US3909322A - Solid gas generating and gun propellant compositions containing a nitroaminotetrazole salt - Google Patents

Solid gas generating and gun propellant compositions containing a nitroaminotetrazole salt Download PDF

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US3909322A
US3909322A US064154A US6415470A US3909322A US 3909322 A US3909322 A US 3909322A US 064154 A US064154 A US 064154A US 6415470 A US6415470 A US 6415470A US 3909322 A US3909322 A US 3909322A
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nitroaminotetrazole
polybutadiene
oxidant
group
solid propellant
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US064154A
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Marguerite S Chang
Charles L Whitman
Hermann S Haiss
John H Highby
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US Department of Navy
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    • CCHEMISTRY; METALLURGY
    • C06EXPLOSIVES; MATCHES
    • C06BEXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B25/00Compositions containing a nitrated organic compound
    • C06B25/34Compositions containing a nitrated organic compound the compound being a nitrated acyclic, alicyclic or heterocyclic amine
    • CCHEMISTRY; METALLURGY
    • C06EXPLOSIVES; MATCHES
    • C06BEXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B45/00Compositions or products which are defined by structure or arrangement of component of product
    • C06B45/04Compositions or products which are defined by structure or arrangement of component of product comprising solid particles dispersed in solid solution or matrix not used for explosives where the matrix consists essentially of nitrated carbohydrates or a low molecular organic explosive
    • C06B45/06Compositions or products which are defined by structure or arrangement of component of product comprising solid particles dispersed in solid solution or matrix not used for explosives where the matrix consists essentially of nitrated carbohydrates or a low molecular organic explosive the solid solution or matrix containing an organic component
    • C06B45/10Compositions or products which are defined by structure or arrangement of component of product comprising solid particles dispersed in solid solution or matrix not used for explosives where the matrix consists essentially of nitrated carbohydrates or a low molecular organic explosive the solid solution or matrix containing an organic component the organic component containing a resin

Definitions

  • ABSTRACT Solid gas generating and gun propellant compositions which employ certain nitroaminotetrazole salts such as guanidinium S-nitroaminotetrazole, ammonium 5- nitroaminotetrazole and hydrazinium 5- nitroaminotetrazole as modifying ingredients in admixture with an oxidant and a suitable compatible binder material.
  • nitroaminotetrazole salts such as guanidinium S-nitroaminotetrazole, ammonium 5- nitroaminotetrazole and hydrazinium 5- nitroaminotetrazole
  • Another object of the present invention is to provide a solid composite gas generating and gun propellant which is cool burning and producesa high percentage of gas.
  • Still another object of the instant invention is to provide a solid composite gas generating and gun propellant which only yields non-corrosive materials upon combustion.
  • a composite propellant composition comprising an oxidant, such as 1,3,5,7-tetrani tro-l ,3,5,7- tetraazacyclooctane HMX), a nitroaminotetrazole salt selected from the group consisting of guanidinium 5- nitroaminotetrazole (GNAT), ammonium 5- nitroaminotetrazole (ANAT), and hydrazinium 5- nitroaminotetrazole (HNAT), and a suitable compatible binder material.
  • an oxidant such as 1,3,5,7-tetrani tro-l ,3,5,7- tetraazacyclooctane HMX
  • a nitroaminotetrazole salt selected from the group consisting of guanidinium 5- nitroaminotetrazole (GNAT), ammonium 5- nitroaminotetrazole (ANAT), and hydrazinium 5- nitroaminotetrazole (HNAT)
  • an improved gas generating and gun propellant is provided by an admixture of an oxidant, preferably 1,3,5,7-tetranitro- 1,3,5,7-tetraazacyclooctane (HMX), in an amount of from about 5 to about 90 percent by weight, a nitroaminotetrazole salt in an amount of from about 5 to about 70 percent by weight and a suitable compatible polymeric binder in an amount of from about 5 to about 28 percent by weight of the total composition.
  • an oxidant preferably 1,3,5,7-tetranitro- 1,3,5,7-tetraazacyclooctane (HMX)
  • HMX 1,3,5,7-tetranitro- 1,3,5,7-tetraazacyclooctane
  • HMX is the preferred oxidant of the instant invention
  • other oxidants which are traditionally employed for this purpose and are compatible with the nitroaminotetrazole salt modifiers of this invention, may also be employed.
  • Some of these are, for example, ammonium nitrate,5-aminotetrazole nitrate, ammonium perchlorate (AP), and mixtures thereof. It should be noted, however, that where the absence of noncorrosive gases upon combustion is desired ammonium 0 perchlorate is not particularly well suited.
  • nitroaminotetrazole salts of the present invention which impart the low flame temperature and high percentage of gas upon combustion to the propellant compositions of this invention are selected from the group consisting of guanidinium S-nitroaminotetrazole, ammonium S-nitroaminotetrazole and hydrazinium 5- nitroaminotetrazole. These nitrogen rich salts also provide good burning rate characteristics to the compositions.
  • nitroaminotetrazole salt utilized in the propellant compositions of this invention is generally dependent upon the application of the composition.
  • nitroaminotetrazole salt content should not exceed about percent by weight of the total composition while for gun propellant use higher quantities are applicable.
  • the oxidant and nitroaminotetrazole salts of the present invention may be incorporated into any compatible conventional binder matrix material.
  • these are for example, polyesters, polybutadienes, polyurethanes, polyglycols, polybutadienes with hydroxy or carboxy functionality, polyesters with hydroxyfunctionality, polyethers, vinyltetrazoles, glycidyl ether epoxy resins, and copolymers, etc.
  • binder materials such as polyglycol adipate, Butarez CTL I (a mixture of carboxyl-terminated polybutadiene and non-functional polybutadiene), Butarez CTL ll (carboxyl-terminated polybutadiene), the terpolymer of 2-me'thyl-S-vinyltetrazole: butyl acrylate: acrylic acid, and R-45 (a hydroxyl-terminated'polybutadiene) are within the scope of this invention.
  • Anumberof other materials may also be added in minor amounts to the propellant compositions of this invention, such as other coolants like oxamide, ammonium oxalaterlaxalic acid and guanidine nitrate, plasticizers such as dioctyladipate, wetting agents such as lecithin, crosslinking and curing agents like di and tri functional epoxides and ferric acetylacetonate (FeAA) and other burning rate and ballistic modifiers such as lead chromate (PbCrO Having generally described the invention the following Tables are set forth for purposes of illustration. It will be understood that the invention is not limited to these examples, but is susceptible to different modifications that will be recognized by one of ordinary skill in the art. It should be understood that all percentages are by weight.
  • compositions of the hereinabove examples exhibit a flame temperature of about 2500K, or less, which is desirable for gun wear reduction as well as other hardware wear reduction.
  • propellant compositions made in accordance with this invention are useful in gun propellant applications and as gas generators.
  • gas generators they may be employed, for example, for actuating gas pressure operated mechanical devices for driving engines, electric generator or motors and turbines; for operating pneumatic tools; and for the propulsion and guidance of rockets or other gas escape reaction propelled devices.
  • a solid propellant composition comprising an oxidant, a nitroaminotetrazole salt selected from the group consisting of guanidinium S-nitroaminotetrazole,
  • said compatible binder is a polymer selected from the group consisting of a polyester, a polyurethane, a polyglycol, a polybutadiene, a polybutadiene having carboxy functionality, a polybutadiene having hydroxy functionality, a polyester having hydroxy functionality, a polyether, a vinyltetrazole, a glycidyl ether epoxy resin and copolymers thereof.
  • the solid propellant composition of claim 4 wherein said oxidant is l,3,5,7-tetranitro-l,3.5,7- tetraazacyclooctane and said compatible binder is selected from the group consisting of the terpolymer of 2-methyl-5-vinyltetrazole: butyl acrylate: acrylic acid, hydroxyl-terminated polybutadiene cured with an isocyanate and polyglycol adipate.
  • said compatible binder is a polymer selected from the group consisting of a polyester, a polyurethane, a polyglycol, a polybutadiene having carboxy and copolymers thereof.

Abstract

Solid gas generating and gun propellant compositions which employ certain nitroaminotetrazole salts such as guanidinium 5nitroaminotetrazole, ammonium 5-nitroaminotetrazole and hydrazinium 5-nitroaminotetrazole as modifying ingredients in admixture with an oxidant and a suitable compatible binder material.

Description

United States Patent 1191 Chang et a1.
[ 1 Sept. 30, 1975 [73] Assignee: The United States of America as represented by the Secretary of the Navy, Washington, DC.
[22] Filed: Aug. 3, 1970 [21] Appl. No.: 64,154
[52] US. Cl. 149/l9.4; 149/19.5; l49/19 .6;
149/19.9; 149/l9.9l; 149/92; 149/36 [51 lnt. C11 C06D 5/06 [58] Field of Search 149/18, 19, 20, 92, 109,
[56] References Cited UNITED STATES PATENTS 3,117,044 1/1964 Sauer 149/19 3,123,507 3/1964 Butts et a1 149/92 X 3,173,921 3/1965 Einberg 149/92 X 3,269,880 8/1966 Visnov ct 149/92 X 3,348,985 10/1967 Stadler et a1.... 149/92 X 3,354,172 11/1967 Takacs 149/19 X 3,677,841 7/1972 Ayres et a1 149/92 Prinmry E.\'uminerBcnjamin R. Padgett Assistant E.\-aminerE. A. Miller Attorney, Agent, or Firm-R. S, Sciascia; J, A. Cooke [57] ABSTRACT Solid gas generating and gun propellant compositions which employ certain nitroaminotetrazole salts such as guanidinium S-nitroaminotetrazole, ammonium 5- nitroaminotetrazole and hydrazinium 5- nitroaminotetrazole as modifying ingredients in admixture with an oxidant and a suitable compatible binder material.
6 Claims, N0 Drawings SOTJID GAS GENERATING AND GUN PROPELLANT COMPOSITIONS CONTAINING A NITROAMINOTETRAZOLE SALT BACKGROUND OF THE INVENTION This invention relates generally to solid composite propellant compositions and more particularly to solid composite propellant compositions especially useful as gas generating and gun propellants.
Recently, there has been a great demand for gas generating propellants and gun propellants which are cool burning, non-corrosive and produce a high percentage of gas.
In the past, attemps to improve gas generating compositions and gun propellants have been unsuccessful for various reasons. For example, while the addition of certain modifiers have lowered the flame temperature and increased gas production, these modifiers have contributed to the production of undesirable corrosive products. Other modifiers which have been utilized, while not producing corrosive materials, have not succeeded to significantly lower the flame temperature or increase gas evolution.
SUMMARY OF THE INVENTION Accordingly, it is one object ofthis invention to provide a solid composite gas generating and gun propellant.
Another object of the present invention is to provide a solid composite gas generating and gun propellant which is cool burning and producesa high percentage of gas.
Still another object of the instant invention is to provide a solid composite gas generating and gun propellant which only yields non-corrosive materials upon combustion.
These and other objects areachieved by providing a composite propellant composition comprising an oxidant, such as 1,3,5,7-tetrani tro-l ,3,5,7- tetraazacyclooctane HMX), a nitroaminotetrazole salt selected from the group consisting of guanidinium 5- nitroaminotetrazole (GNAT), ammonium 5- nitroaminotetrazole (ANAT), and hydrazinium 5- nitroaminotetrazole (HNAT), and a suitable compatible binder material.
DESCRIPTION OF THE PREFERRED EMBODIMENTS Pursuant to the present invention, an improved gas generating and gun propellant is provided by an admixture of an oxidant, preferably 1,3,5,7-tetranitro- 1,3,5,7-tetraazacyclooctane (HMX), in an amount of from about 5 to about 90 percent by weight, a nitroaminotetrazole salt in an amount of from about 5 to about 70 percent by weight and a suitable compatible polymeric binder in an amount of from about 5 to about 28 percent by weight of the total composition.
Although HMX is the preferred oxidant of the instant invention, other oxidants, which are traditionally employed for this purpose and are compatible with the nitroaminotetrazole salt modifiers of this invention, may also be employed. Some of these are, for example, ammonium nitrate,5-aminotetrazole nitrate, ammonium perchlorate (AP), and mixtures thereof. It should be noted, however, that where the absence of noncorrosive gases upon combustion is desired ammonium 0 perchlorate is not particularly well suited.
The nitroaminotetrazole salts of the present invention which impart the low flame temperature and high percentage of gas upon combustion to the propellant compositions of this invention are selected from the group consisting of guanidinium S-nitroaminotetrazole, ammonium S-nitroaminotetrazole and hydrazinium 5- nitroaminotetrazole. These nitrogen rich salts also provide good burning rate characteristics to the compositions.
The optimum amount of the nitroaminotetrazole salt utilized in the propellant compositions of this invention is generally dependent upon the application of the composition. For gas generator purposes the nitroaminotetrazole salt content should not exceed about percent by weight of the total composition while for gun propellant use higher quantities are applicable.
The oxidant and nitroaminotetrazole salts of the present invention may be incorporated into any compatible conventional binder matrix material. Generally, these are for example, polyesters, polybutadienes, polyurethanes, polyglycols, polybutadienes with hydroxy or carboxy functionality, polyesters with hydroxyfunctionality, polyethers, vinyltetrazoles, glycidyl ether epoxy resins, and copolymers, etc. More specifically, binder materials such as polyglycol adipate, Butarez CTL I (a mixture of carboxyl-terminated polybutadiene and non-functional polybutadiene), Butarez CTL ll (carboxyl-terminated polybutadiene), the terpolymer of 2-me'thyl-S-vinyltetrazole: butyl acrylate: acrylic acid, and R-45 (a hydroxyl-terminated'polybutadiene) are within the scope of this invention.
Anumberof other materials may also be added in minor amounts to the propellant compositions of this invention, such as other coolants like oxamide, ammonium oxalaterlaxalic acid and guanidine nitrate, plasticizers such as dioctyladipate, wetting agents such as lecithin, crosslinking and curing agents like di and tri functional epoxides and ferric acetylacetonate (FeAA) and other burning rate and ballistic modifiers such as lead chromate (PbCrO Having generally described the invention the following Tables are set forth for purposes of illustration. It will be understood that the invention is not limited to these examples, but is susceptible to different modifications that will be recognized by one of ordinary skill in the art. It should be understood that all percentages are by weight.
Table 1 Example 7: binder" Burning rate in/sec S-ATN GNAT 7c ANAT HNAT at 1000 psi; 77F
l 20 ll 20 Ill 20 Table II Example 7( bindcr' '71 HMX 7; ANAT 7: HNAT V! GNAT burning rate in/sec at 1000 psi; 77F
"'ll.2 parts R45M (a hydroXyl-terminatcd polybutadiene. molecular weight 2600. OH functionality 2.4, a
product of Sinclair Petrochemicals. N.Y. N.Y.) to 0.8 parts toluene diisocyanate '"pulyglycol adipatc, KOPOX l70 (trilunctionul cpoxidc crosslinking agent) Koppcrs, Pittsburgh. Pa. FcAA.
Most of the compositions of the hereinabove examples exhibit a flame temperature of about 2500K, or less, which is desirable for gun wear reduction as well as other hardware wear reduction.
The propellant compositions made in accordance with this invention are useful in gun propellant applications and as gas generators. As gas generators, they may be employed, for example, for actuating gas pressure operated mechanical devices for driving engines, electric generator or motors and turbines; for operating pneumatic tools; and for the propulsion and guidance of rockets or other gas escape reaction propelled devices.
Having thus described the invention, what is claimed as new and desired to be secured by Letters Patent of the United States is:
l. A solid propellant composition comprising an oxidant, a nitroaminotetrazole salt selected from the group consisting of guanidinium S-nitroaminotetrazole,
ammonium S-nitroaminotetrazole and hydrazinium 5- nitroaminotetrazole and a compatible binder.
2. The solid propellant composition of claim 1 wherein said oxidant is present in amount within the range of from about 5 to about 90 percent by weight, said nitroaminotetrazole salt is present in an amount within the range of from about 5 to about percent by weight and said binder is present in the amount within the range of from about 5 to about 28 percent by weight of the total composition.
3. The solid propellant composition of claim 2 wherein said oxidant is selected from the group consisting of l ,3,5 ,7-tetranitrol ,3,5,7-tetraazacylcooctane, ammonium nitrate, S-aminotetrazole nitrate, ammonium perchlorate and mixtures thereof.
4. The solid propellant composition of claim 3 wherein said compatible binder is a polymer selected from the group consisting of a polyester, a polyurethane, a polyglycol, a polybutadiene, a polybutadiene having carboxy functionality, a polybutadiene having hydroxy functionality, a polyester having hydroxy functionality, a polyether, a vinyltetrazole, a glycidyl ether epoxy resin and copolymers thereof.
5. The solid propellant composition of claim 4 wherein said oxidant is l,3,5,7-tetranitro-l,3.5,7- tetraazacyclooctane and said compatible binder is selected from the group consisting of the terpolymer of 2-methyl-5-vinyltetrazole: butyl acrylate: acrylic acid, hydroxyl-terminated polybutadiene cured with an isocyanate and polyglycol adipate.
6. The solid propellant composition of claim 2 wherein said compatible binder is a polymer selected from the group consisting of a polyester, a polyurethane, a polyglycol, a polybutadiene having carboxy and copolymers thereof.

Claims (6)

1. A SOLID PROPELLANT COMPOSITION COMPRISING AN OXIDANT, A NITROAMINOTETRAZOLE SALT SELECTED FROM THE GROUP CONSISTING OF GUANIDINIUM 5-NITROAMINOTETRAZOLE, AMMONIUM 5NITROAMININOTETRAZOLE AND HYDRAZINIUM 5-NITROAMINOTETRAZOLE AND A COMPATIBLE BINDER.
2. The solid propellant composition of claim 1 wherein said oxidant is present in amount within the range of from about 5 to about 90 percent by weight, said nitroaminotetrazole salt is present in an amount within the range of from about 5 to about 70 percent by weight and said binder is present in the amount within the range of from about 5 to about 28 percent by weight of the total composition.
3. The solid propellant composition of claim 2 wherein said oxidant is selected from the group consisting of 1,3,5,7-tetranitro-1,3,5,7-tetraazacylcooctane, ammonium nitrate, 5-aminotetrazole nitrate, ammonium perchlorate and mixtures thereof.
4. The solid propellant composition of claim 3 wherein said compatible binder is a polymer selected from the group consisting of a polyester, a polyurethane, a polyglycol, a polybutadiene, a polybutadiene having carboxy functionality, a polybutadiene having hydroxy functionality, a polyester having hydroxy functionality, a polyether, a vinyltetrazole, a glycidyl ether epoxy resin and copolymers thereof.
5. The solid propellant composition of claim 4 wherein said oxidant is 1,3,5,7-tetranitro-1,3,5,7-tetraazacyclooctane and said compatible binder is selected from the group consisting of the terpolymer of 2-methyl-5-vinyltetrazole: butyl acrylate: acrylic acid, hydroxyl-terminated polybutadiene cured with an isocyanate and polyglycol adipate.
6. The solid propellant composition of claim 2 wherein said compatible binder is a polymer selected from the group consisting of a polyester, a polyurethane, a polyglycol, a polybutadiene having carboxy functionality, a polybutadiene having hydroxy functionality, a polyester having hydroxy functionality, a polyether, a vinlytetrazole, a glycidyl ether epoxy resin and copolymers thereof.
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Cited By (33)

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US4091729A (en) * 1977-03-07 1978-05-30 The United States Of America As Represented By The Secretary Of The Army Low vulnerability booster charge caseless ammunition
US4300962A (en) * 1979-10-18 1981-11-17 The United States Of America As Represented By The United States Department Of Energy Ammonium nitrate explosive systems
US4315785A (en) * 1980-04-09 1982-02-16 The United States Of America As Represented By The Secretary Of The Army Propellant charge with reduced muzzle smoke and flash characteristics
US4358327A (en) * 1980-10-14 1982-11-09 The United States Of America As Represented By The Secretary Of The Navy Gas generant propellants
US4373976A (en) * 1977-03-09 1983-02-15 Rockwell International Corporation Gun propellant containing nitroaminoguanidine
US4601344A (en) * 1983-09-29 1986-07-22 The United States Of America As Represented By The Secretary Of The Navy Pyrotechnic fire extinguishing method
US4875949A (en) * 1988-05-18 1989-10-24 The United States Of America As Represented By The Secretary Of The Army Insensitive binder for propellants and explosives
US5053086A (en) * 1985-03-15 1991-10-01 The United States Of America As Represented By The Secretary Of The Navy Gas generant compositions containing energetic high nitrogen binders
US5061329A (en) * 1982-08-03 1991-10-29 The United States Of America As Represented By The Secretary Of The Navy High nitrogen smoke compositions
US5092945A (en) * 1982-03-01 1992-03-03 The United States Of America As Represented By The Secretary Of The Navy Glycidyl azide propellant with antigassing additives
EP0503341A1 (en) * 1991-03-14 1992-09-16 Fraunhofer-Gesellschaft Zur Förderung Der Angewandten Forschung E.V. Stable nitrogen-rich compound
US5160386A (en) * 1991-11-04 1992-11-03 Morton International, Inc. Gas generant formulations containing poly(nitrito) metal complexes as oxidants and method
US5197758A (en) * 1991-10-09 1993-03-30 Morton International, Inc. Non-azide gas generant formulation, method, and apparatus
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US5514230A (en) * 1995-04-14 1996-05-07 Automotive Systems Laboratory, Inc. Nonazide gas generating compositions with a built-in catalyst
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US6156136A (en) * 1998-05-13 2000-12-05 Sri International N,N'-azobis-nitroazoles and analogs thereof as igniter compounds for use in energetic compositions
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Cited By (44)

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Publication number Priority date Publication date Assignee Title
US4091729A (en) * 1977-03-07 1978-05-30 The United States Of America As Represented By The Secretary Of The Army Low vulnerability booster charge caseless ammunition
US4373976A (en) * 1977-03-09 1983-02-15 Rockwell International Corporation Gun propellant containing nitroaminoguanidine
US4300962A (en) * 1979-10-18 1981-11-17 The United States Of America As Represented By The United States Department Of Energy Ammonium nitrate explosive systems
US4315785A (en) * 1980-04-09 1982-02-16 The United States Of America As Represented By The Secretary Of The Army Propellant charge with reduced muzzle smoke and flash characteristics
US4358327A (en) * 1980-10-14 1982-11-09 The United States Of America As Represented By The Secretary Of The Navy Gas generant propellants
US5092945A (en) * 1982-03-01 1992-03-03 The United States Of America As Represented By The Secretary Of The Navy Glycidyl azide propellant with antigassing additives
US5061329A (en) * 1982-08-03 1991-10-29 The United States Of America As Represented By The Secretary Of The Navy High nitrogen smoke compositions
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