JPS5854144B2 - Method for producing 3,4,5,6-tetrahydrophthalic anhydride - Google Patents
Method for producing 3,4,5,6-tetrahydrophthalic anhydrideInfo
- Publication number
- JPS5854144B2 JPS5854144B2 JP52130090A JP13009077A JPS5854144B2 JP S5854144 B2 JPS5854144 B2 JP S5854144B2 JP 52130090 A JP52130090 A JP 52130090A JP 13009077 A JP13009077 A JP 13009077A JP S5854144 B2 JPS5854144 B2 JP S5854144B2
- Authority
- JP
- Japan
- Prior art keywords
- mono
- thpa
- reaction
- producing
- tetrahydrophthalic anhydride
- 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
Links
Classifications
-
- 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
Landscapes
- Furan Compounds (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
【発明の詳細な説明】
本発明は１・２・３・６−テトラヒドロ無水フタル酸（
以下「△’−ＴＨＰＡＪと略す）の異性化により高純度
の３・４・５・６−チトラヒド□無水フタル酸（以下「
△’−ＴＨＰＡＪ と略す）を製造する方法に関する
ものであり、詳しくはパラジウム触媒及び塩基性化合物
の存在下に△４−ＴＨＰＡを異性化反応し好収率で△’
−ＴＨＰＡを得んとする方法である。DETAILED DESCRIPTION OF THE INVENTION The present invention provides 1,2,3,6-tetrahydrophthalic anhydride (
By isomerizing 3,4,5,6-titrahydro□phthalic anhydride (hereinafter abbreviated as ``△'-THPAJ'')
This article relates to a method for producing Δ4-THPA (abbreviated as Δ'-THPAJ), and in detail, Δ4-THPA is isomerized in the presence of a palladium catalyst and a basic compound to produce Δ' in good yield.
- This is a method for obtaining THPA.
△１−ＴＨＰＡは主として農薬原料、エポキシ樹脂硬化
剤、ポリエステル原料等として有用であるが一般には、
Δ’−ＴＨＰＡの異性化反応により得られている。△1-THPA is mainly useful as a raw material for agricultural chemicals, an epoxy resin curing agent, a raw material for polyester, etc., but in general,
It is obtained by isomerization reaction of Δ'-THPA.
異性化反応は従来様々の方法が提案されておるが、収率
、純度などの点で満足すべき方法がなかった。Various methods have been proposed for the isomerization reaction, but none of them has been satisfactory in terms of yield, purity, etc.
例えば、五酸化リン、リン酸、硫酸等の無機強酸を触媒
として、１５０〜２２０℃の反応温度の場合、反応時に
原料が著しく酸化され△”−ＴＨＰＡの収率が対原料で
４０〜６０％しか得られない。For example, when a strong inorganic acid such as phosphorus pentoxide, phosphoric acid, or sulfuric acid is used as a catalyst and the reaction temperature is 150 to 220°C, the raw material is significantly oxidized during the reaction, resulting in a yield of △”-THPA of 40 to 60% based on the raw material. I can only get it.
又、パラジウムを触媒とする方法も公知であるが、これ
も反応時に多量のへキサヒドロ無水フタル酸や無水フタ
ル酸が副生じ、高純度の目的物を得ることは困難である
。A method using palladium as a catalyst is also known, but this also produces a large amount of hexahydrophthalic anhydride or phthalic anhydride as a by-product during the reaction, making it difficult to obtain a highly pure target product.
これら公知の方法で、品質の良好な目的物を得るには、
反応後、さらに蒸留、再結晶等の精製手段によらねばな
らず、工程の増加やコストの上昇により、工業的製造に
は不適である。In order to obtain a target product of good quality using these known methods,
After the reaction, purification methods such as distillation and recrystallization must be carried out, which increases the number of steps and costs, making it unsuitable for industrial production.
又、反応時の収率が極端に悪い場合は実質上精製方法が
採用できないこともあり得る。Furthermore, if the yield during the reaction is extremely poor, the purification method may not be practically applicable.
本発明者はパラジウムが二重結合の異性化触媒に有効で
あること、副生ずる無水フタル酸、ヘキサヒドロ無水フ
タル酸はパラジウムによる脱水素反応及び水添反応に基
因することに着目しく以下「不均化反応」という）、鋭
意検討の結果パラジウムを触媒とする反応系に塩基性化
合物を少量添加することにより、この不均化反応が抑制
されて副生物を生成せず、好収率、高純度のΔ１−ＴＨ
ＰＡが得られる方法を発明したのである。The present inventor focused on the fact that palladium is effective as a double bond isomerization catalyst, and that the by-product phthalic anhydride and hexahydrophthalic anhydride are caused by dehydrogenation and hydrogenation reactions by palladium. As a result of extensive research, by adding a small amount of a basic compound to the reaction system using palladium as a catalyst, this disproportionation reaction is suppressed and no by-products are produced, resulting in good yields and high purity. Δ1-TH
He invented a method to obtain PA.
パラジウム触媒は金属単独よりも、アルミナ、カーボン
、シリカアスベスト等の担体にパラジウムとして０．１
〜１０％、好ましくは１〜５％担持させたものが使用さ
れる。Palladium catalysts are made by adding 0.1% palladium to a carrier such as alumina, carbon, or silica asbestos, rather than using a metal alone.
-10%, preferably 1-5% is used.
塩基性化合物としては、無機、有機の塩基性化合物及び
弱酸と強塩基よりなる塩の内より選ばれた化合物が適用
され、代表的には、アルカリ金属、アルカリ土類金属の
水酸化物、アンモニア化合物、無機弱酸と強塩基との塩
、有機カルボン酸の強アルカリ塩、有機アミン等があげ
られる。As the basic compound, compounds selected from inorganic and organic basic compounds and salts made of weak acids and strong bases are used, and typical examples include hydroxides of alkali metals and alkaline earth metals, and ammonia. Examples include compounds, salts of inorganic weak acids and strong bases, strong alkali salts of organic carboxylic acids, and organic amines.
塩基性化合物の具体的な例としては、カセイソーダ、カ
セイカリ、水酸化マグネシウム、水酸化カルシウム、ア
ンモニア水、炭酸水素カリウム、炭酸水素ナトリウム、
炭酸カリウム又はナトリウム、フタル酸モノ又はジカリ
ウム、フタル酸モノ又はジナトリウム、テトラヒドロフ
タル酸モノ又はジカリウム、テトラヒドロフタル酸モノ
又はジナトリウム、コハク酸モノ又はジカリウム、コハ
ク酸モノ又はジナトリウム、アジピン酸モノ又はジカリ
ウム、アジピン酸モノ又はジナトリウム、酢酸カリウム
又はナトリウム、酪酸カリウム又はナトリウム、オクチ
ル酸カリウム又はナトリウムステアリン酸カリウム又は
ナトリウム、オレイン酸カリウム又はナトリウム、モノ
、ジ又はトリメチルアミン、モノ、ジ又はトリエチルア
ミン、モノ、ジ又はトリラウリルアミン、モノ、ジ又は
トリステアリルアミン、ジメチルブチルアミン、ジメチ
ルラウリルアミン、ジメチルステアリルアミン、シクロ
ヘキシルアミン、ジシクロヘキシルアミン、Ｎ−Ｎ−ジ
メチルシクロヘキシルアミン、Ｎ−メチルシクロヘキシ
ルアミン、４・４′−ジアミノジシクロヘキシルメタン
、４・４′−ジアミノジシクロヘキシルプロパン、アニ
リン、Ｎ−メチルアニリン、Ｎ−Ｎ−ジメチルアニリン
、ジフェニルアミン、トルイジン、キシリジン、ナフチ
ルアミン、アミノフェノール、ベンジルアミン、ジ＊メ
チルベンジルアミン、１・３・５−トリスジメチル、ア
ミノメチルフェノール、ピリジン、ピラジン、ピペリジ
ン、ピペラジン、キノリン、モルホリン等があげられる
。Specific examples of basic compounds include caustic soda, caustic potash, magnesium hydroxide, calcium hydroxide, aqueous ammonia, potassium hydrogen carbonate, sodium hydrogen carbonate,
Potassium or sodium carbonate, mono- or dipotassium phthalate, mono- or disodium phthalate, mono- or dipotassium tetrahydrophthalate, mono- or disodium tetrahydrophthalate, mono- or dipotassium succinate, mono- or disodium succinate, mono- or adipic acid Dipotassium, mono- or disodium adipate, potassium or sodium acetate, potassium or sodium butyrate, potassium or sodium octylate, potassium or sodium stearate, potassium or sodium oleate, mono-, di- or trimethylamine, mono-, di- or triethylamine, mono, Di- or trilaurylamine, mono-, di- or tristearylamine, dimethylbutylamine, dimethyllaurylamine, dimethylstearylamine, cyclohexylamine, dicyclohexylamine, N-N-dimethylcyclohexylamine, N-methylcyclohexylamine, 4,4'-diamino Dicyclohexylmethane, 4,4'-diaminodicyclohexylpropane, aniline, N-methylaniline, N-N-dimethylaniline, diphenylamine, toluidine, xylidine, naphthylamine, aminophenol, benzylamine, di*methylbenzylamine, 1.3. Examples include 5-trisdimethyl, aminomethylphenol, pyridine, pyrazine, piperidine, piperazine, quinoline, and morpholine.
本発明の実施態様は原料△’−ＴＨＰＡ １００部に
対しパラジウム（純分換算）を０．００２〜０．０５部
、塩基性化合物を０．０４〜７部の割合で配合し、かく
拌機、還流冷却器、チッ素ガス導入口のついた反応器に
おいて好ましくはチッ素ガス雰囲気下、１３０〜２３０
℃、好ましくは１５０〜２００℃で、３〜１２時間、反
応を行なうと、△１−ＴＨＰＡを９４〜９９％含有する
反応物が得られる。In an embodiment of the present invention, palladium (purity equivalent) is blended at a ratio of 0.002 to 0.05 parts and a basic compound is blended in a ratio of 0.04 to 7 parts to 100 parts of raw material Δ'-THPA. , preferably in a nitrogen gas atmosphere in a reactor equipped with a reflux condenser and a nitrogen gas inlet, 130 to 230
C., preferably 150-200.degree. C. for 3-12 hours, a reaction product containing 94-99% Δ1-THPA is obtained.
これを沢過又は傾瀉法で触媒を分離し、このまま製品と
して使用することができる。The catalyst can be separated from this by filtration or decanting, and the product can be used as it is as a product.
さらに必要とする場合は、蒸留等により、より高純度の
△”−ＴＨＰＡ を得ることができる。If further required, higher purity Δ''-THPA can be obtained by distillation or the like.
かくの如く、本発明は、経済的、工業的にすぐれたΔ’
−ＴＨＰＡの製造方法である。As described above, the present invention provides an economically and industrially excellent Δ'
- A method for producing THPA.
実施例 １１
原料△’−ＴＨＰＡ １００部に対してパラジウム（純
分換算）０．００３部、炭酸水素ナトリウム０．２部の
割合で配合し、攪拌器、還流冷却器のついた反応器にお
いて空気中で１８０℃、９時間反応を行なうと△’−Ｔ
ＨＰＡを９５％含有する反応物が９５％の収率で得られ
た。Example 11 100 parts of raw material △'-THPA was mixed with 0.003 parts of palladium (purity equivalent) and 0.2 parts of sodium hydrogen carbonate, and air was added in a reactor equipped with a stirrer and a reflux condenser. When the reaction is carried out for 9 hours at 180℃ in
A reaction product containing 95% HPA was obtained in 95% yield.
Claims (1)
・３・６−テトラヒドロ無水フタル酸を異性化すること
を特徴とする３・４・５・６−テトラヒドロ無水フタル
酸の製造方法。1 1・2 in the presence of a palladium catalyst and a basic compound
- A method for producing 3,4,5,6-tetrahydrophthalic anhydride, which comprises isomerizing 3,6-tetrahydrophthalic anhydride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP52130090A JPS5854144B2 (en) | 1977-10-29 | 1977-10-29 | Method for producing 3,4,5,6-tetrahydrophthalic anhydride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP52130090A JPS5854144B2 (en) | 1977-10-29 | 1977-10-29 | Method for producing 3,4,5,6-tetrahydrophthalic anhydride |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5463053A JPS5463053A (en) | 1979-05-21 |
| JPS5854144B2 true JPS5854144B2 (en) | 1983-12-02 |
Family
ID=15025722
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP52130090A Expired JPS5854144B2 (en) | 1977-10-29 | 1977-10-29 | Method for producing 3,4,5,6-tetrahydrophthalic anhydride |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5854144B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2948414C2 (en) * | 1979-12-01 | 1985-10-17 | New Japan Chemical Co. Ltd., Kyoto | Process for the preparation of 3,4,5,6-tetrahydrophthalic anhydrides and their derivatives |
| JP2533391B2 (en) * | 1989-12-15 | 1996-09-11 | 新日本理化株式会社 | Method for purifying 3,4,5,6-tetrahydrophthalic anhydride |
-
1977
- 1977-10-29 JP JP52130090A patent/JPS5854144B2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5463053A (en) | 1979-05-21 |
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