PRESSURIZING-GAS-PRODUCING CHARGES CONTAINING AN AMINOGUANIDINE TETRAZOLE AND AN OXYGEN-LIBERATING OR GAS-EVOLVING ADDITIVE
United States Patent 3719604
Novel gas-generating compositions comprising 40 to 100 weight percent aminoguanidine salts of azotetrazole of the formula: ##SPC1## Or of ditetrazole of the formula: ##SPC2## Optional other components of such compositions include oxygen-liberating or other gas-evolving substances which may be present in 0 to 60 weight percent of the composition. There are also disclosed pressurizing gas-actuated devices utilizing these compositions.
Inventors:
Prior, Josef (521 Troisdorf, DT)
Siegelin, Werner (8504 Stein b. Nuremberg, DT)
Siegelin, Werner (8504 Stein b. Nuremberg, DT)
Application Number:
05/110601
Publication Date:
03/06/1973
Filing Date:
01/28/1971
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Export Citation:
Assignee:
Dynamit Nobel AG (Troisdorf, DT)
Primary Class:
Other Classes:
422/164, 149/61, 423/240R, 252/187.310, 252/186.100, 252/372, 149/46, 252/4, 149/77, 423/240S, 534/765, 516/2, 423/235, 149/40, 252/186.250, 252/186.440, 548/251, 252/183.130, 149/19.800
International Classes:
C06B43/00; C06D5/00
Field of Search:
252/186,187,372,350,4 23/281,2 260/157,308 423/235,240
Primary Examiner:
Guynn, Herbert B.
Assistant Examiner:
Gluck, Irwin
Claims:
What is claimed is
1. A gas-producing composition comprising an aminoguanidine salt of at least one member selected from the group consisting of azotetrazole of the formula: ##SPC5##
2. A composition as claimed in claim 1, wherein said oxygen-liberating additive is a member selected from the group consisting of inorganic chlorates, perchlorates and nitrates; nitroguanidine; guanidine nitrate; nitrocellulose; nitropolystyrene; polynitrophenols; and polynitrocresols.
3. A composition as claimed in claim 1, additionally containing about 0.5 to 5 weight percent, referred to the entire composition, of a metal compound catalyst wherein said metal is a member selected from the group consisting of vanadium, tungsten, molybdenum, chromium and cobalt.
4. A composition as claimed in claim 3, wherein said metal is in its highest valence state.
5. In a process for liberating gas under pressure in which a charge comprising an oxygen-liberating or gas-evolving mixture is ignited, the improvement to reduce explosive spontaneous decomposition of the charge and improve safety in handling which comprises adding to said charge an aminoguanidine salt of at least one member selected from the group consisting of azotetrazole of the formula: ##SPC7##
6. An improvement according to claim 5 wherein the oxygen-liberating additive is a member selected from the group consisting of inorganic chlorates, perchlorates and nitrates nitroguanidine; guanidine nitrate; nitropolystyrene; nitrocellulose; polynitrophenols; and polynitrocresols.
7. An improvement according to claim 5 wherein the oxygen-liberating or gas-evolving substance additionally contains about 0.5 to 5 weight percent, referred to the entire composition, of a metal compound catalyst wherein said metal is a member selected from the group consisting of vanadium, tungsten, molybdenum, chromium and cobalt.
8. An improvement according to claim 7 wherein said metal is in its highest valence state.
1. A gas-producing composition comprising an aminoguanidine salt of at least one member selected from the group consisting of azotetrazole of the formula: ##SPC5##
2. A composition as claimed in claim 1, wherein said oxygen-liberating additive is a member selected from the group consisting of inorganic chlorates, perchlorates and nitrates; nitroguanidine; guanidine nitrate; nitrocellulose; nitropolystyrene; polynitrophenols; and polynitrocresols.
3. A composition as claimed in claim 1, additionally containing about 0.5 to 5 weight percent, referred to the entire composition, of a metal compound catalyst wherein said metal is a member selected from the group consisting of vanadium, tungsten, molybdenum, chromium and cobalt.
4. A composition as claimed in claim 3, wherein said metal is in its highest valence state.
5. In a process for liberating gas under pressure in which a charge comprising an oxygen-liberating or gas-evolving mixture is ignited, the improvement to reduce explosive spontaneous decomposition of the charge and improve safety in handling which comprises adding to said charge an aminoguanidine salt of at least one member selected from the group consisting of azotetrazole of the formula: ##SPC7##
6. An improvement according to claim 5 wherein the oxygen-liberating additive is a member selected from the group consisting of inorganic chlorates, perchlorates and nitrates nitroguanidine; guanidine nitrate; nitropolystyrene; nitrocellulose; polynitrophenols; and polynitrocresols.
7. An improvement according to claim 5 wherein the oxygen-liberating or gas-evolving substance additionally contains about 0.5 to 5 weight percent, referred to the entire composition, of a metal compound catalyst wherein said metal is a member selected from the group consisting of vanadium, tungsten, molybdenum, chromium and cobalt.
8. An improvement according to claim 7 wherein said metal is in its highest valence state.
Description:
This invention relates to gas-evolving systems. It more particularly refers to novel gas-evolving systems which are relatively safe from detonation and explosion.
The energy of gases liberated in a chemical reaction is utilized in industry to force liquids or solids out of a container, for example, in fire extinguishes. Other devices make use of this force to actuate slide bars or bolts or to do other work. (See, for example, German patent 854,770, introduction.)
As gas-generating charges, substances or mixtures are known for this purpose which are formulated entirely or largely from combustible, gas- and heat-evolving substances. Such substances, for example, as nitrocellulose powder or nitropolystyrene, are capable of burning without any independent feed of oxygen. These materials may also consist of mixtures of oxygen-liberating substances, such as potassium chlorate, and gas-evolving substances such as ammonium nitrate or guanidine nitrate. (See, for example, German patents 854,770, 851,919, and 909,424.)
Often the heat generated in these gas-evolving reactions is undesirable, and mixtures have therefore come into use which absorb the heat evolved on oxidation by a concurrent endothermal process. Such mixtures contain, for example, ammonium oxalate, or hydrocarbons which decompose in an endothermal reaction, such as cyclopentadiene. (German patents 882,825, and 1,150,914), respectively.)
What is desired in all cases is the evolution of as large a quantity of gas as possible, without the explosive spontaneous decomposition of the charge during such gas evolution, and maximum safety in handling, that is to say, a high degree of insensitivity to ignition by friction and shock. In contrast to this desideratum, mixture containing fairly high proportions of guanidine nitrate, for example, have a tendency to explosively decompose, which may result in destruction of the container.
It is therefore an object of this invention to provide a novel gas-generating composition.
Other and additional objects of this invention will become apparent from a consideration of this entire specification, including the claims hereof.
In accord with, and fulfilling these objects, one aspect of this invention resides in novel pressurizing-gas-producing charges, particularly for use in pressurizing-gas-actuated devices, which are characterized by the fact that they comprise from 40 to 100 weight percent aminoguanidine salts of azotetrazole and/or ditetrazole. Other components of the composition may include oxygen-liberating and/or other gas-evolving substances which do not cause detonation. These may be used singly or in combination in proportion of 0 to 60 weight percent.
Azotetrazole has the formula ##SPC3##
And ditetrazole has the formula ##SPC4##
The hydrogen atoms of these compounds have an acid reaction and consequently form, with aminoguanidine, the corresponding salts. These salts are prepared, for example, by mixing aqueous solutions of salts of aminoguanidine, such as aminoguanidine sulfate, with aqueous solutions of alkali salts of said tetrazoles. The insoluble salt compounds suitable for use in accordance with the present invention precipitate from this reaction mixture and can be recovered by conventional chemical engineering techniques.
Suitable oxygen-liberating optional additives are chlorates, perchlorates and nitrates of inorganic bases which are all preferred. Nitroguanidine, guanidine nitrate, nitrocellulose, nitropolystyrene, polynitrophenols, polynitrocresols or the like can also be incorporated as oxygen liberators.
Solely gas-evolving optional additives which are suitable are, for example, ammonium oxalate, urea, aminoguanidine, sugar, tartaric acid or the like.
Catalysts promoting decomposition, such as compounds of vanadium, tungsten, molybdenum, chromium, cobalt or the like, particularly in the highest degree of oxidation of the metal, may advantageously be added to the compositions of this invention in a proportion of from 0.5 to 5 weight percent, referred to the total mixture.
The compositions of this invention are prepared by simple mixing of the ingredients. The resultant solid composition may be pressed, but this is not absolutely necessary.
The following examples serve to illustrate this invention without being in any way limiting thereon.
EXAMPLE 1
A mixture of 500 g of azotetrazole-aminoguanidine salt and 500 g of barium nitrate was pressed into bodies which were then ignited in a pressure pipe with nozzle. A strong gas jet was thus produced. The mixture furnished 350 cc gas/g of mixture. It was not ignited by the shock of a falling weight of 2 kg dropped from a height of 2 meters.
EXAMPLE 2
An intimate mixture of 700 g of ditetrazole-aminoguanidine salt and 300 g of potassium nitrate was pressed into bodies which were ignited in a pressure pipe with nozzle by the use of an electric primer pellet. The quantity of gas evolved was 400 cc/g. The mixture was not ignited by the shock of a falling weight of 2 kg dropped from a height of 2 meters.
EXAMPLE 3
A pressure composition was prepared from 50 g of barium nitrate (Ba(NO 3 ) 2 ), 50 g of azotetrazole-aminoguanidine salt, 4 g of vanadium pentoxide V 2 O 5 and 15 g of an aluminum-titanium alloy. After ignition of the composition by means of an ignition mixture disposed in a central ignition tube, a reaction of the composition set in with evolution of heat. The heat generated was 768 cal/g.
EXAMPLE 4
A pressure composition was prepared from 40 g of barium nitrate (Ba(NO 3 ) 2 ) and 60 g of azotetrazole-aminoguanidine salt. After ignition of the composition by means of the ignition mixture disposed in a central ignition tube, a reaction of the composition set in with evolution of heat. The heat generated was 613 cal/g., Volumen of evolved gas: 440 cm 3 /g.
EXAMPLE 5
A pressure composition was prepared from 45 g of barium nitrate (Ba(NO 3 ) 2), 45 g of azotetrazole-aminoguanidine salt and 10 g of amorphous boron. After ignition of the composition by means of the ignition mixture disposed in a central ignition tube, a reaction of the composition set in with evolution of heat. The heat generated was 826 cal/g., amount of evolved gas: 520 cm 3 /g.
EXAMPLE 6
A pressure composition was prepared from 30 g of barium nitrate (Ba(NO 3 ) 2 ), 50 g of azotetrazole-aminoguanidine salt and 20 g of potassium nitrate (KNO 3 ). After ignition of the composition by means of the ignition mixture disposed in a central ignition tube, a reaction of the composition set in with evolution of heat. The heat generated was 687 cal/g.
The energy of gases liberated in a chemical reaction is utilized in industry to force liquids or solids out of a container, for example, in fire extinguishes. Other devices make use of this force to actuate slide bars or bolts or to do other work. (See, for example, German patent 854,770, introduction.)
As gas-generating charges, substances or mixtures are known for this purpose which are formulated entirely or largely from combustible, gas- and heat-evolving substances. Such substances, for example, as nitrocellulose powder or nitropolystyrene, are capable of burning without any independent feed of oxygen. These materials may also consist of mixtures of oxygen-liberating substances, such as potassium chlorate, and gas-evolving substances such as ammonium nitrate or guanidine nitrate. (See, for example, German patents 854,770, 851,919, and 909,424.)
Often the heat generated in these gas-evolving reactions is undesirable, and mixtures have therefore come into use which absorb the heat evolved on oxidation by a concurrent endothermal process. Such mixtures contain, for example, ammonium oxalate, or hydrocarbons which decompose in an endothermal reaction, such as cyclopentadiene. (German patents 882,825, and 1,150,914), respectively.)
What is desired in all cases is the evolution of as large a quantity of gas as possible, without the explosive spontaneous decomposition of the charge during such gas evolution, and maximum safety in handling, that is to say, a high degree of insensitivity to ignition by friction and shock. In contrast to this desideratum, mixture containing fairly high proportions of guanidine nitrate, for example, have a tendency to explosively decompose, which may result in destruction of the container.
It is therefore an object of this invention to provide a novel gas-generating composition.
Other and additional objects of this invention will become apparent from a consideration of this entire specification, including the claims hereof.
In accord with, and fulfilling these objects, one aspect of this invention resides in novel pressurizing-gas-producing charges, particularly for use in pressurizing-gas-actuated devices, which are characterized by the fact that they comprise from 40 to 100 weight percent aminoguanidine salts of azotetrazole and/or ditetrazole. Other components of the composition may include oxygen-liberating and/or other gas-evolving substances which do not cause detonation. These may be used singly or in combination in proportion of 0 to 60 weight percent.
Azotetrazole has the formula ##SPC3##
And ditetrazole has the formula ##SPC4##
The hydrogen atoms of these compounds have an acid reaction and consequently form, with aminoguanidine, the corresponding salts. These salts are prepared, for example, by mixing aqueous solutions of salts of aminoguanidine, such as aminoguanidine sulfate, with aqueous solutions of alkali salts of said tetrazoles. The insoluble salt compounds suitable for use in accordance with the present invention precipitate from this reaction mixture and can be recovered by conventional chemical engineering techniques.
Suitable oxygen-liberating optional additives are chlorates, perchlorates and nitrates of inorganic bases which are all preferred. Nitroguanidine, guanidine nitrate, nitrocellulose, nitropolystyrene, polynitrophenols, polynitrocresols or the like can also be incorporated as oxygen liberators.
Solely gas-evolving optional additives which are suitable are, for example, ammonium oxalate, urea, aminoguanidine, sugar, tartaric acid or the like.
Catalysts promoting decomposition, such as compounds of vanadium, tungsten, molybdenum, chromium, cobalt or the like, particularly in the highest degree of oxidation of the metal, may advantageously be added to the compositions of this invention in a proportion of from 0.5 to 5 weight percent, referred to the total mixture.
The compositions of this invention are prepared by simple mixing of the ingredients. The resultant solid composition may be pressed, but this is not absolutely necessary.
The following examples serve to illustrate this invention without being in any way limiting thereon.
EXAMPLE 1
A mixture of 500 g of azotetrazole-aminoguanidine salt and 500 g of barium nitrate was pressed into bodies which were then ignited in a pressure pipe with nozzle. A strong gas jet was thus produced. The mixture furnished 350 cc gas/g of mixture. It was not ignited by the shock of a falling weight of 2 kg dropped from a height of 2 meters.
EXAMPLE 2
An intimate mixture of 700 g of ditetrazole-aminoguanidine salt and 300 g of potassium nitrate was pressed into bodies which were ignited in a pressure pipe with nozzle by the use of an electric primer pellet. The quantity of gas evolved was 400 cc/g. The mixture was not ignited by the shock of a falling weight of 2 kg dropped from a height of 2 meters.
EXAMPLE 3
A pressure composition was prepared from 50 g of barium nitrate (Ba(NO 3 ) 2 ), 50 g of azotetrazole-aminoguanidine salt, 4 g of vanadium pentoxide V 2 O 5 and 15 g of an aluminum-titanium alloy. After ignition of the composition by means of an ignition mixture disposed in a central ignition tube, a reaction of the composition set in with evolution of heat. The heat generated was 768 cal/g.
EXAMPLE 4
A pressure composition was prepared from 40 g of barium nitrate (Ba(NO 3 ) 2 ) and 60 g of azotetrazole-aminoguanidine salt. After ignition of the composition by means of the ignition mixture disposed in a central ignition tube, a reaction of the composition set in with evolution of heat. The heat generated was 613 cal/g., Volumen of evolved gas: 440 cm 3 /g.
EXAMPLE 5
A pressure composition was prepared from 45 g of barium nitrate (Ba(NO 3 ) 2), 45 g of azotetrazole-aminoguanidine salt and 10 g of amorphous boron. After ignition of the composition by means of the ignition mixture disposed in a central ignition tube, a reaction of the composition set in with evolution of heat. The heat generated was 826 cal/g., amount of evolved gas: 520 cm 3 /g.
EXAMPLE 6
A pressure composition was prepared from 30 g of barium nitrate (Ba(NO 3 ) 2 ), 50 g of azotetrazole-aminoguanidine salt and 20 g of potassium nitrate (KNO 3 ). After ignition of the composition by means of the ignition mixture disposed in a central ignition tube, a reaction of the composition set in with evolution of heat. The heat generated was 687 cal/g.