CN101307034A - Manufacturing method of gas generant for air cell - Google Patents
Manufacturing method of gas generant for air cell Download PDFInfo
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- CN101307034A CN101307034A CNA2008100996093A CN200810099609A CN101307034A CN 101307034 A CN101307034 A CN 101307034A CN A2008100996093 A CNA2008100996093 A CN A2008100996093A CN 200810099609 A CN200810099609 A CN 200810099609A CN 101307034 A CN101307034 A CN 101307034A
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Abstract
The invention provides gas generant for air bag reducing the residue of sulfur as impurity having high quality and even grain diameter formed by BHT ammonium salt and the preparing method thereof. The preparing method of the gas generant for air bag is characterized in: adding with 1.05 to 1.2 times mol of sodium carbonate to react with 5,5'-cross-1H-tetrazole manganese salt under the existence of hydrosolvent, filtering the manganese as manganous carbonate, adding with 1.05 to 1.2 times mol of ammonium sulphate under the existence of hydrosolvent, heating the temperature to the range of 70 to 95 centigrade to ensure the determined temperature to react with the 5,5'-cross-1H-tetrazole sodium salt.
Description
Technical field
The present invention relates to by 5 gas generant for air cell and manufacture method thereof that the ammonium salt of 5 '-Lian-1H-tetrazolium (being designated hereinafter simply as BHT) forms.
Background technology
In the past, manufacture method as the salt of above-mentioned BHT, the known aqueous solution that has modulated acetate, the vitriol oil, copper sulfate that has at water solvent, drip to sodiumazide, sodium cyanide, Manganse Dioxide under the low temperature, in 90 ℃ of reactions, steam and remove unreacted azoimide and prussic acid, after the manganese salt of acquisition BHT, this manganese salt and yellow soda ash are reacted in the presence of water solvent, make the method (with reference to patent documentation 1) of the sodium salt of BHT.
But, in the method for above-mentioned patent documentation 1,, have the volatile copper azide of impact so in reaction system, generate owing to used copper sulfate.In addition, though removed unreacted azoimide by steaming, therefore the same danger that has blast must be especially careful when handling.In addition, in the method for above-mentioned patent documentation 1, if wish by filtering or centrifugation obtains the manganese salt of BHT, the non-constant of filterableness then filters or centrifugation needs the long period, is unfavorable for industrial production.
In addition, in the method for above-mentioned patent documentation 1, the manganous carbonate of by-product during the manufacturing of sodium salt that must filter BHT, but the non-constant of the filterableness of this filtrate, filtering needs the long period, and has the sodium salt of BHT to sneak in the filtrate, so just cause a large amount of losses, be unfavorable for industrial production equally.
Therefore, manufacture method as the BHT salt that filterableness has been improved, when the cupric nitrate that has proposed to substitute above-mentioned patent documentation 1 uses acetate by low temperature and two elementary reactions of pyritous, form the manganese salt of BHT, in the presence of water solvent, add the manganese reactant salt that sodium sulphite or sodium sulfhydrate make itself and this BHT then, manganese is made the method (with reference to patent documentation 2) of the sodium salt of BHT after as the sulfide elimination.
In addition, propose in the presence of water solvent to add ammonia chloride the sodium salt of its and this BHT is reacted, obtained the method (with reference to patent documentation 3) of the ammonium salt of hypotoxic tractable BHT.
No. 2710297 communique of patent documentation 1 United States Patent (USP)
No. 3394796 communique of patent documentation 2 Japanese Patents
Patent documentation 3 Japanese Patent spies open the 2001-270868 communique
Summary of the invention
But in the manufacture method of above-mentioned patent documentation 2 records, sulphur is residual as impurity in the BHT salt of gained, therefore can't obtain high-quality gas generant for air cell.In addition, owing to used human body had pungency and toxic sodium sulphite, so the expense for the processing of the manganese sulfide of by-product improves when the operating environment load increases.
In addition, in the manufacture method of above-mentioned patent documentation 3 records, because production unit is easily corroded by used ammonium chloride, so cause the equipment control complexity, equipment overhead cost improves, thereby is unfavorable for that industry produces.
In addition, from nearest research as can be known, for as the good performance of gas generant for air cell performance, wish that the particle diameter of ammonium salt of the BHT of gained is the regulation particle diameter.But, no matter be the salt of the BHT that will obtain by the manufacture method of above-mentioned patent documentation 1 and 2 records forms BHT by the method for above-mentioned patent documentation 3 records ammonium salt, or the ammonium salt of the BHT that the method for putting down in writing by above-mentioned patent documentation 3 obtains, all there is deviation in its particle diameter.Usually under the situation of the particle diameter of needs adjustment material, can be by suitably selecting the size of the crushing medium of dispersion machine, improve the filling ratio of crushing medium or adjust the material that the pulverization process time obtains to have desirable particle diameter, but can not use such dispersion machine during as gas generant for air cell.Therefore, for the ammonium salt of the BHT that obtains to have desirable particle diameter, must carry out classification and obtain desirable size distribution with strainer or the separating centrifuge ammonium salt to the BHT that generates, operation just becomes and bothers very much like this.
The present invention is the invention of In view of the foregoing finishing, and its objective is to provide under the prerequisite that does not cause operating environment deterioration or cost to increase to possess gas generant for air cell and the manufacture method thereof that the ammonium salt by BHT suitable particle diameter, high-quality as gas generant for air cell forms.
The manufacture method that is used to solve the gas generant for air cell of the present invention of above-mentioned problem is to add the manganese reactant salt that yellow soda ash makes itself and BHT in the presence of water solvent, with manganese as the manganous carbonate elimination after, in the presence of water solvent, add the ammonium sulfate of 1.05～1.2 times of moles, temperature is risen in 70～95 ℃ scope the specified temperature of determining, its sodium salt with the BHT of gained is reacted.
Promptly, the present inventor has carried out conscientiously research back discovery to above-mentioned various problems, in the manufacturing process of the ammonium salt of BHT, behind the interpolation ammonium sulfate temperature is risen to the specified temperature of determining in 70～95 ℃ scope and make its reaction, thereby can generate the ammonium salt of the high-quality BHT of target grain size, finish the present invention by this.
In the manganese salt manufacturing process of BHT, pack into simultaneously sodiumazide, sodium cyanide, Manganse Dioxide and water, dissolving.Under 20～40 ℃, preferred 28～33 ℃ low temperature, at short notice, splash into acetate apace in preferred 30 minutes, after reacting 3～6 hours under the above-mentioned low temperature, change pyroreaction over to.Pyroreaction is 80～100 ℃, better is 88～95 ℃, reacts more than 5 hours for example 5～8 hours.
Then, reaction system is cooled to about 50 ℃, drips the sodium nitrite in aqueous solution of 0.05～1 times of mole, in reaction system, handle unreacted azoimide by this.Then, steam and remove unreacted prussic acid, removed the manganese salt of the BHT of prussic acid by filtration or centrifugation acquisition.
The sodium cyanide that is used for above-mentioned reaction is 1.0～1.2 times of moles, and preferred 1.02 times of moles, Manganse Dioxide are 0.5～0.6 times of mole, and preferred 0.51 times of mole, acetate are 3.3 times more than the mole.Acetate can be that Glacial acetic acid also can be industrial (90%) acetate.
In the sodium salt manufacturing process of BHT, the manganese salt of the BHT that will obtain by aforesaid method is packed into yellow soda ash and water and is heated to 50～70 ℃ slaking 1～3 hour.Then, by filtering the manganous carbonate of easily removing by-product, obtain the aqueous solution of the sodium salt of BHT.When separating the sodium salt of BHT, can steam the back that dewaters and use ethanol to make its partial crystallization, easily obtain the sodium salt of BHT by filtration or centrifugation as the partial crystallization solvent.
With respect to manganese salt, use the yellow soda ash of 1.05～1.2 times of moles, the yellow soda ash of preferred 1.1 times of moles.When the consumption of this yellow soda ash was less than 1.05 times of above-mentioned moles, yield was low, the manganese content height (more than the 25ppm) in the finished product.In addition, when surpassing 1.2 times of above-mentioned moles, if the consumption of ammonium sulfate disproportionately increases then yield is low, if the proportional increase of the consumption of ammonium sulfate, then the ammonia content in the waste liquid improves, and the load of environment is strengthened.
In the aqueous solution of the sodium salt of the BHT that utilizes aforesaid method to obtain, drip ammonium sulfate, after temperature risen in 70～95 ℃ scope the specified temperature of determining and implement reaction, by the cooling partial crystallization, filter again or centrifugation, thereby can easily obtain ammonium salt as the BHT of gas generant for air cell.
At this moment, with respect to ammonium salt, ammonium sulfate is 1.05～1.2 times of moles, preferred 1.1 times of moles.When the consumption of this ammonium sulfate was less than 1.05 times of above-mentioned moles, yield descended.When surpassing 1.2 times of above-mentioned moles, the ammonia content in the waste liquid improves, to the load increase of environment.
In addition, the particle diameter of the ammonium salt of gained BHT is relevant with temperature, diminishes if temperature of reaction is 70 ℃ then particle diameter, if be 95 ℃ then particle diameter becomes big.Therefore, by temperature being risen to the specified temperature of in 70～95 ℃ scope, determining,, can obtain the ammonium salt of the BHT of target grain size with state and the ammonium sulfate reaction of keeping this temperature.As gas generant for air cell, its particle diameter is compared with the regulation particle diameter when too small, and gas generation speed accelerates.Compare particle diameter with the regulation particle diameter when excessive, it is slack-off that gas produces speed, can't guarantee that the gas that designs produces speed.Among the present invention,, can obtain the particle diameter of tool practicality, by being warming up in 70～95 ℃ scope the specified temperature of determining, and keep this temperature, can in usage range, realize the homogenization of particle diameter by selecting this temperature from 70～95 ℃ scope.The practicality particle diameter of gas generant for air cell is meant that 50% particle diameter (meso-position radius) is 15 μ m～35 μ m, and the ratio of the particle of particle diameter in 15 μ m～35 mu m ranges is more than 30% in all particles.
Gas generant for air cell of the present invention is owing to used the ammonium salt of the BHT that obtains by above-mentioned manufacture method, so less residue of sulphur, 50% particle diameter can be controlled in the scope of 15 μ m～35 μ m, and the ratio of the particle of particle diameter in 15 μ m～35 mu m ranges can be more than 30% in all particles.Therefore, can obtain the few high-quality gas generant for air cell of impurity.
As mentioned above, can obtain the few high-quality gas generant for air cell of impurity by the present invention with suitable particle diameter.
Description of drawings
Fig. 1 is the figure of the size-grade distribution of the ammonium salt of the BHT of expression embodiment 1 acquisition.
Fig. 2 is the figure of the size-grade distribution of the ammonium salt of the BHT of expression embodiment 2 acquisitions.
Fig. 3 is the figure of the size-grade distribution of the ammonium salt of the BHT of expression comparative example 1 acquisition.
Fig. 4 is the figure of the size-grade distribution of the ammonium salt of the BHT of expression comparative example 2 acquisitions.
Nomenclature: M represents 50% particle diameter.
Embodiment
Below, the present invention is described in detail to exemplify embodiment, but the present invention is not limited in these embodiment.
[embodiment 1]
(manufacturing of the manganese salt of BHT) pack in 4 mouthfuls of flasks of 1 liter of band stirrer water, 78g sodiumazide, 60g sodium cyanide and 54g Manganse Dioxide of 560 milliliters is cooled to below 10 ℃.In dripping 90% acetate 265g with 15 minutes below 30 ℃, be warming up to 90 ℃ of reactions 5 hours after 3 hours in 25～35 ℃ of reactions.Then, be cooled to room temperature, drip the sodium nitrite in aqueous solution of 0.1 times of mole, in reaction system, unreacted azoimide is handled.Then, remove unreacted prussic acid, filter the manganese salt of BHT, drying, manganese salt (2 hydrate) 122g of acquisition BHT by steaming.Purity is more than 99.5%, and yield is 90%.
(manufacturing of the ammonium salt of BHT) be pack into 200 milliliters water, the manganese salt of BHT (2 hydrate) 68g, yellow soda ash 35g (the manganese salt with respect to 1 mole of BHT is 1.1 moles) in 4 mouthfuls of flasks of 500 milliliters of band stirrer, is heated to 50 ℃, slaking 1 hour.Then, by removing by filter the manganous carbonate of by-product, obtain the aqueous solution of the sodium salt of BHT.
Pack in 4 mouthfuls of flasks of 500 milliliters of the band stirrer aqueous solution of sodium salt of BHT is warming up to and adds ammonium sulfate 44g (sodium salt with respect to 1 mole of BHT is 1.1 moles) after 50 ℃, is warming up to 70 ℃ again, slaking 0.5 hour.Then, be cooled to 20 ℃, obtain the ammonium salt of the BHT of 45g by centrifugation.Yield is 87%, and purity is more than 99.5%.In addition, the size-grade distribution of measuring by the dynamic scattering method is shown in Fig. 1.Consequently, 50% particle diameter M is about 18 μ m, and the ratio that the particle of particle diameter between 15 μ m～35 μ m accounts for total amount is about 46%.
[embodiment 2]
(manufacturing of the ammonium salt of BHT) in 4 mouthfuls of flasks of 500 milliliters of band stirrer, pack into manganese salt (2 hydrate) 68g, yellow soda ash 35g (the manganese salt with respect to 1 mole of BHT is 1.1 moles) of BHT of 200 milliliters water, the acquisition of the manufacture method by similarly to Example 1, be heated to 50 ℃, slaking 1 hour.Then, by removing by filter the manganous carbonate of by-product, obtain the aqueous solution of the sodium salt of BHT.
Pack in 4 mouthfuls of flasks of 500 milliliters of the band stirrer aqueous solution of sodium salt of BHT is warming up to and adds ammonium sulfate 44g (sodium salt with respect to 1 mole of BHT is 1.1 moles) after 50 ℃, is warming up to 95 ℃ again, slaking 0.5 hour.Then, be cooled to 20 ℃, obtain the ammonium salt of the BHT of 45g by centrifugation.Yield is 87%, and purity is more than 99.5%.In addition, the size-grade distribution of measuring by the dynamic scattering method is shown in Fig. 2.Consequently, 50% particle diameter M is about 26 μ m, and the ratio that the particle of particle diameter between 15 μ m～35 μ m accounts for total amount is about 38%.
[comparative example 1]
(manufacturing of the ammonium salt of BHT) in 4 mouthfuls of flasks of 500 milliliters of band stirrer, pack into manganese salt (2 hydrate) 68g, yellow soda ash 35g (the manganese salt with respect to 1 mole of BHT is 1.1 moles) of BHT of 200 milliliters water, the acquisition of the manufacture method by similarly to Example 1, be heated to 50 ℃, slaking 1 hour.Then, by removing by filter the manganous carbonate of by-product, obtain the aqueous solution of the sodium salt of BHT.
Pack in 4 mouthfuls of flasks of 500 milliliters of the band stirrer aqueous solution of sodium salt of BHT is warming up to and adds ammonium sulfate 44g (sodium salt with respect to 1 mole of BHT is 1.1 moles) after 50 ℃, is warming up to 58 ℃ again, slaking 0.5 hour.Then, be cooled to 20 ℃, obtain the ammonium salt of the BHT of 45g by centrifugation.Yield is 87%, and purity is more than 99.5%.In addition, the size-grade distribution of measuring by the dynamic scattering method is shown in Fig. 3.Consequently, 50% particle diameter M is about 9 μ m, and the ratio that the particle of particle diameter between 15 μ m～35 μ m accounts for total amount is about 22%.
[comparative example 2]
(manufacturing of the ammonium salt of BHT) in 4 mouthfuls of flasks of 500 milliliters of band stirrer, pack into manganese salt (2 hydrate) 68g, yellow soda ash 35g (the manganese salt with respect to 1 mole of BHT is 1.1 moles) of BHT of 200 milliliters water, the acquisition of the manufacture method by similarly to Example 1, be heated to 50 ℃, slaking 1 hour.Then, by removing by filter the manganese sulfide of by-product, obtain the aqueous solution of the sodium salt of BHT.
Pack in 4 mouthfuls of flasks of 500 milliliters of the band stirrer aqueous solution of sodium salt of BHT is warming up to and adds ammonium sulfate 44g (sodium salt with respect to 1 mole of BHT is 1.1 moles) after 50 ℃, is warming up to 60 ℃ again, slaking 0.5 hour.Then, be cooled to 20 ℃, obtain the ammonium salt of the BHT of 45g by centrifugation.Yield is 87%, and purity is more than 99.5%.In addition, the size-grade distribution of measuring by the dynamic scattering method is shown in Fig. 4.Consequently, 50% particle diameter M is about 7.2 μ m, and the ratio that the particle of particle diameter between 15 μ m～35 μ m accounts for total amount is about 14%.
Can confirm from The above results, by in the sodium salt of BHT, adding ammonium sulfate, be warming up to 70～95 ℃ reaction is carried out, can be used as 50% particle diameter, the ammonium salt that the particle of particle diameter between 15 μ m～35 μ m is adjusted to the BHT more than 30% of total amount obtains gas generant for air cell of the present invention with 15～35 μ m.
Can be used as and bring into play 5 of superperformance in gas generant for air cell or whipping agent, 5 '-Lian-1H-tetrazolium di-ammonium salts is used.
Claims (2)
1. the manufacture method of gas generant for air cell, it is characterized in that, the yellow soda ash that in the presence of water solvent, adds 1.05～1.2 times of moles make itself and 5, the manganese reactant salt of 5 '-Lian-1H-tetrazolium, with manganese as the manganous carbonate elimination after, in the presence of water solvent, add the ammonium sulfate of 1.05～1.2 times of moles, temperature is risen to the specified temperature of in 70～95 ℃ scope, determining, make 5 of itself and gained, the sodium salt reaction of 5 '-Lian-1H-tetrazolium.
2. gas generant for air cell is characterized in that, obtains by the described manufacture method of claim 1.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007131693A JP5114735B2 (en) | 2007-05-17 | 2007-05-17 | Method for producing gas generating agent for airbag |
| JP2007-131693 | 2007-05-17 |
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| Publication Number | Publication Date |
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| CN101307034A true CN101307034A (en) | 2008-11-19 |
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| CNA2008100996093A Pending CN101307034A (en) | 2007-05-17 | 2008-05-16 | Manufacturing method of gas generant for air cell |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3394796B2 (en) * | 1993-07-20 | 2003-04-07 | 東洋化成工業株式会社 | Process for producing 5,5'-bi-1H-tetrazole salts |
| JP2000256332A (en) * | 1999-03-11 | 2000-09-19 | Japan Hydrazine Co Inc | Production of 5,5'-bi-1h-tetrazole salt |
| JP4568400B2 (en) * | 2000-03-24 | 2010-10-27 | 株式会社日本ファインケム | Method for producing 5,5'-bi-1H-tetrazole diammonium salt using hydrated hydrazine and dicyan as raw materials |
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| JP5114735B2 (en) | 2013-01-09 |
| JP2008285360A (en) | 2008-11-27 |
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Application publication date: 20081119 |