JPH0733754A - Production of 5,5'-bi-1h-tetrazoles - Google Patents
Production of 5,5'-bi-1h-tetrazolesInfo
- Publication number
- JPH0733754A JPH0733754A JP20112493A JP20112493A JPH0733754A JP H0733754 A JPH0733754 A JP H0733754A JP 20112493 A JP20112493 A JP 20112493A JP 20112493 A JP20112493 A JP 20112493A JP H0733754 A JPH0733754 A JP H0733754A
- Authority
- JP
- Japan
- Prior art keywords
- sodium
- bht
- manganese
- salt
- producing
- 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.)
- Granted
Links
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 17
- MTAYYBKXNAEQOK-UHFFFAOYSA-N 5-(2h-tetrazol-5-yl)-2h-tetrazole Chemical class N1N=NC(C2=NNN=N2)=N1 MTAYYBKXNAEQOK-UHFFFAOYSA-N 0.000 title claims abstract description 7
- 150000002696 manganese Chemical class 0.000 claims abstract description 18
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 14
- 159000000000 sodium salts Chemical class 0.000 claims abstract description 13
- PXIPVTKHYLBLMZ-UHFFFAOYSA-N Sodium azide Chemical compound [Na+].[N-]=[N+]=[N-] PXIPVTKHYLBLMZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- JUINSXZKUKVTMD-UHFFFAOYSA-N hydrogen azide Chemical compound N=[N+]=[N-] JUINSXZKUKVTMD-UHFFFAOYSA-N 0.000 claims abstract description 10
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- 229910052979 sodium sulfide Inorganic materials 0.000 claims abstract description 8
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims abstract description 8
- KXZJHVJKXJLBKO-UHFFFAOYSA-N chembl1408157 Chemical compound N=1C2=CC=CC=C2C(C(=O)O)=CC=1C1=CC=C(O)C=C1 KXZJHVJKXJLBKO-UHFFFAOYSA-N 0.000 claims abstract description 7
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 claims abstract description 7
- 235000010288 sodium nitrite Nutrition 0.000 claims abstract description 5
- 239000002904 solvent Substances 0.000 claims abstract description 5
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 4
- 239000011572 manganese Substances 0.000 claims abstract description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 6
- 239000003125 aqueous solvent Substances 0.000 claims description 4
- 238000007039 two-step reaction Methods 0.000 claims description 2
- 150000003536 tetrazoles Chemical class 0.000 claims 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 abstract description 32
- 238000001914 filtration Methods 0.000 abstract description 12
- 239000006227 byproduct Substances 0.000 abstract description 8
- 150000003839 salts Chemical class 0.000 abstract description 8
- 239000004088 foaming agent Substances 0.000 abstract description 3
- 229920005992 thermoplastic resin Polymers 0.000 abstract description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 abstract 1
- 239000011734 sodium Substances 0.000 abstract 1
- 229910052708 sodium Inorganic materials 0.000 abstract 1
- 230000001988 toxicity Effects 0.000 abstract 1
- 231100000419 toxicity Toxicity 0.000 abstract 1
- -1 copper azide Chemical compound 0.000 description 13
- 229960000583 acetic acid Drugs 0.000 description 9
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 238000005119 centrifugation Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 229910000365 copper sulfate Inorganic materials 0.000 description 4
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical class CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 150000004683 dihydrates Chemical class 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- CADICXFYUNYKGD-UHFFFAOYSA-N sulfanylidenemanganese Chemical compound [Mn]=S CADICXFYUNYKGD-UHFFFAOYSA-N 0.000 description 2
- 239000004322 Butylated hydroxytoluene Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 231100001231 less toxic Toxicity 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 229940093474 manganese carbonate Drugs 0.000 description 1
- 239000011656 manganese carbonate Substances 0.000 description 1
- 235000006748 manganese carbonate Nutrition 0.000 description 1
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 1
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000004686 pentahydrates Chemical class 0.000 description 1
- 238000009527 percussion Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は毒性の少ない次世代エア
バツグ用インフレ−タ−として、また高分子、その中で
も熱可塑性樹脂の成型品の軽量化、ヒケ・ソリのない精
密成型用発泡剤としても有用な５，５′−ビ−１Ｈ−テ
トラゾ−ル（以下ＢＨＴと略称）の塩類の製造方法に関
するものである。FIELD OF THE INVENTION The present invention is used as an inflator for next-generation air bags with low toxicity, and as a foaming agent for high-precision molding without weight reduction or warping or warping of polymers, especially thermoplastic resins. It also relates to a method for producing a useful salt of 5,5'-bi-1H-tetrazole (hereinafter abbreviated as BHT).
【０００２】[0002]
【従来の技術】従来前記ＢＨＴの塩類の製造方法として
はアジ化ナトリウム、シアン化ナトリウム、二酸化マン
ガンを水溶媒の下で酢酸、濃硫酸、硫酸銅の水溶液を調
製して低温で滴下し、９０℃で反応し、未反応のアジ化
水素及びシアン化水素を留去し、ＢＨＴのマンガン塩を
得ている。またこのマンガン塩と炭酸ナトリウムとを水
溶媒下で反応させてＢＨＴのナトリウム塩を製造する方
法が知られている。（Water Friederich, Ｕ．Ｓ．Ｐ．
2,710,297 号）2. Description of the Related Art Conventionally, as a method for producing the above-mentioned salts of BHT, sodium azide, sodium cyanide, and manganese dioxide are prepared in an aqueous solution of acetic acid, concentrated sulfuric acid, and copper sulfate and added dropwise at a low temperature. After reacting at 0 ° C., unreacted hydrogen azide and hydrogen cyanide are distilled off to obtain a manganese salt of BHT. Also known is a method of producing the sodium salt of BHT by reacting this manganese salt with sodium carbonate in an aqueous solvent. (Water Friederich, USP.
(2,710,297)
【０００３】[0003]
【発明が解決しようとする課題】しかしながら前記Ｕ．
Ｓ．Ｐ．2,710,297 号の方法の第１の課題は硫酸銅を使
用しているため系内で打撃爆発性のあるアジ化銅が生成
する。また未反応のアジ化水素を留去により除去してい
るが、同様に爆発の危険性があり、取扱いに充分注意す
る必要がある。第２の課題としてはＢＨＴのマンガン塩
を濾過又は遠心分離によつて得ようとすると濾過性が著
しく悪く、濾過又は遠心分離に長時間を要し、工業的に
は不利である。かつ取扱い上の安全の確保可能な新規な
ＢＨＴマンガン塩を提供することにある。更に第３の課
題としてはＢＨＴのナトリウム塩の製造時に副生する炭
酸マンガンを濾過する必要があるが、この濾過物の濾過
性がまた著しく悪く、濾過に長時間を必要とするし、か
つ濾過物中にＢＨＴのナトリウム塩が混入されてかなり
の量がロスになり、同様に工業的に不利である。However, the above U.S. Pat.
S. P. The first problem of the method of No. 2,710,297 is that copper azide, which has a percussion explosive property, is generated in the system because copper sulfate is used. Although unreacted hydrogen azide is removed by distillation, there is a danger of explosion as well, and it is necessary to handle with care. The second problem is that if the BHT manganese salt is to be obtained by filtration or centrifugation, the filterability is extremely poor, and filtration or centrifugation requires a long time, which is industrially disadvantageous. Another object of the present invention is to provide a novel BHT manganese salt which can ensure safety in handling. A third problem is that it is necessary to filter manganese carbonate, which is a by-product during the production of sodium salt of BHT. However, the filterability of this filtrate is remarkably poor, and it requires a long time for filtration, and the filtration is difficult. The sodium salt of BHT is mixed in the product, which causes a considerable amount of loss, which is also industrially disadvantageous.
【０００４】本発明は従来Ｕ．Ｓ．Ｐ．2,710,297 号の
製造方法の上記の種々な課題に鑑み、工業的に有利に、
安全に、かつＢＨＴのマンガン塩並びにナトリウム塩製
造時に副生する塩類の濾過性を向上させ、高品質、高収
率で工業的に有利なＢＨＴの塩類の製造法を確立するこ
とを目的とするものである。The present invention has been described in U.S. Pat. S. P. In view of the above various problems of the manufacturing method of No. 2,710,297, industrially advantageous,
An object of the present invention is to safely and improve the filterability of salts produced as a by-product during production of BHT manganese salt and sodium salt, and to establish an industrially advantageous production method of BHT salts with high quality and high yield. It is a thing.
【０００５】[0005]
【課題を解決するための手段】本発明はアジ化ナトリウ
ム、シアン化ナトリウム、二酸化マンガンを水溶媒下、
酢酸を１５〜４０℃の低温で滴下して、下記に示すよう
な一定時間反応し、ついで反応温度を８０〜100 ℃の高
温に上昇させ、更に一定時間反応することによつて低温
及び高温の二段階の反応を行う。更に、未反応のアジ化
水素を亜硝酸ナトリウムを使用して系内で処理すること
により、５，５′−ビ−１Ｈ−テトラゾ−ルのマンガン
塩を製造する方法であり、更にかくして得られた該マン
ガン塩を水溶媒の下、硫化ナトリウム又は水硫化ナトリ
ウムを添加しマンガンを硫化物として濾別して製造する
５，５′−ビ−１Ｈ−テトラゾ−ルの製造法を提出する
ものである。The present invention comprises sodium azide, sodium cyanide and manganese dioxide in an aqueous solvent,
Acetic acid was added dropwise at a low temperature of 15 to 40 ° C. to react for a certain period of time as shown below, and then the reaction temperature was raised to a high temperature of 80 to 100 ° C. Perform a two-step reaction. Furthermore, it is a method for producing a manganese salt of 5,5'-bi-1H-tetrazole by treating unreacted hydrogen azide in the system using sodium nitrite, and thus obtained. In addition, a method for producing 5,5'-bi-1H-tetrazole is proposed, in which sodium sulfide or sodium hydrosulfide is added to the manganese salt in an aqueous solvent and manganese is filtered out as a sulfide.
【０００６】即ち、本発明者等は前記した種々な課題に
ついて鋭意検討した結果、ＢＨＴのマンガン塩の製造工
程において、硫酸銅を使用することなしに、酢酸を上記
のような低温で滴下して低温で一定時間反応し、更に温
度を上昇せしめて一定時間反応させる低温と高温との二
段階の反応によつて、ＢＨＴのマンガン塩の濾過性を向
上させ、かつ未反応のアジ化水素は亜硝酸ナトリウムに
よつて、系内で処理可能なことを確認し、更にＢＨＴの
ナトリウム塩の製造工程において、炭酸ナトリウムの代
わりに硫化ナトリウム又は水硫化ナトリウムを使用する
ことによつて副生塩の濾過性が向上することを見出て前
記の目的を達成して本発明を完成するに至つた。That is, the inventors of the present invention have made extensive studies on the above-mentioned various problems, and as a result, in the process of producing the manganese salt of BHT, acetic acid was added dropwise at the above-mentioned low temperature without using copper sulfate. By reacting at low temperature for a certain period of time and further raising the temperature for a certain period of time, the two-stage reaction of low temperature and high temperature improves the filterability of BHT manganese salt, and unreacted hydrogen azide is removed. It was confirmed that in-situ treatment was possible with sodium nitrate, and in the manufacturing process of the sodium salt of BHT, sodium sulfide or sodium hydrosulfide was used instead of sodium carbonate to filter the by-product salt. The inventors have found that the properties are improved and achieved the above-mentioned object to complete the present invention.
【０００７】ＢＨＴのマンガン塩製造工程において、ア
ジ化ナトリウム、シアン化ナトリウム、二酸化マンガン
を水と共に仕込み、溶解する。酢酸を２０〜４０℃、好
ましくは２８〜３３℃の低温で短時間、好ましくは３０
分以内に素早く滴下し、上記の低温で３〜６時間反応
し、その後、高温反応に移行する。高温反応は８０〜10
0 ℃、好適には８８〜９５℃で５時間以上、例えば５〜
８時間反応する。In the BHT manganese salt production process, sodium azide, sodium cyanide and manganese dioxide are charged and dissolved together with water. Acetic acid at a low temperature of 20 to 40 ° C, preferably 28 to 33 ° C for a short time, preferably 30
It is dripped quickly within a minute, reacted at the above-mentioned low temperature for 3 to 6 hours, and then transferred to the high temperature reaction. High temperature reaction is 80-10
0 ° C., preferably 88 to 95 ° C. for 5 hours or more, for example 5 to
React for 8 hours.
【０００８】ついで、反応系を室温まで冷却して、0.05
〜0.1 倍モルの亜硝酸ナトリウム水溶液を滴下すること
によつて未反応のアジ化水素を系内で処理する。ついで
未反応のシアン化水素を留去し、シアン化水素の除去さ
れたＢＨＴのマンガン塩が濾過、又は遠心分離によつて
得られる。Then, the reaction system is cooled to room temperature, and then 0.05
Unreacted hydrogen azide is treated in the system by dropwise addition of an aqueous solution of sodium nitrite having a molar ratio of about 0.1. Then, unreacted hydrogen cyanide is distilled off, and the hydrogen cyanide-free BHT manganese salt is obtained by filtration or centrifugation.
【０００９】上記の反応において使用するシアン化ナト
リウムは1.0 〜1.2 倍モル、好ましくは1.02倍モル、二
酸化マンガンは0.5 〜0.6 倍モル、好ましくは0.51倍モ
ル、また酢酸は3.3 倍モル以上である。酢酸は氷酢酸で
も工業用（９０％）酢酸でもよい。ＢＨＴのナトリウム
塩製造工程において、上記の方法によつて得られたＢＨ
Ｔのマンガン塩と硫化ナトリウム又は水硫化ナトリウム
を水と共に仕込み５０℃まで加温し、１〜３時間熟成す
る。その後、濾過により容易に副生硫化マンガンを除去
しＢＨＴのナトリウム塩の水溶液を得る。ＢＨＴのナト
リウム塩を単離する場合は水を留去した後、エタノ−ル
を晶析溶媒として使用して析出させ、容易に濾過又は遠
心分離にて得られる。硫化ナトリウムはマンガン塩に対
して1.0〜1.1 倍モル、好適には1.0 倍モルを使用す
る。また硫化ナトリウムは結晶水を持つものを使用して
も差支えない。水硫化ナトリウムはマンガン塩に対して
1.8〜2.2 倍モル、好ましくは2.0 倍モルである。また
水硫化ナトリウムは結晶又は水溶液の何れでもよい。Ｂ
ＨＴは上記の方法で得られたＢＨＴナトリウム塩の水溶
液に塩酸を滴下し、冷却することにより析出させ容易に
濾過又は遠心分離によつて得られる。The sodium cyanide used in the above reaction is 1.0 to 1.2 times, preferably 1.02 times, manganese dioxide is 0.5 to 0.6 times, preferably 0.51 times, and acetic acid is 3.3 times or more. The acetic acid may be glacial acetic acid or industrial (90%) acetic acid. BH obtained by the above-mentioned method in the production process of sodium salt of BHT
A manganese salt of T and sodium sulfide or sodium hydrosulfide are charged together with water, heated to 50 ° C., and aged for 1 to 3 hours. Then, the by-product manganese sulfide is easily removed by filtration to obtain an aqueous solution of BHT sodium salt. When the sodium salt of BHT is isolated, water is distilled off, ethanol is used as a crystallization solvent for precipitation, and the salt is easily obtained by filtration or centrifugation. Sodium sulfide is used in an amount of 1.0 to 1.1 times, preferably 1.0 times the molar amount of manganese salt. Also, it is possible to use sodium sulfide having water of crystallization. Sodium hydrosulfide is the manganese salt
It is 1.8 to 2.2 times mol, preferably 2.0 times mol. Further, sodium hydrosulfide may be either a crystal or an aqueous solution. B
HT can be easily obtained by filtering or centrifuging to precipitate the solution by adding hydrochloric acid dropwise to the aqueous solution of BHT sodium salt obtained by the above method and cooling.
【００１０】次に本発明を実施例によつて説明するが、
本発明は実施例のみに限定されるものではない。Next, the present invention will be described with reference to examples.
The invention is not limited to the examples.
【実施例１】 （ＢＨＴのマンガン塩の製造）撹拌機付き１ｌ四ツ口フ
ラスコに水560ml 、アジ化ナトリウム７８ｇ、シアン化
ナトリウム６０ｇ、二酸化マンガン５４ｇを仕込み、１
０℃以下に冷却する。９０％酢酸265 ｇを３０℃以下で
１５分間をかけて滴下し、２５〜３５℃にて３時間反応
した後、９０℃まで昇温し、５時間反応した。ついで、
室温まで冷却し、0.1 倍モルの亜硝酸ナトリウム水溶液
を滴下して、未反応のアジ化水素を系内で処理した。そ
の後、未反応のシアン化水素を留去によつて除去し、Ｂ
ＨＴのマンガン塩を濾過し、乾燥して、ＢＨＴのマンガ
ン塩（２水和物）122 ｇを得た。純度99.5％以上、収率
は９０％であつた。問題となる濾過液中のアジ化水素濃
度は0.00％、シアン化水素濃度は１ｐｐｍ以下であつ
た。またマンガン塩の濾過性も良かつた。Example 1 (Manufacture of BHT manganese salt) A 1-liter four-necked flask equipped with a stirrer was charged with 560 ml of water, 78 g of sodium azide, 60 g of sodium cyanide and 54 g of manganese dioxide.
Cool to below 0 ° C. 265 g of 90% acetic acid was added dropwise at 30 ° C or lower over 15 minutes, reacted at 25 to 35 ° C for 3 hours, heated to 90 ° C and reacted for 5 hours. Then,
After cooling to room temperature, a 0.1-fold molar aqueous sodium nitrite solution was added dropwise to treat unreacted hydrogen azide in the system. Then, unreacted hydrogen cyanide is removed by distillation, and B
The HT manganese salt was filtered and dried to obtain 122 g of BHT manganese salt (dihydrate). The purity was 99.5% or more and the yield was 90%. The hydrogen azide concentration in the filtrate, which was a problem, was 0.00%, and the hydrogen cyanide concentration was 1 ppm or less. In addition, the manganese salt has good filterability.
【００１１】[0011]
【実施例２】 （ＢＨＴのナトリウム塩の製造）撹拌機付き500ml 四ツ
口フラスコに水200ml 、ＢＨＴのマンガン塩（２水和
物）６８ｇ、硫化ナトリウム（９水和物）７６ｇを仕込
み、５０℃まで加熱し、１時間熟成した。その後、濾過
により副生硫化マンガンを除去し、ＢＨＴのナトリウム
塩の水溶液250 ｇを得た。水を100 ｇ留去し、エタノ−
ルを200 ｇ晶析溶媒として添加し２０℃以下まで冷却
し、濾過し、乾燥してＢＨＴのナトリウム塩（５水和
物）８１ｇを得た。収率は９８％、純度は99.5％以上で
あつた。問題となる副生マンガン塩の濾過性は非常に良
く、炭酸ナトリウムを用いた場合に対して、濾過時間を
１／２０以下にできた。Example 2 (Production of sodium salt of BHT) A 500 ml four-necked flask equipped with a stirrer was charged with 200 ml of water, 68 g of manganese salt of BHT (dihydrate) and 76 g of sodium sulfide (9 hydrate), and charged to 50 The mixture was heated to ° C and aged for 1 hour. Then, the by-product manganese sulfide was removed by filtration to obtain 250 g of an aqueous solution of sodium salt of BHT. 100 g of water was distilled off, and ethanol was added.
(200 g) was added as a crystallization solvent, cooled to 20 ° C. or lower, filtered, and dried to obtain 81 g of BHT sodium salt (pentahydrate). The yield was 98% and the purity was 99.5% or more. The problematic by-product manganese salt has very good filterability, and the filtration time could be reduced to 1/20 or less as compared with the case of using sodium carbonate.
【００１２】[0012]
【発明の効果】本発明は毒性の少ない次世代エア−バツ
グ用インフレ−タ−として、また高分子、中でも熱可塑
性樹脂の成型品の軽量化、ヒケ・ソリのない精密成型用
発泡剤としても有用である５，５′−ビ−１Ｈ−テトラ
ゾ−ルの塩類を硫酸銅を用いずに、未反応のアジ化水素
を系内で処理でき、更にＢＨＴのマンガン塩及びナトリ
ウム塩の合成時に副生する濾過物の濾過性が大幅に向上
し、濾過時間又は遠心分離時間を大幅に短縮でき、安全
で収率及び純度の高い有用なマンガン塩及びナトリウム
塩を製造することが可能となつた。INDUSTRIAL APPLICABILITY The present invention can be used as an inflator for a next-generation air bag which is less toxic, and can be used as a foaming agent for precision molding, which is free from sink marks and warps, and which is a lightweight polymer molded product made of a thermoplastic resin. The useful 5,5'-bi-1H-tetrazole salts can be treated in-situ with unreacted hydrogen azide without using copper sulfate, and can be used as a by-product during the synthesis of BHT manganese salt and sodium salt. The filterability of the resulting filtrate is significantly improved, the filtration time or the centrifugation time can be greatly shortened, and it is possible to produce useful manganese salt and sodium salt which are safe and have high yield and purity.
Claims (2)
ム、二酸化マンガンを水溶媒下、酢酸を１５〜４０℃の
低温で滴下して一定時間反応し、ついで反応温度を８０
〜100 ℃の高温に上昇させ、一定時間反応することによ
る低温及び高温の二段階反応と、更に未反応のアジ化水
素を亜硝酸ナトリウムを使用して系内で処理することを
特徴とする５，５′−ビ−１Ｈ−テトラゾ−ルのマンガ
ン塩の製造方法。1. Sodium azide, sodium cyanide and manganese dioxide are added dropwise at a low temperature of 15 to 40 ° C. in an aqueous solvent at a low temperature of 15 to 40 ° C. to react for a fixed time, and then the reaction temperature is set to 80.
It is characterized by a two-step reaction of low temperature and high temperature by raising the temperature to a high temperature of -100 ° C and reacting for a certain period of time, and further treating unreacted hydrogen azide in the system using sodium nitrite. A process for producing a manganese salt of 5,5'-bi-1H-tetrazole.
−テトラゾ−ルのマンガン塩を水溶媒の下、硫化ナトリ
ウム又は水硫化ナトリウムを添加し、マンガンを硫化物
として濾別することを特徴とする５，５′−ビ−１Ｈ−
テトラゾ−ルのナトリウム塩の製造方法。2. The 5,5'-bi-1H produced in claim 1.
-5,5'-bi-1H-, characterized in that sodium sulfide or sodium hydrosulfide is added to a manganese salt of tetrazole under a water solvent to separate manganese as a sulfide.
A method for producing a sodium salt of tetrazole.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20112493A JP3394796B2 (en) | 1993-07-20 | 1993-07-20 | Process for producing 5,5'-bi-1H-tetrazole salts |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20112493A JP3394796B2 (en) | 1993-07-20 | 1993-07-20 | Process for producing 5,5'-bi-1H-tetrazole salts |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0733754A true JPH0733754A (en) | 1995-02-03 |
| JP3394796B2 JP3394796B2 (en) | 2003-04-07 |
Family
ID=16435816
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP20112493A Expired - Lifetime JP3394796B2 (en) | 1993-07-20 | 1993-07-20 | Process for producing 5,5'-bi-1H-tetrazole salts |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3394796B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100817973B1 (en) * | 2004-02-05 | 2008-03-31 | 닛코킨조쿠 가부시키가이샤 | Surface-treating agent for metal |
| JP2008285359A (en) * | 2007-05-17 | 2008-11-27 | Toyo Kasei Kogyo Co Ltd | Method for producing gas generating agent for airbag |
| JP2008285360A (en) * | 2007-05-17 | 2008-11-27 | Toyo Kasei Kogyo Co Ltd | Method for producing gas generating agent for airbag |
-
1993
- 1993-07-20 JP JP20112493A patent/JP3394796B2/en not_active Expired - Lifetime
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100817973B1 (en) * | 2004-02-05 | 2008-03-31 | 닛코킨조쿠 가부시키가이샤 | Surface-treating agent for metal |
| US7393395B2 (en) * | 2004-02-05 | 2008-07-01 | Nippon Mining & Metals Co., Ltd. | Surface-treating agent for metal |
| JP2008285359A (en) * | 2007-05-17 | 2008-11-27 | Toyo Kasei Kogyo Co Ltd | Method for producing gas generating agent for airbag |
| JP2008285360A (en) * | 2007-05-17 | 2008-11-27 | Toyo Kasei Kogyo Co Ltd | Method for producing gas generating agent for airbag |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3394796B2 (en) | 2003-04-07 |
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