JP2540618B2 - Novel aromatic diamine compound and method for producing the same - Google Patents
Novel aromatic diamine compound and method for producing the sameInfo
- Publication number
- JP2540618B2 JP2540618B2 JP63287609A JP28760988A JP2540618B2 JP 2540618 B2 JP2540618 B2 JP 2540618B2 JP 63287609 A JP63287609 A JP 63287609A JP 28760988 A JP28760988 A JP 28760988A JP 2540618 B2 JP2540618 B2 JP 2540618B2
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- JP
- Japan
- Prior art keywords
- aromatic diamine
- general formula
- aromatic
- compound represented
- reaction
- 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)
- Epoxy Resins (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は新規な芳香族ジアミン系化合物およびその製
造方法に関する。TECHNICAL FIELD The present invention relates to a novel aromatic diamine compound and a method for producing the same.
現在、エポキシ樹脂硬化剤としてアミン類、酸無水物
類などが一般に用いられている。アミン類はさらに脂肪
族アミン類、芳香族アミン類に大別されている。以下、
本発明に関連の深い芳香族アミン類について説明する。At present, amines and acid anhydrides are generally used as epoxy resin curing agents. Amines are further classified into aliphatic amines and aromatic amines. Less than,
Aromatic amines closely related to the present invention will be described.
芳香族アミン類の代表的なものとして、ｍ−フエニレ
ンジアミン,4,4′−ジアミノジフエニルエーテル,4,4′
−ジアミノジフエニルメタン,4,4′−ジアミノジフエニ
ルスルホンなどが挙げられる。これらを硬化剤としてエ
ポキシ樹脂に混合して得られる硬化物は機械的強度、接
着性、電気絶縁性などの性能に優れ、FRP用マトリツク
ス、構造材料、コーテイング材料、電気絶縁材料、接着
剤その他諸々の用途に使用されている。Typical aromatic amines include m-phenylenediamine, 4,4′-diaminodiphenyl ether, 4,4 ′.
-Diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfone and the like. The cured product obtained by mixing these with epoxy resin as a curing agent has excellent properties such as mechanical strength, adhesiveness, and electrical insulation, and is used for FRP matrices, structural materials, coating materials, electrical insulation materials, adhesives, etc. Is used for.
しかしながら、近年、軽量化、高性能化を目的にして
金属材料のプラスチツク化が進むにつれ、エポキシ樹脂
硬化物に対する性能の向上がますます要望されている。
従来の芳香族アミン類硬化剤（ｍ−フエニレンジアミ
ン,4,4′−ジアミノジフエニルエーテル,4,4′−ジアミ
ノジフエニルメタン,4,4′−ジアミノジフエニルスルホ
ンなど）ではそのエポキシ樹脂硬化物の機械的性能、耐
熱性などにおいて限界があり、エポキシ樹脂硬化物の機
械的性能、耐熱性をさらに向上させるような新規な芳香
族アミン類硬化剤が望まれていた。However, in recent years, with the progress of plasticization of metal materials for the purpose of weight reduction and high performance, there is an increasing demand for improvement in performance of epoxy resin cured products.
Conventional aromatic amine curing agents (m-phenylenediamine, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfone, etc.) are used as epoxy resins. There is a limit in the mechanical performance and heat resistance of the cured product, and a novel aromatic amine curing agent that further improves the mechanical performance and heat resistance of the cured epoxy resin has been desired.
本発明者らは上述の事情に鑑み、エポキシ樹脂硬化物
の機械的性能、耐熱性を向上させる効果をもつ新規な芳
香族アミン系化合物及びその製造法を提供しようとする
ものである。In view of the above circumstances, the present inventors intend to provide a novel aromatic amine compound having an effect of improving mechanical performance and heat resistance of a cured epoxy resin, and a method for producing the same.
本発明者らは前述した効果をもつ新規な芳香族アミン
系化合物の分子構造およびその合成法を鋭意検討した結
果、下記の一般式（１）で表わされる化合物が上記の目
的を満たすことを確かめ、本発明を達成するに至つた。The inventors of the present invention have extensively studied the molecular structure of a novel aromatic amine compound having the above-mentioned effects and a method of synthesizing the compound, and as a result, confirmed that the compound represented by the following general formula (1) satisfies the above object. The present invention has been accomplished.
すなわち、本発明の第一の発明は、一般式 で表される芳香族ジアミン系化合物である。That is, the first invention of the present invention is represented by the general formula It is an aromatic diamine compound represented by.
そして、本発明の第二の発明は、一般式（１）で表さ
れる芳香族ジアミン系化合物を製造するにあたり、まず
N,N′−ジフエニル−ｐ−フエニレンジアミンとｐ−ニ
トロ塩化ベンゾイルを反応させて、一般式 で表される芳香族ジニトロ系化合物を合成し、つぎに、
一般式（II）で表される芳香族ジニトロ系化合物のニト
ロ基を還元して一般式（１）で表される芳香族ジアミン
系化合物を合成する芳香族ジアミン系化合物の製造方法
である。And the 2nd invention of this invention WHEREIN: When manufacturing the aromatic diamine type compound represented by General formula (1),
N, N'-diphenyl-p-phenylenediamine is reacted with p-nitrobenzoyl chloride to give a compound of the general formula The aromatic dinitro compound represented by
A method for producing an aromatic diamine-based compound, which comprises reducing an nitro group of an aromatic dinitro-based compound represented by the general formula (II) to synthesize an aromatic diamine-based compound represented by the general formula (1).
以下、芳香族ジアミン系化合物の製造方法をさらに詳
しく説明する。Hereinafter, the method for producing the aromatic diamine compound will be described in more detail.
本発明の原料物質であるN,N′−ジフエニル−ｐ−フ
エニレンジアミンおよびｐ−ニトロ塩化ベンゾイルは工
業的に容易に入手できる。N,N′−ジフエニル−ｐ−フ
エニレンジアミンとｐ−ニトロ塩化ベンゾイルを反応さ
せて一工程で上記一般式（II）で表される芳香族ジニト
ロ系化合物を得ることができる。この反応で使用するｐ
−ニトロ塩化ベンゾイルの量はN,N′−ジフエニル−ｐ
−フエニレンジアミンに対して２当量が適当である。こ
の反応で使用しうる溶媒は、アンニソール、1,1,2,2−
テトラクロロエタン、ｏ−ジクロロベンゼン、ニトロベ
ンゼンなどである。この反応を行う温度としては150〜1
60℃が好ましい。この反応の反応時間は、用いた試薬の
量、溶媒の種類、反応温度などに大きく左右されるが、
この反応の副生成物である塩化水素が発生しなくなるま
で、数時間から数日間反応させるのが好ましい。かくし
て得られた一般式（II）で表される芳香族ジニトロ系化
合物を還元して一般式（Ｉ）で表される芳香族ジアミン
系化合物を得るのであるが、還元の方法としては水素と
触媒、塩化第一スズと塩酸、スズまたは亜鉛と酸などを
用いる方法が挙げられる。これらのうち水素と触媒を用
いる方法が好ましい。この反応で用いられる触媒として
は白金、パラジウム、ロジウムなどである。この反応で
使用しうる溶媒はN,N−ジメチルホルムアミド、テトラ
ヒドロフランなどであるがN,N−ジメチルホルムアミド
が好ましい。この反応を行う温度としては20〜40℃が好
ましく、この反応の反応時間は、用いた芳香族ジニトロ
系化合物の量、撹拌の激しさ、反応温度などに大きく左
右されるが、水素ガスの消費が起こらなくなるまで、数
時間から数日間反応させるのが好ましい。The starting materials of the present invention, N, N'-diphenyl-p-phenylenediamine and p-nitrobenzoyl chloride, are industrially easily available. An aromatic dinitro compound represented by the above general formula (II) can be obtained in one step by reacting N, N'-diphenyl-p-phenylenediamine with p-nitrobenzoyl chloride. P used in this reaction
-The amount of benzoyl nitrochloride is N, N'-diphenyl-p
2 equivalents to phenylenediamine are suitable. Solvents that can be used in this reaction include annisole, 1,1,2,2-
Tetrachloroethane, o-dichlorobenzene, nitrobenzene and the like. The temperature for carrying out this reaction is 150-1
60 ° C is preferred. The reaction time of this reaction largely depends on the amount of reagents used, the type of solvent, the reaction temperature, etc.
It is preferable to carry out the reaction for several hours to several days until hydrogen chloride, which is a by-product of this reaction, is not generated. The aromatic dinitro-based compound represented by the general formula (II) thus obtained is reduced to obtain the aromatic diamine-based compound represented by the general formula (I). The reduction method is hydrogen and a catalyst. , Stannous chloride and hydrochloric acid, tin or zinc and an acid, and the like. Of these, the method using hydrogen and a catalyst is preferable. The catalyst used in this reaction is platinum, palladium, rhodium or the like. Solvents that can be used in this reaction include N, N-dimethylformamide and tetrahydrofuran, but N, N-dimethylformamide is preferred. The temperature for carrying out this reaction is preferably 20 to 40 ° C., and the reaction time of this reaction largely depends on the amount of the aromatic dinitro compound used, the intensity of stirring, the reaction temperature, etc. The reaction is preferably carried out for several hours to several days until the reaction does not occur.
かくして得られた一般式（Ｉ）で表される芳香族ジア
ミン系化合物はエポキシ樹脂の硬化剤として使用できる
他、種々の高分子化合物（ポリアミド、ポリイミドな
ど）の原料となり得る。The aromatic diamine-based compound represented by the general formula (I) thus obtained can be used as a curing agent for an epoxy resin and can be a raw material for various polymer compounds (polyamide, polyimide, etc.).
窒素雰囲気下でN,N′−ジフエニル−ｐ−フエニレン
ジアミン1.3g（5mmol）を50mlの1,1,2,2−テトラクロロ
エタンに加え、120℃に加熱して溶解させた。これにｐ
−ニトロ塩化ベンゾイル1.9g（10mmol）を加え155℃に
加熱して還流下、12時間撹拌を続けた。得られた溶液を
500mlのｎ−ヘキサンに投入して沈澱物を別し、ｎ−
ヘキサンでよく洗浄した。この生成物は乾燥後、2.8gあ
つた。Under a nitrogen atmosphere, 1.3 g (5 mmol) of N, N'-diphenyl-p-phenylenediamine was added to 50 ml of 1,1,2,2-tetrachloroethane and heated to 120 ° C to dissolve it. P to this
-Benzoyl nitrochloride (1.9 g, 10 mmol) was added, and the mixture was heated to 155 ° C and stirred under reflux for 12 hours. The resulting solution
The precipitate was separated by pouring into 500 ml of n-hexane, and n-
Washed well with hexane. After the product was dried, 2.8 g was collected.
この生成物をベンゼンで数回再結晶して、淡黄色の結
晶を得た。この結晶の赤外線吸収スペクトル（IR）測定
により、原料物質であるN,N′−ジフエニル−ｐ−フエ
ニレンジアミンのＮ−Ｈ伸縮振動による吸収が認められ
ないこと、およびアミド結合に起因する吸収が1650cm-1
に認められることがわかつた。生成物はN,N′−ジフエ
ニル−N,N′−1,4−フエニレンビス（４−ニトロベンズ
アミド）であつた。収量1.8g（再結晶２回） 融点273〜275℃ IR（KBr）:1650cm-1,1520cm-1,1320cm-1 元素分析値 計算値（％）C:68,81 H:3.97 N:10.03 実測値（％）C:69.05 H:3.87 N:10.02 次に窒素雰囲気下で、上記反応で得られたN,N′−ジ
フエニル−N,N′−1,4−フエニレンビス（４−ニトロベ
ンズアミド）1.12g（2mmol）を50mlのN,N−ジメチルホ
ルムアミドに溶解した溶液に10％パラジウム炭素を0.2g
加えた。この溶液を水素雰囲気下で、30℃に加熱し12時
間、激しく撹拌した。得られた溶液からパラジウム炭素
を別し、液を氷水中に投入して沈澱を別した。こ
の生成物は乾燥後、0.84gあつた。この生成物をN,N−ジ
メチルホルムアミドとエタノールの混合溶媒で再結晶し
た。この結晶の赤外線吸収スペクトル（IR）測定によ
り、N,N′−ジフエニル−N,N′−1,4−フエニレンビス
（４−ニトロベンズアミド）のニトロ基の吸収が認めら
れないこと、およびアミノ基に起因する吸収が3450,336
0cm-1に認められることから、生成物はN,N′−ジフエニ
ル−N,N′−1,4−フエニレンビス（４−アミノベンズア
ミド）であつた。The product was recrystallized several times with benzene to obtain pale yellow crystals. Infrared absorption spectrum (IR) measurement of this crystal showed that no absorption due to N—H stretching vibration of N, N′-diphenyl-p-phenylenediamine as a raw material and absorption due to amide bond were observed. 1650 cm -1
I understand that The product was N, N'-diphenyl-N, N'-1,4-phenylenebis (4-nitrobenzamide). Yield 1.8 g (recrystallized twice) mp 273~275 ℃ IR (KBr): 1650cm -1, 1520cm -1, 1320cm -1 Elemental analysis Calculated (%) C: 68,81 H: 3.97 N: 10.03 Found Value (%) C: 69.05 H: 3.87 N: 10.02 Then, under a nitrogen atmosphere, N, N'-diphenyl-N, N'-1,4-phenylenebis (4-nitrobenzamide) 1.12 obtained in the above reaction was obtained. 0.2 g of 10% palladium-carbon was added to a solution of g (2 mmol) in 50 ml of N, N-dimethylformamide.
added. This solution was heated to 30 ° C. under a hydrogen atmosphere and vigorously stirred for 12 hours. Palladium carbon was separated from the resulting solution, and the solution was poured into ice water to separate the precipitate. After drying, the product weighed 0.84 g. The product was recrystallized from a mixed solvent of N, N-dimethylformamide and ethanol. Infrared absorption spectrum (IR) measurement of this crystal showed that absorption of nitro group of N, N'-diphenyl-N, N'-1,4-phenylenebis (4-nitrobenzamide) was not observed, and that amino group Absorption due to 3450,336
The product was N, N'-diphenyl-N, N'-1,4-phenylenebis (4-aminobenzamide) since it was observed at 0 cm -1 .
収量0.61g（再結晶後）、融点324〜326℃IR（KBr）34
50cm-1,3360cm-1,1600cm-1,1280cm-1 〔参考例〕 エポキシ当量190のビスフエノールＡジグリシジルエ
ーテル型エポキシ樹脂1.0gに0.66gのN,N′−ジフエニル
−N,N′−1,4−フエニレンビス（４−アミノベンズアミ
ド）を混合し、5mmHgの減圧下、80℃で12時間かけて脱
泡した。この混合物を２時間かけて250℃に加熱し、250
℃で10分間加熱を続けた後、２時間かけて室温まで冷却
して黄色透明の硬化物を得た。Yield 0.61g (after recrystallization), melting point 324-326 ℃ IR (KBr) 34
50cm -1, 3360cm -1, 1600cm -1 , 1280cm -1 Reference Example] having an epoxy equivalent of 190 bisphenol A diglycidyl ether type epoxy resin 1.0g to 0.66g of N, N'-diphenyl -N, N' 1,4-Phenylene bis (4-aminobenzamide) was mixed and degassed under reduced pressure of 5 mmHg at 80 ° C. for 12 hours. The mixture is heated to 250 ° C. for 2 hours, 250
After continuing heating at 0 ° C for 10 minutes, the mixture was cooled to room temperature over 2 hours to obtain a yellow transparent cured product.
この硬化物の引張強度、伸び、弾性率はそれぞれ73MP
a,4.2％,1.9GPaであつた。また、この硬化物の熱重量測
定法による10％重量減少温度は334℃（窒素気流中）で
あつた。The cured product has a tensile strength, elongation, and elastic modulus of 73MP each.
It was a, 4.2%, 1.9 GPa. The 10% weight loss temperature of this cured product measured by a thermogravimetric method was 334 ° C. (in a nitrogen stream).
本発明は前記一般式（Ｉ）で表される芳香族ジアミン
系化合物およびその有利な製造方法を提供する。本発明
の芳香族ジアミン系化合物を硬化剤として用いて硬化し
たエポキシ樹脂硬化物は優れた機械的性能、耐熱性を示
した。また、本発明の芳香族ジアミン系化合物はそのま
まポリアミド、ポリイミドなどの耐熱性樹脂の原料とな
り得るので工業材料としての価値が大きい。The present invention provides an aromatic diamine compound represented by the above general formula (I) and an advantageous production method thereof. The epoxy resin cured product cured using the aromatic diamine compound of the present invention as a curing agent showed excellent mechanical performance and heat resistance. Further, the aromatic diamine-based compound of the present invention can be used as it is as a raw material for heat-resistant resins such as polyamide and polyimide, and thus has great value as an industrial material.
Claims (2)
ミンとｐ−ニトロ塩化ベンゾイルを反応させて、 一般式 で表される芳香族ジニトロ系化合物を合成し、ついでこ
の芳香族ジニトロ系化合物のニトロ基を還元することを
特徴とする一般式 で表される芳香族ジアミン系化合物の製造方法。2. N, N'-diphenyl-p-phenylenediamine is reacted with p-nitrobenzoyl chloride to give a compound of the general formula A general formula characterized by synthesizing an aromatic dinitro compound represented by and then reducing the nitro group of the aromatic dinitro compound The manufacturing method of the aromatic diamine type compound represented by.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63287609A JP2540618B2 (en) | 1988-11-16 | 1988-11-16 | Novel aromatic diamine compound and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63287609A JP2540618B2 (en) | 1988-11-16 | 1988-11-16 | Novel aromatic diamine compound and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02134351A JPH02134351A (en) | 1990-05-23 |
| JP2540618B2 true JP2540618B2 (en) | 1996-10-09 |
Family
ID=17719486
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63287609A Expired - Lifetime JP2540618B2 (en) | 1988-11-16 | 1988-11-16 | Novel aromatic diamine compound and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2540618B2 (en) |
-
1988
- 1988-11-16 JP JP63287609A patent/JP2540618B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH02134351A (en) | 1990-05-23 |
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