JP2771011B2 - Method for stabilizing aromatic amine - Google Patents
Method for stabilizing aromatic amineInfo
- Publication number
- JP2771011B2 JP2771011B2 JP8893290A JP8893290A JP2771011B2 JP 2771011 B2 JP2771011 B2 JP 2771011B2 JP 8893290 A JP8893290 A JP 8893290A JP 8893290 A JP8893290 A JP 8893290A JP 2771011 B2 JP2771011 B2 JP 2771011B2
- Authority
- JP
- Japan
- Prior art keywords
- aromatic amine
- hydrazine
- added
- coloring
- heat
- 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.)
- Expired - Lifetime
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【発明の詳細な説明】 ［産業上の利用分野］ 本発明は芳香族アミンの安定化方法に関し、特に空
気、光および熱に対する着色の安定性を改善する方法に
関する。Description: FIELD OF THE INVENTION The present invention relates to a method for stabilizing an aromatic amine, and more particularly to a method for improving the stability of coloring to air, light and heat.
［従来の技術］ 一般に芳香族アミンは製造直後には実質的に無色であ
るが、貯蔵中空気等と接触すると急速に着色してくる。
そしてこの着色の度合いは熱、光または酸素等に曝され
ることにより促進される。例えばアニリン、トルイジ
ン、キシリジンのようなモノアミンベンゼン類は１日以
内に顕著な着色を示し、著しく商品価値を低下させるの
みならず誘導品の品質を悪化させる。ウレタン等の合成
樹脂製造中間体、医薬品または染料等の原料として芳香
族アミンが使用される際に、原料アミン類が光または熱
で着色すると最終商品に重大な影響を与えるため、芳香
族アミンを光、熱、酸素などに対して着色せず安定化さ
せることは工業的に重要な課題である。[Prior Art] Generally, aromatic amines are substantially colorless immediately after production, but rapidly color when contacted with air or the like during storage.
The degree of coloring is promoted by exposure to heat, light, oxygen, or the like. For example, monoamine benzenes such as aniline, toluidine, and xylidine show remarkable coloring within one day, which not only significantly reduces the commercial value but also deteriorates the quality of derivatives. When aromatic amines are used as raw materials for synthetic resin production intermediates such as urethane, pharmaceuticals, dyes, etc., if the raw material amines are colored by light or heat, they will have a significant effect on the final product. It is an industrially important task to stabilize light, heat, oxygen and the like without coloring.
芳香族アミンの安定化法に関して従来多数提案されて
いる。例えば没食子酸アルキルエステル類及び没食子酸
アミド類を添加する方法（特公昭49−15252号）、及び
ホスフィン、亜リン酸エステル及びリン酸エステル類を
添加する方法（特開昭55−31135号）等がある。Many methods for stabilizing aromatic amines have been proposed. For example, a method of adding an alkyl gallate and a gallic amide (Japanese Patent Publication No. 49-15252), and a method of adding a phosphine, a phosphite and a phosphate (Japanese Patent Laid-Open No. 55-135). There is.
［発明が解決すべき課題］ しかし、このような従来の方法では芳香族アミンに添
加したエステル類等が、芳香族アミンの反応により生成
するアニリン誘導体、例えばウレタン等の合成樹脂中に
不純物として残留するという欠点を有している。[Problems to be Solved by the Invention] However, in such a conventional method, an ester or the like added to an aromatic amine remains as an impurity in a synthetic resin such as an aniline derivative generated by a reaction of the aromatic amine, for example, urethane. Has the disadvantage of doing so.
［発明の目的］ 本発明はこのような従来方法の欠点を解決し、次工程
における残留の問題がなく、しかも酸素、光および熱の
いずれに対しても芳香族アミンを長時間安定化させるこ
とのできる方法を提供することを目的とする。[Object of the Invention] The present invention solves the drawbacks of the conventional method, has no problem of remaining in the next step, and further stabilizes the aromatic amine for all of oxygen, light and heat for a long time. The purpose is to provide a method that can
［課題を解決するための手段］ このような目的を達成する本発明の芳香族アミンの安
定化方法は、芳香族アミンにヒドラジン又はヒドラジン
ハイドレートを添加するものである。[Means for Solving the Problems] The method for stabilizing an aromatic amine of the present invention for achieving the above object is to add hydrazine or hydrazine hydrate to an aromatic amine.
本発明における芳香族アミンとしてはアニリン、トル
イジン、キシリジン、アミノフェノール、ベンチジン、
クロルアニリン、ナフチルアミンの如き第一級芳香族ア
ミン、Ｎ−モノメチルアニリン、Ｎ−モノエチルアニリ
ン、ジフェニルアミンの如き第二級芳香族アミンなどあ
げることができる。これらの芳香族アミンは個々の基本
的物性に基因して空気、熱および光で促進される品質悪
化の度合や速度は異なるが、本発明の安定化方法により
従来公知の安定剤を添加する場合に比しはるかにすぐれ
た着色の安定性向上の効果を奏する。As the aromatic amine in the present invention, aniline, toluidine, xylidine, aminophenol, benzidine,
Primary aromatic amines such as chloroaniline and naphthylamine, and secondary aromatic amines such as N-monomethylaniline, N-monoethylaniline and diphenylamine can be mentioned. These aromatic amines differ in the degree and speed of deterioration caused by air, heat and light due to the basic physical properties of each. However, when a conventionally known stabilizer is added by the stabilization method of the present invention. The effect of improving the stability of coloring which is much better than that of
これら芳香族アミンに対し、ヒドラジン、ヒドラジン
ハイドレートはそれぞれ固体のままあるいは液体のまま
添加してもよいが水溶液として添加するのが好ましい。Hydrazine and hydrazine hydrate may be added to these aromatic amines as solids or liquids, respectively, but are preferably added as aqueous solutions.
特にヒドラジンは水溶液として添加した場合、芳香族
アミンに対する溶解性が優れ、且つ着色に対する安定性
も顕著に向上する。又、取扱いも固体ヒドラジンに比べ
格段に容易かつ安全である。In particular, when hydrazine is added as an aqueous solution, the solubility in aromatic amines is excellent, and the stability to coloring is significantly improved. Also, handling is much easier and safer than solid hydrazine.
添加されるヒドラジン、ヒドラジンハイドレートの量
は、芳香族アミンの種類、芳香族アミンの使用される分
野により変化するものであるが、通常芳香族アミンに対
して重量比で1ppmないし１％、好ましくは5ppmないし10
00ppmである。The amount of hydrazine and hydrazine hydrate to be added varies depending on the kind of the aromatic amine and the field in which the aromatic amine is used, but is usually 1 ppm to 1% by weight relative to the aromatic amine, preferably Is 5ppm to 10
00 ppm.
［作用］ ヒドラジン及び／又はヒドラジンハイドレートを、好
適には水溶液として芳香族アミンに添加することによ
り、当該芳香族アミンの空気、光、熱に対する着色の安
定性が向上する。特に熱に対する着色の安定性が顕著に
向上する。[Action] By adding hydrazine and / or hydrazine hydrate to the aromatic amine, preferably as an aqueous solution, the stability of coloring of the aromatic amine with respect to air, light, and heat is improved. In particular, the stability of coloring to heat is significantly improved.
又、添加したヒドラジン及びヒドラジンハイドレート
は芳香族アミンを他の誘導体へ転化する際、加熱処理す
ることにより、ヒドラジンはアンモニアと窒素に容易に
熱分解し、又、水は留去することで不純物として残留し
ない。When hydrazine and hydrazine hydrate are added, the hydrazine is easily thermally decomposed into ammonia and nitrogen by converting the aromatic amine into another derivative by heat treatment, and water is distilled off to remove impurities. Does not remain.
［実施例］ 以下、実施例により本発明を更に説明する。[Examples] Hereinafter, the present invention will be further described with reference to examples.
尚、実施例において熱安定性試験はASTMD−1544−63T
の方法により行ない、得られた値をガードナー表示し
た。In the examples, the thermal stability test was performed according to ASTM D-1544-63T.
And the obtained value was displayed in Gardner.
実施例１ アニリン（色相、ハーゼン番号15）にヒドラジンハイ
ドレート80％水溶液を使用量を変えて添加し、熱安定性
試験を実施した。熱安定性は空気中で150℃、25分間加
熱した後、色相（ハーゼン番号（APHA））を測定したも
のである。その結果を表１に示す。Example 1 A heat stability test was carried out by adding an 80% aqueous solution of hydrazine hydrate to aniline (hue, Hazen No. 15) in a varying amount. Thermal stability is measured by measuring the hue (Hazen number (APHA)) after heating in air at 150 ° C. for 25 minutes. Table 1 shows the results.
表１からも明らかなように、ヒドラジン無添加の場合
には、加熱によって色相が大きく変化したのに対し、ヒ
ドラジンを添加した場合には、着色が抑制された。特に
1000ppm添加の場合、効果が顕著であった。 As is clear from Table 1, when hydrazine was not added, the hue was significantly changed by heating, whereas when hydrazine was added, coloring was suppressed. Especially
When 1000 ppm was added, the effect was remarkable.
実施例２ アニリン（色相、ハーゼン番号15）にヒドラジンハイ
ドレート80％水溶液をヒドラジン換算添加量100ppm添加
した後、空気雰囲気で、25℃で暗所に放置し、光に対す
る経時着色変化を試験し、その色相（APHA）を測定し
た。同条件における無添加の場合と比較した結果を表２
に示す。Example 2 An hydrazine hydrate 80% aqueous solution was added to aniline (hue, Hazen No. 15) in an amount of 100 ppm in terms of hydrazine. The hue (APHA) was measured. Table 2 shows the result of comparison with the case of no addition under the same conditions.
Shown in
表２からも明らかなように、ヒドラジン添加によって
約１ヶ月経過後も色相に変化がなかった。 As is clear from Table 2, the hue did not change even after about one month due to the addition of hydrazine.
実施例３ ジフェニルアミン（色相、ハーゼン番号30）及びｐ−
トルイジン（色相、ハーゼン番号50）にそれぞれヒドラ
ジンハイドレート40％水溶液を100ppm添加し、実施例１
と同様に熱安定性試験を行った。その結果を表３に示
す。表３からも明らかなように、いずれの芳香族アミン
の場合もヒドラジン添加によって着色が顕著に抑制され
た。Example 3 Diphenylamine (hue, Hazen No. 30) and p-
Example 1 Toluidine (hue, Hazen number 50) was added with 100 ppm of a 40% aqueous solution of hydrazine hydrate, respectively.
A thermal stability test was performed in the same manner as in the above. Table 3 shows the results. As is clear from Table 3, the coloring was significantly suppressed by the addition of hydrazine in any of the aromatic amines.
［発明の効果］ 以上の実施例からも明らかなように、本発明によれば
芳香族アミンに、ヒドラジン又はヒドラジンハイドレー
ドを添加することによって当該芳香族アミンの空気、
光、熱に対する着色安定性を改善することができる。 [Effects of the Invention] As is clear from the above examples, according to the present invention, by adding hydrazine or hydrazine hydrate to an aromatic amine, air of the aromatic amine,
The coloring stability to light and heat can be improved.
又、ヒドラジン、ヒドラジンハイドレートは加熱によ
って極めて容易にアンモニアと窒素に分解するので、次
工程において不純物として残留することがない。Also, hydrazine and hydrazine hydrate decompose into ammonia and nitrogen very easily by heating, so that they do not remain as impurities in the next step.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 ＦＩ Ｃ０７Ｃ 211/50 Ｃ０７Ｃ 211/50 211/52 211/52 211/58 211/58 213/10 213/10 215/76 215/76 (56)参考文献 特開 昭56−115745（ＪＰ，Ａ) 特開 昭63−63645（ＪＰ，Ａ) 特開 昭49−49911（ＪＰ，Ａ) 特開 昭63−284150（ＪＰ，Ａ) (58)調査した分野(Int.Cl.6，ＤＢ名) C07C 211/45 C07C 211/46 C07C 211/47 C07C 211/48 C07C 211/50 C07C 211/52 C07C 211/55 C07C 211/58 C07C 213/10 C07C 215/76 C07C 209/90──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 6 Identification code FI C07C 211/50 C07C 211/50 211/52 211/52 211/58 211/58 213/10 213/10 215/76 215/76 (56) References JP-A-56-115745 (JP, A) JP-A-63-63645 (JP, A) JP-A-49-49911 (JP, A) JP-A-63-284150 (JP, A) ( 58) Fields investigated (Int.Cl. 6 , DB name) C07C 211/45 C07C 211/46 C07C 211/47 C07C 211/48 C07C 211/50 C07C 211/52 C07C 211/55 C07C 211/58 C07C 213 / 10 C07C 215/76 C07C 209/90
Claims (2)
ハイドレートを添加することを特徴とする芳香族アミン
の安定化方法。1. A method for stabilizing an aromatic amine, comprising adding hydrazine or hydrazine hydrate to the aromatic amine.
トは水溶液として添加することを特徴とする請求項１記
載の芳香族アミンの安定化方法。2. The method for stabilizing an aromatic amine according to claim 1, wherein said hydrazine or hydrazine hydrate is added as an aqueous solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8893290A JP2771011B2 (en) | 1990-04-03 | 1990-04-03 | Method for stabilizing aromatic amine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8893290A JP2771011B2 (en) | 1990-04-03 | 1990-04-03 | Method for stabilizing aromatic amine |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03287566A JPH03287566A (en) | 1991-12-18 |
| JP2771011B2 true JP2771011B2 (en) | 1998-07-02 |
Family
ID=13956672
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8893290A Expired - Lifetime JP2771011B2 (en) | 1990-04-03 | 1990-04-03 | Method for stabilizing aromatic amine |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2771011B2 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0641027A (en) * | 1992-05-05 | 1994-02-15 | Hoechst Ag | Stabilized aminobenzotrifluoride composition |
| DE10228594B4 (en) | 2002-06-26 | 2006-06-08 | Lanxess Deutschland Gmbh | Preparation of colorless dibenzylamine |
| CN105330551B (en) * | 2015-12-10 | 2017-09-29 | 常州市宝隆化工有限公司 | A kind of method for preventing N methylanilines from changing colour |
| US20230257339A1 (en) | 2020-07-03 | 2023-08-17 | Central Glass Company, Limited | Alkylamine composition and method for storing said alkylamine composition |
-
1990
- 1990-04-03 JP JP8893290A patent/JP2771011B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH03287566A (en) | 1991-12-18 |
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