JPH06157484A - New 5,5'-bi-1h-tetrazoleamine salt - Google Patents
New 5,5'-bi-1h-tetrazoleamine saltInfo
- Publication number
- JPH06157484A JPH06157484A JP4341388A JP34138892A JPH06157484A JP H06157484 A JPH06157484 A JP H06157484A JP 4341388 A JP4341388 A JP 4341388A JP 34138892 A JP34138892 A JP 34138892A JP H06157484 A JPH06157484 A JP H06157484A
- Authority
- JP
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- Prior art keywords
- salt
- bht
- piperazine
- sensitivity
- tetrazoleamine
- Prior art date
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- Compositions Of Macromolecular Compounds (AREA)
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Abstract
Description
【０００１】[0001]
【産業上の利用分野】前記化学式(1) で示される新規化
合物は毒性の少ない次世代エアバツグ用ガス発生剤とし
て、また高分子、その中でも熱可塑性樹脂成型品の軽量
化、ヒケ・ソリのない精密成型をして、成型後発泡させ
ることにより特殊な用途に使用されるなど高分子発泡剤
としても有用であり、衝撃感度、摩擦感度などの物理的
感度が抑えられるため安全かつ取扱いが容易なガス発生
剤として広い用途が期待されるものである。[Industrial application] The novel compound represented by the above chemical formula (1) is used as a gas generator for the next-generation air bag with low toxicity, and also for polymers, and in particular, for weight reduction of thermoplastic resin molded products and no sink or warp. It is also useful as a polymer foaming agent that is used for special purposes by precision molding and foaming after molding, and physical sensitivity such as impact sensitivity and friction sensitivity is suppressed, so it is safe and easy to handle. It is expected to have a wide range of uses as a gas generating agent.
【０００２】[0002]
【従来の技術】従来上記化学式(1) の遊離基〔５，５′
−ビ−１Ｈ−テトラゾ−ル（以下ＢＨＴと略称す
る。）〕がエア−バツグ用ガス発生剤や高分子用発泡剤
として使用に供される本出願人の発明になる特願平２−
324953号、特願平３−240402号発明がある。エア−バツ
グ用のガス発生剤として上記ＢＨＴを使用する場合、熱
分解を速やかにするための、微粉末に粉砕し容器に装填
する作業を伴うが、衝撃感度、摩擦感度が高いため粉砕
時に分解したり装填時に爆発するなどの危険が伴つた。
また該ＢＨＴを高分子用の発泡剤として使用する場合、
成型すべき高分子への添加を容易にし、かつ好ましい分
散を得るため、成型すべき高分子より幾分融点の低い熱
可塑性樹脂に添加して、マスタ−チツプを作る必要があ
つた。2. Description of the Related Art Conventionally, the free radical of the above chemical formula (1) [5,5 '
-Bi-1H-tetrazole (hereinafter abbreviated as BHT)] is used as a gas generating agent for air-bags and a foaming agent for polymers.
There are 324953 and Japanese Patent Application No. 3-240402 inventions. When the above BHT is used as a gas generating agent for air bagging, it involves the work of pulverizing it into fine powder and loading it into a container in order to accelerate thermal decomposition, but it decomposes during pulverization because of its high impact sensitivity and friction sensitivity. There was a danger of doing it and exploding during loading.
When the BHT is used as a foaming agent for polymers,
To facilitate addition to the polymer to be molded and to obtain a preferred dispersion, it was necessary to add it to a thermoplastic resin having a somewhat lower melting point than the polymer to be molded to make a master chip.
【０００３】[0003]
【発明が解決しようとする課題】前記のようにＢＨＴの
物理的感度が高いと本来の分解温度（成型すべき高分子
より幾分融点の低い熱可塑性樹脂に添加し、マスタ−チ
ツプの成型温度）で分解し、マスタ−チツプが得られな
いという課題があつた。本発明はＢＨＴの衝撃感度、摩
擦感度を低下せしめ、エア−バツグ用ガス発生剤や高分
子発泡剤の用途に使用可能な熱的分解性を保ちながら粉
砕を容易ならしめ、マスタ−チツプの作成可能にし、か
つ取扱い上の安全の確保可能な新規なＢＨＴアミン塩を
提供することを目的とするものである。As described above, when the physical sensitivity of BHT is high, it is added to a thermoplastic resin having an original decomposition temperature (a melting point somewhat lower than that of the polymer to be molded, and the molding temperature of the master chip is increased). ), The master chip could not be obtained. The present invention reduces the impact sensitivity and friction sensitivity of BHT, facilitates pulverization while maintaining thermal decomposability that can be used for gas-generating agents for air-bags and polymer foaming agents, and creates master chips. It is an object of the present invention to provide a novel BHT amine salt which enables the treatment and ensures the safety in handling.
【０００４】[0004]
【課題を解決するための手段】本発明は下記化学式(1)
で示される新規な５，５′−ビ−１Ｈ−テトラゾ−ルア
ミン塩を提供するもので、ＢＨＴの衝撃感度、摩擦感度
を低下せしめたエア−バツグ用ガス発生剤や高分子発泡
剤としての用途に使用されるものである。The present invention provides the following chemical formula (1)
The present invention provides a novel 5,5'-bi-1H-tetrazoleamine salt represented by the following, and is used as a gas generating agent for air-bags and a polymer foaming agent, which has reduced the impact sensitivity and friction sensitivity of BHT. Is used for.
【０００５】ここに化学式(1) は の構造式で示される５，５′−ビ−１Ｈ−テトラゾ−ル
アミン塩である。Where the chemical formula (1) is 5,5'-bi-1H-tetrazoleamine salt represented by the structural formula:
【０００６】Ｚはメチルアミン、エチルアミン、プロピ
ロアミン、イソプロピルアミン、ペンチルアミン、タ−
シヤルプチルアミン、アニリン、ベンジルアミン、フエ
ネチルアミン、１−アミノ−４−フエニルプタン、ベン
ズヒドリルアミン、シクロヘキシルアミンの１級アミ
ン。ジチメルアミン、ジエチルアミン、ジ−ｎ−プロピ
ルアミン、ジ−ｎ−ペンチルアミン、プロピレンイミ
ン、ピロリジン、ピペラジン、Ｎ−メチルモルホリンの
２級アミン。トリメチルアミン、トリエチルアミン、ト
リ−ｎ−ペンチルアミン、トリフエニルアミン、ピリジ
ン、１，８−ジアザビシクロ〔５，４，０〕−７−ウン
デセンの３級アミン。ヒドラジン、トリメチレンジアミ
ン、ペンタメチレンジアミン、ヘキサメチレンジアミ
ン、ピペラジン、ｍ−フエニレンジアミン、１，３−ジ
アザシクロヘキサン、トリエチレンジアミン、Ｎ，Ｎ，
Ｎ′，Ｎ′−テトラメチルエチレンジアミンのジアミン
類。カルボヒドラジド、チオカルボヒドラジド、アゾジ
カルボンアミド、グアニジン、ジシアンジアミド、アミ
ノグアニジン、Ｎ，Ｎ′−ビス（３−アミノプロピル）
ピペラジン、メラミン、アセトグアナミン、３−アミノ
−１，２，４−トリアゾ−ル、ヘキサメチレントラミ
ン。である。Z is methylamine, ethylamine, propyroamine, isopropylamine, pentylamine, teramine.
Primary amines such as syarptylamine, aniline, benzylamine, phenethylamine, 1-amino-4-phenylbutane, benzhydrylamine and cyclohexylamine. Secondary amines of dithymelamine, diethylamine, di-n-propylamine, di-n-pentylamine, propyleneimine, pyrrolidine, piperazine, N-methylmorpholine. Tertiary amines of trimethylamine, triethylamine, tri-n-pentylamine, triphenylamine, pyridine, 1,8-diazabicyclo [5,4,0] -7-undecene. Hydrazine, trimethylenediamine, pentamethylenediamine, hexamethylenediamine, piperazine, m-phenylenediamine, 1,3-diazacyclohexane, triethylenediamine, N, N,
Diamines of N ', N'-tetramethylethylenediamine. Carbohydrazide, thiocarbohydrazide, azodicarbonamide, guanidine, dicyandiamide, aminoguanidine, N, N'-bis (3-aminopropyl)
Piperazine, melamine, acetoguanamine, 3-amino-1,2,4-triazole, hexamethylene tramine. Is.
【０００７】[0007]
【実施例】本発明を説明するために下記に実施例を示
す。EXAMPLES Examples are shown below to illustrate the present invention.
【０００８】〔実施例１〕 ＢＨＴのピペラジン塩 ＢＨＴ13.8g とピペラジン六水化物9.7gと水200gを仕込
み、80℃まで昇温し、その温度で１時間反応した。その
後、室温まで冷却し、濾過にてＢＨＴピペラジン塩9.5g
を得た。ＢＨＴは分解温度＝266 ℃、落鎚感度＝ＪＩＳ
４級、摩擦感度＝ＪＩＳ２級であるが、新規化合物であ
るＢＨＴピペラジン塩では分解温度＝330℃、落鎚感度
＝ＪＩＳ８級、摩擦感度＝ＪＩＳ７級となり目的を達成
した。1 Ｈ ＮＭＲ(60MHz)(ppm) δ3.10(s,4H,CH2),8.75(m,4
H,NH2) ＩＲ(neat)(cm-1) 2400(br),1660(s),1470(s),1380
(m),1310(s),1290(s),1180(s),1160(s),1080(m),1050
(m),1010(m),990(m),735(s),620(s) 元素分析 C6 H12 N10(224.23) 計算値(%) ：Ｃ,32.
14；Ｈ,5.39 ；Ｎ,62.47 分析値(%) ：Ｃ,32.23；Ｈ,5.32 ；Ｎ,62.44Example 1 BHT Piperazine Salt BHT 13.8 g, piperazine hexahydrate 9.7 g and water 200 g were charged, the temperature was raised to 80 ° C., and the reaction was carried out at that temperature for 1 hour. Then, it is cooled to room temperature and filtered to obtain 9.5 g of BHT piperazine salt.
Got BHT has decomposition temperature = 266 ℃, falling hammer sensitivity = JIS
Class 4 and friction sensitivity = JIS class 2, but with the new compound BHT piperazine salt, decomposition temperature = 330 ° C., falling hammer sensitivity = JIS class 8 and friction sensitivity = JIS class 7 were achieved. 1 H NMR (60MHz) (ppm) δ3.10 (s, 4H, CH 2 ), 8.75 (m, 4
H, NH 2 ) IR (neat) (cm -1 ) 2400 (br), 1660 (s), 1470 (s), 1380
(m), 1310 (s), 1290 (s), 1180 (s), 1160 (s), 1080 (m), 1050
(m), 1010 (m), 990 (m), 735 (s), 620 (s) Elemental analysis C 6 H 12 N 10 (224.23) Calculated value (%): C, 32.
14; H, 5.39; N, 62.47 Analytical value (%): C, 32.23; H, 5.32; N, 62.44
【０００９】〔実施例２〕 ＢＨＴのｍ−フエニレンジ
アミン塩 ＢＨＴ2.7gとｍ−フエニレンジアミン2.3gと水200gを仕
込み、室温下で１時間反応した。その後、溶媒をほぼ完
全に留去し、濾過にてＢＨＴｍ−フエニレンジアミン塩
4.3gを得た。ＢＨＴは分解温度＝266 ℃、落鎚感度＝Ｊ
ＩＳ４級、摩擦感度＝ＪＩＳ２級であるが、新規化合物
であるＢＨＴｍ−フエニレンジアミン塩では分解温度＝
330 ℃、落鎚感度＝ＪＩＳ８級、摩擦感度＝ＪＩＳ７級
となり目的を達成した。1 Ｈ ＮＭＲ(60MHz)(ppm) δ6.60,7.09(m,4H,ph),8.89
(m,6H,NH2) ＩＲ(neat)(cm-1) 2850(br),2600(br),1550(br),1500
(s),1330(s),1310(s),1180(s),1140(s),1080(m),1050
(m),1020(s),805(s),735(s),690(s) 元素分析 C8 H10 N10(246.24) 計算値(%) ：Ｃ,39.
02；Ｈ,4.09 ；Ｎ,56.88 分析値(%) ：Ｃ,38.98；Ｈ,4.14 ；Ｎ,56.76 その他前記Ｚで示される化合物を使用しても反応温度、
時間が多少異なるものの、同様にしてＢＨＴのアミン塩
が得られる。[Example 2] m-phenylenediamine salt of BHT 2.7 g of BHT, 2.3 g of m-phenylenediamine and 200 g of water were charged and reacted at room temperature for 1 hour. Then, the solvent was distilled off almost completely, and the BHTm-phenylenediamine salt was filtered.
Obtained 4.3 g. BHT has decomposition temperature = 266 ℃, drop hammer sensitivity = J
IS4 grade, friction sensitivity = JIS2 grade, but with the new compound BHTm-phenylenediamine salt, decomposition temperature =
At 330 ° C, falling hammer sensitivity = JIS class 8, friction sensitivity = JIS class 7, and the objective was achieved. 1 H NMR (60MHz) (ppm) δ6.60,7.09 (m, 4H, ph), 8.89
(m, 6H, NH 2 ) IR (neat) (cm -1 ) 2850 (br), 2600 (br), 1550 (br), 1500
(s), 1330 (s), 1310 (s), 1180 (s), 1140 (s), 1080 (m), 1050
(m), 1020 (s), 805 (s), 735 (s), 690 (s) Elemental analysis C 8 H 10 N 10 (246.24) Calculated value (%): C, 39.
02; H, 4.09; N, 56.88 Analytical value (%): C, 38.98; H, 4.14; N, 56.76
The amine salt of BHT is obtained in the same manner, although the time is slightly different.
【００１０】[0010]
【発明の効果】遊離基（ＢＨＴ）は化合物の毒性、分解
ガスの毒性が低いことなどから、次世代エア−バツグ用
ガス発生剤として、又、熱的分解温度が高いことから高
分子用発泡剤として有用な化合物として知られながら、
物理的感度が高いため使用に支障を来していた。本発明
はこうした問題点を解決できたことはエア−バツグ用ガ
ス発生剤又は高分子発泡剤の分野に新たな道が開けたこ
とになり、その効果は計り知れないものがある。EFFECTS OF THE INVENTION Free radical (BHT) is a gas generator for the next generation air bag because of its low toxicity of compounds and decomposition gas, and also has a high thermal decomposition temperature, and thus foams for polymers. Known as a compound useful as an agent,
Its high physical sensitivity hindered its use. The fact that the present invention has solved these problems opens up a new path in the field of gas generating agents for air-bags or polymer foaming agents, and their effects are immeasurable.
─────────────────────────────────────────────────────
─────────────────────────────────────────────────── ───
【手続補正書】[Procedure amendment]
【提出日】平成５年４月９日[Submission date] April 9, 1993
【手続補正１】[Procedure Amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】全文[Correction target item name] Full text
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【書類名】 明細書[Document name] Statement
【発明の名称】 新規な５，５′−ビ−１Ｈ−テトラ
ゾールアミン塩Title: Novel 5,5'-bi-1H-tetrazoleamine salt
【特許請求の範囲】[Claims]
【発明の詳細な説明】Detailed Description of the Invention
【０００１】[0001]
【産業上の利用分野】前記化学式（１）で示される新規
化合物は毒性の少ない次世代エアーバツグ用ガス発生剤
として、また高分子、その中でも熱可塑性樹脂成型品の
軽量化、ヒケ・ソリのない精密成型用途に、又は成型後
発泡させるという特殊な用途に使用されるなど高分子発
泡剤としても有用であり、衝撃感度、摩擦感度などの物
理的感度が抑えられるため安全かつ取扱いが容易なガス
発生剤として広い用途が期待されるものである。[Industrial application] The novel compound represented by the chemical formula (1) is used as a gas generator for the next-generation air bag with low toxicity, and is also a polymer, in particular, a lightweight thermoplastic resin molded product without sink marks and warps. A gas that is safe and easy to handle because it is also useful as a polymer foaming agent, such as used for precision molding or for special applications such as foaming after molding, and physical sensitivity such as impact sensitivity and friction sensitivity is suppressed. It is expected to have a wide range of uses as a generator.
【０００２】[0002]
【従来の技術】従来上記化学式（１）の遊離基〔５，
５′−ビ−１Ｈ−テトラゾール（以下ＢＨＴと略称す
る。）〕がエアーバツグ用ガス発生剤や高分子用発泡剤
として使用に供される本出願人の発明になる特願平２−
３２４９５３号、特願平３−２４０４０２号発明があ
る。エアーバツグ用のガス発生剤として上記ＢＨＴを使
用する場合には、熱分解を速やかにするため微粉末に粉
砕し、容器に装填する作業を伴うが、衝撃感度、摩擦感
度が高いため粉砕時に分解したり装填時に爆発するなど
の危険が伴つた。また該ＢＨＴを高分子用の発泡剤とし
て使用する場合、成型すべき高分子への添加を容易に
し、かつ好ましい分散を得るため、成型すべき高分子よ
り幾分融点の低い熱可塑性樹脂に添加して、マスターチ
ツプを作る必要があつた。2. Description of the Related Art Conventionally, the free radical of the above chemical formula (1) [5,
5'-bi-1H-tetrazole (hereinafter abbreviated as BHT)] is used as a gas generating agent for air bag and a foaming agent for polymer.
There are 324953 and Japanese Patent Application No. 3-240402. When the above BHT is used as a gas generating agent for air bagging, it is necessary to grind it into fine powder in order to accelerate thermal decomposition and load it into a container, but since it has high impact sensitivity and friction sensitivity, it decomposes during grinding. There was a danger of explosion when loading or loading. When the BHT is used as a foaming agent for a polymer, it is added to a thermoplastic resin having a melting point somewhat lower than that of the polymer to be molded in order to facilitate addition to the polymer to be molded and obtain a preferable dispersion. Then I needed to make a master chip.
【０００３】[0003]
【発明が解決しようとする課題】前記のようにＢＨＴの
物理的感度が高いと本来の分解温度以下（成型すべき高
分子より幾分融点の低い熱可塑性樹脂に添加したマスタ
ーチツプの成型温度）で分解し、マスターチツプが得ら
れないという課題があつた。本発明はＢＨＴの衝撃感
度、摩擦感度を低下せしめ、エアーバツグ用ガス発生剤
や高分子発泡剤の用途に使用可能な熱的分解性を保ちな
がら粉砕を容易ならしめ、マスターチツプの作成可能に
し、かつ取扱い上の安全の確保可能な新規なＢＨＴアミ
ン塩を提供することを目的とするものである。As described above, when the physical sensitivity of BHT is high, it is below the original decomposition temperature (molding temperature of a master chip added to a thermoplastic resin having a melting point somewhat lower than that of the polymer to be molded). There was a problem that the master chip could not be obtained by disassembling. INDUSTRIAL APPLICABILITY The present invention reduces impact sensitivity and friction sensitivity of BHT, facilitates pulverization while maintaining thermal decomposability that can be used for gas generating agents for air bags and polymer foaming agents, and enables master chips to be prepared. Moreover, it is an object of the present invention to provide a novel BHT amine salt capable of ensuring safety in handling.
【０００４】[0004]
【課題を解決するための手段】本発明は下記化学式
（１）で示される新規な５，５′−ビ−１Ｈ−テトラゾ
ールアミン塩を提供するもので、ＢＨＴの衝撃感度、摩
擦感度を低下せしめたエアーバツグ用ガス発生剤や高分
子発泡剤としての用途に使用されるものである。The present invention provides a novel 5,5'-bi-1H-tetrazoleamine salt represented by the following chemical formula (1), which reduces impact sensitivity and friction sensitivity of BHT. It is also used for gas generators for air bags and polymer foaming agents.
【０００５】ここに化学式（１）は の構造式で示される５，５′−ビ−１Ｈ−テトラゾール
アミン塩である。Where the chemical formula (1) is 5,5'-bi-1H-tetrazoleamine salt represented by the structural formula:
【０００６】Ｚはメチルアミン、エチルアミン、ｎ−プ
ロピロアミン、イソプロピルアミン、ｎ−ブチルアミ
ン、ターシヤルブチルアミン、ｎ−ペンチルアミン、ｎ
−ヘキシルアミン、ルアミン、アニリン、ベンジルアミ
ン、フエネチルアミン、１−アミノ−４−フエニルプタ
ン、ベンズヒドリルアミン、シクロヘキシルアミンの１
級アミン。ジメチルアミン、ジエチルアミン、ジ−ｎ−
プロピルアミン、ジ−ｎ−ペンチルアミン、ジ−ｎ−ヘ
キシルアミン、プロピレンイミン、ピロリジン、ピペリ
ジン、Ｎ−メチルモルホリンの２級アミン。トリメチル
アミン、トリエチルアミン、トリ−ｎ−ペンチルアミ
ン、トリ−ｎ−ヘキシルアミン、トリフエニルアミン、
ピリジン、１，８−ジアザビシクロ〔５，４，０〕−７
−ウンデセンの３級アミン。ヒドラジン、トリメチレン
ジアミン、ペンタメチレンジアミン、ヘキサメチレンジ
アミン、ピペラジン、ｍ−フエニレンジアミン、１，３
−ジアザシクロヘキサン、トリエチレンジアミン、Ｎ，
Ｎ，Ｎ′，Ｎ′−テトラメチルエチレンジアミンのジア
ミン類。カルボヒドラジド、チオカルボヒドラジド、ア
ゾジカルボンアミド、グアニジン、ジシアンジアミド、
Ｎ，Ｎ′−ビス（３−アミノプロピル）ピペラジン、メ
ラミン、アセトグアナミン、３−アミノ−１，２，４−
トリアゾール、ヘキサメチレントラミン。である。Z is methylamine, ethylamine, n-propyroamine, isopropylamine, n-butylamine, tert-butylamine, n-pentylamine, n
1-hexylamine, luamine, aniline, benzylamine, phenethylamine, 1-amino-4-phenylbutane, benzhydrylamine, cyclohexylamine
Class amine. Dimethylamine, diethylamine, di-n-
Secondary amines of propylamine, di-n-pentylamine, di-n-hexylamine, propyleneimine, pyrrolidine, piperidine, N-methylmorpholine. Trimethylamine, triethylamine, tri-n-pentylamine, tri-n-hexylamine, triphenylamine,
Pyridine, 1,8-diazabicyclo [5,4,0] -7
-Undecene tertiary amine. Hydrazine, trimethylenediamine, pentamethylenediamine, hexamethylenediamine, piperazine, m-phenylenediamine, 1,3
-Diazacyclohexane, triethylenediamine, N,
Diamines of N, N ', N'-tetramethylethylenediamine. Carbohydrazide, thiocarbohydrazide, azodicarbonamide, guanidine, dicyandiamide,
N, N'-bis (3-aminopropyl) piperazine, melamine, acetoguanamine, 3-amino-1,2,4-
Triazole, hexamethylene tramine. Is.
【０００７】[0007]
【実施例】本発明を説明するために下記に実施例を示
す。EXAMPLES Examples are shown below to illustrate the present invention.
【０００８】〔実施例１〕 ＢＨＴのピペラジン塩 ＢＨＴ１３．８ｇとピペラジン六水化物９．７ｇと水２
００ｇを仕込み、８０℃まで昇温し、その温度で１時間
反応した。その後、室温まで冷却し、濾過にてＢＨＴピ
ペラジン塩９．５ｇを得た。ＢＨＴは分解温度＝２５４
℃、落鎚感度＝ＪＩＳ４級、摩擦感度＝ＪＩＳ２級であ
るが、新規化合物であるＢＨＴピペラジン塩では分解温
度＝３３０℃、落鎚感度＝ＪＩＳ８級、摩擦感度＝ＪＩ
Ｓ７級となり目的を達成した。１ Ｈ ＮＭＲ（６０ＭＨｚ）（ｐｐｍ） δ３．１０
（ｓ，４Ｈ，ＣＨ２），８．７５（ｍ，４Ｈ，ＮＨ２） ＩＲ（ｎｅａｔ）（ｃｍ−１） ２４００（ｂｒ），１
６６０（ｓ），１４７０（ｓ），１３８０（ｍ），１３
１０（ｓ），１２９０（ｓ），１１８０（ｓ），１１６
０（ｓ），１０８０（ｍ），１０５０（ｍ），１０１０
（ｍ），９９０（ｍ），７３５（ｓ），６２０（ｓ） 元素分析 Ｃ６Ｈ１２Ｎ１０（２２４．２３） 計算値（％）：Ｃ，３２．１４；Ｈ，５．３９；Ｎ，６
２．４７ 分析値（％）：Ｃ，３２．２３；Ｈ，５．３２；Ｎ，６
２．４４Example 1 BHT Piperazine Salt BHT 13.8 g, piperazine hexahydrate 9.7 g and water 2
00 g was charged, the temperature was raised to 80 ° C., and the reaction was carried out at that temperature for 1 hour. Then, the mixture was cooled to room temperature and filtered to obtain 9.5 g of BHT piperazine salt. BHT has a decomposition temperature of 254
℃, drop hammer sensitivity = JIS4 class, friction sensitivity = JIS2 class, but with the new compound BHT piperazine salt, decomposition temperature = 330 ℃, drop hammer sensitivity = JIS class 8, friction sensitivity = JI
It became S7 grade and achieved the purpose. 1 H NMR (60 MHz) (ppm) δ 3.10
(S, 4H, CH 2) , 8.75 (m, 4H, NH 2) IR (neat) (cm -1) 2400 (br), 1
660 (s), 1470 (s), 1380 (m), 13
10 (s), 1290 (s), 1180 (s), 116
0 (s), 1080 (m), 1050 (m), 1010
(M), 990 (m), 735 (s), 620 (s) Elemental analysis C 6 H 12 N 10 (224.23) Calculated value (%): C, 32.14; H, 5.39; N , 6
2.47 analytical value (%): C, 32.23; H, 5.32; N, 6
2.44
【０００９】〔実施例２〕 ＢＨＴのｍ−フエニレンジ
アミン塩 ＢＨＴ２．７ｇとｍ−フエニレンジアミン２．３ｇと水
２００ｇを仕込み、室温下で１時間反応した。その後、
溶媒をほぼ完全に留去し、濾過にてＢＨＴｍ−フエニレ
ンジアミン塩４．３ｇを得た。ＢＨＴは分解温度＝２５
４℃、落鎚感度＝ＪＩＳ４級、摩擦感度＝ＪＩＳ２級で
あるが、新規化合物であるＢＨＴｍ−フエニレンジアミ
ン塩では分解温度＝２５０℃、落鎚感度＝ＪＩＳ８級、
摩擦感度＝ＪＩＳ７級となり目的を達成した。１ Ｈ ＮＭＲ（６０ＭＨｚ）（ｐｐｍ） δ６．６０，
７．０９（ｍ，４Ｈ，ｐｈ），８．８９（ｍ，６Ｈ，Ｎ
Ｈ２） ＩＲ（ｎｅａｔ）（ｃｍ−１） ２８５０（ｂｒ），２
６００（ｂｒ），１５５０（ｂｒ），１５００（ｓ），
１３３０（ｓ），１３１０（ｓ），１１８０（ｓ），１
１４０（ｓ），１０８０（ｍ），１０５０（ｍ），１０
２０（ｓ），８０５（ｓ），７３５（ｓ），６９０
（ｓ） 元素分析 Ｃ８Ｈ１０Ｎ１０（２４６．２４） 計算値（％）：Ｃ，３９．０２；Ｈ，４．０９；Ｎ，５
６．８８ 分析値（％）：Ｃ，３８．９８；Ｈ，４．１４；Ｎ，５
６．７６ その他前記Ｚで示される化合物を使用しても反応温度、
時間が多少異なるものの、同様にしてＢＨＴのアミン塩
が得られる。[Example 2] m-phenylenediamine salt of BHT 2.7 g of BHT, 2.3 g of m-phenylenediamine and 200 g of water were charged and reacted at room temperature for 1 hour. afterwards,
The solvent was distilled off almost completely, and 4.3 g of BHTm-phenylenediamine salt was obtained by filtration. BHT has a decomposition temperature = 25
4 ° C, falling hammer sensitivity = JIS4 grade, friction sensitivity = JIS2 grade, but with the new compound BHTm-phenylenediamine salt, decomposition temperature = 250 ° C, falling hammer sensitivity = JIS8 grade,
Friction sensitivity = JIS7 grade and the objective was achieved. 1 H NMR (60 MHz) (ppm) δ 6.60,
7.09 (m, 4H, ph), 8.89 (m, 6H, N)
H 2 ) IR (neat) (cm −1 ) 2850 (br), 2
600 (br), 1550 (br), 1500 (s),
1330 (s), 1310 (s), 1180 (s), 1
140 (s), 1080 (m), 1050 (m), 10
20 (s), 805 (s), 735 (s), 690
(S) Elemental analysis C 8 H 10 N 10 (246.24) Calculated value (%): C, 39.02; H, 4.09; N, 5
6.88 Analytical value (%): C, 38.98; H, 4.14; N, 5
6.76 Other than the above, when the compound represented by Z is used, the reaction temperature,
The amine salt of BHT is obtained in the same manner, although the time is slightly different.
【００１０】[0010]
【発明の効果】遊離基（ＢＨＴ）は化合物の毒性、分解
ガスの毒性が低いことなどから、次世代エアーバツグ用
ガス発生剤として、又、熱的分解温度が高いことから高
分子用発泡剤として有用な化合物として知られながら、
物理的感度が高いため使用に支障を来していた。本発明
はこうした問題点を解決できたことはエアーバツグ用ガ
ス発生剤又は高分子発泡剤の分野に新たな道が開けたこ
とになり、その効果は計り知れないものがある。EFFECTS OF THE INVENTION Free radicals (BHT) have low toxicity of compounds and low toxicity of decomposition gas, and are therefore used as a gas generating agent for the next generation air bag, and as a foaming agent for polymers due to their high thermal decomposition temperature. Known as a useful compound,
Its high physical sensitivity hindered its use. The fact that the present invention has solved these problems opens up a new path in the field of gas generating agents for air bagging or polymer foaming agents, and their effects are immeasurable.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.5 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ０７Ｃ 211/51 9280−4Ｈ 211/54 9280−4Ｈ 243/10 9160−4Ｈ 279/02 7188−4Ｈ 281/16 7188−4Ｈ Ｃ０７Ｄ 295/02 Ａ Ｚ Ｃ０８Ｋ 5/3472 ＫＢＭ 7242−4Ｊ Ｃ０９Ｋ 3/00 １１１ 8517−4Ｈ // Ｃ０６Ｄ 5/00 Ｚ 7106−4Ｈ Ｃ０８Ｊ 9/10 9268−4Ｆ ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 5 Identification code Internal reference number FI Technical display location C07C 211/51 9280-4H 211/54 9280-4H 243/10 9160-4H 279/02 7188-4H 281/16 7188-4H C07D 295/02 AZ C08K 5/3472 KBM 7242-4J C09K 3/00 111 8517-4H // C06D 5/00 Z 7106-4H C08J 9/10 9268-4F
Claims (1)
５′−ビ−１Ｈ−テトラゾ−ルアミン塩。ここに化学式
(1) は の構造式で示される５，５′−ビ−１Ｈ−テトラゾ−ル
アミン塩である。 Ｚはメチルアミン、エチルアミン、プロピロアミン、イ
ソプロピルアミン、ペンチルアミン、タ−シヤルプチル
アミン、アニリン、ベンジルアミン、フエネチルアミ
ン、１−アミノ−４−フエニルブタン、ベンズヒドリル
アミン、シクロヘキシルアミンの１級アミン。ジチメル
アミン、ジエチルアミン、ジ−ｎ−プロピルアミン、ジ
−ｎ−ペンチルアミン、プロピレンイミン、ピロリジ
ン、ピペラジン、Ｎ−メチルモルホリンの２級アミン。
トリメチルアミン、トリエチルアミン、トリ−ｎ−ペン
チルアミン、トリフエニルアミン、ピリジン、１，８−
ジアザビシクロ〔５，４，０〕−７−ウンデセンの３級
アミン。ヒドラジン、トリメチレンジアミン、ペンタメ
チレンジアミン、ヘキサメチレンジアミン、ピペラジ
ン、ｍ−フエニレンジアミン、１，３−ジアザシクロヘ
キサン、トリエチレンジアミン、Ｎ，Ｎ，Ｎ′，Ｎ′−
テトラメチルエチレンジアミンのジアミン類。カルボヒ
ドラジド、チオカルボヒドラジド、アゾジカルボンアミ
ド、グアニジン、ジシアンジアミド、アミノグアニジ
ン、Ｎ，Ｎ′−ビス（３−アミノプロピル）ピペラジ
ン、メラミン、アセトグアナミン、３−アミノ−１，
２，４−トリアゾ−ル、ヘキサメチレントラミン。であ
る。1. A novel compound represented by the following chemical formula (1):
5'-bi-1H-tetrazoleamine salt. Chemical formula here
(1) is 5,5'-bi-1H-tetrazoleamine salt represented by the structural formula: Z is a primary amine such as methylamine, ethylamine, propyroamine, isopropylamine, pentylamine, tasyalptylamine, aniline, benzylamine, phenethylamine, 1-amino-4-phenylbutane, benzhydrylamine and cyclohexylamine. Secondary amines of dithymelamine, diethylamine, di-n-propylamine, di-n-pentylamine, propyleneimine, pyrrolidine, piperazine, N-methylmorpholine.
Trimethylamine, triethylamine, tri-n-pentylamine, triphenylamine, pyridine, 1,8-
Tertiary amine of diazabicyclo [5,4,0] -7-undecene. Hydrazine, trimethylenediamine, pentamethylenediamine, hexamethylenediamine, piperazine, m-phenylenediamine, 1,3-diazacyclohexane, triethylenediamine, N, N, N ', N'-
Diamines of tetramethylethylenediamine. Carbohydrazide, thiocarbohydrazide, azodicarbonamide, guanidine, dicyandiamide, aminoguanidine, N, N'-bis (3-aminopropyl) piperazine, melamine, acetoguanamine, 3-amino-1,
2,4-triazole, hexamethylene tramine. Is.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP34138892A JP3468787B2 (en) | 1992-11-27 | 1992-11-27 | Novel 5,5'-bi-1H-tetrazolamine salt |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP34138892A JP3468787B2 (en) | 1992-11-27 | 1992-11-27 | Novel 5,5'-bi-1H-tetrazolamine salt |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06157484A true JPH06157484A (en) | 1994-06-03 |
| JP3468787B2 JP3468787B2 (en) | 2003-11-17 |
Family
ID=18345680
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP34138892A Expired - Lifetime JP3468787B2 (en) | 1992-11-27 | 1992-11-27 | Novel 5,5'-bi-1H-tetrazolamine salt |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3468787B2 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09501134A (en) * | 1993-08-02 | 1997-02-04 | サイオコル・コーポレーション | Bitetrazole amine gas generant composition and method of use |
| WO2000066518A1 (en) * | 1999-04-30 | 2000-11-09 | Daicel Chemical Industries, Ltd. | Gas generator composition |
| JP2001504432A (en) * | 1996-11-08 | 2001-04-03 | オートモーティブ システムズ ラボラトリー インコーポレーテッド | Non-azide gas generating composition |
| CN103724287A (en) * | 2012-10-10 | 2014-04-16 | 同济大学 | 1,1'-dihydroxy-5,5'-bitetrazole ammonium salt and preparation method |
| CN105541525A (en) * | 2016-01-29 | 2016-05-04 | 北京理工大学 | Pyrotechnic gas generating agent and preparation method |
| CN111320735A (en) * | 2018-12-17 | 2020-06-23 | 万华化学集团股份有限公司 | Use of N, N-dimethylcyclohexane tertiary amine derivatives as catalysts for the preparation of polyurethane and/or polyisocyanurate foams |
-
1992
- 1992-11-27 JP JP34138892A patent/JP3468787B2/en not_active Expired - Lifetime
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09501134A (en) * | 1993-08-02 | 1997-02-04 | サイオコル・コーポレーション | Bitetrazole amine gas generant composition and method of use |
| JP2001504432A (en) * | 1996-11-08 | 2001-04-03 | オートモーティブ システムズ ラボラトリー インコーポレーテッド | Non-azide gas generating composition |
| WO2000066518A1 (en) * | 1999-04-30 | 2000-11-09 | Daicel Chemical Industries, Ltd. | Gas generator composition |
| CN103724287A (en) * | 2012-10-10 | 2014-04-16 | 同济大学 | 1,1'-dihydroxy-5,5'-bitetrazole ammonium salt and preparation method |
| CN105541525A (en) * | 2016-01-29 | 2016-05-04 | 北京理工大学 | Pyrotechnic gas generating agent and preparation method |
| CN111320735A (en) * | 2018-12-17 | 2020-06-23 | 万华化学集团股份有限公司 | Use of N, N-dimethylcyclohexane tertiary amine derivatives as catalysts for the preparation of polyurethane and/or polyisocyanurate foams |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3468787B2 (en) | 2003-11-17 |
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