CN101508681A - Method of preparing high purity tetrazole ammonium salt - Google Patents
Method of preparing high purity tetrazole ammonium salt Download PDFInfo
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- CN101508681A CN101508681A CNA2008100128599A CN200810012859A CN101508681A CN 101508681 A CN101508681 A CN 101508681A CN A2008100128599 A CNA2008100128599 A CN A2008100128599A CN 200810012859 A CN200810012859 A CN 200810012859A CN 101508681 A CN101508681 A CN 101508681A
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- ammonium salt
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- tetrazole
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- bistetrazole
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Abstract
The invention relates to a preparation method of high-purity bistetrazole ammonium salt which is a low-toxic and safe gas generant of new generation used in an automobile airbag. In the method, sodium azide and sodium cyanide are taken as basic raw materials, and the method comprises four steps: synthesis of an intermediate, removal of metal ions such as copper and the like, crude product preparation and refinement. Firstly, the sodium azide and the sodium cyanide are subject to oxidation reaction and addition reaction in acidic aqueous solution to generate bistetrazole sodium salt in the presence of copper sulfate; then the metal ions such as the copper and the like are removed with sulfide by complexation, and the bistetrazole sodium salt is converted into crude bistetrazole ammonium salt with inorganic ammonium salt; finally, the crude product is refined into the high-purity bistetrazole ammonium salt. The preparation method has the advantages of simple process, mild reaction conditions, safe and convenient operation, ready available raw materials, high product yield and purity, and being suitable for industrial production.
Description
(1) technical field
The present invention relates to a kind of preparation method of high purity tetrazole ammonium salt.
(2) background technology
Tetrazole ammonium salt is a young mobile airbag gas propellant, and is therefore very high to the purity requirement of its product, not only require its principal product greater than 99%, and all mineral ions all requires the level at ppm.
American Fred Einberg (J.Org.Chem.29,2021 (1964)) separates from dinitrobenzene acetonitrile sodium, sodiumazide and ammonium chloride are the reaction mixture of raw material and has obtained tetrazole ammonium salt.But this method long reaction time, productive rate are very low, and raw material dinitrobenzene acetonitrile sodium is difficult to.
Japanese Patent (JP2000-191649) is a main raw material with prussic acid, sodiumazide and ammonium chloride, and under copper sulfate catalysis, hydrogen peroxide is an oxygenant, and one pot reaction has prepared tetrazole ammonium salt.Because contain the cupric ion of several thousand ppm, its product is light blue.
(JP2000-256332 is US6040453) with dicyanogen (CN) for Japanese Patent
2, sodiumazide and ammonium chloride is that raw material reaction has prepared tetrazole ammonium salt.Though it is whiter that this method obtains product, productive rate is higher, and needing in addition in reaction, device is the feedstock production dicyanogen with hypertoxic prussic acid gas.If calculate productive rate with prussic acid, its productive rate is just very low.
European patent (EP1162198 is a main raw material with sodium cyanide, sodiumazide and ammonium chloride US6433181B1), and under copper sulfate catalysis, hydrogen peroxide is an oxygenant, prepared in reaction tetrazole ammonium salt.In the prepared in reaction process, form precipitable complex compound (BHTCuNH with ammoniacal liquor and a part of product and cupric ion complexing
3) remove the most copper ion; Further remove cupric ion by resin column again.This method is not only loaded down with trivial details, and the raw materials used purity that requires is very high.
(3) goal of the invention
The objective of the invention is to have developed one material purity be less demanding, technology is simple, reaction conditions is gentle, operational safety, product yield height and purity is up to standard, and the preparation method of the high purity tetrazole ammonium salt of suitable suitability for industrialized production.
(4) summary of the invention
The present invention is a kind of preparation method of high purity tetrazole ammonium salt, it is characterized in that this method is a basic raw material with sodiumazide and sodium cyanide, prepare high-purity tetrazole ammonium salt through four main processes such as synthetic and refining of the removing of the metal ions such as synthetic, copper of bistetrazole sodium salt, thick product tetrazole ammonium salt; 1) under copper sulfate catalysis, the oxidation in acidic aqueous solution of sodiumazide and sodium cyanide, addition reaction generate the bistetrazole sodium salt; 2) remove metal ions such as copper with the sulphide salt complexing; 3) the bistetrazole sodium salt converts thick product tetrazole ammonium salt under the effect of inorganic ammonium salt; 4) thick product purification is become high-purity tetrazole ammonium salt.
With the tetrazole ammonium salt of this method preparation, organism and mineral ion impurity are all very low, meet or exceed the requirement of relevant department to the automotive airbag gas-evolution agent.The inventive method technology is simple, the reaction conditions gentleness, and operational safety, convenience, raw material is easy to get, and product yield and purity height are suitable for suitability for industrialized production.
Synthesizing of bistetrazole sodium salt among the above-mentioned preparation method, promptly under copper sulfate catalysis, the oxidation in acidic aqueous solution of sodiumazide and sodium cyanide, addition reaction generate the bistetrazole sodium salt; Acid in the reaction comprises formic acid, acetate, hydrochloric acid, sulfuric acid and their mixing acid thereof; Oxygenant in the reaction comprises hydrogen peroxide (hydrogen peroxide) and Manganse Dioxide; 10 ℃ to 120 ℃ of temperature of reaction.
The process of removing metal ions such as copper among the above-mentioned preparation method is promptly removed metal ion processes such as copper with the sulfide complexing; Wherein sulfide comprises hydrogen sulfide, sodium sulphite, Sodium sulfhydrate, potassium sulphide and potassium bisulfide etc.; 0 ℃ to 110 ℃ of temperature of reaction.This process can be carried out (as accompanying drawing route 1) in second step, also can merge to final step treating process (as accompanying drawing route 2).
Synthesizing of thick product tetrazole ammonium salt among the above-mentioned preparation method, promptly the bistetrazole sodium salt converts thick product tetrazole ammonium salt under the effect of inorganic ammonium salt; Inorganic ammonium salt comprises ammonia, ammonium hydroxide (ammoniacal liquor), ammonium sulfate and ammonium halide salt; 20 ℃ to 120 ℃ of temperature of reaction.
Treating process among the above-mentioned preparation method is about to thick product tetrazole ammonium salt and is dissolved in the acid, and ammonification makes the high purity tetrazole ammonium again; Acid wherein comprises hydrogen chloride gas, hydrogen sulfide, hydrochloric acid, sulphur hydracid and sulfuric acid; Ammonia wherein comprises ammonia, ammonium hydroxide (ammoniacal liquor), ammonium sulfate and ammonium halide salt; 20 ℃ to 120 ℃ of temperature of reaction.
(5) description of drawings
Accompanying drawing is latter half reaction of the present invention and purifying schema.
(6) embodiment
Further specify the mode that the present invention and the inventive method are carried out below in conjunction with drawings and Examples.These examples of implementation only are not to be that protection scope of the present invention only limits to this in order further to set forth the present invention.
Embodiment 1:
Mechanical stirring, thermometer and dropping funnel are installed on three mouthfuls of reaction flasks of two decaliters, add 1Kg (20.5mol) sodium cyanide (technical pure, 98%) and 6L water then.After stirring is molten entirely, system is cooled to about 5 ℃ with the cryosel bath, adds 1.38Kg (21.2mol) sodiumazide (technical pure, 99%).After the system for the treatment of is molten entirely, drips 2.1Kg (20.7mol) 36% hydrochloric acid (reagent is pure), and keep system temperature below 5 ℃; Add 30g (0.12mol) CuSO afterwards again
45H
2The mixing solutions of O, 120g acetate and 2L water.After stirring, slowly drip 1.5Kg (11.07mol) 25% hydrogen peroxide (technical pure) in system, the control rate of addition makes the interior temperature of system be no more than 10 ℃, approximately needs 1.5 hours.Dropwise, reaction system slowly heats to 40 ℃ again in stirring at room half an hour, and this process approximately needs 35 minutes.40 ℃ of insulations slowly heat to 90 ℃ after 1 hour again, and this process approximately needs 50 minutes.90 ℃ of insulations slowly heat to backflow after 2 hours again, and this process approximately needs 25 minutes.Reflux insulation after 6 hours, stop heating, treat that system temperature drops to about 76 ℃, (control reaction temperature is between the 70-80 degree for 1.2Kg, aqueous solution 22.4mol) under agitation to drip ammonium chloride.Dropwise, under agitation be incubated one hour between the 70-80 degree, cool to room temperature then naturally.After the filtration, light blue solid is washed (2L) once with distillation, and 50 ℃ of following vacuum dryings got 1.65Kg in 6 hours.Yield is 93%, perchloric acid titration content 96.3%, and HPLC analyzes content 96.5%, copper content 5984ppm, sodium content 1085ppm.
Embodiment 2:
The solid product 1Kg that will obtain from example 1 is suspended in 5 liters of distilled water, and in this system, drip the concentrated hydrochloric acid (approximately 0.7Kg) of SILVER REAGENT, slowly feed hydrogen sulfide when being heated to 55 ℃ of left and right sides, approximately ventilation is after 2 minutes, system is warmed up to 76 ℃, and insulated and stirred 2 hours, filtered while hot filters the black insolubles.Filtrate is transferred in the new reactor, heats to about 75 ℃, slowly feeds ammonia, and it is qualified to detect until sampling HPLC.Naturally cool to room temperature then, after the filtration, white solid is washed (1.5L) once with distillation, and 50 ℃ of following vacuum dryings got 0.95Kg in 6.5 hours.Yield is 95%, perchloric acid titration content 99.3%, and HPLC analyzes content 99.7%, copper content 4.3ppm, sodium content 150ppm.
Embodiment 3:
Mechanical stirring, thermometer and dropping funnel are installed on three mouthfuls of reaction flasks of two decaliters, add 1Kg (20.5mol) sodium cyanide (technical pure, 98%) and 6L water then.After stirring is molten entirely, system is cooled to about 5 ℃ with the cryosel bath, adds 1.38Kg (21.2mol) sodiumazide (technical pure, 99%).After the system for the treatment of is molten entirely, drips 2.1Kg (20.7mol) 36% hydrochloric acid (reagent is pure), and keep system temperature below 5 ℃; Add 30g (0.12mol) CuSO afterwards again
45H
2The mixing solutions of O, 120g acetate and 2L water.After stirring, slowly drip 1.5Kg (11.07mol) 25% hydrogen peroxide (technical pure) in system, the control rate of addition makes the interior temperature of system be no more than 10 ℃, approximately needs 1.5 hours.Dropwise, reaction system slowly heats to 40 ℃ again in stirring at room half an hour, and this process approximately needs 35 minutes.40 ℃ of insulations slowly heat to 90 ℃ after 1 hour again, and this process approximately needs 50 minutes.90 ℃ of insulations slowly heat to backflow after 2 hours again, and this process approximately needs 25 minutes.Reflux insulation after 6 hours, stop heating, and in system, drip sodium sulphite (78g, aqueous solution 1.0mol).Stir after 2 hours, system temperature drops to 76 ℃, filters the black insolubles is filtered.Filtrate is transferred in the new reactor, heats to about 75 ℃, and (control reaction temperature is between the 70-80 degree for 1.2Kg, aqueous solution 22.4mol) under agitation to drip ammonium chloride.Dropwise, under agitation be incubated one hour between the 70-80 degree, cool to room temperature then naturally.After the filtration, white solid is washed (2L) once with distillation, and 50 ℃ of following vacuum dryings got 1.55Kg in 6 hours.Yield is 88%, perchloric acid titration content 98.4%, and HPLC analyzes content 99.5%, copper content 4.8ppm, sodium content 1245ppm.
Embodiment 4:
The solid product 1Kg that will obtain from example 3 is suspended in 5 liters of distilled water, and in this system, drip the concentrated hydrochloric acid (approximately 0.7Kg) of SILVER REAGENT, be heated to 55 ℃ of left and right sides systems and become clear (if having insolubles to refilter once), slowly feed ammonia in the time of 70 ℃, it is qualified to detect until sampling HPLC.Naturally cool to room temperature then, after the filtration, white solid is washed (1.5L) once with distillation, and 50 ℃ of following vacuum dryings got 0.93Kg in 6.5 hours.Yield is 93%, perchloric acid titration content 99.4%, and HPLC analyzes content 99.8%, copper content 4.6ppm, sodium content 210ppm.
Embodiment 5:
Mechanical stirring, thermometer and dropping funnel are installed on three mouthfuls of reaction flasks of two decaliters, then 1Kg (20.5mol) sodium cyanide (technical pure, 98%) and 1.33Kg (20.5mol) sodiumazide (technical pure, 99%) are dissolved in the 10L water.Under agitation 1.1Kg (14.5mol) Manganse Dioxide is joined in the system, then system is cooled to below 10 ℃, again with the 2L vitriol oil, the mixed solution of 1.6L Glacial acetic acid and 40g cupric sulfate pentahydrate and 2L water slowly adds in the system of stirring.The control rate of addition makes the interior temperature of system be no more than 10 ℃, approximately needs 1.5 hours.Dropwise, reaction system slowly heats to 40 ℃ again in stirring at room half an hour, and this process approximately needs 30 minutes.40 ℃ of insulations slowly heat to 90 ℃ after 1 hour again, and this process approximately needs 2 hours.90-95 ℃ of insulation is after 4 hours, and system cools to room temperature naturally, and after the filtration, solid manganese salt and sodium carbonate solution boil, heat filtering; Filtrate is transferred in the reaction flask, and under agitation the drip sodium sulphite aqueous solution of (100g), again system is incubated 2 hours about 76 ℃, filter the black insolubles is filtered.Filtrate is transferred in the new reactor, heats to about 75 ℃, and (control reaction temperature is between the 70-80 degree for 1.2Kg, aqueous solution 22.4mol) under agitation to drip ammonium chloride.Dropwise, under agitation be incubated one hour between the 70-80 degree, cool to room temperature then naturally.After the filtration, white solid is washed (2L) once with distillation, and 50 ℃ of following vacuum dryings got 1.43Kg in 6 hours.Yield is 81%, perchloric acid titration content 97.1%, and HPLC analyzes content 98.8%, copper content 4.7ppm, sodium content 1320ppm.
Embodiment 6:
The solid product 1Kg that will obtain from example 5 is suspended in 5 liters of distilled water, and in this system, drip the concentrated hydrochloric acid (approximately 0.7Kg) of SILVER REAGENT, be heated to 55 ℃ of left and right sides systems and become clear (if having insolubles to refilter once), slowly feed ammonia in the time of 70 ℃, it is qualified to detect until sampling HPLC.Naturally cool to room temperature then, after the filtration, white solid is washed (1.5L) once with distillation, and 50 ℃ of following vacuum dryings got 0.91Kg in 7.5 hours.Yield is 91%, perchloric acid titration content 99.5%, and HPLC analyzes content 99.9%, copper content 4.5ppm, sodium content 220ppm.
Claims (7)
1. the preparation method of a high purity tetrazole ammonium salt, it is characterized in that this method is a basic raw material with sodiumazide and sodium cyanide, prepare high-purity tetrazole ammonium salt through the process such as synthetic and refining of the removing of the metal ions such as synthetic, copper of bistetrazole sodium salt, thick product tetrazole ammonium salt.
Route1：BHT-2Na+Sulfide→Filtration?of?insoluble?components+NH
4 +→Crude?BHT-2NH
3+H
+→Solution+NH
3→Highly?pure?BHT-2NH
3.
Route2：BHT-2Na+NH
4 +→Crude?BHT-2NH
3+H
+→Solution+Sulfide→Filtration?of?insoluble?components+NH
3→Highly?pure?BHT-2NH
3.
2. the preparation method of high purity tetrazole ammonium salt according to claim 1 is characterized in that the preparation method of above-mentioned high purity tetrazole ammonium salt divided for four steps carried out: the synthetic and treating process of the removing of metal ions such as synthetic, the copper of bistetrazole sodium salt, thick product tetrazole ammonium salt.1) under copper sulfate catalysis, the oxidation in acidic aqueous solution of sodiumazide and sodium cyanide, addition reaction generate the bistetrazole sodium salt; 2) remove metal ions such as copper with the sulfide complexing; 3) the bistetrazole sodium salt converts thick product tetrazole ammonium salt under the effect of inorganic ammonium salt; 4) thick product purification is become high-purity tetrazole ammonium salt.
3. according to the preparation method of claim 1 and 2 described high purity tetrazole ammonium salts, it is characterized in that the synthetic of above-mentioned bistetrazole sodium salt, promptly under copper sulfate catalysis, the oxidation in acidic aqueous solution of sodiumazide and sodium cyanide, addition reaction generate the bistetrazole sodium salt; Acid in the reaction comprises formic acid, acetate, hydrochloric acid, sulfuric acid and their mixing acid thereof; Oxygenant in the reaction comprises hydrogen peroxide (hydrogen peroxide) and Manganse Dioxide; Temperature of reaction is from 10 ℃ to 120 ℃.
4. according to the preparation method of claim 1 and 2 described high purity tetrazole ammonium salts, it is characterized in that the above-mentioned process of removing metal ions such as copper, promptly remove metal ion processes such as copper with the sulfide complexing; Wherein sulfide comprises hydrogen sulfide, sodium sulphite, Sodium sulfhydrate, potassium sulphide and potassium bisulfide; Temperature of reaction is from 0 ℃ to 110 ℃.
5. according to the preparation method of claim 1 and 2 described high purity tetrazole ammonium salts, it is characterized in that the synthetic of above-mentioned thick product tetrazole ammonium salt, promptly the bistetrazole sodium salt converts thick product tetrazole ammonium salt under the effect of inorganic ammonium salt; Inorganic ammonium salt comprises ammonia, ammonium hydroxide (ammoniacal liquor), ammonium sulfate and ammonium halide salt; Temperature of reaction is from 20 ℃ to 120 ℃.
6. according to the preparation method of claim 1 and 2 described high purity tetrazole ammonium salts, it is characterized in that above-mentioned treating process, be about to thick product tetrazole ammonium salt and be dissolved in the acid that ammonification makes the high purity tetrazole ammonium again; Acid wherein comprises hydrogen chloride gas, hydrogen sulfide, hydrochloric acid, sulphur hydracid and sulfuric acid; Ammonia wherein comprises ammonia, ammonium hydroxide (ammoniacal liquor), ammonium sulfate and ammonium halide salt; Temperature of reaction is from 20 ℃ to 120 ℃.
7. according to the preparation method of claim 1,2,4 and 6 described high purity tetrazole ammonium salts, it is characterized in that the process of removing of above-mentioned metal ions such as copper, can carry out (route 1), also can merge to final step treating process (route 2) in second step.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103524444A (en) * | 2013-09-27 | 2014-01-22 | 北京理工大学 | Synthetic method of 5, 5'-bistetrazole-1, 1'-dioxo hydroxyl ammonium salt (TKX-50) |
| CN103724287A (en) * | 2012-10-10 | 2014-04-16 | 同济大学 | 1,1'-dihydroxy-5,5'-bitetrazole ammonium salt and preparation method |
| CN104277007A (en) * | 2013-07-10 | 2015-01-14 | 湖北航天化学技术研究所 | Method of synthesizing 5,5'-bistetrazole-1,1'-dioxodihydroxy ammonium salt |
-
2008
- 2008-08-19 CN CNA2008100128599A patent/CN101508681A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103724287A (en) * | 2012-10-10 | 2014-04-16 | 同济大学 | 1,1'-dihydroxy-5,5'-bitetrazole ammonium salt and preparation method |
| CN104277007A (en) * | 2013-07-10 | 2015-01-14 | 湖北航天化学技术研究所 | Method of synthesizing 5,5'-bistetrazole-1,1'-dioxodihydroxy ammonium salt |
| CN103524444A (en) * | 2013-09-27 | 2014-01-22 | 北京理工大学 | Synthetic method of 5, 5'-bistetrazole-1, 1'-dioxo hydroxyl ammonium salt (TKX-50) |
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Open date: 20090819 |