JPH0529392B2 - - Google Patents
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- Publication number
- JPH0529392B2 JPH0529392B2 JP63267300A JP26730088A JPH0529392B2 JP H0529392 B2 JPH0529392 B2 JP H0529392B2 JP 63267300 A JP63267300 A JP 63267300A JP 26730088 A JP26730088 A JP 26730088A JP H0529392 B2 JPH0529392 B2 JP H0529392B2
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- JP
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- Prior art keywords
- reaction
- aromatic diamine
- general formula
- present
- compound represented
- 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.)
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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化合物及びその
製造方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a novel aromatic diamine compound and a method for producing the same.
（従来の技術）
従来、全芳香族ポリイミドやポリアミドなどは
優れた耐熱性とともに優れた機械特性を有し、広
く工業材料として使用されてきたが、これらの多
くは有機溶媒に不溶であり、成形性に多くの問題
があつた。このような樹脂の中でジアミノテトラ
フエニルチオフエンを原料として製造されるポリ
イミドやポリアミドは有機溶媒に可溶であること
が知られている（例えば、Y.Imai et al.，J.
Polym.Sci.，Polym.Chem.Ed.，22，2189
（1984），idid，23．1797（1985））。(Prior technology) In the past, fully aromatic polyimides and polyamides have excellent heat resistance and excellent mechanical properties, and have been widely used as industrial materials, but many of these are insoluble in organic solvents and cannot be molded. There were many problems with sexuality. Among such resins, polyimide and polyamide produced using diaminotetraphenylthiophene as a raw material are known to be soluble in organic solvents (for example, Y. Imai et al., J.
Polym.Sci., Polym.Chem.Ed., 22, 2189
(1984), idid, 23 . 1797 (1985)).
然し、現在のところ、有機溶媒に可溶で且つ成
形性に優れた耐熱性樹脂が得られる芳香族ジアミ
ンは知られていない。 However, at present, no aromatic diamine is known that is soluble in organic solvents and from which a heat-resistant resin with excellent moldability can be obtained.
（発明が解決しようとする課題）
本発明は有機溶媒に可溶で且つ成形性に優れた
耐熱性樹脂が得られる新規な芳香族ジアミンと、
その製造方法を提供するものである。(Problems to be Solved by the Invention) The present invention provides a novel aromatic diamine from which a heat-resistant resin that is soluble in organic solvents and has excellent moldability,
The present invention provides a method for manufacturing the same.
（課題を解決するための手段）
本発明者らはこのような新規な芳香族ジアミン
化合物とそれを得る方法について鋭意研究を重ね
た結果、テトラフエニルエチレンを出発物質とし
て、さらにビス（ニトロフエニル）ジフエニルエ
チレンを経由する合成法によりこの目的に適合す
る新規な芳香族ジアミン化合物が得られることを
見出し、本発明を達成するに至つた。(Means for Solving the Problems) As a result of intensive research into such novel aromatic diamine compounds and methods for obtaining them, the present inventors found that using tetraphenylethylene as a starting material, bis(nitrophenyl) The present inventors have discovered that a novel aromatic diamine compound suitable for this purpose can be obtained by a synthesis method via diphenylethylene, and have achieved the present invention.
本発明の第一の発明は、次の一般式 で表わされる芳香族ジアミン化合物である。 The first invention of the present invention is based on the following general formula It is an aromatic diamine compound represented by
本発明の第二の発明は、テトラフエニルエチレ
ンをニトロ化反応によりジニトロ化合物とし、こ
れを還元することを特徴とする一般式
で表わされる芳香族ジアミン化合物の製造方法で
ある。 The second invention of the present invention is a general formula characterized in that tetraphenylethylene is converted into a dinitro compound by a nitration reaction, and this is reduced. This is a method for producing an aromatic diamine compound represented by
本発明における出発原料となるテトラフエニル
エチレン（式）
は、ジクロロジフエニルメタンの自己二量化反応
により容易に合成される（例えば、Org.Syn.
Collective Vol.IV.914（1963））。 Tetraphenylethylene (formula), which is the starting material in the present invention is easily synthesized by the self-dimerization reaction of dichlorodiphenylmethane (for example, Org.Syn.
Collective Vol.IV.914 (1963)).
次の一般式（）
で表わされるジニトロエチレン化合物は、一般式
（）で表わされるテトラフエニルエチレンを硝
酸によりニトロ化することにより得られる。実際
には、一般式（）で表わされるテトラフエニル
エチレンを硝酸存在下に加熱反応させることによ
り行なう。この反応の温度は、０〜200℃である
が、経済的には30〜150℃の温度で行なうのが好
ましい。この反応に使用し得る溶媒としては、実
質的に硝酸と反応しない溶媒が用いられ、特に
水、酢酸等が好ましい。また、硫酸、塩酸等の酸
を共存させることにより、反応を促進することも
できる。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、数十分
から数日間反応させるのが好ましい。 The following general formula () The dinitroethylene compound represented by is obtained by nitrating tetraphenylethylene represented by general formula () with nitric acid. Actually, the reaction is carried out by heating and reacting tetraphenylethylene represented by the general formula () in the presence of nitric acid. The temperature of this reaction is 0 to 200°C, but economically it is preferably carried out at a temperature of 30 to 150°C. As a solvent that can be used in this reaction, a solvent that does not substantially react with nitric acid is used, and water, acetic acid, etc. are particularly preferred. The reaction can also be promoted by coexisting an acid such as sulfuric acid or hydrochloric acid. Although the reaction time largely depends on the amount of reagent used, the type of solvent, the reaction temperature, etc., it is preferable to allow the reaction to occur for several tens of minutes to several days.
一般式（）で表わされる芳香族ジアミン化合
物は、一般式（）で表わされるジニトロ化合物
を還元剤を用いて還元することにより得られる。
ここで用いる還元剤は、水素、鉄−塩酸系、錫−
塩酸系、塩化第一錫−塩酸系、亜鉛−酢酸系など
を挙げることができる。特に、接触水素化法又は
塩化第一錫−塩酸法がこの反応の還元法として好
ましい。 The aromatic diamine compound represented by the general formula () can be obtained by reducing the dinitro compound represented by the general formula () using a reducing agent.
The reducing agents used here are hydrogen, iron-hydrochloric acid, tin-
Examples include hydrochloric acid, stannous chloride-hydrochloric acid, and zinc-acetic acid. In particular, a catalytic hydrogenation method or a stannous chloride-hydrochloric acid method is preferred as a reduction method for this reaction.
（実施例）
以下本発明を実施例と参考例につきさらに詳細
に説明する。(Examples) The present invention will be described in more detail below with reference to Examples and Reference Examples.
参考例 １
１，１−ビス（４−ニトロフエニル）−２，２
−ジフエニルエチレン（式）の合成
テトラフエニルエチレン（式）13ｇ（0.04モ
ル）を氷酢酸220mlに分散させた。この溶液を100
℃に保ちつつ、濃硝酸（ｄ＝1.38）30ｇと氷酢酸
60mlの混合溶液を１−1.5時間かけて滴下した。
その後100℃で１時間攪拌した。反応後、放冷に
より析出した黄色結晶を濾過し蒸留水で十分洗浄
後、乾燥した。シクロヘキサンより再結晶して黄
色の粒状晶を得た。収量は6.1ｇ（収率36％）で
あつた。Reference example 1 1,1-bis(4-nitrophenyl)-2,2
-Synthesis of diphenylethylene (formula) 13 g (0.04 mol) of tetraphenylethylene (formula) was dispersed in 220 ml of glacial acetic acid. 100% of this solution
30g of concentrated nitric acid (d=1.38) and glacial acetic acid while keeping at ℃
60 ml of the mixed solution was added dropwise over 1-1.5 hours.
Thereafter, the mixture was stirred at 100°C for 1 hour. After the reaction, yellow crystals precipitated by cooling were filtered, thoroughly washed with distilled water, and then dried. Recrystallization from cyclohexane gave yellow granular crystals. The yield was 6.1 g (yield 36%).
融点 195〜197℃
赤外吸収スペクトル（KBr）1340cm-1（NO2）
13C−NMR（CDCl3）：δ（ppm）＝149.7，
146.8，146.5，141.8，136.7，132.1，131.2，
128.3，128.0，123.4
赤外吸収スペクトル（エタノール）：
λmax＝245，348nm
元素分析値
Ｃ Ｈ Ｎ
計算値(%)73.91 4.28 6.64
実測値(%)73.92 4.26 6.50
実施例 １
１，１−ビス（４−アミノフエニル）−２，２
−ジフエニルエチレン（式）の合成
１，１−ビス（４−ニトロフエニル）−２，２
−ジフエニルエチレン（式）7.3ｇ（0.017モ
ル）を氷酢酸80mlに分散し、これに、塩化第一錫
二水和物37.8ｇ（0.17モル）を溶かした濃塩酸46
mlを加え、徐々に100℃まで加熱し、100℃で４時
間攪拌した。反応後、反応溶液を40％水酸化ナト
リウム水溶液で氷冷下に中和した。得られた懸濁
液を大量の蒸留水に投入し、析出物を濾別した。
次いで、これを蒸留水で十分に洗浄して乾燥し
た。トルエンで二回再結晶し、淡黄色の針状晶を
得た。収量は3.7ｇ（収率60％）であつた。 Melting point 195-197℃ Infrared absorption spectrum (KBr) 1340cm -1 (NO 2 ) 13C-NMR (CDCl 3 ): δ (ppm) = 149.7,
146.8, 146.5, 141.8, 136.7, 132.1, 131.2,
128.3, 128.0, 123.4 Infrared absorption spectrum (ethanol): λmax = 245, 348 nm Elemental analysis value C H N Calculated value (%) 73.91 4.28 6.64 Actual value (%) 73.92 4.26 6.50 Example 1 1,1-bis(4 -aminophenyl)-2,2
-Synthesis of diphenylethylene (formula) 1,1-bis(4-nitrophenyl)-2,2
- Disperse 7.3 g (0.017 mol) of diphenylethylene (formula) in 80 ml of glacial acetic acid, and add 46 ml of concentrated hydrochloric acid to which 37.8 g (0.17 mol) of stannous chloride dihydrate is dissolved.
ml was added, gradually heated to 100°C, and stirred at 100°C for 4 hours. After the reaction, the reaction solution was neutralized with a 40% aqueous sodium hydroxide solution under ice cooling. The resulting suspension was poured into a large amount of distilled water, and the precipitate was filtered off.
Next, this was thoroughly washed with distilled water and dried. It was recrystallized twice from toluene to obtain pale yellow needle-like crystals. The yield was 3.7 g (yield 60%).
融点 259〜260℃
赤外吸収スペクトル（KBr）：
3450，3420cm-1（Ｎ−Ｈ）
1340cm-1のニトロ基の吸収は消失
元素分析値
Ｃ Ｈ Ｎ
計算値(%) 86.14 6.12 7.73
実測値(%) 86.23 6.15 7.75
参考例 ２
１，１−ビス（４−アミノフエニル）−２，２
−ジフエニルエチレン0.362ｇ（1.0ミリモル）を
５mlのＮ−メチル−２−ピロリドンに溶解し、ド
ライアイス−アセトン浴で凍結した。これに
0.203ｇ（1.0ミリモル）のイソフタル酸クロリド
を固体のまま一度加えた。ドライアイス−アセト
ン浴から氷浴に変え、０℃で３時間攪拌後、粘稠
な重合溶液を300mlの蒸留水中に投入することに
よりポリアミドを得た。赤外吸収スペクトルによ
り、3350cm-1にアミド結合のＮ−Ｈの吸収、1650
cm-1にカルボニルの吸収がそれぞれ観測された。 Melting point 259-260℃ Infrared absorption spectrum (KBr): 3450, 3420cm -1 (NH) Absorption of nitro group at 1340cm -1 disappears Elemental analysis value C H N Calculated value (%) 86.14 6.12 7.73 Actual value ( %) 86.23 6.15 7.75 Reference example 2 1,1-bis(4-aminophenyl)-2,2
0.362 g (1.0 mmol) of -diphenylethylene was dissolved in 5 ml of N-methyl-2-pyrrolidone and frozen in a dry ice-acetone bath. to this
0.203 g (1.0 mmol) of isophthalic acid chloride was added once as a solid. The dry ice-acetone bath was changed to an ice bath, and after stirring at 0° C. for 3 hours, the viscous polymerization solution was poured into 300 ml of distilled water to obtain a polyamide. The infrared absorption spectrum shows the absorption of N-H of the amide bond at 3350 cm -1 and the absorption of N-H at 1650 cm -1
Carbonyl absorption was observed at cm -1 .
収率 99％
固有粘度 1.36dl／ｇ（濃硫酸中30℃、0.5
ｇ／dlの濃度で測定）
元素分析
炭素 水素 窒素
計算値(%)82.90 4.91 5.69
実測値(%)81.94 4.76 5.75
ガラス転移点（示差走査熱量測定）310℃
熱重量測定装置による10％重量減少温度は、空
気中485℃、窒素中495℃であつた。 Yield 99% Intrinsic viscosity 1.36dl/g (30℃ in concentrated sulfuric acid, 0.5
Elemental analysis Carbon Hydrogen Nitrogen Calculated value (%) 82.90 4.91 5.69 Actual value (%) 81.94 4.76 5.75 Glass transition point (differential scanning calorimetry) 310°C 10% weight loss temperature measured by thermogravimetry The temperature was 485°C in air and 495°C in nitrogen.
Ｎ，Ｎ−ジメチルアセトアミド溶液よりキヤス
ト法により作製されたフイルムの機械特性は、引
つ張り強度40MPa、破断伸び３％、引つ張り弾
性率1.9GPaであつた。 The mechanical properties of the film produced by casting from an N,N-dimethylacetamide solution were a tensile strength of 40 MPa, an elongation at break of 3%, and a tensile modulus of 1.9 GPa.
このポリアミドは、Ｎ，Ｎ−ジメチルアセトア
ミド、Ｎ−メチル−２−ピロリドン、ジメチルス
ルホキシド、ｍ−クレゾール、ピリジンに可溶で
アセトン、クロロホルム、メチルアルコールに不
溶であつた。 This polyamide was soluble in N,N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethylsulfoxide, m-cresol, and pyridine, and insoluble in acetone, chloroform, and methyl alcohol.
（発明の効果）
本発明は一般式（）で表わされる芳香族ジア
ミン化合物及びその有利な製造方法を提供する。
従来の多くの芳香族ジアミン化合物を原料として
製造された全芳香族ポリアミドなどの耐熱性樹脂
が多くの有機溶媒に対して低い溶解性を有する為
に成形が困難であつたのに対し、本発明のジアミ
ン化合物を原料として製造された耐熱性樹脂は有
機溶媒に可溶で成形が容易であり、しかも優れた
耐熱性、電気的特性、機械的特性を有するので、
工業材料としての価値が大きい。(Effects of the Invention) The present invention provides an aromatic diamine compound represented by the general formula () and an advantageous method for producing the same.
Conventional heat-resistant resins such as fully aromatic polyamides manufactured using many aromatic diamine compounds as raw materials have low solubility in many organic solvents and are difficult to mold, whereas the present invention The heat-resistant resin produced using the diamine compound as a raw material is soluble in organic solvents and easy to mold, and has excellent heat resistance, electrical properties, and mechanical properties.
It has great value as an industrial material.
本発明を特定の実施例及び数値につき説明した
が、本発明の広汎な精神を視野を逸脱することな
く種々の変更と修整が可能なこと勿論である。 Although the invention has been described with reference to specific embodiments and numerical values, it will be understood that various changes and modifications may be made without departing from the broader spirit of the invention.
Claims (1)
合物。 ２ テトラフエニルエチレンをニトロ化反応によ
りジニトロ化合物とし、これを還元することを特
徴とする一般式 で表わされる芳香族ジアミン化合物の製造方法。[Claims] 1. General formula An aromatic diamine compound represented by: 2 General formula characterized by converting tetraphenylethylene into a dinitro compound through a nitration reaction and reducing this A method for producing an aromatic diamine compound represented by
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26730088A JPH02115149A (en) | 1988-10-25 | 1988-10-25 | Aromatic diamine compound and its manufacturing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26730088A JPH02115149A (en) | 1988-10-25 | 1988-10-25 | Aromatic diamine compound and its manufacturing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02115149A JPH02115149A (en) | 1990-04-27 |
| JPH0529392B2 true JPH0529392B2 (en) | 1993-04-30 |
Family
ID=17442914
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP26730088A Granted JPH02115149A (en) | 1988-10-25 | 1988-10-25 | Aromatic diamine compound and its manufacturing method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02115149A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104003886B (en) * | 2013-02-25 | 2015-11-25 | 北京师范大学 | Many nitros replace preparation and the application thereof of tetraphenylethylene compound |
| CN113461546B (en) * | 2021-07-27 | 2022-04-29 | 华中科技大学 | A kind of sterically hindered tetrastyrene helix that emits dark blue fluorescence and synthesis method |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6483054A (en) * | 1987-09-24 | 1989-03-28 | Toshiba Corp | Production of stilbene derivative |
-
1988
- 1988-10-25 JP JP26730088A patent/JPH02115149A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPH02115149A (en) | 1990-04-27 |
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