JP3541396B2 - Method for producing 4-aminodiphenylamine - Google Patents
Method for producing 4-aminodiphenylamine Download PDFInfo
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- JP3541396B2 JP3541396B2 JP09770293A JP9770293A JP3541396B2 JP 3541396 B2 JP3541396 B2 JP 3541396B2 JP 09770293 A JP09770293 A JP 09770293A JP 9770293 A JP9770293 A JP 9770293A JP 3541396 B2 JP3541396 B2 JP 3541396B2
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- Japan
- Prior art keywords
- nitrosodiphenylamine
- aminodiphenylamine
- activated carbon
- catalyst
- salt
- 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 - Fee Related
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
【０００１】
【産業上の利用分野】
本発明は、４−アミノジフェニルアミンの製造方法に関する。詳しくは４−ニトロソジフェニルアミン、４−ニトロソジフェニルアミンのアルカリ金属塩又は４−ニトロソジフェニルアミンのテトラアルキルアンモニウム塩（以下、４−ニトロソジフェニルアミン類と称する）を水添触媒の存在下に水添して４−アミノジフェニルアミンを製造する方法の改良に関する。
本発明により得られる４−アミノジフェニルアミンはゴム製品に使用される酸化防止剤、抗オゾン剤の製造に、また染料の中間体として有用な化合物である。
【０００２】
【従来の技術】
従来、４−アミノジフェニルアミンの製造方法としては、４−ニトロソジフェニルアミンのアルカリ金属塩水溶液を通常の水添触媒の存在下に水添して製造されている。例えば特開昭６１−１７１４５４号にはパラジウム触媒の存在下に水添を行うことが、米国特許第４３１３００２号には芳香族炭化水素及び飽和脂肪族アルコール中でパラジウム触媒の存在下に水添を行うことが、また特開昭５０−７７３２７号には４−ニトロソジフェニルアミンをラネー・ニッケル触媒の存在下に水添を行うことが開示されている。
【０００３】
【発明が解決しようとする課題】
これらの方法は、非常に高価な水添触媒を使用するために、１回の反応に使用する量をできるだけ低減させるか、又は再使用することが必要である。しかしながら、使用量が少ないと収率が低下し、再使用する場合でも使用回数が多くなると触媒が被毒されるために収率が著しく低下する。
【０００４】
【課題を解決するための手段】
本発明者らは、４−ニトロソジフェニルアミン類から、触媒の活性低下を防ぎ、収率良く４−アミノジフェニルアミンを製造する方法について鋭意検討した結果、水添触媒と共に活性炭を共存させることにより触媒量を低減させることができ、しかも再使用した際に水添触媒の活性低下をできるだけ防ぎ、収率良く４−アミノジフェニルアミンを製造することができることを見い出し、本発明に達した。
【０００５】
すなわち本発明は、４−ニトロソジフェニルアミン類を水添触媒の存在下に水添して４−アミノジフェニルアミンを製造する方法において、活性炭の共存下に反応させることを特徴とする４−アミノジフェニルアミンの製造方法である。
【０００６】
以下本発明の構成を詳細に説明する。
本発明における４−ニトロソジフェニルアミンのアルカリ金属塩としては、ナトリウム塩、カリウム塩が挙げられる。
【０００７】
４−ニトロソジフェニルアミンのテトラアルキルアンモニウム塩としては、テトラメチルアンモニウム塩、テトラエチルアンモニウム塩が挙げられる。
【０００８】
本反応において、溶媒として水、又は水と水に不溶な溶媒の混合溶媒が用いられる。特に、水と水に不溶な溶媒の混合溶媒を使用した場合は、生成する４−アミノジフェニルアミンは水に不溶な溶媒中に溶解するため、抽出操作が不必要となる。水に不溶な溶媒として、ベンゼン、トルエン、キシレン等の芳香族炭化水素類、ブタノール、ヘキサノール、オクタノール、２−エチルヘキサノール等の高級アルコール類が挙げられる。
【０００９】
本反応において使用される水添触媒としては、通常の水添反応に用いられるパラジウム触媒、白金触媒等が挙げられる。これらの触媒は通常、活性炭にパラジウム又は白金が約１〜５重量％担持されている（以下、Ｐｄ／Ｃ、Ｐｔ／Ｃと略記する）。触媒は原料である４−ニトロソジフェニルアミン類に対し、有姿で約０．０１〜１０重量％、好ましくは約０．０５〜１重量％用いられる。これより少ないと水添速度が著しく低下し、多くてもそれに見合った効果は得られない。
【００１０】
本反応において、活性炭は通常、粉末活性炭が用いられるが、特に制限されるものではない。含水品でも問題なく使用できる。活性炭は原料である４−ニトロソジフェニルアミン類に対し、約０．１〜１０重量％、好ましくは約１〜５重量％用いられる。これより少ないと活性炭の添加効果は十分に発揮されず、多くてもそれに見合った効果は得られない。
【００１１】
触媒量が少ない場合、初回反応における活性炭の効果は大きいが、触媒量が
多い場合はほとんどない。しかし、触媒を再使用する場合は、活性炭の添加効果は非常に大きい。
【００１２】
反応温度は約０〜１００℃、好ましくは約３０〜８０℃である。この温度以下では反応速度が著しく低下し、この温度以上では原料である４−ニトロソジフェニルアミンの分解反応が並行して起こり、収率の低下を招くので好ましくない。
【００１３】
水素ガスによる水添圧力は、約５〜５０kg／cm2 G 、好ましくは約８〜３０kg／cm2 G の範囲である。この圧力以下では水添が起こらず、この圧力以上であってもそれに見合った効果は得られない。
【００１４】
反応時間は、使用する水素圧、触媒量および反応温度により変わるが、通常０．５〜１０時間の範囲である。
【００１５】
本発明における、反応方法は回分反応でも連続反応でも良い。連続反応において触媒および活性炭の供給方法は、原料である４−ニトロソジフェニルアミン類の水溶液に所定量混合して供給するか、又は原料とは別に、溶媒と混合して供給してもよい。
【００１６】
【発明の効果】
本発明によれば、水添触媒の使用量を低減することができ、また再使用した際に、触媒活性の低下を極力おさえることができる。
【００１７】
【実施例】
以下、実施例により本発明を更に説明するが、本発明はこれらに限定されるものではない。
【００１８】
実施例１
０．５リットルのオートクレーブに４−ニトロソジフェミルアミンのナトリウム塩水溶液３００ｇ（４−ニトロソジフェニルアミンとして３０ｇ、０．１５ｍｏｌ）、トルエン５０ｇ、Ｐｄ／Ｃ（Ｐｄ担持量：５％）触媒（５０％含水品）０．０５ｇ、活性炭０．５ｇを仕込み、水素圧を１０kg／cm2 G と成るよう水素を充填し、７０℃において、３時間反応を行った。反応終了後、４−アミノジフェニルアミンが２３ｇ（収率８３％）得られた。
【００１９】
実施例２
０．５リットルのオートクレーブに４−ニトロソジフェニルアミンのナトリウム塩水溶液３００ｇ（４−ニトロソジフェニルアミンとして３０ｇ、０．１５ｍｏｌ）、トルエン５０ｇ、Ｐｄ／Ｃ（Ｐｄ担持量：５％）触媒（５０％含水品）０．１５ｇ、粉末活性炭（二村化学工業製、太閤活性炭Ａ）１ｇを仕込み、水素圧を１０kg／cm2 G と成るよう水素を充填し、７０℃において、３時間反応を行った。反応終了後、４−アミノジフェニルアミンが２５ｇ（収率９１％）得られた。
【００２０】
本反応において使用したＰｄ／Ｃ触媒、活性炭を濾過して回収し、回収触媒を用いて上記と同様にして反応を繰り返した。その結果を表１に示す。
【００２１】
【表１】
比較例１
活性炭０．５ｇを仕込まなかった以外は実施例１と同様にして反応を行った。反応終了後、４−アミノジフェニルアミン１５ｇ（収率５４％）、アニリン２ｇ（収率１４％）が得られ、４−ニトロソジフェニルアミンが３２％未反応であった。
【００２３】
比較例２
活性炭１ｇを加えなかった以外は実施例２と同様にして行った。その結果を表２に示す。
【００２４】
【表２】
[Industrial applications]
The present invention relates to a method for producing 4-aminodiphenylamine. Specifically, 4-nitrosodiphenylamine, an alkali metal salt of 4-nitrosodiphenylamine or a tetraalkylammonium salt of 4-nitrosodiphenylamine (hereinafter referred to as 4-nitrosodiphenylamines) is hydrogenated in the presence of a hydrogenation catalyst to form 4-nitrosodiphenylamine. The present invention relates to an improvement in a method for producing aminodiphenylamine.
The 4-aminodiphenylamine obtained according to the present invention is a compound useful for producing antioxidants and antiozonants used in rubber products and as an intermediate for dyes.
[0002]
[Prior art]
Conventionally, 4-aminodiphenylamine is produced by hydrogenating an aqueous solution of an alkali metal salt of 4-nitrosodiphenylamine in the presence of a normal hydrogenation catalyst. For example, JP-A-61-171454 discloses that hydrogenation is carried out in the presence of a palladium catalyst. US Pat. No. 4,331,002 discloses that hydrogenation is carried out in the presence of a palladium catalyst in an aromatic hydrocarbon and a saturated aliphatic alcohol. JP-A-50-77327 discloses that 4-nitrosodiphenylamine is hydrogenated in the presence of a Raney nickel catalyst.
[0003]
[Problems to be solved by the invention]
Since these methods use a very expensive hydrogenation catalyst, it is necessary to reduce the amount used in one reaction as much as possible or to reuse it. However, if the amount used is small, the yield decreases, and even if it is reused, if the number of uses increases, the catalyst is poisoned and the yield decreases significantly.
[0004]
[Means for Solving the Problems]
The present inventors have conducted intensive studies on a method for producing 4-aminodiphenylamine with a high yield by preventing the activity of the catalyst from 4-nitrosodiphenylamines, and as a result, the amount of the catalyst was reduced by coexisting activated carbon with the hydrogenation catalyst. The present inventors have found that 4-aminodiphenylamine can be produced with a high yield while reducing the activity of the hydrogenation catalyst as much as possible when reused, thereby achieving the present invention.
[0005]
That is, the present invention provides a method for producing 4-aminodiphenylamine by hydrogenating 4-nitrosodiphenylamines in the presence of a hydrogenation catalyst, wherein the reaction is carried out in the presence of activated carbon. Is the way.
[0006]
Hereinafter, the configuration of the present invention will be described in detail.
Examples of the alkali metal salt of 4-nitrosodiphenylamine in the present invention include a sodium salt and a potassium salt.
[0007]
Examples of the tetraalkylammonium salt of 4-nitrosodiphenylamine include a tetramethylammonium salt and a tetraethylammonium salt.
[0008]
In this reaction, water or a mixed solvent of water and a solvent insoluble in water is used as the solvent. In particular, when a mixed solvent of water and a solvent insoluble in water is used, the resulting 4-aminodiphenylamine is dissolved in the solvent insoluble in water, so that an extraction operation is unnecessary. Examples of the solvent insoluble in water include aromatic hydrocarbons such as benzene, toluene, and xylene, and higher alcohols such as butanol, hexanol, octanol, and 2-ethylhexanol.
[0009]
Examples of the hydrogenation catalyst used in this reaction include palladium catalysts and platinum catalysts used in ordinary hydrogenation reactions. In these catalysts, about 1 to 5% by weight of palladium or platinum is usually supported on activated carbon (hereinafter abbreviated as Pd / C or Pt / C). The catalyst is used in an amount of about 0.01 to 10% by weight, preferably about 0.05 to 1% by weight, based on the raw material, 4-nitrosodiphenylamines. If the amount is less than this, the hydrogenation rate is remarkably reduced, and even if it is too large, the effect corresponding thereto cannot be obtained.
[0010]
In this reaction, powdered activated carbon is usually used as activated carbon, but is not particularly limited. Even hydrous products can be used without any problems. Activated carbon is used in an amount of about 0.1 to 10% by weight, preferably about 1 to 5% by weight, based on the starting material, 4-nitrosodiphenylamines. If the amount is less than this, the effect of adding activated carbon is not sufficiently exhibited, and even if the amount is too large, the effect corresponding thereto cannot be obtained.
[0011]
When the amount of catalyst is small, the effect of activated carbon in the initial reaction is large, but when the amount of catalyst is large, there is almost no effect. However, when the catalyst is reused, the effect of adding activated carbon is very large.
[0012]
The reaction temperature is about 0-100 ° C, preferably about 30-80 ° C. If the temperature is lower than this temperature, the reaction rate is remarkably reduced, and if the temperature is higher than this temperature, the decomposition reaction of the raw material 4-nitrosodiphenylamine occurs in parallel, which is not preferable because the yield is reduced.
[0013]
The hydrogenation pressure with hydrogen gas is in the range of about 5 to 50 kg / cm 2 G, preferably about 8 to 30 kg / cm 2 G. Hydrogenation does not occur below this pressure, and the effect corresponding thereto cannot be obtained even above this pressure.
[0014]
The reaction time varies depending on the hydrogen pressure used, the amount of the catalyst and the reaction temperature, but is usually in the range of 0.5 to 10 hours.
[0015]
The reaction method in the present invention may be a batch reaction or a continuous reaction. In the continuous reaction, the catalyst and the activated carbon may be supplied by mixing a predetermined amount with an aqueous solution of 4-nitrosodiphenylamines, which is a raw material, or by mixing with a solvent separately from the raw material.
[0016]
【The invention's effect】
ADVANTAGE OF THE INVENTION According to this invention, the usage-amount of a hydrogenation catalyst can be reduced, and when it reuses, a fall of a catalyst activity can be suppressed as much as possible.
[0017]
【Example】
Hereinafter, the present invention will be further described with reference to examples, but the present invention is not limited thereto.
[0018]
Example 1
In a 0.5 liter autoclave, 300 g of an aqueous solution of sodium salt of 4-nitrosodiphemilamine (30 g as 4-nitrosodiphenylamine, 0.15 mol), 50 g of toluene, Pd / C (Pd loading: 5%) catalyst (50% water content) (Product) 0.05 g and activated carbon 0.5 g were charged, hydrogen was charged to a hydrogen pressure of 10 kg / cm 2 G, and a reaction was carried out at 70 ° C. for 3 hours. After completion of the reaction, 23 g (yield 83%) of 4-aminodiphenylamine was obtained.
[0019]
Example 2
In a 0.5 liter autoclave, 300 g of aqueous solution of sodium salt of 4-nitrosodiphenylamine (30 g as 4-nitrosodiphenylamine, 0.15 mol), 50 g of toluene, Pd / C (Pd loading: 5%) catalyst (50% water-containing product) 0.15 g and 1 g of powdered activated carbon (Taiko activated carbon A, manufactured by Nimura Chemical Industry Co., Ltd.) were charged, charged with hydrogen to a hydrogen pressure of 10 kg / cm 2 G, and reacted at 70 ° C. for 3 hours. After the completion of the reaction, 25 g (yield 91%) of 4-aminodiphenylamine was obtained.
[0020]
The Pd / C catalyst and activated carbon used in this reaction were recovered by filtration, and the reaction was repeated in the same manner as described above using the recovered catalyst. Table 1 shows the results.
[0021]
[Table 1]
Comparative Example 1
The reaction was carried out in the same manner as in Example 1 except that 0.5 g of activated carbon was not charged. After completion of the reaction, 15 g (yield 54%) of 4-aminodiphenylamine and 2 g (yield 14%) of aniline were obtained, and 32-nitrosodiphenylamine was 32% unreacted.
[0023]
Comparative Example 2
The procedure was performed in the same manner as in Example 2 except that 1 g of activated carbon was not added. Table 2 shows the results.
[0024]
[Table 2]
Claims (4)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP09770293A JP3541396B2 (en) | 1993-04-23 | 1993-04-23 | Method for producing 4-aminodiphenylamine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP09770293A JP3541396B2 (en) | 1993-04-23 | 1993-04-23 | Method for producing 4-aminodiphenylamine |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06306021A JPH06306021A (en) | 1994-11-01 |
| JP3541396B2 true JP3541396B2 (en) | 2004-07-07 |
Family
ID=14199262
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP09770293A Expired - Fee Related JP3541396B2 (en) | 1993-04-23 | 1993-04-23 | Method for producing 4-aminodiphenylamine |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3541396B2 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4500302B2 (en) | 2003-07-04 | 2010-07-14 | チアンス・シノケム・テクノロジー・カンパニー・リミテッド | Method for producing 4-aminodiphenylamine |
| ATE526305T1 (en) | 2003-07-04 | 2011-10-15 | Jiangsu Sinorgchem Tech Co Ltd | METHOD FOR PRODUCING 4-AMINODIPHENYLAMINE |
| US8486223B2 (en) | 2003-07-04 | 2013-07-16 | Jiangsu Sinorgchem Technology Co., Ltd. | Falling film evaporator |
| US8686188B2 (en) | 2003-07-04 | 2014-04-01 | Jiangsu Sinorgchem Technology Co., Ltd. | Process for preparing 4-aminodiphenylamine |
| CN102259029B (en) | 2010-05-24 | 2014-12-10 | 江苏圣奥化学科技有限公司 | Solid alkali catalyst |
-
1993
- 1993-04-23 JP JP09770293A patent/JP3541396B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH06306021A (en) | 1994-11-01 |
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