properties can be improved. Specifically, the gas generating composition and the propellant composition containing the high oxygen balance fuel according to the present invention generate a large amount of gas, but do not generate solid combustion products (ash) at all, or Even if it occurs, it is very small. Furthermore, it has a relatively low hygroscopicity, a high combustion rate, and gives a more suitable pressure index. As a result, even if the same burning rate is obtained, the composition of the present invention requires a significantly lower operating pressure as compared with the above-mentioned gas generating propellant composition containing ammonium nitrate. There is no need to pack in a high pressure and moisture barrier container.

As described above, the gas generating composition of the present invention can function alone as a self-deflagrating monopropellant, or may contain an oxidizing agent. Processing, ignition assistance,
Adding other substances to the above composition for the purpose of improving shooting characteristics, avoiding deterioration due to heat and improving stability, improving dangerous characteristics, suppressing generation of particles, binding, or trapping unwanted gas combustion products You may.

One or more oxidizers are combined with the high oxygen balance fuel of the present invention so that additional oxygen is supplied so that the fuel-to-fuel balance (O / F) during combustion reaches a desired value. It may be. The high oxygen balance fuel of the present invention contains a greater amount of oxygen than conventional gas generating compositions, so that the desired oxygen to fuel (O /
F) The amount of oxidizing agent required to achieve balance is less. Suitable oxidizing agents include those already known, both metallic and nonmetallic, and generally include nonmetallic, alkali metal, alkaline earth metal, transition metal, or transition metal complexes. Each nitrite, nitrate, chlorite, chlorate, perchlorate, oxide, hydroxide, peroxide, persulfate, chromate, perchromate, and mixtures thereof There is something consisting of. Preferred oxidizing agents include ammonium perchlorate, potassium perchlorate, strontium nitrate, potassium nitrate, sodium nitrate, barium nitrate, potassium chlorate, and mixtures thereof.

In order not to impair the excellent characteristics of the high oxygen balance fuel of the present invention, the oxidizing agent preferably has no hygroscopicity. In addition, these suitable oxidizing agents are generally used preferably in a concentration of about 0% to 98% by weight, and preferably in a concentration of about 5% to 50% by weight, based on the whole gas generating composition. It is more preferred to use

Preferably, a scavenger is used to control the generation of corrosive substances as a result of combustion. For example, when a nonmetallic oxidizing agent such as ammonium perchloric acid is used, hydrogen chloride (HCl) is generated as a reaction product, but this is clearly not preferable. To prevent the formation of hydrogen chloride, it is possible to use a scavenger such as sodium nitrate and instead to form sodium chloride (NaCl). Corrosive / toxic gas supplements other than sodium nitrate may be used.

The combustion of the high oxygen balance fuel of the present invention may be regulated by adding ballistic modifiers, and may also affect temperature sensitivity, pressure index, and propellant burn rate. A rate catalyst may be included. Although these ballistic modifiers were developed primarily for use in solid rocket fuels, inflatable devices (inflata
It has also proven useful in use in gas generating materials for ble devices. Useful ballistic modifiers for the compositions of the present invention include, for example, oxides and halogen compounds of Group 4 to 12 elements (prepared by IUPAC, published by CRC Press, 1989); sulfur and Metal sulfides; transition metal salts including copper, chromium, cobalt, nickel and the like, and mixtures thereof;
Alkali metal borohydride and alkaline earth metal borohydride; and the like. Guanidine borohydride and triaminoguanidine borohydride have also been used previously as ballistic modifiers. Examples of some organometallic ballistic modifiers include, but are not limited to, metal chelates, metal oxalates, metallocenes, ferrocenes, and metal acetylacetonates. Still other ballistic modifiers include dicyanamide, nitroguanidine, guanidine chromate, guanidine dichromate, guanidine trichromate, guanidine perchromate, and the like. The ballistic modifier is generally used at a concentration of about 0.1% to 25% by weight based on the entire gas generating composition. Since the high-oxygen fuel of the present invention has the characteristics of self-deflagration and high combustion rate, the fuel has a low concentration (that is, 0.1 to 2).
5% by weight) in other gas generating compositions as ballistic modifiers.

The addition of a slag former promotes the formation of a filterable slag. But,
In the present invention, such slag formers may not be necessary given the limited amount of solid matter generated by combustion. If you still need them, you can use lime, borosilicate, vigograss, bentonite clay, silica, alumina, silicates, aluminates, transition metal oxides, alkaline earth metal compounds, lanthanum elements, and A mixture of these and the like can be mentioned as a suitable slag forming agent.

Other additives that have been found to assist in igniting and burning the gas generating composition and improve combustion temperatures are ignition aids. Examples of ignition aids include sulfur, boron, potassium potassium boron nitrate (BKNO ₃ ), each of which is present as a single element of very small size.
Examples include carbon, magnesium, and aluminum, and further include a transition metal of Group IV, an oxide of a transition metal, a hydride of a transition metal, a sulfide of a transition metal, and the like, and 3-nitro-1,2,4-triazole- Examples thereof include hydrazine salts of 5-one and mixtures thereof. The ignition aid is usually used at a concentration of about 0.1% to 15% by weight based on the entire gas generating composition.

In order to facilitate blending and obtain a uniform mixture, it is desirable to add a blending agent. Some examples of suitable binders and processing or compounding aids include molybdenum disulfide, graphite, boron nitride, alkali metals, alkaline earth and transition metal stearate, and also water, methanol ,ethanol,
Examples include various solvents such as ethyl ether, acetone, isopropanol, and methylene chloride, and further include polyethylene glycol, polyacetal, polyvinyl acetate, and polyvinyl alcohol. Q-PAC, cellulose acetate (CA), and cellulose acetate butyrate (CAB) , Cellulose nitrate (CN
), And fluoropolymers marketed under the trade name TEFLON, as well as silicon. These adjuvants are usually used at a concentration of about 0.1 to 15% by weight based on the whole gas generating composition, but this value is not always applied.

The high oxygen balance fuel of the present invention may be used in combination with other fuels and / or energetic nitro and / or nitrato plasticizers and / or energetic and non-energy binders in addition to the additives described above. A gas generating and propelling composition may be formed. Some examples of fuels suitable for use in combination with the fuels of the present invention include azides, hydrazines, guanidines, tetraazoles, triazoles, triazines, polyamines, nitroamines (linear and cyclic).
, Derivatives of these compounds, and mixtures thereof. Some preferred examples of the energetic plasticizer include butanetriol trinitrate (BTTN), nitroglycerin (NG), and triethylene glycol dinitrate (
TEGDN), trimethyl oletan trinitrate (TMETN), and mixtures thereof. An example of an energetic binder is glycidyl azide polymer (GAP).

As far as possible, a structurally balanced, well-mixed and homogeneous mixture is obtained, and without any undue danger, under conditions in which the components in use do not decompose. The method of mixing and blending the components of the gas generating composition of the present invention and the order thereof are not so important. For example, the materials may be placed in a ball mill or "Red Devil" type paint shaker and wet mixed in aqueous or non-aqueous liquids,
You may dry-mix. When mixing, a binder or a processing aid may be used,
It is not necessary to use it. Further, the mixture may be extruded, compression molded into small spheres, or castable or compression molded monolayer grains. The constituent materials may be individually crushed or crushed simultaneously. At the time of crushing, the material is jet milled and “SWECO” vibration energy mill (v
It may be carried out in any of an ibroenergy mill and a light-grade micro-pulverizer, and may or may not contain a binder or other additives. After the crushing, mixing may be performed, and the mixture may be transferred to a V-type mixer before consolidation and mixed.

The above various components used with the novel high oxygen balance fuel according to the present invention are those conventionally used in other gas generating compositions. Gas Generating Compositions Among such prior art references that describe various additives are described, for example, in U.S. Pat. Nos. 5,035,757, 5,084,118, 5,139,588,4.
, 948, 439, 4,909, 549, 4, 370, 181 and the like. As described in these prior art documents and as will be apparent to those skilled in the art, one composition can have the function of a plurality of additives. For example, alkaline earth metal salts of tetraazole, bitetraazole, and triazole not only function as a gas generating component, but can also be used as a slag forming agent. Further, for example, strontium nitrate has been found to be effective not only as an oxidizing agent and a slag forming agent, but also as a ballistic modifier, an ignition aid, a density increasing agent, and a synthesis aid.

In using the high oxygen balance fuel of the present invention, a conventional gas generator can be employed. The details of the device are described in U.S. Pat. No. 4,369,079, and the detailed description is hereby incorporated by reference. Conventional methods generally use a hermetically sealed metal cartridge containing the gas generating composition. Of the fuels of the present invention, this type of cartridge can be used for hydraazodicarbonamidine, diazoguanidine, formamidine, bisformamidine, and azobisformamidine type fuels. Specifically, when starting the combustion by igniting the squib, the sealing mechanism ruptures, and as a result, gas can flow out of the combustion chamber to the outside through the plurality of openings. Of course, the gas generating composition of the present invention can be similarly used in other gas generating devices.

Referring to a vehicle airbag, FIG. 1 illustrates a typical, passenger-side hybrid inflator (infla) for a vehicle that may use the high oxygen balance fuel of the present invention.
tor). Hereinafter, the actual operation will be described. When a sensor (not shown) detects a sudden deceleration indicating a collision, the initiator 1 is ignited in response thereto. The initiator emits hot gas, which is charged with an ignition charge 2
Ignite. In addition, this ignition charge 2 is now a main gas generant charge.
By igniting the charge 8, the main gas generating charge 8 burns. Thus, the expanded mixed gas 3 is heated and further subjected to pressure. When the pressure of the inflated mixed gas increases to a certain level, the sealing plate 6 ruptures, and the mixed gas obtained in the flow path flows out of the manifold 4 through the outlet 5 to inflate the air bag. The gas generating vessel 9 contains the main gas generating filling 8. All the fillers in the expanded gas mixture are stored in the pressure tank 7
Is trapped inside.

FIG. 2 shows an ignition-only (all pyrotechnic) gas generator to which the present invention can be applied. Since no storage space is provided in the present expansion device, the size is smaller than that of the hybrid expansion device. In the figure, an initiator 11 is provided. In response to a signal generated by a sensor (not shown), as a result of a change in conditions, such as an excessively high temperature of the vehicle in which the inflator is installed, or a sudden deceleration of the vehicle (indicating a collision), The initiator 11 burns. Initiator 11
Emits a hot gas which, when ignited to the main gas generating charge 16, causes the main gas generating charge 16 to burn and produce an expanded gas mixture. The gas mixture flows out of the manifold 14 through the outlet 15. The self-ignition temperature (T
ig) to ensure that the gas generating propellant 16 is ignited at a temperature sufficiently lower than the temperature below which the strength of the component materials of the device is reduced, and an autoignited propellant (AIP) having a reasonably low Tig. ) 13 must be used, and this is the ignition charge 1
2, and the propellant 16 is further ignited by this ignition.

Since the high oxygen balance fuel of the present invention has a high combustion rate at an operating pressure from a medium level to a low level, it can be used in the form of a monolayer grain (monolithic grain).

The use of the high oxygen balance fuel of the present invention successfully produces a self-deflagration capability similar to a solid monopropellant. Moreover, with the high oxygen balance fuel of the present invention, it is possible to further reduce the amount of the oxidizing component used. Therefore, the concentration of solid combustion products is greatly reduced, and the amount of generated gas is greatly increased. This is a particularly convenient feature in systems with limited capacity. That is,
The high oxygen balance fuel of the present invention is applicable to both of the above-described systems generalized in FIGS.

A yellow solid reaction product resulting from the reaction between nitric acid and aminoguanidine nitrate, and a yellow solid reaction product resulting from the reaction between other aminoguanidine salts such as aminoguanidine hydrogencarbonate or aminoguanidine sulfate and nitric acid Are considered to be both azodiformamidine dinitrate (azobisformamidine dinitrate), but the invention is not limited to only this particular high oxygen balance fuel. But,
In the present invention, azodiformamidine dinitrate (azobisformamidine dinitrate) has been particularly specifically described. However, for simplicity of description, hereafter AZO
The term DN is used, unless otherwise specified, to refer to both hydrated and anhydrous type reaction products and azodiformamidine dinitrate. Similar results can be obtained by using azodiformamidine dinitrate obtained by reacting one or both of aminoguanidine hydrogencarbonate and aminoguanidine sulfate with nitric acid.

The high oxygen balance fuel of the present invention, that is, AZODN is replaced with another high oxygen balance fuel (
Compared with HOB and CAPS), as shown in Table 1, it can be seen that AZODN has a higher oxygen balance with respect to carbon dioxide and water.

[0048]

[Table 1]

The AZODN of the present invention has a better oxygen balance as compared to other high oxygen balance fuels such as guanidine nitrate, and therefore, even with the use of lower concentrations of oxidizer, the fuel-to-fuel ratio in the generated gas generating composition. The oxygen balance (O / F) can be in the desired range of 0.90 / 1 to 1.1 / 1. However, if a gas-generating substance containing no or substantially no solid combustion products is required, an oxidizing agent such as phase-stabilized ammonium nitrate or non-phase-stabilized ammonium nitrate may be used together with the high oxygen balance fuel of the present invention. Can be used. In this case, the fuel of the present invention must account for 40% to 60% by weight of the total gas generating composition. When the AZODN according to the present invention is used in the form of a reaction product generated by the reaction between aminoguanidine nitrate and nitric acid, or specifically, in the form of azobisformamidine dinitrate, the amount of generated gas increases, The amount of solid combustion products is reduced.

As shown in Table 2, in a conventional fuel such as 5-aminotetrazole (5ATZ: described in the description of the background art), guanidine nitrate (GN), and ethylenediamine dinitrate (EDDN), the balance of oxygen with respect to fuel is shown. To make (O / F) 0.95 / 1, a larger amount of strontium nitrate (SrN) is required as compared with the present invention. In addition, these conventional fuel-containing gas generating compositions can be used with the AZODN of the present invention.
As compared with a gas-generating composition containing, a smaller amount of gas is generated and a larger amount of solid combustion products is generated.

[0051]

[Table 2]

As shown in the results of Table 2, in order to set the value of O / F to 0.95 / 1, which is a reference here, in a composition containing EDDN, GN, or 5ATZ, the present invention Compared to gas generating compositions comprising high oxygen balance fuel (AZODN), S
rN was required in excess of 10% by weight or more. Although 5ATZ exhibited a combustion temperature close to that of the present invention, the amount of gas generation was much smaller than that of the composition containing AZODN, and the content of solid combustion products was twice or more. became.

If it is deemed necessary to adjust the elasticity, part of the strontium nitrate can be replaced by potassium perchlorate (KP). When this replacement is performed, as shown in Table 3, the amount of solid combustion products generated further decreases.

[0054]

[Table 3]

Nevertheless, in a composition comprising EDDN or GN as a fuel, A
Higher amounts of potassium perchlorate and strontium nitrate were required compared to compositions comprising ZODN. In addition, the gas generation amounts of the above three compositions were all the same, but the solid combustion product generation amount in the composition containing AZODN was lower than that of the other two compositions. It was very small. Therefore, AZODN
Is more suitable for the ignition type gas generation system shown in FIG. 1 and FIG.

A composition containing a high oxygen balance fuel (AZODN) of the present invention and an oxidizing agent, which can provide a desired value of O / F balance in the range of 0.90 / 1 to 1.1 / 1. Are shown in Tables 4 to 7 below. Specifically, Table 4 shows a composition containing AZODN and ammonium nitrate (AN), and Table 5 shows a composition containing AZODN, ammonium perchlorate (AP), and strontium nitrate (SrN). Table 6 shows compositions comprising AZODN, ammonium perchlorate (AP), and sodium nitrate (SN). Table 7 shows a composition containing AZODN, ammonium perchlorate (AP), and potassium nitrate (KN). Although the compositions shown in Table 4 have hygroscopicity, the amount of solid combustion products generated is almost equal to zero. Also, the use of phase-stabilized ammonium nitrate is preferred.

[0057]

[Table 4]

[0058]

[Table 5]

[0059]

[Table 6]

[0060]

[Table 7]

To help understand the function of the high balance fuel of the present invention, the following is an example of the theoretical reaction of the AZODN of the present invention. Here, the structural formula of AZODN is as follows.

[0062]

Embedded image

The molecular formula of AZODN is C ₂ H ₈ N ₈ O ₆ .

[0064] (1) a hybrid system or of a monopropellant agent used in the ignition system pure _{AZODN C 2 H 8 N 8 O} 6 → 4H 2 O + 2CO + 4N 2 240 72 56 112 = 240 100.0% 30.0% 23.33% 46.67% 1.667M 0.833M 1.667M Total amount of generated gas 100% by weight Total amount of generated gas (mol) 4.167mol / 100g Total amount of solid combustion products 0% by weight

(2) Normal or phase stabilized ammonium nitrate and AZODN 2 C ₂ H ₈ N ₈ O ₆ + ₃ NH ₄ NO ₃ → 14 H ₂ O + ₃ CO ₂ + CO + 11 N ₂ 480 240 252 132 28 308 = 720 66.67 % 33.33% 35.00% 18.33% 3.89% 42.78% 1.944M 0.417M 0.139M 1.528M Total amount of generated gas 100% by weight (O / F = 1.00) 100% by weight (O / F = 0.95) Total amount of generated gas ( 4.04 mol / 100 g Total combustion products in solid form 0% by weight

(3) Lithium nitrate, ammonium perchlorate and AZODN 5C ₂ H ₈ N ₈ O ₆ + 2LiNO ₃ + 2NH ₄ ClO ₄ → 2LiCl + 24H ₂ O + 10CO ₂ + 22N ₂ 1200 138 234 84 432 440 440 616 = 1572 76.33% 8.78% 14.89% 5.34% 27.48% 27.99% 39.19% 0.127M 1.53M 0.636M 1.400M Total generated gas 94.7% by weight (O / F = 1.00) 95.6% by weight (O / F = 0.95) Total amount of generated gas (mol) 3.69 mol / 100 g Total amount of solid combustion products 5.3% by weight (O / F = 1.00) 4.4% by weight (O / F = 0) .95)

(4) Sodium nitrate, ammonium perchlorate and AZODN 5C ₂ H ₈ N ₈ O ₆ + 2NaNO ₃ + 2NH ₄ ClO ₄ → 2NaCl + 24H ₂ O + 10CO ₂ + 22N ₂ 1200 170 234 116 432 440 616 = 1604 74.81% 10.60% 14.59% 7.23% 26.93% 27.43% 38.41% 0.125M 1.50M 0.623M 1.372M Total generated gas 92.8% by weight (O / F = 1.00) 93.8% by weight (O / F) = 0.95) Total amount of generated gas (mol) 3.50 mol / 100 g Total amount of solid combustion products 7.2% by weight (O / F = 1.00) 6.2% by weight (O / F = 0) .95)

(5) Potassium nitrate, ammonium perchlorate and AZODN 5C ₂ H ₈ N ₈ O ₆ + 2KNO ₃ + 2NH ₄ ClO ₄ → 2KCl + 24H ₂ O + 10CO ₂ + 22N ₂ 1200 202 234 148 432 440 416 616 = 1636 73.35% 12.35% 14.30% 9.05% 26.41% 26.89% 37.65% 0.122M 1.467M 0.611M 1.345M Total generated gas 91.0% by weight (O / F = 1.00) 92.0% by weight (O / F = 0.95) Total amount of generated gas (mol) 3.42 mol / 100 g Total amount of solid combustion products 9.0% by weight (O / F = 1.00) 8.0% by weight (O / F = 0. 95)

(6) Strontium nitrate, ammonium perchlorate and AZODN 5C ₂ H ₈ N ₈ O ₆ + Sr (NO ₃ ) ₂ + 2NH ₄ ClO ₄ → SrCl ₂ + 24H ₂ O + 10CO ₂ + 22N ₂ 1200 212 234 157 432 440 616 = 1645 72.90% 12.89% 14.21% 9.54% 26.26% 26.75% 37.45% 0.061M 1.459M 0.608M 1.338M Total generated gas 90.5% by weight (O / F = 1.00) 92.0% by weight % (O / F = 0.95) Total amount of generated gas (mol) 3.405 mol / 100 g Total amount of solid combustion products 9.5% by weight (O / F = 1.00) 8.0% by weight ( O / F = 0.95)

(7) Ammonium perchlorate, lithium carbonate as coolant and AZODN 14C ₂ H ₈ N ₈ O ₆ + 9NH ₄ ClO ₄ + 5Li ₂ CO ₃ 3360 1053 370 70.25% 22.01% 7.74% → 9LiCl + 1 / 2Li ₂ O + 74H ₂ O + 27CO ₂ + 6CO + 60 1 / 2N ₂ + 1 / 4O ₂ 378 15 1332 1188 168 1694 8 = 4783 7.90% 0.31% 27.85% 24.84% 3.51% 35.42% 0.17% 0.188M 0.010 M 1.547M 0.565M 0.125M 1.265M 0.005M Total amount of generated gas 91.79% by weight (O / F = 1.00) 92.00% by weight (O / F = 0.95) Total amount of generated gas (mol) 3. 51 mol / 100 g 3.73 mol / 100 g Total combustion products in solid form 8.20% by weight (O / F = 1.00) 8.00% by weight (O / F = 0.95)

(8) Scandium nitrate, ammonium perchlorate and AZODN 2C ₂ H ₈ N ₈ O ₆ + 1 / 3Sc (NO ₃ ) ₃ + 2 / 3NH ₄ ClO ₄ 480 77 78 75.59% 12.13% 12.28% → 1 / 3ScC ₁₂ + 9 1 / 3H ₂ O + 4CO ₂ + 9N ₂ + 1 / 6O ₂ 38 167.4 176 251 2.6 = 635 5.98% 26.36% 27.72% 39.53% 0.41% 0.05M 1.46M 0.63M 1.41M 0.01M Emitted gas Total amount 94.0% by weight (O / F = 1.00) 3.51 mol / 100 g (O / F = 1.00)
Total weight of solid combustion products 6.0% by weight (O / F = 1.00)

(9) Sodium nitrate and AZODN 5C ₂ H ₈ N ₈ O ₆ + 4NaNO ₃ → 2Na ₂ O + 20H ₂ O + 10CO ₂ + 22N ₂ 1200 340 124 360 440 616 = 1540 77.92% 22.08% 8.05% 23.38 % 28.57% 40.00% 0.130M 1.299M 0.649M 1.429M Total generated gas 92.0% by weight (O / F = 1.00) 93.0% by weight (O / F = 0.95) Total generated gas (mol) 3.38 mol / 100 g Total amount of solid combustion products 8.0% by weight (O / F = 1.00) 7.00% by weight (O / F = 0.95)

(10) Strontium nitrate and AZODN 5C ₂ H ₈ N ₈ O ₆ + 2Sr (NO ₃ ) ₂ → 2SrO + 20H ₂ O + 10CO ₂ + 22N ₂ 1200 424 208 360 440 616 = 1624 73.89% 26.11% 12.81 % 22.17% 27.09% 37.93% 0.123M 1.232M 0.616M 1.355M Total generated gas 87.2% by weight (O / F = 1.00) 89.3% by weight (O / F = 0.95) Total generated gas ( Mol) 3.20 mol / 100 g Total amount of combustion products in solid state 12.8% by weight (O / F = 1.00) 10.7% by weight (O / F = 0.95)

(11) Potassium perchlorate and AZODN 2C ₂ H ₈ N ₈ O ₆ + KClO ₄ → KCl + 8H ₂ O + 4CO ₂ + 8N ₂ 480 138 74 144 176 224 = 618 77.67% 22.33% 11.97% 23.30 % 28.48% 36.25% 0.162M 1.294M 0.647M 1.295M Total generated gas 88.03% by weight (O / F = 1.00) 89.90% by weight (O / F = 0.95) Total generated gas (mol) 3.24 mol / 100 g 3.56 mol / 100 g Total combustion products in solid form 11.97% by weight (O / F = 1.00) 10.10% by weight (O / F = 0.95)

(12) Aminoguanidine hexanitratoserate and AZODN CeC ₂ H ₁₂ N ₁₄ O ₁₈ + 3 C ₂ H ₈ N ₈ O ₆ → CeO ₂ + 18 H ₂ O + 8 CO ₂ + 19 N ₂ 660 720 172 324 352 352 532 = 1380 47.82% 52.18% 12.46% 23.48% 25.51% 38.55% = 100% Total generated gas 87.54% Total solid combustion products 12.46%

[0076] (13) aminoguanidine hexane Sanitora Tosca emissions dating _{AZODN ScC 2 H 12 N 14 O} 18 + 3C 2 H 8 N 8 O 6 → ScO 2 + 18H 2 O + 8CO 2 + 19N 2 565 720 77 324 352 532 = 1285 43.97% 56.03% 5.99% 25.21% 27.39% 41.40% = 100% Total gas generated 94.01% Total solid combustion products 5.99%

As shown by the above-mentioned theoretical reaction of AZODN, the use of the fuel according to the present invention makes it possible to generate a considerably large amount of gas. In almost all cases, the amount of gas generated is 90% by weight. Beyond. In addition, even when a large amount of solid combustion products are generated, the amount of the gas generating substance according to the present invention using AZODN is reduced as compared with a conventional gas generating composition.

In the following description, a specific process for reacting aminoguanidine nitrate with nitric acid to obtain the reaction product of the present invention will be described. Further, the case where the reaction product obtained as a result of this reaction is used together with various additives will be described, and the effect will be clarified. Therefore, in Examples 1 to 12 below, “A
The term "ZODN" shall refer to the yellow precipitate actually obtained in Example 1. In the following examples, this "AZODN" is used, but as described above, even when a reaction product of nitric acid and another aminoguanidine salt such as aminoguanidine hydrogencarbonate or aminoguanidine sulfate is used. , Essentially "AZODN"
The result is equivalent to using. This has been demonstrated by an additional test which verifies that the product obtained by the reaction of these added salts with nitric acid has the same properties as "AZODN" of Example 1.

Example 1 A high oxygen balance fuel according to the present invention was prepared by the following method. First, 10 g of aminoguanidine nitrate (AGN) was weighed and prepared in a 400 ml glass beaker. Thereto, a volume of about 20-25 ml of water, or preferably distilled water, was added to prepare an AGN / water slurry. By pouring 150 ml of reagent grade nitric acid (70%) into this AGN / water slurry with gentle stirring, a dispersion was formed, the total volume of which was about 170-175 ml. A 10 degree temperature increase occurred when the acid was first added, and the temperature returned to normal as acid was added. Thereafter, while the dispersion liquid is appropriately stirred, the dispersion liquid is placed on a hot plate for 55 minutes.
Heated at ６５65 ° C. As a result, all the remaining AGN was dissolved in the solution.

The temperature was maintained at 55-65 ° C. until the color of the solution changed from clear and colorless to pale yellow and deep light yellow (similar to the color of potassium dichromate solution), and heating was continued. . It is strongly recommended that you do this in a hood and have an ice tub. In addition, the reaction must be limited so that the maximum temperature does not exceed 65 ° C. Immediately before the exotherm begins, the color of the solution is observed to convert to a deeper yellow.

By placing the beaker in an ice bath, the contents are cooled and the effervescence subsides. The reaction mixture was placed in an ice bath at 0-5 <0> C and a yellow precipitate appeared when cooled below 12 <0> C. The yellow precipitate was vacuum filtered and washed several times with distilled water. Thereafter, the precipitate was washed several times with ethanol and dried at 62 ° C.

Example 2 FIG. 3 shows the infrared absorption spectrum of the product produced by the treatment described in Example 1. The above absorption spectrum was cited from the document `` Anal.Chem. 23, 1594 (1951) ''
Comparison with the infrared absorption spectrum of azodicarbamidine dinitrate. When FIG. 3 is compared with the reference spectrum shown in FIG. 11, the reaction product of the synthetic azobisformamidine system of the present invention is 1,1′-azodiformamidine dinitrate (azodicarbamidine dinitrate). ).

Example 3 Using the differential scanning calorimetry (DSC), the reaction product after washing obtained in Example 1 was heat-aged (at 107 ° C. for 17 days). And the thermal stability was compared. From the DSC plot of the reaction product after washing and the heat aging reaction product, it was found that the amount of change in the exothermic peak temperature and the exothermic onset temperature of the product due to aging was very small. Specifically, the heat generation starting temperature is 160.82
° C to 170.21 ° C, and the exothermic peak temperature changes from 183.32 ° C to 185.
Changed to 47 ° C. Thus, the AZODN fuel of the present invention shows good aging characteristics.

Example 4 Pure A produced by the method of Example 1 without additives such as oxidizing agents
The ZODN powder caused rapid spontaneous deflagration by ignition at ambient temperature and atmospheric pressure. That is, a small amount (1/2 g) of the high oxygen balance fuel (sample) of Example 1 was used.
) Placed in the center of the watch glass and inserted a lit stalk into the sample. The sample ignited immediately, like a smokeless rifle gunpowder, and its burning was rapid and clean. As described above, the AZODN fuel of the present invention performs rapid self-combustion, so that it is very effective for a heterogeneous and / or hybrid type expansion device, an auto-igniting agent (AIP), and a gas generation device of ignition only type. It can be used for

Example 5 0.269 AZODN of the present invention was placed on a pre-weighed aluminum balance dish, and ignited with a lighted shaft. After ignition, the pan was weighed again. 0.005 g of a light brown residue remained in the AZODN reaction product, and the combustion residue was 1.84% by weight.
Met.

Further experiments were performed on small propellant batches containing the AZDON reaction product of the present invention to determine sensitivity, heat aging, weight loss, and ballistic properties. The density of the product and various propellants composed of the product was determined by measuring the weight and the pellet size, and was 1.66 g / cc or more.

EXAMPLE 6 Pure AZODN of the present invention was formed into 1/4 inch by 5/8 inch compacted pellets and fired in a strand bomb state without additives such as oxidizing agents to give 100%.
0.122, 0.342, .0 at psi, 500 psi, and 750 psi, respectively.
It exhibited a burn rate of 428 ips (inch / second). From these combustion rates, the combustion index
(burning rate exponent) was determined to be 0.63.

Example 7 A propellant containing 10.60% of sodium nitrate (SN) as an oxidizing agent and a scavenger, 14.59% of ammonium perchlorate (AP), and 74.81% of AZDON of the present invention ( Batch No. 11899) was prepared to give an O / F ratio of 1.0 on combustion and was fired to give 7% solid combustion products per 100 grams of composition and 3.7 harmless gases. Mole was produced. In this preparation, 50
At 0 psi and 750 psi, the burn rates were 0.32 ips and 0.46 ips, respectively. From these combustion rates, the pressure index was determined to be 0.90.

Example 8 22.05% of sodium nitrate (SN) oxidizing agent and AZDON of the present invention at 77.
Propellant containing 92% (batch number 11900) was prepared and burned,
For 100 g of the composition, the solid combustion product level was 8% and the production of almost harmless gas was 3.4 mol. When tested for its elastic properties as 1/4 inch x 5/8 inch pellets, 250 psi, 500 psi, 750 psi,
0.17 ips and 0.32 at 1000 psi and 1250 psi, respectively.
It exhibited burn rates of ips, 0.47 ips, 0.59 ips, and 0.73 ips. From these combustion rates, the pressure index was determined to be 0.90.

Example 9 Lithium carbonate (LC) scavenger / coolant 7.74%, AP oxidizer 22.01
%, And a propellant containing 70.25% of the AZDON of the present invention (batch number 11
901) showed a burn rate of 0.34 ips at 500 psi, but with a severe weight loss of 5.9% as a result of exposure to 107 ° C. for 24 hours. In the differential scanning calorimetry for this preparation, the exothermic onset temperature was 146 ° C, and the exothermic peak temperature was 179 ° C.
showed that.

Example 10 Propellant containing 12.35% of potassium nitrate (KN), 14.3% of ammonium perchlorate (AP) and 73.35% of AZDON of the present invention as a scavenger / oxidizer
(Batch No. 11903) was prepared to give an O / F ratio of 1.0 on combustion and was fired to give a solid combustion product level of 9% per 100 g of composition, producing almost harmless gas. Was 3.6 mol. When tested for its ballistic properties as 1/4 inch by 5/8 inch pellets, this preparation yielded 50
At 0 psi and 750 psi, the burn rates were 0.40 ips and 0.52 ips, respectively, and the pressure index was 0.56.

Example 11 A propellant containing 12.89% of strontium nitrate (SrN), 14.21% of AP, and 72.90% of AZDON of the present invention (batch number 11905) was used for combustion at an O / F ratio of 1 2.0 (SrN acts as a clinker / scavenger / oxidizer) and is burned to give a solid combustion product level of 9.5% per 100 g of composition, an almost harmless gas. Was 3.5 moles. The mixture was 0.34 ips and 0.6 psi at 500 psi and 1000 psi, respectively.
It exhibited a burn rate of 1 ips and a pressure index of 0.85.

The exothermic onset temperatures and exothermic peak temperatures for the various propellant mixtures are shown in Table 8. These temperatures were determined from the results of differential scanning calorimetry performed on each of the samples.

[0094]

[Table 8]

The burning rates of the AZODN propellant under the conditions of the above-mentioned examples under pressure are shown in Table 9 below.

[0096]

[Table 9]

Table 10 shows the weight loss due to aging (aging) for the various AZODN preparations described above.

[0098]

[Table 10]

The sample of the above example is AZODN which has been filtered, washed and dried but not recrystallized. Table 10 shows that little weight loss was seen when aging was performed at 107 ° C. and 90 ° C. at an accelerated rate. The pellets (1/2 inch in diameter x 1/2 inch in height) were previously dried at 62 ° C (no reduced pressure) before being placed in any of the aging ovens. Some weight loss occurred during the course of the first day (24 hours), likely due to aqueous or non-aqueous volatile contents.

Example 12 When each sample of the above propellant was re-prepared to have an O / F ratio of 0.90, 0.95, the level of solid combustion products was between 6 and 7.5%. Range. In the AP / AZODN system (in which the scavenger prevents and removes hydrogen chloride), the use of SN instead of KN as scavenger / oxidizer results in a lower O / F ratio. The solid combustion product levels at 0.95 and 0.90 were 6% and 4.5%, respectively.

Like the pure AZODN, the propellant batch using the high oxygen balance fuel according to the present invention has all of the permissible characteristics of impact, friction and electrostatic sensitivity exhibited in the experiment in powder form within the allowable range. Met. Initial propellant impact tests all gave a negative result of 2.5 kg (100 kg-cm) at 50 cm for all 10 cases. In later experiments with the dried material, the hazard properties were still acceptable. However, the shock experimental values obtained in these later experiments show somewhat higher sensitivity, for example, 5
It was 0 kg-cm. In the electrostatic discharge experiment, 6 joules for all 10 cases,
A negative result of 5 kV was obtained. Also in the friction test (ABL type), a negative result of 300 psi-90 ° was obtained for all 10 cases, and a negative result of 1800 psi-90 ° was also obtained for the LS, SN, and KN propellants (see Examples below). Came out.

For some of the samples of high oxygen balance products that are considered AZODN prepared by the method of Example 1, the thermal stability including differential scanning calorimetry (DSC), accelerated aging test at high temperature, etc. is considered. did. Obtained by DSC for propellants containing 12.9%, 14.2%, 72.9% by weight of strontium nitrate (SrN), ammonium perchlorate (AP), and unrecrystallized AZODN respectively. As a result, the exothermic onset temperature was 161 ° C, and the full decomposition temperature was 184.5 ° C.
showed that.

According to the DSC results, the exothermic decomposition onset temperature of all the propellants was about 160 ° C. This suggests that the propellant containing the high oxygen balance fuel or AZODN of the present invention does not necessarily require the use with an auto-ignition agent (AIP). Both pure AZODN and propellants containing AZODN have high burning rates at low operating pressures, low but acceptable autoignition temperatures and acceptable pressure exponents.
Since both have been achieved, the present invention provides an inflator with limited volume and weight.
Can be applied very effectively. In addition, if these expansion devices are made of aluminum, high-performance plastic, low-gauge steel components, etc., by operating the expansion devices using the propellant of the present invention, the expansion devices are not crushed. It would be possible to pass a higher rate of the bonfire test, which requires a burst to pass.

Example 13 A high oxygen balance fuel of the present invention is prepared according to the method of Example 1 using aminoguanidine bicarbonate in combination with nitric acid instead of aminoguanidine nitrate. Thereby, the high oxygen balance fuel according to the second embodiment is provided.

Example 14 A high oxygen balance fuel of the present invention is prepared according to the method of Example 1 using aminoguanidine sulfate in combination with nitric acid instead of aminoguanidine nitrate.
This provides a high oxygen balance fuel according to the third embodiment.

Example 15 A high oxygen balance fuel of the present invention is prepared according to the method of Example 1 using aminoguanidine sulfate in combination with nitric acid instead of aminoguanidine nitrate.
Further, by using the acid used in the method of Example 1 as the nitric acid component,
A high oxygen balance fuel according to a fourth aspect is provided. That is, since the nitric acid can be reused after the fuel of the present invention is recovered, the yield of the final product is improved. Regardless of the type of aminoguanidate and whether the aminoguanidate is used in the initial reaction or in subsequent reactions, the nitric acid used in one reaction can be used in subsequent reactions .

FIG. 4 is a supplementary DSC graph relating to AZODN of Example 1.
As can be seen from this figure, the exothermic onset temperature was about 160 ° C, and the actual decomposition occurred at 185.1 ° C. FIG. 5 shows the fuel produced by the method of Example 13 (
FIG. 4 is a DSC graph of the second embodiment), wherein the exothermic onset temperature was 157.69 ° C., and 184.98 ° C. at which full-scale decomposition occurred. That is, the fuel of Example 13 using aminoguanidine bicarbonate is substantially equivalent to the fuel of Example 1, and is azodiformamidine dinitrate. In the present invention, it is preferable to use aminoguanidine bicarbonate as the aminoguanidine salt.

FIG. 6 is a DSC graph of the fuel (third embodiment) produced by the method of Example 14, with an exothermic onset temperature of 150.39 ° C. and full-scale decomposition occurring at 182.
. 44 ° C. That is, the fuel of Example 14 using aminoguanidine sulfate is substantially equivalent to the fuel of Example 1, and is azodiformamidine dinitrate.

FIG. 7, FIG. 8, and FIG. 9 show infrared spectra of the fuels according to Examples 1, 13, and 14, respectively, in order. 10 (a) to 10 (d) also show Example 15,
The infrared spectra of fuels 1, 13, and 14 are shown in order, respectively. Comparison of these spectra with the infrared spectra shown in FIG. 11 quoted from the document "Analytical Chemistry Vol. 23, p. 1594 (1951)" shows that aminoguanidine nitrate,
The high oxygen balance fuel of the present invention using aminoguanidine salts, such as aminoguanidine bicarbonate, aminoguanidine sulfate, etc., has been shown to be azodiformamidine dinitrate. The same can be said for the case of acid reuse according to Example 15.

Tables 11 to 15 show the use of typical AZODN produced from aminoguanidine nitrate, aminoguanidine bicarbonate, aminoguanidine sulfate, or a combination thereof. As is evident from the results shown in Table 11, the proportion of the total amount of ash in the product is low, the combustion temperature is within the allowable range, and the result of the risk test is “Green” which means “within the allowable range”. is there. In particular, Table 11 shows the propellant properties of each of the AZODNs obtained with five different formulations without using a binder.

Table 12 shows the evaluation when a binder was used as the composition of the AZODN propellant. In particular, QPAC-40 binder (polycarbonate) manufactured by PAC Polymer and CAB (butyl) manufactured by Eastman Chemical Company were used. Cellulose acetate). From this table, it can be seen that generally, as the binder component increases, the initial impact durability of the AZODN propellant composition increases.

Tables 13 through 15 show the effect of annealing time and particle size on compression resistance and burn rate for various AZODN propellant compositions with and without the QPZC-40 binder. ing.

[0113]

[Table 11]

[0114]

[Table 12]

[0115]

[Table 13]

[0116]

[Table 14]

[0117]

[Table 15]

[0118]

[Table 16]

Table 16 shows that the gas generating propellant composition of the present invention produced from the reaction of aminoguanidine salts such as aminoguanidine nitrate, aminoguanidine sulfate and aminoguanidine bicarbonate with nitric acid was used without filtering. 2 shows the amounts of insoluble and soluble degradation products produced during the swelling experiment. In particular, this experiment used a PD-67 full-size weight experimental inflator ignition unit without a filtering collection system. The propellant sample was washed after being ignited in a 60 liter tank, and the amount of solid decomposition products in the tank was measured. The pH of the solid decomposition product formed was also measured. As can be seen from Table 16 above, the pH of the decomposition products is relatively neutral. This is important in that it does not harm the occupants of the vehicle in which the propellant of the invention is used in the airbag unit in the event of a collision. In addition, the amount of unfiltered, insoluble, soluble degradation products is relatively small.

As can be seen from the above examples and corresponding tests, the high oxygen balance fuels of the present invention, preferably azodiformamidine dinitrate, exhibit attractive propellant properties and can be used in a variety of ignitable gas generating environments. Available at

[Brief description of the drawings]

FIG. 1 is a conventional passenger-side inflation device that can be used with the composition according to the present invention.

FIG. 2 is a conventional driver-side inflation device that can be used with the composition according to the present invention.

FIG. 3 shows an infrared absorption spectrum of a reaction product according to Example 1 of the present invention.

FIG. 4 shows the differential scanning calorimetry of the reaction product according to Example 1 of the present invention.

FIG. 5 shows differential scanning calorimetry of a reaction product according to Example 2 of the present invention.

FIG. 6 shows differential scanning calorimetry of a reaction product according to Example 3 of the present invention.

FIG. 7 shows an infrared absorption spectrum of a reaction product according to Example 1 of the present invention.

FIG. 8 shows an infrared absorption spectrum of a reaction product according to Example 2 of the present invention.

FIG. 9 shows an infrared absorption spectrum of a reaction product according to Example 3 of the present invention.

10 (a) to 10 (d) show infrared absorption spectra of reaction products according to Examples 4, 1, 2, and 3 of the present invention, respectively.

FIG. 11 shows an infrared absorption spectrum of azodicarbamidine dinitrate measured conventionally.

FIG. 12 is a graph showing a typical transition when the reaction product of the present invention is ignited.

──────────────────────────────────────────────────続 き Continuation of front page (72) Inventor Greso, Alone, Jay. United States, Virginia 22701, Culpeper, Friendship Way Number 102 600 (72) Inventor Sheffi, Robert, S.S. 22079, Virginia, USA Lawton, Jericho Court 9450

Claims (25)

[Claims] 1. An ignitable gas generating composition comprising a high oxygen balance fuel, wherein the high oxygen balance fuel is a solid yellow reaction product obtained by a reaction between nitric acid and an aminoguanidine salt. , Ignition type gas generating composition. 2. The ignitable gas generating composition according to claim 1, wherein the aminoguanidine salt is any one selected from the group consisting of aminoguanidine bicarbonate, aminoguanidine sulfate, and a mixture thereof. 3. The ignitable gas generating composition according to claim 2, wherein the high oxygen balance fuel is contained in a ratio of 2% by weight to 100% by weight. 4. The ignitable gas generating composition according to claim 3, wherein the high oxygen balance fuel is contained in a ratio of 40% by weight to 100% by weight. 5. A yellow reaction product obtained by reacting the aminoguanidine salt with nitric acid, comprising: (a) a step of preparing the aminoguanidine salt; and (b) a dispersion obtained by combining the aminoguanidine salt with nitric acid. Wherein the color transitions from colorless and transparent to pale yellow to light yellow, the color of which is comparable to that of the potassium dichromate solution. The ignitable gas generating composition according to claim 2. 6. The ignitable gas generating composition of claim 5, wherein 70% reagent grade nitric acid is combined with the aminoguanidine salt. 7. A yellow reaction product obtained by the reaction between the aminoguanidine salt and nitric acid, comprising: (a) a step of forming a slurry by combining the aminoguanidine salt and water; and (b) a 70% nitric acid solution. Into the slurry and stirring to form a dispersion; and (c) dissolving and bubbling the dispersion while producing a colorless, transparent to pale yellow color, and a light yellow color comparable to a potassium dichromate solution. Heating the dispersion until a color transition occurs to form a solution; and (d) cooling the solution to precipitate the solid yellow reaction product. The ignitable gas generating composition according to claim 2, which is prepared by: 8. The ignitable gas generating composition according to claim 7, wherein the dispersion is heated to 55 ° C. to 65 ° C. and the solution is cooled to less than 12 ° C. 9. The composition further comprises at least one oxidizing agent, wherein the content of the oxidizing agent is 0% by weight.
The ignitable gas generating composition according to claim 2, wherein the composition is in a proportion of ~ 98% by weight. 10. The ignitable gas generating composition according to claim 9, wherein the content ratio of the at least one oxidizing agent is 0% by weight to 60% by weight. 11. The ignitable gas generating composition according to claim 9, wherein the at least one oxidizing agent is substantially non-hygroscopic. 12. A scavenger, an ignition aid, an ignition initiator, a gas conversion catalyst, a ballistic modifier, a slag former, a binder, an energy binder, a plasticizer, an energy plasticizer, a fuel, a stabilizer,
The ignitable gas according to claim 9, further comprising at least one additive selected from the group consisting of a curing agent, a curing catalyst, a crosslinking agent, an inorganic coolant, an organic coolant, a synthesis auxiliary, and a mixture thereof. Generating composition. 13. A nitrite, nitrate, chlorite, chlorate, perchlorate, chromate salt of a non-metal, alkali metal, alkaline earth metal, transition metal or transition metal complex, respectively.
The ignitable gas-generating composition according to claim 9, comprising, as the at least one oxidizing agent, any one selected from the group consisting of: and a mixture thereof. 14. The ignitable gas generating composition of claim 13, wherein said oxidizing agent comprises sodium nitrate. 15. The ignitable gas generating composition according to claim 14, wherein the oxidizing agent further comprises ammonium perchlorate. 16. The ignitable gas generating composition according to claim 9, wherein the oxidizing agent comprises phase stabilized ammonium nitrate. 17. The oxidizing agent comprises ammonium perchlorate, wherein the composition comprises ammonium perchlorate, ammonium nitrate, potassium perchlorate, strontium nitrate, potassium nitrate, lithium nitrate, lithium carbonate, and mixtures thereof. The ignitable gas generating composition according to claim 9, further comprising at least one additive selected from the group consisting of: 18. The ignitable gas generating composition according to claim 2, wherein the reaction product is crystallized or recrystallized. 19. The method of claim 1, further comprising at least one other high oxygen balance fuel.
The ignitable gas generating composition according to claim 1. 20. The other high oxygen balance fuel is any one selected from the group consisting of hydrazodicarbonamidine, diazoguanidine, formamidine, bisformamidine, azobisformamidine derivative fuel, and mixtures thereof. 20.
The ignitable gas generating composition according to claim 1. 21. The azobisformamidine derivative is selected from the group consisting of guanyl azide nitrate, diazoguanidine nitrate, azobisnitroformamidine, 1,1′-azodiformamidine dipicrate, and a mixture thereof. 21. The ignitable gas generating composition of claim 20, which is any one of: 22. A chemical delivery system for flame suppression, comprising a container, said container containing a high oxygen balance fuel, wherein said high oxygen balance fuel reacts with an aminoguanidine salt and nitric acid. A chemical delivery system for flame suppression, which is a reaction product obtained by the above and is also a flame suppression chemical. 23. The aminoguanidine salt is any one selected from the group consisting of aminoguanidine bicarbonate, aminoguanidine sulfate, and mixtures thereof.
The chemical delivery system for flame suppression according to claim 1. 24. A method of expanding an object capable of holding a gas, comprising: igniting a gas generating composition comprising a yellow reaction product of a reaction between an aminoguanidine salt and nitric acid as a high oxygen balance fuel; Generating a gas and a solid as a product of the reaction of the high oxygen balance fuel; passing the gas and the solid through a filter; retaining at least a portion of the solid on the filter; A method of inflating an object capable of holding a gas, comprising the steps of: passing through; and passing the filtered gas through an object to fill or inflate the object. 25. The aminoguanidine salt is any one selected from the group consisting of aminoguanidine bicarbonate, aminoguanidine sulfate, and mixtures thereof.
The method described in.