CN100436384C - Gas generating composition - Google Patents
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- CN100436384C CN100436384C CNB2006100025663A CN200610002566A CN100436384C CN 100436384 C CN100436384 C CN 100436384C CN B2006100025663 A CNB2006100025663 A CN B2006100025663A CN 200610002566 A CN200610002566 A CN 200610002566A CN 100436384 C CN100436384 C CN 100436384C
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Abstract
The present invention provides a heat-treated oxidizing agent for gas generator compositions which is obtained by mixing ammonium nitrate with an inorganic compound having as a component at least one atom of one or more elements selected from the group consisting of copper, iron, nickel, zinc, cobalt, manganese, and titanium and heating the mixture; and a gas generator composition containing the oxidizing agent. The gas generator composition, which contains ammonium nitrate, can be safely produced, does not change in density with phase transition, and has sufficient combustibility.
Description
Patent application of the present invention is that international application no is PCT/JP02/03881, and international filing date is on April 18th, 2002, and the application number that enters the China national stage is 02808377.6, and name is called the dividing an application of application for a patent for invention of " gas generating composition ".
Technical field
The present invention relates to be used for a kind of oxygenant of gas generating composition and the gas generating composition that uses this oxygenant, this class gas generating composition is used to retrain the device of automotive occupant, as air bag in the automobile or pre-prop.
Background technology
As the gas generating composition that is used for air bag, propose gas generating composition with a kind of non-azide based in recent years and replace the metal azide compound that always using so far, the gas generating composition of this non-azide based comprises a kind of itrogenous organic substance fuel compound, the use that combines of the component that acts as a fuel it and a kind of inorganic oxidizer.As the gas generating composition of non-azide based, require the said composition of unit weight can produce a large amount of gas molecules, make producer gas generator small and light.
Gas generating composition should be safe when it is produced also.If gas generating composition catches fire when producing, will produce the gas of a large amount of High Temperature High Pressure, will cause the heavy losses of lives and properties like this.Therefore, production process must not have a step can make gas generating composition or its raw material catch fire and explode.
Proposed to use a kind of gas generating composition of ammonium nitrate in recent years as oxygenant.Ammonium nitrate is a kind of ideal raw material of gas generating composition, because it can produce a large amount of gas and the charge is small.But ammonium nitrate is also unsatisfactory, because in the temperature range that the performance that gas generating composition requires is guaranteed, along with the phase transformation that takes place, ammonium nitrate can bring the change of density.Also have a problem with ammonium nitrate as the gas generating composition of oxygenant, promptly rate of combustion is lower than usually desired to gas generating composition.
For addressing these problems, attempted using by a kind of sylvite is added to obtaining mutually stable ammonium nitrate in the ammonium nitrate.For example, ammonium nitrate and a kind of sylvite can be dissolved in the aqueous solution, it be precipitated obtain desired ammonium nitrate then.
Also have, can ammonium nitrate be used for gas generating composition by the phase transformation that suppresses ammonium nitrate, WO2000/18704 (and EP0405272, DE3642850, US5071630) described a kind of ammonium nitrate of the phase of stabilization basically that has, it is to make an ammonium nitrate and a transistion metal compound form a complex compound preparing by what be shown below:
2NH
4NO
3+Cu(OH)
2→[Cu(NH
3)
2]
2+·(NO
3 -)
2+2H
2O
But the ammonium nitrate with stable phase fails to solve such as the low problem of rate of combustion.Ammonium nitrate and a fuel element mutually stable by order generate eutectic mixture, and this eutectic mixture is fusing (hereinafter being referred to as the eutectic phenomenon) under the fusing point of the fusing point that is lower than ammonium nitrate and this fuel element.For example, a kind of gas generating composition composition, the 5-amino tetrazole as the excellent performance of fuel element in the gas generating composition that it contains the mutually stable ammonium nitrate of useful saltpetre and combines in the 108c fusing, can not be used for the producer gas generator of car safety air bag fully.
US6224697, US6143102, US6132538, US6103030, US6039820, US5592812, US5673935 and US5725699 have described a kind of gas generating composition, and it uses a kind of metal ammonia complex, roughly are equivalent to above-mentioned passing through and generate the mutually stable ammonium nitrate of complex compound.Especially US6103030 has described a kind of gas generating composition, and it uses a kind of transition metal complex, as a nitric acid diamino copper (II) and a fuel element, as ammonium nitrate and Guanidinium nitrate.But, in the patent that these are delivered, imagination has been used a kind of fuel, for example with mutually stable ammonium nitrate more solito use Guanidinium nitrate together, perhaps this fuel element is as a kind of auxiliary agent, and but not talkative fuel element can select to design only gas generating composition arbitrarily.
The purpose of this invention is to provide a kind of oxygenant that is used to contain the gas generating composition of ammonium nitrate, can produce safely, can not undergo phase transition and change density, do not limit the itrogenous organic substance component that acts as a fuel, and the abundant flammable gas generating composition that has that uses this oxygenant is provided.
The inventor has carried out extensive studies for addressing the above problem, found that, by with ammonium nitrate be selected from Cu, Fe, Ni, Zn, Co, at least a atoms metal of Mn and Ti mixes as the mineral compound of element, and is especially suitable for use as the oxygenant of gas generating composition through a kind of oxygenant (hereinafter being referred to as the oxygenant through heat treated) that heat treated makes, and has finished the present invention.
Summary of the invention
The present invention relates to
(1) be used for gas generating composition through the oxygenant of heat treated and use this gas generating composition through the oxygenant of heat treated, this oxygenant be by with ammonium nitrate be selected from Cu, Fe, Ni, Zn, Co, at least a atoms metal of Mn and Ti do to constitute the mineral compound mixing of element, and this mixture of heat treated obtains.
(2) as above-mentioned (1) described oxygenant through heat treated, described heat treated is to carry out under the temperature of the fusing point that is not higher than ammonium nitrate.
(3) as above-mentioned (1) or (2) described oxygenant through heat treated, described heat treated is to carry out 5 hours or the longer time 120-160 ℃ of temperature.
(4) as each described oxygenant through heat treated of above-mentioned (1) to (3), the meta particle diameter of described ammonium nitrate and mineral compound is 100 μ m or littler.
(5) as each described oxygenant through heat treated of above-mentioned (1) to (4), described mineral compound is a kind of carbonate that is selected from least, nitrate, oxyhydroxide, the compound of subcarbonate and subnitrate.
(6) as each described oxygenant through heat treated of above-mentioned (1) to (5), described mineral compound is a basic copper nitrate.
(7) as each described oxygenant through heat treated of above-mentioned (1) to (6), wherein the ratio of mixture of ammonium nitrate and mineral compound is as follows:
(a) ammonium nitrate, 30-95 weight %
(b) mineral compound, 5-70 weight %
(8) as each described oxygenant through heat treated of above-mentioned (1) to (6), mineral compound wherein is a basic copper nitrate, and the ratio of mixture of ammonium nitrate and basic copper nitrate is as follows:
(a) ammonium nitrate, 40-95 weight %
(b) basic copper nitrate, 6-60 weight %
(9) as each described oxygenant through heat treated of above-mentioned (1) to (6), the described mineral compound and the ammonium nitrate that are equal to or less than 50% stoichiometric quantity of having used forms complex compound.
(10) comprise the gas generating composition of organic compounds containing nitrogen fuel and oxygenant, part or all of described oxygenant is as each described oxygenant through heat treated of above-mentioned (1) to (9).
(11) as above-mentioned (10) described gas generating composition, when combining with ammonium nitrate, this organic compounds containing nitrogen fuel is being lower than the temperature fusing of ammonium nitrate fusing point and fuel fusing point.
(12) as above-mentioned (10) or (11) described gas generating composition, described organic compounds containing nitrogen fuel is one or both or the multiple compound that is selected from tetrazolium class and guanidine derivative.
(13) as above-mentioned (10) or (11) described gas generating composition, wherein organic compounds containing nitrogen fuel is one or both or the multiple 5-of being selected from nitrogen base tetrazolium, the metal amino tetrazolium, two tetrazoliums, metal tetrazotic acid hydrogen salt, tetrazotic acid hydrogen ammonium, nitroguanidine, Guanidinium nitrate, the compound of triaminoguanidine and Dyhard RU 100.
(14) as above-mentioned (10) or (11) described gas generating composition, described organic compounds containing nitrogen fuel comprises the 5-amino tetrazole.
(15) gas generating composition is characterized in that it comprises at least a following component:
(a) 5-amino tetrazole,
(b) ammonium nitrate,
(c) basic copper nitrate,
Wherein above-mentioned (b) and (c) through heat treated.
(16) gas generating composition, it comprises at least a following component:
(a) 5-amino tetrazole,
(b) ammonium nitrate,
(c) basic copper nitrate,
Wherein above-mentioned (b) and (c) through heat treated, and pass through heat treated with (a) and water again.
(17) gas generating composition, it comprises following at least component by weight percentage:
(a) 5-amino tetrazole, 10-40 weight %;
(b) ammonium nitrate, 30-70 weight %;
(c) basic copper nitrate, 5-40 weight %,
Wherein above-mentioned (b) and (c) through heat treated.
(18) gas generating composition is characterized in that it comprises by weight percentage following at least component:
(a) 5-amino tetrazole, 10-40 weight %;
(b) ammonium nitrate, 30-70 weight %;
(c) basic copper nitrate, 5-40 weight %;
Wherein above-mentioned (b) and (c) through heat treated, and further with account for component (a), (b) and (c) water of the 1-20 weight % of gross weight is through heat treated for the second time.
(19) as above-mentioned (16) or (18) described gas generating composition, heat treated is to carry out 10 hours under 90-120 ℃ of temperature or the longer time for the second time.
(20) gas generating composition, it comprises following at least component:
(a) tetrazolium class;
(b) ammonium nitrate;
(c) with the mineral compound of Cu as the formation element,
Wherein, add water again, mixture heating up is handled above-mentioned (a) and (b) and (c) mixing.
(21) gas generating composition, it comprises following at least component:
(a) 5-amino tetrazole,
(b) ammonium nitrate,
(c) basic copper nitrate,
Wherein, add water again, mixture heating up is handled above-mentioned (a) and (b) and (c) mixing.
(22) gas generating composition, it comprises following at least component by weight percentage:
(a) 5-amino tetrazole, 10-40 weight %;
(b) ammonium nitrate, 30-70 weight %;
(c) basic copper nitrate, 5-40 weight %,
Wherein, add water again, mixture heating up is handled above-mentioned (a) and (b) and (c) mixing.
(23) gas generating composition, it comprises following at least component by weight percentage:
(a) 5-amino tetrazole, 10-40 weight %;
(b) ammonium nitrate, 30-70 weight %;
(c) basic copper nitrate, 5-40 weight %,
Wherein with above-mentioned (a) and (b) and (c) mixing, add and account for component (a) and (b) and (c) water of total amount 1-20 weight %, mixture heating up is handled.
(24) as each described gas generating composition of above-mentioned (20) to (23), heat treated is to carry out 5 hours or the longer time 120-160 ℃ of temperature.
(25) as each described gas generating composition of above-mentioned (10) to (24), it also comprises one or both or the multiple silicon nitride that is selected from, silicon carbide, silicon-dioxide, talcum, clay, aluminum oxide, the component of molybdic oxide and synthetic hydrotalcite.
(26) as each described gas generating composition of above-mentioned (10) to (25), it also comprises one or both or the multiple silane compound that is selected from, guar gum, polyvinyl alcohol, carboxymethyl cellulose, the component of polyvinylpyrrolidone and methylcellulose gum.
(27) use as the described gas generating composition in above-mentioned (10) to (26) or comprise gas generating composition, be used to retrain the producer gas generator of the device of automotive occupant as the described oxygenant through heat treated in above-mentioned (1) to (9).
Implement best mode of the present invention
The present invention through the oxygenant of heat treated be by with ammonium nitrate be selected from Cu, Fe, Ni, Zn, Co, one or both of Mn and Ti or multiple atoms metal mix as the mineral compound that constitutes element, mixture heating up handled obtaining again, and gas generating composition of the present invention comprises this oxygenant through heat treated.Can not cause the phase transformation of ammonium nitrate by what heat treated made through the oxygenant of heat treated, higher combustibility in the time of when being used for gas generating composition, reaching than independent use ammonium nitrate.
Be used in combination the mineral compound that forms through the oxygenant of heat treated with ammonium nitrate and do not have what restriction, as long as it is a kind of Cu of being selected from, Fe, Ni, Zn, Co, one or both of Mn and Ti or multiple atoms metal are as the mineral compound that constitutes element, all these can stability exist, this mineral compound can be a kind of mineral compound that contains multiple atoms metal as the formation element, such mineral compound can use separately, also can two or more use as mixture.
In specific words, this mineral compound is one or two or a plurality of Cu that is selected from preferably, Fe, Ni, Zn, Co, the carbonate of Mn and Ti, nitrate, vitriol, oxyhydroxide, oxide compound and subcarbonate and subnitrate, more preferably one or two or a plurality of Cu that is selected from, the carbonate of Co or Fe, nitrate, vitriol, oxyhydroxide, oxide compound and subcarbonate and subnitrate, especially preferred is the carbonate of one or two or a plurality of Cu of being selected from, nitrate, vitriol, oxyhydroxide, oxide compound and subcarbonate and subnitrate.This mineral compound is also preferable to be one or more Cu of being selected from, Fe, Ni, Zn, Co, the nitrate of Mn and Ti, subcarbonate and subnitrate, even more preferably one or two or a plurality of Cu that is selected from, Fe, Ni, Zn, Co, the subnitrate of Mn and Ti, particularly preferably be one or more Cu of being selected from, the subnitrate of Co and Fe.This mineral compound is basic copper nitrate preferably.Usually recently obtain oxygenant with the mixing of the mineral compound of the ammonium nitrate of 30-95 weight % and 5-70 weight % through heat treated.When using basic copper nitrate, preferred ratio of mixture is the ammonium nitrate of 40-95 weight % and the basic copper nitrate of 5-60 weight %.
The oxidation capacity that oxygenant showed through heat treated of the present invention is attributable to be included in the Sauerstoffatom that wherein conduct constitutes element, the H that generates when it burns to gas generating composition
2O and CO
2Oxygen is provided, in the gas generating composition oxygenant preferably can produce the more oxygen of unit weight so that reduce the oxidant content be used for fuel element.Oxygenant through heat treated also produces N when burning
2And H
2O, therefore the also contribution to some extent of total gas volume to producing from gas generating composition can think that concerning gas generating composition oxygenant preferably can produce more N with unit weight
2And H
2O.Oxygenant mineral compound through heat treated of the present invention, but the atoms metal of composition mineral compound there is no contribution to the generation of gas, produce undesirable slag on the contrary, thus the contained atoms metal quantity of the mineral compound of unit weight with low for well.
According to above viewpoint, the present invention in the oxygenant of heat treated ammonium nitrate and the ratio of mixture of mineral compound preferably decide like this, promptly the amount of mineral compound will reduce to minimum level.For example, can be according to generating complex compound as [Cu (NH
3)
2]
2+(NO
3 -)
2Stoichiometric quantity decide ratio of mixture, it is owing to generating complex compound that but the present invention's phase stabilization of ammonium nitrate in the oxygenant of heat treated has more than, therefore, ratio of mixture can not be higher than stoichiometric quantity, the consumption of mineral compound preferably is not higher than 50 weight % of the stoichiometric quantity that generates complex compound, more preferably in preparation during through the oxygenant of heat treated, the mineral compound consumption is no more than 30 weight % of the stoichiometric quantity that generates complex compound.But when the mineral compound amount was too low, the phase stabilization may be not obvious, and therefore, the mineral compound consumption in the oxygenant of heat treated preferably is not less than 5 weight %.
The mixture of how describing in detail now ammonium nitrate and mineral compound carries out heat treated, and it is changed into oxygenant through heat treated.
Heat treated is carried out in not being higher than the melting temperature scope of ammonium nitrate usually.In specific words, heat treated more fortunately 120-160 ℃ of temperature carry out.The minimizing of the time that heat treated is required and the temperature of heat treated are proportional, but 120 ℃ or lower be worthless finish heat treated because will take long to.The temperature that is higher than 160 ℃ also is worthless, because ammonium nitrate will melt.Ammonium nitrate one fusing just is solidified into piece during its cooling, causes subsequent handling for example to pulverize difficulty, and it is Powdered to need special operation to be ground into.The present invention is in the oxygenant of heat treated, and for example the mixture of ammonium nitrate and basic copper nitrate begins exothermic decomposition in the time of about 220 ℃, catches fire and decomposition rapidly so the heat treated under the high temperature can easily cause.Ammonium nitrate does not melt in heat treated temperature range of the present invention, thereby does not lump through the oxygenant of heat treated, makes follow-up pulverizing process carry out easily, and can produce as safe as a housely.
Heat treated can proceed to weight and reduce 10-30%, and till heat treated wanted weight no longer to reduce after beginning, the time of heat treated was generally 5-48 hour, depends on the temperature of heat treated, used mineral compound and ratio of mixture.
During heat treated, ammonium nitrate and mineral compound can be at the V-arrangement mixing machines, mix in the ball mill etc., promptly carry out heat treated with mixed state in process furnace then, but mixture are preferably in heat treated under the agitation condition.When using the process furnace of band mixing paddle, just can carry out heat treated simultaneously at blended.Heat treated under agitation, the time can shorten.
Be used for the ammonium nitrate of heat treated and the meta particle diameter of mineral compound and be preferably 200 μ m or littler, more preferably 100 μ m or littler.When particle diameter surpasses 200 μ m, need the very long time to finish heat treated.
Mix and/or the heat treated stage at ammonium nitrate and mineral compound, but doping in case of necessity such as water.
Through the oxygenant of heat treated can be directly and fuel mix form gas generating composition, but preferably pulverize again, adjust the meta particle diameter before use.
The oxygenant through heat treated of Huo Deing can form gas generating composition with the organic compounds containing nitrogen fuel mix like this.So not only through the oxygenant of heat treated, but also can use other oxygenants that allow to be used for gas generating composition, the example of such oxygenant comprises metal nitrate, as strontium nitrate.Also can use various additives when needing.
Describe now and be used for of the present invention/organic compounds containing nitrogen fuel.The organic compounds containing nitrogen fuel that is used as fuel element among the present invention can be those widely used compounds in this field, but preferably a kind of or two or the multiple guanidine derivative that is selected from, the tetrazolium class, two terazole derivatives, triazole derivative, hydrazine derivative, pyrrolotriazine derivatives, the Cellmic C 121 derivative, dicyanamide derivative and nitrogen containing transition metal complex compound, more preferably one or both or multiple tetrazolium class and the guanidine derivative of being selected from.These examples comprise nitroguanidine, Guanidinium nitrate, 5-amino tetrazole, metal amino tetrazotic acid salt, metal tetrazotic acid hydrogen salt, tetrazotic acid hydrogen one ammonium, tetrazotic acid hydrogen two ammoniums, 5-oxo-1,2,4 triazines, dicyanodiamide, triaminoguanidine, the nitric acid triaminoguanidine, trihydrazinotriazine, burette, Cellmic C 121, two ureas, carbohydrazide, nitric acid carbohydrazide transition metal complex, two hydrazides oxalate, the hydrazine nitrate metal complex, dicyanamide sodium, triaminoguanidine, two (dicyanamide) copper (I) nitrate, the compound of 5-amino tetrazole copper complex etc.Nitrogenous organic compounds fuel is one or both or the multiple 5-amino tetrazole that is selected from preferably, amino tetrazotic acid metal-salt, two tetrazoliums, tetrazotic acid hydrogen metal-salt, tetrazotic acid hydrogen ammonium, nitroguanidine, Guanidinium nitrate, the compound of triaminoguanidine and dicyanamide.
Especially in gas generating composition of the present invention, the generation of eutectic phenomenon depends on combining of above-mentioned and ammonium nitrate, even that will melt at low temperatures on the level of practicality, do not experience the eutectic phenomenon at least with a kind of combination organic compounds containing nitrogen fuel (hereinafter being referred to as eutectic fuel) yet, eutectic fuel is used as organic compounds containing nitrogen fuel, can farthest utilizes the oxidant in effect of the present invention through heat treated.
Eutectic fuel comprises terazole derivatives, though the eutectic degree is variable, especially will mention the 5-amino tetrazole, because it is general in gas generating composition.
Eutectic fuel can perhaps be used two or more mixture only with a kind of.And, in a kind of organic compounds containing nitrogen fuel that does not in fact cause the eutectic phenomenon and a kind of eutectic fuel-bound mixing in the organic compounds containing nitrogen fuel of (non low eutectic/eutectic propellant combination hereinafter referred to as) together, cause the combination ratio of eutectic phenomenon with ammonium nitrate, be that the weight ratio of eutectic fuel in non low eutectic/eutectic propellant combination is generally 10% or higher, comparatively be typically 50% or higher, better be typically 75% or higher, the present invention can perform at utmost through the oxidant in effect of heat treated like this, is reached when only using eutectic fuel.
When the present invention uses a kind of eutectic fuel, especially during the 5-amino tetrazole, it mixes with oxygenant through heat treated, add water then, granulation, heat treated (this is referred to as heat treated for the second time below heat treated, to be different from the heat treated that oxygenant is carried out), just obtaining can be with the gas generating composition of higher rate burning and excellent heat resistance.Heat treated can proceed to the water weight minimizing of adding for the second time, and the weight of pellet alleviate again 10-40% and no longer alleviate till, the time of heat treated was generally 10-48 hour, depended on the temperature of heat treated, used mineral compound and portfolio ratio.Composition is placed under the high temperature for a long time during heat treated for the second time, say it is unaccommodated from security standpoint, because composition is made up of explosive substance.Heat treated is very safe for the second time, because its temperature is lower than the heat treated temperature that production is used through the oxygenant of heat treated.
As mentioned above, comprise the gas generating composition fusing of the temperature about 100 ℃ usually of 5-amino tetrazole and ammonium nitrate.Gas generating composition of the present invention even also do not melt 120 ℃ of temperature.This is because the present invention produces the eutectic phenomenon hardly through the oxygenant and the 5-amino tetrazole of heat treated, and heat treated is considered to improve thermotolerance for the second time.The front and back of heat treated for the second time, the color of gas generating composition becomes green from pale blue.If the average particulate diameter of organic compounds containing nitrogen is too big, the intensity of the gas generating composition that the result is molded into is too poor, if its particle diameter is too little, then the cost of Fen Suiing is too high, so the meta particle diameter is advisable with 5-80 μ m, is more preferably 10-50 μ m.
In case of necessity, can use various additives in the gas generating composition of the present invention, can be gas generating composition some additives commonly used, such as enumerating slag former, the spontaneous combustion agent, tackiness agent etc., two or more mix use but these additives can use also separately.The additive of any decomposition of components in the gas generating composition should not be added.
Can be used for slag former of the present invention and comprise as silicon nitride, silicon carbide, silicon-dioxide, talcum, clay, aluminum oxide, the spontaneous combustion agent comprises molybdic oxide etc.The content of the content of slag former and spontaneous combustion agent respectively is 0.1-10 weight %, 0.5-5 weight % preferably, if content is lower than this, the effect of additive possibly can't fully show, and content is when too high, the gas that produces from gas generating composition can reduce.
Tackiness agent comprises for example synthetic hydrotalcite, guar gum, polyvinyl alcohol, carboxymethyl cellulose, polyvinylpyrrolidone, methylcellulose gum etc.Binder content is advisable with 0.5-10 weight %, 1-8 weight % more preferably, if content is lower than this, the effect of tackiness agent possibly can't fully show, and content is when too high, the gas volume that produces from gas generating composition can reduce.Can also mention silane compound also is available additive among the present invention.
Preferably stoichiometric quantity (oxygen balance 0) is compared in the combination of each component in the gas generating composition of the present invention, organic compounds containing nitrogen fuel and can perfect combustion for example wherein through these two kinds of components of the oxygenant of heat treated, but according to the combustion conditions of producer gas generator, oxygen balance may change.The form of gas generating composition of the present invention can be a powder for example, particle, disk, bar have been opened the bar of single hole, have opened porous bar or sheet, but shape there is no particular restriction.
Explanation various preferred combinations of the present invention now.
In the gas generating composition of the present invention, preferably basic copper nitrate is used for oxygenant through heat treated as mineral compound, with the 5-amino tetrazole as organic compounds containing nitrogen fuel.Specifically, with mixing ammonium nitrate and basic copper nitrate, and mixture heating up is handled the oxygenant through heat treated obtain mix with 5-amino tetrazole and other additives (if necessary) and obtain gas generating composition, when the oxygenant through heat treated mixes with 5-amino tetrazole and additive, preferably add water, carry out heat treated (heat treated for the second time) again.The water yield that adds is the oxygenant that accounts for through heat treated, the 5-amino tetrazole and in case of necessity the 1-20 weight % of the total amount of the additive of adding be advisable.
The consumption of each component is with 5-amino tetrazole 10-40 weight %, ammonium nitrate 30-70 weight %, ventilation breather 5-40 weight % be advisable (weight with gas generating composition is benchmark).This combination does not represent that than the consumption that shows each component each component is exactly the content of this regulation in the final gas generating composition.
The additive capacity of Jia Ruing decides according to the character of additive therefor in case of necessity, and the scope of available quantity should not damaged the performance of gas generating composition.For example silicon-dioxide is added fashionablely as additive, its content in gas generating composition is 0.5-5 weight % preferably.
Another embodiment of gas generating composition of the present invention is described now.Gas-evolution agent of the present invention also can be by the tetrazolium class that will act as a fuel, and mixes as the mineral compound that constitutes element as the ammonium nitrate and the cupric of oxygenant, to wherein adding water, then mixture is carried out heat treated.This heat treated can reach heat treated simultaneously in order to form through the oxygenant of heat treated and the effect of the heat treated second time, i.e. the phase stabilising effect of ammonium nitrate and the effect that prevents eutectic fuel and ammonium nitrate generation eutectic phenomenon.
Especially preferably use the 5-amino tetrazole to make fuel.Cupric has ventilation breather as the mineral compound that constitutes element, cupric nitrate, copper sulfate, copper hydroxide, cupric oxide and basic copper nitrate, preferred especially basic copper nitrate.
The water yield that adds does not have any restriction, but 1-20 weight % preferably.Mixture can be made into slurry granulation then, and in this amount of water scope, mixture is the form of wet granular, granulation easily after the heat treated.
Heat treated is carried out under the melting temperature that is not higher than ammonium nitrate usually.Specifically, heat treated is preferably under 120-160 ℃ the temperature and carries out.The temperature of required time of heat treated along with heat treated reduces pro rata, and 120 ℃ or lower temperature are then bad, because need the oversize time finish heat treated this moment.Ammonium nitrate is higher than 160 ℃ melting temperature, because can melt.
The production method of gas generating composition of the present invention is described now.Oxygen-containing organic compound and in V-Mixer or ball mill, mix for example through these components of oxygenant of heat treated.The powder that mixes each component gained directly mold pressing or compressing tablet becomes molded gas generating composition composition.Another kind of way is, each component is mixed, and sprays into an amount of water and organic solvent etc. simultaneously and obtains wet piece, and granulation then is heated to about 100 ℃ dryly, obtains firm particle.Then, the particle compressing tablet becomes molded gas generating composition.Another kind of way is that the wet available single-lead-screw extruding briquetting machine of piece is directly extruded and crowded aftershaping.Under above-mentioned arbitrary situation, all can make firm molded gas generating composition by molded then being heated to about 100 ℃ of dryings to gas generating composition.
In above-mentioned production method, heat drying with preparation particulate process and/or molded after the heat drying process in carrying out heat treated for the second time.Carry out the such heat treated of heat drying for example simultaneously when producing gas generating composition at each component blended of gas generating composition, above-mentioned heat drying also can be used as heat treated for the second time, but also can carry out other heat treated as the heat treated second time.
Narration now is the mixture of heat treated fuel and oxygenant simultaneously, with the heat-treatment process of the oxygenant that omits heat treated.In V-Mixer or ball mill, mix each component, as the tetrazolium class, ammonium nitrate and contain copper as the mineral compound that constitutes element.When mixing these components, spray into an amount of water, organic solvent etc. obtain wet piece, and granulation then is heated to about 120-160 ℃ of drying down, can make firm particle like this.Another kind of way is directly to wet piece extruding and extrusion molding with single-lead-screw extruding briquetting machine.
The device of constraint automotive occupant, for example car safety air bag or the pre-used producer gas generator of prop if adopt gas generating composition of the present invention, can demonstrate better gas generation performance.
Embodiment
Below, with some embodiment the present invention is described in more detail.
Embodiment 1
55.5 weight % ammonium nitrate (meta particle diameter 13 μ m) and 18.5 weight % mix in a V-Mixer as basic copper nitrate (the meta particle diameter 5 μ m) weighing of mineral compound.The mixture of gained heat treated 24 hours in one 150 ℃ process furnace.Gained is crushed to the meta particle diameter through the oxygenant of heat treated and is reduced to 12 μ m in a nail mill pulverizer.24.0 weight % are added to wherein as the silicon-dioxide (meta particle diameter, 3 μ m) of slag former as the 5-amino tetrazole (meta particle diameter 15 μ m) of organic compounds containing nitrogen fuel and 2.0 weight %, in the V-arrangement mixing machine, mix then.This mixture sprays into mixing with the water that accounts for whole mixture amount 8 weight % then, granulation in a wet pipe system then, and forming average particulate diameter is 1mm or littler particle.Particulate material in 105 ℃ of process heat treated 15 hours (heat treated for the second time), with rotary tablet machine compacting, was obtained the disk of gas generating composition of the present invention in 15 hours, its diameter 5mm, high 1.5mm again at 110 ℃ of heat dryings.
Disk carries out 100 hours the oven test and the thermal shock test of 200 circulations (be cooled to-40 ℃, be heated to 107 ℃) at 120 ℃, measures the hardness of disk with a Monsanto sclerometer.The result is as shown in table 1.
Embodiment 2
55.5 weight % ammonium nitrate (meta particle diameter 13 μ m) and 18.5 weight % mix in a V-arrangement mixing machine as basic copper nitrate (the meta particle diameter 5 μ m) weighing of mineral compound.Gained mixture heat treated 24 hours in one 150 ℃ process furnace obtains pulverous oxygenant through heat treated.This powder is analyzed under the temperature of height to 500 ℃ with a DTA-TG differential thermal analyzer.The result is as shown in table 2.
Embodiment 3
24.0 weight % is as the 5-amino tetrazole (meta particle diameter 15 μ m) of organic compounds containing nitrogen fuel, 55.5 weight % ammonium nitrate (meta particle diameter 13 μ m), 18.5 weight % basic copper nitrate (meta particle diameter 5 μ m) and 2.0 weight % are as silicon-dioxide (the meta particle diameter of slag former, 3 μ m) in a V-arrangement mixing machine, mix, this mixture sprays into the water of 10 weight % (accounting for whole blended powder) then, and granulation formation average particulate diameter is 1mm or littler particle in a wet pipe system again.This particulate material is 150 ℃ of following heat treated 24 hours, with rotary tablet machine compacting, then 110 ℃ of following heat dryings 15 hours, obtains the gas generating composition of disc, its diameter 5mm, high 1.5mm.
Disk carries out 100 hours the oven test and the thermal shock test of 200 circulations (be cooled to-40 ℃, be heated to 170 ℃) under 120 ℃, measure the hardness of disk with a Monsanto sclerometer.The result is as shown in table 1.
Comparative example 1
26.5 weight % is as the 5-amino tetrazole (meta particle diameter 15 μ m) of organic compounds containing nitrogen fuel, 72.5 weight % ammonium nitrate (meta particle diameter 13 μ m, carried out the phase stabilization with saltpetre), and 2.0 weight % mix in a V-arrangement mixing machine as the silicon-dioxide (meta particle diameter 3 μ m) of slag former.Then, this mixture sprays into mixing with the water (accounting for whole blended powder) of 8 weight %, and granulation formation average particulate diameter is 1mm or littler particle in a wet pipe system again.This particulate material is 100 ℃ of heat treated 15 hours, with a rotary tablet machine compacting, 100 ℃ of following heat dryings 15 hours, obtains the flaky gas generating composition of circle, its diameter 5mm, high 1.5mm again.
Disk carries out 100 hours the oven test and the thermal shock test of 200 circulations (be cooled to-40 ℃, be heated to 107 ℃) under 120 ℃, measure the hardness of disk with a Monsanto sclerometer.The result is as shown in table 1.
Comparative example 2
55.5 as basic copper nitrate (the meta particle diameter 5 μ m) weighing of mineral compound, mixing, weight % ammonium nitrate (meta particle diameter 13 μ m) and 18.5 weight % obtain pulverous oxygenant without heat treated in a V-arrangement mixing machine.This powder is analyzed under the temperature of height to 500 ℃ with a DTA-TG differential thermal analyzer.The result is as shown in table 2.
Table 1
From table 1 data as seen, oxidant constituents among the embodiment 1 is through heat treated, the data of oven test and thermal shock test there is no deterioration in the table.
Fuel element among the embodiment 3 and oxidant constituents are all passed through heat treated, and the result of oven test and thermal shock test there is no deterioration in the table.But in the comparative example 1, carrying out mutually stable ammonium nitrate with saltpetre combines with the 5-amino tetrazole, fusing has taken place in disk in oven test, in thermal shock test, powder and partial melting, do not keep original shape, obviously find out influence (not observing melting phenomenon) by this influence to ammonium nitrate and 5-amino tetrazole eutectic phenomenon.
Table 2
| The DTA-TG measuring result | |
| Embodiment 2 | To about 220 ℃ temperature, do not observe heat absorption and exothermic peak at height, do not see that weight changes. |
| Comparative example 2 | Show endotherm(ic)peak at 60 ℃ and 130 ℃, weight reduces about 6% in 100-170 ℃ of temperature range. |
From table 2 data as seen, in the comparative example 2 is without the oxygenant of heat treated in contrast, estimates that endotherm(ic)peak is because in the phase transformation of 60 ℃ and 130 ℃.And weight has reduced approximately 6% in 100-170 ℃ temperature range, but in embodiment 2, has carried out heat treated, even identical composition is not observed the endotherm(ic)peak that causes because of phase transformation.Owing to do not observe weight saving, estimate that resistance toheat improves, thermal shocking is the change of no volume down.
Industrial use
According to the present invention, namely used ammonium nitrate also can make a kind of oxidant constituents, it has suppressed phase transformation and compatible with fuel element such as 5-Aminotetrazole, also can make the gas generating composition that uses this oxidant simultaneously. Again, according to the present invention, can produce very safely this oxidant and gas generating composition, and can not undergo phase transition and cause stereomutation, and this is unique for the ammonium nitrate here.
Claims (8)
1. gas generating composition is characterized in that it comprises following at least component:
(a) tetrazolium class;
(b) ammonium nitrate;
(c) contain Cu as a kind of mineral compound that constitutes element,
Wherein above-mentioned (a) and (b) and (c) mixing add entry, again to the temperature heat treated of mixture at 120-160 ℃.
2. gas generating composition is characterized in that it comprises following at least component:
(a) 5-amino tetrazole;
(b) ammonium nitrate;
(c) basic copper nitrate,
Wherein above-mentioned (a) and (b) and (c) mixing add entry, again to the temperature heat treated of mixture at 120-160 ℃.
3. gas generating composition is characterized in that it comprises following at least component, and weight percentage is:
(a) 5-amino tetrazole 10-40 weight %;
(b) ammonium nitrate 30-70 weight %; With
(c) basic copper nitrate 5-40 weight %,
Wherein above-mentioned (a) and (b) and (c) mixing add entry, again to the temperature heat treated of mixture at 120-160 ℃.
4. gas generating composition is characterized in that it comprises following at least component, and weight percentage is:
(a) 5-amino tetrazole 10-40 weight %;
(b) ammonium nitrate 30-70 weight %;
(c) basic copper nitrate 5-40 weight %,
Wherein above-mentioned (a) and (b) and (c) mixing add and account for component (a) and (b) and (c) water of total amount 1-20 weight %, 120-160 ℃ temperature mixture heating up are handled.
5. each described gas generating composition of claim 1 to 4 is characterized in that heat treated was carried out 5 hours or the longer time.
6. each described gas generating composition of claim 1 to 4 is characterized in that it also further comprises one or both or the multiple silicon nitride that is selected from, silicon carbide, silicon-dioxide, talcum, clay, aluminum oxide, the component of molybdic oxide and synthetic hydrotalcite.
7. each described gas generating composition of claim 1 to 4 is characterized in that it also further comprises one or both or the multiple silane compound that is selected from, guar gum, polyvinyl alcohol, carboxymethyl cellulose, polyvinylpyrrolidone, the component in the methylcellulose gum.
8. use the described gas generating composition of claim 1 to 7, be used to retrain the producer gas generator of automotive occupant device.
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| JP2001123086 | 2001-04-20 | ||
| JP2001123086 | 2001-04-20 | ||
| JP2001300166 | 2001-09-28 |
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| CNB028083776A Division CN1262525C (en) | 2001-04-20 | 2002-04-18 | Gas generator composition |
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| CN100436384C true CN100436384C (en) | 2008-11-26 |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1996019422A1 (en) * | 1994-12-21 | 1996-06-27 | Daicel Chemical Industries, Ltd. | Gas generator composition |
| WO1996032363A1 (en) * | 1995-04-14 | 1996-10-17 | Automotive Systems Laboratory, Inc. | Nonazide gas generating compositions with a built-in catalyst |
| WO1998006486A2 (en) * | 1996-07-25 | 1998-02-19 | Cordant Technologies, Inc. | Metal complexes for use as gas generants |
| WO1998042642A1 (en) * | 1997-03-24 | 1998-10-01 | Daicel Chemical Industries, Ltd. | Gas generator composition and molding thereof |
| WO2001000544A1 (en) * | 1999-06-25 | 2001-01-04 | Nippon Kayaku Kabushiki-Kaisha | Gas-generating agent composition |
-
2002
- 2002-04-18 CN CNB2006100025663A patent/CN100436384C/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1996019422A1 (en) * | 1994-12-21 | 1996-06-27 | Daicel Chemical Industries, Ltd. | Gas generator composition |
| WO1996032363A1 (en) * | 1995-04-14 | 1996-10-17 | Automotive Systems Laboratory, Inc. | Nonazide gas generating compositions with a built-in catalyst |
| WO1998006486A2 (en) * | 1996-07-25 | 1998-02-19 | Cordant Technologies, Inc. | Metal complexes for use as gas generants |
| WO1998042642A1 (en) * | 1997-03-24 | 1998-10-01 | Daicel Chemical Industries, Ltd. | Gas generator composition and molding thereof |
| WO2001000544A1 (en) * | 1999-06-25 | 2001-01-04 | Nippon Kayaku Kabushiki-Kaisha | Gas-generating agent composition |
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