EP2231556A2 - Composition generatrice de gaz azote, comprenant de l'azodicarbonamide et procede de generation de gaz azote par decomposition de ladite composition - Google Patents
Composition generatrice de gaz azote, comprenant de l'azodicarbonamide et procede de generation de gaz azote par decomposition de ladite compositionInfo
- Publication number
- EP2231556A2 EP2231556A2 EP09706459A EP09706459A EP2231556A2 EP 2231556 A2 EP2231556 A2 EP 2231556A2 EP 09706459 A EP09706459 A EP 09706459A EP 09706459 A EP09706459 A EP 09706459A EP 2231556 A2 EP2231556 A2 EP 2231556A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- composition
- weight
- azodicarbonamide
- charge
- composition according
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06D—MEANS FOR GENERATING SMOKE OR MIST; GAS-ATTACK COMPOSITIONS; GENERATION OF GAS FOR BLASTING OR PROPULSION (CHEMICAL PART)
- C06D5/00—Generation of pressure gas, e.g. for blasting cartridges, starting cartridges, rockets
- C06D5/06—Generation of pressure gas, e.g. for blasting cartridges, starting cartridges, rockets by reaction of two or more solids
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B43/00—Compositions characterised by explosive or thermic constituents not provided for in groups C06B25/00 - C06B41/00
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06D—MEANS FOR GENERATING SMOKE OR MIST; GAS-ATTACK COMPOSITIONS; GENERATION OF GAS FOR BLASTING OR PROPULSION (CHEMICAL PART)
- C06D5/00—Generation of pressure gas, e.g. for blasting cartridges, starting cartridges, rockets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
- C08J9/102—Azo-compounds
- C08J9/103—Azodicarbonamide
Definitions
- Nitrogen gas generating composition comprising azodicarbonamide and method of generating nitrogen gas by decomposing said composition
- the present invention relates to gas-generating compositions comprising azodicarbonamide as well as methods of generating nitrogen gas using said compositions.
- Nitrogen-generating compositions in large quantities are desired for many civil and military applications, including tank pressurization and structural inflation.
- compositions sought must meet the following specifications:
- compositions based on sodium azide (NaN 3 ) or calcium azide (Ca (Na) 2 ) are recommended in the literature (US 4,547,235; US 4,092,190) for the generation of nitrogen.
- This type of composition has the main disadvantage of containing compounds based on azide, very toxic to humans and the environment, which makes their development complex.
- the present invention relates to compositions generating nitrogen gas (compositions (solids) capable of generating nitrogen gas by decomposition), free of oxidizing charge.
- compositions solids capable of generating nitrogen gas by decomposition
- said compositions of the invention comprise mainly a specific nitrogen reducing charge and the azodicarbonamide compound, in given proportions.
- the compositions of the invention comprise:
- said azodicarbonamide and said nitrogen reducing charge representing at least 90% of their mass and said nitrogen reducing charge comprising:
- At least one compound of a first family of reducing elements chosen from tetrazole, tetrazole derivatives and their salts, salts of biterazole and its derivatives, 5,5'-azobiterazole salts, polyvinyltetrazoles and their derivatives; mixtures thereof; and or
- At least one compound of a second family of reducing elements chosen from dicyandamide, 1-hydrobenzotriazole, silicon nitride, nitroguanidine, guanidine nitrate and their mixtures.
- a second family of reducing elements chosen from dicyandamide, 1-hydrobenzotriazole, silicon nitride, nitroguanidine, guanidine nitrate and their mixtures.
- azodicarbonamide compound which is commonly used as a porophoric compound in the plastics industry (see more particularly the teachings of FR 2,739,389 and US Pat. No. 4,328,320, the product Azobul® from the company ARKEMA).
- Azodicarbonamide has the following chemical formula: C 2 H 4 N 4 O 2 , having the chemical formula developed below:
- porphoric products of which azodicarbonamide is a part, have the main property of decomposing rapidly at a precise temperature, generally around 500 K, generating nontoxic gases.
- compositions of the invention together contain said nitrogenous filler and said azodicarbonamide. They contain mainly said nitrogenous charge and said azodicarbonamide; i.e., said filler and said compound represent at least 90% by weight of said compositions. Advantageously, they represent at least 93% by weight of said compositions.
- compositions of the invention may quite be made up of 100% (by weight) of said nitrogen charge and said azodicarbonamide. They consist of at least 90% by mass
- the nitrogen reducing charge comprises: at least one compound of a first family of reducing elements chosen from tetrazole, the derivatives of tetrazole and their salts, the salts of biterazole and its derivatives, the salts of 5,5'-azobiterazole, the polyvinyltetrazoles (products known as binders) and mixtures thereof; and or
- At least one compound of a second family of reducing elements chosen from dicyandiamide (DCDA), 1-hydrobenzotriazole (HOBT), silicon nitride, nitroguanidine, guanidine nitrate and their mixtures. It includes:
- the derivatives of the compounds in question are mainly said compounds substituted, in particular with an amino group; and the salts in question are mainly the alkaline (preferably sodium, potassium,), alkaline earth (calcium, advantageously) salts and the ammonium salts such as:
- biterazole - the ammonium salt of biterazole, - the sodium salt of biterazole,
- the nitrogen reducing charge of the compositions of the invention contains nitrogen compounds other than those of the two families identified above, in addition to these. According to an advantageous variant, it contains, as nitrogen compounds, only such compounds.
- said nitrogen reducing charge consists of at least 90% by weight (or even 100% by weight) of at least one compound of the first family identified above.
- the 100% complement can be mainly or even totally consisting of at least one additive and / or at least one nitrogen compound belonging neither to the first nor to the second of said families.
- said 100% complement is preferably provided at least in part by at least one compound of the second family.
- compositions of the invention are therefore likely to contain a low level of additive (s).
- the compositions of the invention in addition to the nitrogen reducing charge and azodicarbonamide, in fact comprise, at a content less than 10% by weight, preferably less than 7% by weight, at least one additive.
- Said at least one additive may in particular be chosen from compounds that are capable of lowering the decomposition temperature of the composition (ie azodicarbonamide degradation agents).
- Said at least one such compound is for example chosen from zinc derivatives and urea. It is advantageously chosen from zinc stearate and / or zinc oxide. It is also not excluded that a binder type additive (manufacturing aid) is present within the compositions of the invention.
- the nitrogen reducing charge of the compositions of the invention comprises, advantageously, diamonium biterazole.
- the combination diammonium biterazole + azodicarbonamide is particularly effective in reference to the specifications set out in the introduction to this text.
- compositions of the invention may especially be in pulverulent form (mixtures comprising the nitrogen reducing filler and azodicarbonamide, in the form of powders) or in the form of solid compounds; compacted materials that have a given geometric shape.
- Such solid compounds generally consist of grains (granules), pellets or blocks. Said grains, pellets or blocks have any shape, for example spherical, ovoid or cylindrical. The grains usually have a mass of a few milligrams, the pellets a mass of a few tenths of grams to a few grams and blocks of a few tens of grams to a few hundred grams. Said blocks can be monolithic, mono- or multi-perforated.
- Such solid compounds can thus be obtained from powders by granulation and pelletization, by granulation and compression, or by simple compression.
- the powders are granulated to ensure the flow and homogeneity of the composition without obviously affecting the possibility, ease, to be compressed.
- the granules of the invention comprising the specific nitrogen reducing charge and the azodicarbonamide are interesting Persian.
- compositions of the invention are effective, with reference to the specification set forth in the introduction to this text. They are especially high-yield gas (50 mol / kg), with decomposition temperatures below 1500 K.
- the compositions of the invention generate mainly nitrogen (50% to more than 70% by weight).
- the present invention relates to methods of generating nitrogen gas by decomposition of at least one composition (solid).
- said at least one composition is a composition (comprising the specific nitrogen reducing charge + azodicarbonamide) according to the first subject of the invention, as described above.
- the decomposition in question can be initiated by any method known to those skilled in the art.
- the energy necessary for its initiation can be provided by any conventional means.
- the energy required to initiate said decomposition is advantageously provided by the combustion of a pyrotechnic charge.
- Said pyrotechnic charge is advantageously a charge whose combustion generates (combustion) products that best fit the specifications set out in the introduction to this text.
- Said pyrotechnic charge is very advantageously based on a mixture of guanidine nitrate and basic copper nitrate.
- the methods of the invention can be implemented in different contexts and in particular for the inflation of structures, the pressurizing speakers, extinguishing fires or inerting (inerting operations).
- compositions of Examples 1 to 3 below are compositions of the invention comprising a mixture between, on the one hand, azodicarbonamide and, on the other hand, a reducing charge consisting of a member of the first family reducing elements (Examples 1 and 2) or an element of the second family of reducing elements (Example 3).
- compositions of Examples 4 and 5 below are compositions of the invention comprising a mixture between, on the one hand, azodicarbonamide and, on the other hand, a reducing charge consisting of an element of said first family and an element of said second family.
- composition of Example 6 below is a composition of the invention comprising a mixture between, on the one hand, azodicarbonamide and, on the other hand, a reducing charge consisting of two elements of said first family.
- compositions of said compositions are given in the first part of the tables below.
- results of thermodynamic calculations are given in the second part of said tables. It has more precisely been calculated: - the oxygen balance of the composition (OB),
- DABTZ diammonium biterazole
- PvT polyvinyltetrazole
- GUDN guanyl urea dinitramide
- DCDA dicyandiamide
- compositions of the invention are those containing a mixture of azodicarbonamide and DABTZ (see the text above as well as Examples 1 (above) and 7 (below)), a mixture which is advantageously added, in small quantities, additives zinc oxide and zinc stearate.
- a particularly preferred composition is shown in Example 7 below.
- pellets of the invention having a diameter of 20 mm and a thickness of 6 to 16 mm.
- Said pellets were prepared from suitable powder mixtures (having the mass compositions of the examples above) by wet granulation and then pelletizing.
- these pellets are fragmented into elements of smaller dimensions, for example 2.5 mm in diameter.
- pilot load of smaller mass (typically of mass less than one tenth of the total mass of loading), consisting of a composition pyrotechnic of the prior art with a high combustion temperature.
- a pyrotechnic composition is judiciously retained, the nature of the products of combustion approaching the stated specification, for example a composition containing a mixture of guanidine nitrate and basic copper nitrate.
- Characterizations of the operation of a composition of the invention containing 30% azodicarbonamide and 70% DABTZ associated with a pilot pyrotechnic charge based on a mixture of guanidine nitrate and basic copper nitrate gas have were obtained in a gas generating device, for operation at low combustion pressures of between 0.1 MPa (1 bar) and 0.2 MPa (2 bar).
- a total decomposition of the loading of the composition of the invention is obtained.
- the gas yields ( ⁇ 18 mol / kg) are lower than those provided by the calculations but remain high compared to those of the compositions of the state of the art for equivalent operating conditions.
- the percentage of nitrogen (N 2 ) generated in the gaseous decomposition products is large, greater than 75%.
Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR0850351A FR2926545B1 (fr) | 2008-01-21 | 2008-01-21 | Composition generatrice de gaz azote, comprenant de l'azodicarbonamide et procede de generation de gaz azote par decomposition de ladite composition |
PCT/FR2009/050075 WO2009095578A2 (fr) | 2008-01-21 | 2009-01-20 | Composition generatrice de gaz azote, comprenant de l'azodicarbonamide et procede de generation de gaz azote par decomposition de ladite composition |
Publications (1)
Publication Number | Publication Date |
---|---|
EP2231556A2 true EP2231556A2 (fr) | 2010-09-29 |
Family
ID=39876047
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP09706459A Withdrawn EP2231556A2 (fr) | 2008-01-21 | 2009-01-20 | Composition generatrice de gaz azote, comprenant de l'azodicarbonamide et procede de generation de gaz azote par decomposition de ladite composition |
Country Status (5)
Country | Link |
---|---|
US (1) | US8287834B2 (fr) |
EP (1) | EP2231556A2 (fr) |
BR (1) | BRPI0906572A2 (fr) |
FR (1) | FR2926545B1 (fr) |
WO (1) | WO2009095578A2 (fr) |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
RU2465258C1 (ru) * | 2011-05-25 | 2012-10-27 | Российская Федерация, от имени которой выступает Министерство промышленности и торговли Российской Федерации (Минпромторг России) | Горючее-связующее |
CN103170083B (zh) * | 2011-11-20 | 2016-04-06 | 西安坚瑞安全应急设备有限责任公司 | 一种含有过渡金属化合物的灭火组合物 |
CN103170087B (zh) | 2011-12-20 | 2015-12-09 | 西安坚瑞安全应急设备有限责任公司 | 一种含有糖类及糖类衍生物的灭火组合物 |
FR2992575B1 (fr) | 2012-06-29 | 2015-07-17 | Herakles | Dispositif de pulverisation d'un liquide |
FR2999174B1 (fr) * | 2012-12-10 | 2014-12-26 | Herakles | Composes solides generateurs de gaz azote, comprenant de l'azodicarbonamide et procede de generation de gaz azote par decomposition desdits composes |
FR3012419B1 (fr) | 2013-10-25 | 2017-02-17 | Herakles | Procede et dispositif d'inertage d'une soute de fuel d'un aeronef |
CN107573203B (zh) * | 2016-11-03 | 2019-10-11 | 湖北航天化学技术研究所 | 一种低温气体发生剂 |
Family Cites Families (20)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3004959A (en) * | 1959-09-30 | 1961-10-17 | William G Finnegan | Polymers of substituted tetrazoles |
GB1290418A (fr) * | 1969-12-26 | 1972-09-27 | ||
FR2228043B1 (fr) * | 1972-10-17 | 1977-03-04 | Poudres & Explosifs Ste Nale | |
US3873477A (en) * | 1973-12-17 | 1975-03-25 | Stepan Chemical Co | Metallic salts of tetrazoles used as blowing and intumescent agents for thermoplastic polymers |
CH623600A5 (fr) * | 1976-07-16 | 1981-06-15 | Ciba Geigy Ag | |
US4092190A (en) | 1976-11-01 | 1978-05-30 | Rockwell International Corporation | Hot nitrogen generator containing calcium oxide |
DE3170983D1 (en) * | 1980-03-21 | 1985-07-25 | Fbc Ltd | Chemical blowing agent composition, its composition and use |
US4328320A (en) | 1980-05-12 | 1982-05-04 | Reszniak Waldemar B | Thermoplastic constructional-and-insulating material |
JPS5897984A (ja) * | 1981-12-04 | 1983-06-10 | Sony Corp | 映像信号再生装置 |
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 |
US4547235A (en) | 1984-06-14 | 1985-10-15 | Morton Thiokol, Inc. | Gas generant for air bag inflators |
US4948439A (en) * | 1988-12-02 | 1990-08-14 | Automotive Systems Laboratory, Inc. | Composition and process for inflating a safety crash bag |
JPH08337770A (ja) * | 1995-06-09 | 1996-12-24 | Toyo Kasei Kogyo Co Ltd | テトラゾ−ル系ガス発生剤 |
FR2739389B1 (fr) | 1995-09-29 | 1997-12-19 | Rhone Poulenc Chimie | Composition organopolysiloxane pour mousse elastomere |
US6074502A (en) * | 1996-11-08 | 2000-06-13 | Automotive Systems Laboratory, Inc. | Smokeless gas generant compositions |
WO1999057083A1 (fr) * | 1998-04-30 | 1999-11-11 | Daicel Chemical Industries, Ltd. | Composition ameliorante pour gonfleur |
US6964715B2 (en) * | 2003-03-13 | 2005-11-15 | Special Devices, Inc. | High impetus, high burn rate gas generant propellant and seatbelt pretensioner incorporating same |
DE102004013237A1 (de) * | 2004-03-18 | 2005-10-06 | Cognis Deutschland Gmbh & Co. Kg | Treibmittel zur Herstellung von geschäumten halogenhaltigen organischen Kunststoffen |
US20060030227A1 (en) * | 2004-08-06 | 2006-02-09 | George Hairston | Intumescent flame retardent compositions |
FR2899227B1 (fr) * | 2006-04-04 | 2008-10-24 | Snpe Materiaux Energetiques Sa | Objets pyrotechniques monolithes de grandes dimensions, obtention et utilisation |
-
2008
- 2008-01-21 FR FR0850351A patent/FR2926545B1/fr not_active Expired - Fee Related
-
2009
- 2009-01-20 US US12/863,150 patent/US8287834B2/en not_active Expired - Fee Related
- 2009-01-20 WO PCT/FR2009/050075 patent/WO2009095578A2/fr active Application Filing
- 2009-01-20 BR BRPI0906572-5A patent/BRPI0906572A2/pt not_active Application Discontinuation
- 2009-01-20 EP EP09706459A patent/EP2231556A2/fr not_active Withdrawn
Non-Patent Citations (1)
Title |
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See references of WO2009095578A2 * |
Also Published As
Publication number | Publication date |
---|---|
WO2009095578A2 (fr) | 2009-08-06 |
WO2009095578A3 (fr) | 2009-12-10 |
FR2926545A1 (fr) | 2009-07-24 |
BRPI0906572A2 (pt) | 2015-07-07 |
US20100329960A1 (en) | 2010-12-30 |
US8287834B2 (en) | 2012-10-16 |
FR2926545B1 (fr) | 2010-09-17 |
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