JPH031313B2 - - Google Patents
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- Publication number
- JPH031313B2 JPH031313B2 JP56206079A JP20607981A JPH031313B2 JP H031313 B2 JPH031313 B2 JP H031313B2 JP 56206079 A JP56206079 A JP 56206079A JP 20607981 A JP20607981 A JP 20607981A JP H031313 B2 JPH031313 B2 JP H031313B2
- Authority
- JP
- Japan
- Prior art keywords
- tca
- anhydride
- acid
- present
- 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
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- 150000008064 anhydrides Chemical class 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 10
- 150000008065 acid anhydrides Chemical class 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 150000000000 tetracarboxylic acids Chemical class 0.000 claims description 4
- RHRNYXVSZLSRRP-UHFFFAOYSA-N 3-(carboxymethyl)cyclopentane-1,2,4-tricarboxylic acid Chemical compound OC(=O)CC1C(C(O)=O)CC(C(O)=O)C1C(O)=O RHRNYXVSZLSRRP-UHFFFAOYSA-N 0.000 claims 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 10
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 9
- 239000000843 powder Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 6
- 238000000862 absorption spectrum Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- 239000004642 Polyimide Substances 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000004811 liquid chromatography Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 229920001721 polyimide Polymers 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 2
- 239000012346 acetyl chloride Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- YHASWHZGWUONAO-UHFFFAOYSA-N butanoyl butanoate Chemical compound CCCC(=O)OC(=O)CCC YHASWHZGWUONAO-UHFFFAOYSA-N 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 2
- XNLICIUVMPYHGG-UHFFFAOYSA-N pentan-2-one Chemical compound CCCC(C)=O XNLICIUVMPYHGG-UHFFFAOYSA-N 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- WYVAMUWZEOHJOQ-UHFFFAOYSA-N propionic anhydride Chemical compound CCC(=O)OC(=O)CC WYVAMUWZEOHJOQ-UHFFFAOYSA-N 0.000 description 2
- -1 tetracarboxylic anhydrides Chemical class 0.000 description 2
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- BPIUIOXAFBGMNB-UHFFFAOYSA-N 1-hexoxyhexane Chemical compound CCCCCCOCCCCCC BPIUIOXAFBGMNB-UHFFFAOYSA-N 0.000 description 1
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 1
- PTTPXKJBFFKCEK-UHFFFAOYSA-N 2-Methyl-4-heptanone Chemical compound CC(C)CC(=O)CC(C)C PTTPXKJBFFKCEK-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004962 Polyamide-imide Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- VANNPISTIUFMLH-UHFFFAOYSA-N glutaric anhydride Chemical compound O=C1CCCC(=O)O1 VANNPISTIUFMLH-UHFFFAOYSA-N 0.000 description 1
- NGAZZOYFWWSOGK-UHFFFAOYSA-N heptan-3-one Chemical compound CCCCC(=O)CC NGAZZOYFWWSOGK-UHFFFAOYSA-N 0.000 description 1
- 230000000887 hydrating effect Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000006385 ozonation reaction Methods 0.000 description 1
- 229920005575 poly(amic acid) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- ULIAPOFMBCCSPE-UHFFFAOYSA-N tridecan-7-one Chemical compound CCCCCCC(=O)CCCCCC ULIAPOFMBCCSPE-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Furan Compounds (AREA)
- Pyrane Compounds (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Description
【発明の詳細な説明】
本発明はテトラカルボン酸無水物、特に２，
３，５−トリカルボキシ−シクロペンタン−アセ
チツクアシツド（以下「TCA」と記す。）の無水
物を製造する方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to tetracarboxylic anhydrides, particularly 2,
The present invention relates to a method for producing an anhydride of 3,5-tricarboxy-cyclopentane-acetic acid (hereinafter referred to as "TCA").
一般にテトラカルボン酸は、ポリアミド又はポ
リイミドの原料として、またエポキシ樹脂の硬化
剤、その他として有用であり、具体的にはピロメ
リツト酸等の芳香族テトラカルボン酸、ブタンテ
トラカルボン酸等の脂肪族テトラカルボン酸がよ
く知られている。 In general, tetracarboxylic acids are useful as raw materials for polyamides or polyimides, curing agents for epoxy resins, and other uses. Acid is well known.
斯かるテトラカルボン酸の１種にTCAがあり、
これは次の構造式で示される環状脂肪族テトラカ
ルボン酸である。 One type of such tetracarboxylic acid is TCA,
This is a cycloaliphatic tetracarboxylic acid represented by the following structural formula.
このTCAは、工業的に安価に得られるジシク
ロペンタジエンをオゾン分解し、更に過酸化水素
により酸化する方法（英国特許第872355号明細書
又はジヤーナル オブ オーガニツク ケミスト
リー（J.Org.Chen.）第28巻10号2537〜2541頁
（1963年）参照）、又はジシクロペンタジエンを水
和して得られるヒドロキシ−ジシクロペンタジエ
ンを硝酸酸化する方法（ドイツ特許第1078120号
明細書参照）、その他の方法によつて得ることが
できる。 This TCA is produced by a method in which dicyclopentadiene, which can be obtained industrially at low cost, is decomposed by ozonation and further oxidized with hydrogen peroxide (British Patent No. 872355 or Journal of Organic Chemistry (J.Org.Chen.) No. 28). Vol. 10, pp. 2537-2541 (1963)), a method of oxidizing hydroxy-dicyclopentadiene obtained by hydrating dicyclopentadiene with nitric acid (see German Patent No. 1078120), and other methods. You can get it by twisting it.
このTCAは、そのままで、ポリアミド又はポ
リイミドの原料として、またエポキシ樹脂の硬化
剤等として充分に使用し得るものではあるが、或
る種の用途に供する場合、例えば有機ジアミンと
の反応によりポリイミドの前駆体であるポリアミ
ド酸を製造する場合には、TCAそのものでなく
その無水物を用いたときの方がより高い重合度の
ものが得られる等の利点があり、このため、
TCAの無水物を高い効率で製造し得る方法の開
発が望まれていた。 Although this TCA can be fully used as it is as a raw material for polyamide or polyimide or as a curing agent for epoxy resins, when used for certain purposes, for example, it can be used as a raw material for polyimide by reacting with organic diamines. When producing polyamic acid as a precursor, there are advantages such as a higher degree of polymerization when using TCA's anhydride rather than TCA itself, and for this reason,
It has been desired to develop a method for producing anhydrous TCA with high efficiency.
TCAの無水物の製造方法については、ドイツ
特許第1078120号明細書に記載があり、それは、
TCAとアセチルクロライドを室温で撹拌しなが
ら３〜５週間の間反応を行ない、その後真空乾燥
し、更にアセチルクロライドを小量加えて過
し、ベンゼンにより洗浄する方法であつて融点
170〜172℃のものが得られるが、この方法は非常
に長い反応時間を必要とする上収率も約40％と低
く、従つて非常に効率が低く、しかも生成物の純
度が低い欠点がある。 The method for producing anhydrous TCA is described in German Patent No. 1078120, which is
This is a method in which TCA and acetyl chloride are reacted for 3 to 5 weeks with stirring at room temperature, then vacuum dried, a small amount of acetyl chloride is added, filtered, and washed with benzene.
170-172℃, but this method requires a very long reaction time and has a low yield of about 40%, resulting in very low efficiency and low product purity. be.
本発明者らは、以上の如き事情に基き、鋭意研
究を重ねた結果本発明を完成するに至つたもので
あり、本発明の目的は、高い反応効率でTCAの
無水物を製造することのできる方法を提供するに
ある。 Based on the above circumstances, the present inventors have completed the present invention as a result of intensive research.The purpose of the present invention is to produce anhydrous TCA with high reaction efficiency. We are here to provide you with a possible method.
本発明について詳細に説明すると、本発明にお
いては、TCAを酸無水物と有機溶媒中で反応せ
しめることにより、TCAの無水物を製造する。 To explain the present invention in detail, in the present invention, an anhydride of TCA is produced by reacting TCA with an acid anhydride in an organic solvent.
本発明において使用する酸無水物は、通常、有
機カルボン酸の無水物であり、無水酢酸、無水プ
ロピオン酸、無水酪酸、無水コハク酸、無水マレ
イン酸、無水グルタル酸、無水フタル酸などを例
示することができるが、好ましい有機カルボン酸
無水物は脂肪族カルボン酸の無水物、特に無水酢
酸、無水プロピオン酸、無水酪酸などの脂肪族モ
ノカルボン酸の無水物である。 The acid anhydride used in the present invention is usually an anhydride of an organic carboxylic acid, and examples include acetic anhydride, propionic anhydride, butyric anhydride, succinic anhydride, maleic anhydride, glutaric anhydride, and phthalic anhydride. However, preferred organic carboxylic acid anhydrides are anhydrides of aliphatic carboxylic acids, particularly anhydrides of aliphatic monocarboxylic acids such as acetic anhydride, propionic anhydride, butyric anhydride.
また本発明に好適に使用される有機溶媒として
は、それ自体が目標生成物であるTCAの無水物
を溶解しないものが好ましく、更に、使用される
酸無水物と相溶性の大きいものが好ましく、この
ような有機溶媒を使用することによつて高純度の
TCAの無水物を容易に得ることができる。この
ような有機溶媒としては、例えば芳香族炭化水素
類、ケトン類又はエーテル類があり、具体的に
は、ベンゼン、トルエン、キシレン、エチルベン
ゼン、イソプロピルベンゼン、メチルエチルケト
ン、メチルプロピルケトン、メチルイソブチルケ
トン、メチルヘキシルケトン、エチルブチルケト
ン、ジイソブチルケトン、エチルエーテル、イソ
プロピルエーテル、ブチルエーテル、ヘキシルエ
ーテル、その他を挙げることができる。 Further, as the organic solvent suitably used in the present invention, it is preferable that the organic solvent itself does not dissolve the anhydride of TCA, which is the target product, and furthermore, it is preferable that the organic solvent has high compatibility with the acid anhydride used. High purity can be obtained by using such organic solvents.
TCA anhydride can be easily obtained. Such organic solvents include, for example, aromatic hydrocarbons, ketones, or ethers, and specifically include benzene, toluene, xylene, ethylbenzene, isopropylbenzene, methyl ethyl ketone, methyl propyl ketone, methyl isobutyl ketone, methyl Mention may be made of hexyl ketone, ethyl butyl ketone, diisobutyl ketone, ethyl ether, isopropyl ether, butyl ether, hexyl ether, and others.
次に反応条件について説明する。使用すべき酸
無水物の量は、当該酸無水物によつて定量的に脱
水作用を行わしむるために、通常TCAのモル数
の２倍以上を使用するが、好ましくは２〜50倍モ
ル使用する。有機溶媒の量は、その種類によつて
も異なるが、好ましくは酸無水物の重量の0.1〜
10倍程度とされる。また、反応温度は好ましくは
20℃以上であり、実際上は還流しながら反応を行
なうようにすれば、一層高い反応効率が得られ
る。反応時間は、反応温度によつても異なるが、
還流温度で反応を実行する場合には、通常0.2〜
10時間である。上記反応によつて得られるTCA
の無水物は、通常２無水物であるが１無水物も得
ることができる。 Next, reaction conditions will be explained. The amount of acid anhydride to be used is usually at least twice the number of moles of TCA, preferably 2 to 50 times the number of moles of TCA, in order to quantitatively dehydrate the acid anhydride. use. The amount of organic solvent varies depending on the type, but is preferably 0.1 to 0.1 of the weight of the acid anhydride.
It is said to be about 10 times as large. Also, the reaction temperature is preferably
If the temperature is 20°C or higher and the reaction is actually carried out under reflux, even higher reaction efficiency can be obtained. The reaction time varies depending on the reaction temperature, but
When carrying out the reaction at reflux temperature, it is usually 0.2~
It is 10 hours. TCA obtained by the above reaction
The anhydride is usually dianhydride, but monoanhydride can also be obtained.
本発明は以上のような方法であるので、後述す
る実施例からも明かなように、目的とするTCA
の無水物を反応効率良く、即ち反応時間で、しか
も高い収率で確実に製造することができる。 Since the present invention is a method as described above, as will be clear from the examples described later, the target TCA
can be reliably produced with high reaction efficiency, that is, within a short reaction time, and in high yield.
次に本発明を実施例によつて具体的に説明する
が、本発明はこれらの実施例に限定されるもので
はない。 EXAMPLES Next, the present invention will be specifically explained using Examples, but the present invention is not limited to these Examples.
実施例 １
容量２のフラスコに、TCA100ｇ（0.385モ
ル）と無水酢酸500ｇ（4.90モル）及びトルエン
750ｇを仕込み、還流させながら３時間反応せし
め、その後反応液を温度20℃で48時間放置して晶
析を行ない、析出した結晶を別して取り出し、
トルエンにより洗浄した後、温度80℃で減圧乾燥
を行なつて、融点190℃の白色粉末65ｇを得た。
収率は75モル％である。Example 1 In a flask with a capacity of 2, 100 g (0.385 mol) of TCA, 500 g (4.90 mol) of acetic anhydride, and toluene were added.
Charge 750g and react for 3 hours while refluxing, then leave the reaction solution at a temperature of 20℃ for 48 hours to crystallize, separate the precipitated crystals, and take out.
After washing with toluene, it was dried under reduced pressure at a temperature of 80°C to obtain 65 g of white powder with a melting point of 190°C.
Yield is 75 mol%.
得られた白色粉末をテトラヒドロフランに溶解
せしめて液体クロマトグラフイーで調べたとこ
ろ、目的物であるTCAの２無水物に相当するピ
ーク以外の、原料であるTCA及びTCAの１無水
物のピークはトレースであり、この結果、高純度
のTCAの２無水物が得られていることが確認さ
れた。 When the obtained white powder was dissolved in tetrahydrofuran and examined by liquid chromatography, the peaks of the raw material TCA and TCA monoanhydride were traced, except for the peak corresponding to the target TCA dianhydride. As a result, it was confirmed that highly purified TCA dianhydride was obtained.
更に前述の白色粉末について赤外線吸収スペク
トルを測定した。そのチヤートを第１図に示す。
このチヤートにおいて、1770cm-1及び1820cm-1の
位置に酸無水物の−COによる吸収が認められる
一方、カルボン酸の−COによる1700cm-1での吸
収及び−OHによる3400cm-1付近での吸収が認め
られず、これらの分析からも当該白色粉末は
TCAの２無水物であることが確認された。 Furthermore, the infrared absorption spectrum of the above-mentioned white powder was measured. The chart is shown in Figure 1.
In this chart, absorption by -CO of acid anhydride is observed at positions of 1770 cm -1 and 1820 cm -1 , while absorption of carboxylic acid by -CO at 1700 cm -1 and absorption by -OH near 3400 cm -1 was not observed, and these analyzes also indicated that the white powder was
It was confirmed that it was TCA dianhydride.
実施例 ２
実施例１におけるトルエンの代りに、メチルイ
ソブチルケトンを有機溶媒として用いたほかは、
実施例１と同様の操作を行ない、融点188℃の白
色粉末47ｇを得た。収率は55モル％である。そし
て実施例１におけると同様に液体クロマトグラフ
イー及び赤外線吸収スペクトルによる分析の結
果、当該白色粉末はTCAの２無水物であること
が確認された。Example 2 Except that methyl isobutyl ketone was used as an organic solvent instead of toluene in Example 1,
The same operation as in Example 1 was carried out to obtain 47 g of white powder with a melting point of 188°C. Yield is 55 mol%. As a result of analysis by liquid chromatography and infrared absorption spectrum in the same manner as in Example 1, it was confirmed that the white powder was TCA dianhydride.
実施例 ３
実施例におけるトルエンの代りにイソプロピル
エーテル500ｇを有機溶媒として用いたほかは、
実施例１と同様の操作を行ない、融点189℃の白
色粉末53ｇを得た。収率は62モル％である。そし
て実施例１におけると同様に液体クロマトグラフ
イー及び赤外線吸収スペクトルによる分析の結
果、当該白色粉末はTCAの２無水物であること
が確認された。Example 3 Except that 500 g of isopropyl ether was used as an organic solvent instead of toluene in Example 3,
The same operation as in Example 1 was carried out to obtain 53 g of white powder with a melting point of 189°C. Yield is 62 mol%. As a result of analysis by liquid chromatography and infrared absorption spectrum in the same manner as in Example 1, it was confirmed that the white powder was TCA dianhydride.
第１図は、本発明の一実施例による生成物の赤
外線吸収スペクトルのチヤートである。
FIG. 1 is a chart of an infrared absorption spectrum of a product according to an embodiment of the present invention.
Claims (1)
ン−アセチツクアシツドを酸無水物と有機溶媒中
で反応せしめて２，３，５−トリカルボキシ−シ
クロペンタン−アセチツクアシツドの無水物を得
ることを特徴とするテトラカルボン酸無水物の製
造方法。1 Reacting 2,3,5-tricarboxy-cyclopentane-acetic acid with an acid anhydride in an organic solvent to obtain anhydride of 2,3,5-tricarboxy-cyclopentane-acetic acid. A method for producing a tetracarboxylic acid anhydride, characterized by:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56206079A JPS58109479A (en) | 1981-12-22 | 1981-12-22 | Preparation of tetracarboxylic acid anhydride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56206079A JPS58109479A (en) | 1981-12-22 | 1981-12-22 | Preparation of tetracarboxylic acid anhydride |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS58109479A JPS58109479A (en) | 1983-06-29 |
| JPH031313B2 true JPH031313B2 (en) | 1991-01-10 |
Family
ID=16517472
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP56206079A Granted JPS58109479A (en) | 1981-12-22 | 1981-12-22 | Preparation of tetracarboxylic acid anhydride |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS58109479A (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011131649A1 (en) | 2010-04-23 | 2011-10-27 | Rolic Ag | Photoaligning material |
| CN103702970B (en) | 2011-08-02 | 2018-10-19 | 罗利克有限公司 | photoalignment material |
| JP6525590B2 (en) | 2011-08-25 | 2019-06-05 | ロリク アーゲーＲｏｌｉｃ Ａｇ | Photoreactive compound |
| KR101998557B1 (en) | 2011-10-03 | 2019-07-10 | 롤리크 아게 | Photoaligning materials |
| WO2013050121A1 (en) | 2011-10-03 | 2013-04-11 | Rolic Ag | Photoaligning materials |
| WO2013105523A1 (en) | 2012-01-12 | 2013-07-18 | 和光純薬工業株式会社 | Liquid crystal aligning agent |
| US20150056367A1 (en) | 2012-03-16 | 2015-02-26 | Soki Corporation | Composition for forming liquid crystal alignment film and liquid crystal display element |
| US10696795B2 (en) | 2015-11-11 | 2020-06-30 | Rolic Technologies AG | Photoaligning materials |
| CN109804306A (en) | 2016-10-11 | 2019-05-24 | 罗利克技术有限公司 | Light orientation copolymer material |
-
1981
- 1981-12-22 JP JP56206079A patent/JPS58109479A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS58109479A (en) | 1983-06-29 |
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