JPH07101899A - Production of cyclopentanedicarboxylic acid - Google Patents
Production of cyclopentanedicarboxylic acidInfo
- Publication number
- JPH07101899A JPH07101899A JP5244297A JP24429793A JPH07101899A JP H07101899 A JPH07101899 A JP H07101899A JP 5244297 A JP5244297 A JP 5244297A JP 24429793 A JP24429793 A JP 24429793A JP H07101899 A JPH07101899 A JP H07101899A
- Authority
- JP
- Japan
- Prior art keywords
- acid
- water
- solvent
- cyclopentanedicarboxylic acid
- cyclopentanedicarboxylic
- 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.)
- Pending
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
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】Ｃ５留分から得られるシクロペン
タジエンの有効利用に関し、得られるシクロペンタンジ
カルボン酸は可塑剤、ポリエステル樹脂等の原料として
有用な新規な機能が発現することが期待される。BACKGROUND OF THE INVENTION Regarding the effective use of cyclopentadiene obtained from C5 fraction, the obtained cyclopentanedicarboxylic acid is expected to exhibit a novel function useful as a raw material for plasticizers, polyester resins and the like.
【０００２】[0002]
【従来の技術】シクロペンタンー1,3ー ジカルボン酸（以
下、シクロペンタンジカルボン酸と略す）の製造方法と
してシクロペンタジエンとブタジエンから得られるノル
ボルネンを硝酸で酸化する方法（DD217506、特開昭48-7
9850）、あるいは、シクロペンタジエンと二酸化炭素か
ら得られるシクロペンタジエン-1,3- ジカルボン酸（以
下、シクロペンタジエンジカルボン酸と略す））をアセ
トン溶媒中でPd/C触媒により水添する方法が知られてい
る（井上祥平他, "Organic and Bio-reorganic Chemist
ry of Carbon Dioxide",第２章, 講談社、1981 ）。2. Description of the Related Art As a method for producing cyclopentane-1,3-dicarboxylic acid (hereinafter abbreviated as cyclopentanedicarboxylic acid), a method of oxidizing norbornene obtained from cyclopentadiene and butadiene with nitric acid (DD217506, JP-A-48- 7
9850), or cyclopentadiene-1,3-dicarboxylic acid obtained from cyclopentadiene and carbon dioxide (hereinafter abbreviated as cyclopentadiene dicarboxylic acid)) is hydrogenated in an acetone solvent with a Pd / C catalyst. Iru (Shohei Inoue et al., "Organic and Bio-reorganic Chemist
ry of Carbon Dioxide ", Chapter 2, Kodansha, 1981).
【０００３】一方、シクロペンタンジカルボン酸と構造
が類似であるインデン-1,3- ジカルボン酸をアセトン溶
媒中、Pd/C触媒で水添した場合、カルボン酸の一つが脱
離しインデンー1ー カルボン酸が生成するが、アセトン溶
媒に酢酸を添加してカルボン酸の脱離を防止し、インデ
ンー1,3ー ジカルボン酸を得る方法も知られている（井上
祥平他の前出文献同上）。On the other hand, when indene-1,3-dicarboxylic acid, which has a structure similar to that of cyclopentanedicarboxylic acid, is hydrogenated with a Pd / C catalyst in an acetone solvent, one of the carboxylic acids is eliminated to give indene-1-carboxylic acid. However, a method is known in which acetic acid is added to an acetone solvent to prevent elimination of carboxylic acid to obtain indene-1,3-dicarboxylic acid (Shohei Inoue et al., Supra).
【０００４】[0004]
【発明が解決しようとする課題】公知の方法で得られる
原料のシクロペンタジエンジカルボン酸は淡黄色〜黄色
に着色している。本発明者らは原料を精製し、水添すべ
く原料の精製方法の検討を行ったが、原料のシクロペン
タジエンジカルボン酸は殆どの有機溶媒、無機溶媒に溶
解しないことがわかった。特に水溶媒を使用した場合、
80℃まで加熱すると、原料のカルボン酸の殆どが二酸化
炭素として脱離し、水は原料の分解を促進し不適当な溶
媒であると推定された。そこで、本発明者らは有機溶媒
を使用した公知の方法でシクロペンタジエンジカルボン
酸の水添反応を行った結果、着色は軽減されるものの生
成物のシクロペンタンジカルボン酸は依然として淡黄色
に着色するとがわかった。このようなシクロペンタンジ
カルボン酸は製品としての価値は低い。したがって、着
色の少ないシクロペンタンジカルボン酸の製造方法を開
発することは本反応を工業的に実施する上で不可欠であ
る。The starting material cyclopentadiene dicarboxylic acid obtained by a known method is colored in a pale yellow to yellow color. The present inventors refined the raw material and studied a method for purifying the raw material so as to hydrogenate it. However, it was found that the cyclopentadienedicarboxylic acid as the raw material was insoluble in most organic solvents and inorganic solvents. Especially when using a water solvent,
When heated to 80 ° C, most of the carboxylic acid as a raw material was desorbed as carbon dioxide, and water was presumed to be an unsuitable solvent because it promotes the decomposition of the raw material. Therefore, the present inventors carried out the hydrogenation reaction of cyclopentadiene dicarboxylic acid by a known method using an organic solvent, as a result, although the coloring is reduced, the product cyclopentanedicarboxylic acid is still colored in pale yellow. all right. Such cyclopentanedicarboxylic acid has a low value as a product. Therefore, it is indispensable to industrially carry out this reaction to develop a method for producing cyclopentanedicarboxylic acid with little coloration.
【０００５】[0005]
【課題を解決するための手段】本発明者らは着色の少な
い製造方法を鋭意検討した結果、水添時の溶媒として水
を使用た場合、驚いたことに原料の脱炭酸は全く起こら
ず、さらに、反応液の着色が大幅に抑制される事を見い
出し本発明を完成した。すなわち本発明はシクロペンタ
ジエンジカルボン酸を水あるいは水を主成分とする溶媒
中で水添することを特徴とするシクロペンタンジカルボ
ン酸の製造方法である。Means for Solving the Problems As a result of intensive investigations by the present inventors on a production method with little coloring, surprisingly, when water was used as a solvent during hydrogenation, decarboxylation of the raw material did not occur at all, Furthermore, they have found that the coloring of the reaction solution is significantly suppressed and completed the present invention. That is, the present invention is a method for producing cyclopentanedicarboxylic acid, which comprises hydrogenating cyclopentadienedicarboxylic acid in water or a solvent containing water as a main component.
【０００６】本反応で使用する水添触媒は汎用の触媒が
使用できる。たとえば、（１）Pd／シリカ、Pd／アルミ
ナ、Pd／シリカ・アルミナ、Pd/C、Pd/BaSO4、Pd/CaC
O3、Pd/SrCO3等のPd系触媒、（２）RuO2、Ru/C等のRu系
触媒、（３）Ni／シリカ、Ni／アルミナ、Ni／シリカ・
アルミナ、Ni／C 、Ni／シリカゲル等の担持Ni、ラネー
Ni、漆原Ni等のNi系触媒、（４）Rh/C、Rh／アルミナ等
のRh系触媒（５）PtO2、Pt/C 等のPt系触媒が挙げられ
る。このような不均一系触媒を用いることにより、生成
物であるシクロペンタンジカルボン酸は水あるいは水を
主成分とする溶媒に溶解するので触媒との分離が容易で
ある。As the hydrogenation catalyst used in this reaction, a general-purpose catalyst can be used. For example, (1) Pd / silica, Pd / alumina, Pd / silica-alumina, Pd / C, Pd / BaSO 4 , Pd / CaC
Pd-based catalysts such as O 3 and Pd / SrCO 3 ; (2) Ru-based catalysts such as RuO 2 and Ru / C; (3) Ni / silica, Ni / alumina, Ni / silica.
Alumina, Ni / C, Ni / Silica gel supported Ni, Raney
Ni-based catalysts such as Ni and Urushibara Ni, (4) Rh-based catalysts such as Rh / C and Rh / alumina (5) Pt-based catalysts such as PtO 2 and Pt / C. By using such a heterogeneous catalyst, the product cyclopentanedicarboxylic acid is dissolved in water or a solvent containing water as a main component, and therefore it is easy to separate it from the catalyst.
【０００７】本発明の方法で使用する溶媒は水あるいは
水を主成分とする溶媒であり、水単独で使用した方が水
添速度も速くなり好ましいが、水と汎用の溶媒と混合し
た混合水溶媒を使用する場合、水は少なくとも50％以上
存在することが好ましい。このような汎用の溶媒の例と
して、アセトン、メチルエチルケトンのようなケトン
類、メタノール、エタノールのようなアルコール類、ア
セトニトリル、ピリジンのような含窒素溶媒が挙げられ
る。The solvent used in the method of the present invention is water or a solvent containing water as a main component, and it is preferable to use water alone because the hydrogenation rate becomes faster, but mixed water obtained by mixing water and a general-purpose solvent is preferable. If a solvent is used, it is preferred that at least 50% water is present. Examples of such general-purpose solvents include ketones such as acetone and methyl ethyl ketone, alcohols such as methanol and ethanol, and nitrogen-containing solvents such as acetonitrile and pyridine.
【０００８】本発明の水添反応に用いられる水素は、メ
タンや一酸化炭素が含有されていても使用可能であり、
反応における水素圧力が高いほど水添速度は速くなる
が、余りに高いと高耐圧の反応器を必要とし不経済であ
り、実用的な水添圧力は０〜50Kg/cm2-G、好ましくは０
〜10Kg/cm2-Gの範囲である。The hydrogen used in the hydrogenation reaction of the present invention can be used even if it contains methane or carbon monoxide.
The higher the hydrogen pressure in the reaction, the faster the hydrogenation rate, but if it is too high, it is uneconomical because a high pressure resistant reactor is required, and the practical hydrogenation pressure is 0 to 50 kg / cm 2 -G, preferably 0.
The range is up to 10 Kg / cm 2 -G.
【０００９】また、水添温度は低いと水添反応速度は遅
く、また高すぎると原料のシクロペンタジエンジカルボ
ン酸の分解が促進されることからも、好ましい水添温度
は10〜80℃であり、さらに好ましくは20〜60℃である。Further, the hydrogenation reaction rate is slow when the hydrogenation temperature is low, and when the hydrogenation temperature is too high, the decomposition of the starting material cyclopentadiene dicarboxylic acid is promoted. Therefore, the preferable hydrogenation temperature is 10 to 80 ° C. More preferably, it is 20 to 60 ° C.
【００１０】原料であるシクロペンタジエンジカルボン
酸は水あるいは水を主成分とする溶媒に溶解しないので
水添における反応形態としては、例えば、原料および溶
媒を反応器に装入しておき、次いで所定の圧力を保ちな
がら水素を連続的に供給するような半回分式が挙げられ
る。この場合、未反応の水素は反応圧力を保つために一
部をパージして残りは再び反応器へ循環される。Since the starting material cyclopentadienedicarboxylic acid is not dissolved in water or a solvent containing water as a main component, the reaction form in hydrogenation is, for example, that the starting material and the solvent are charged in a reactor, and then a predetermined amount is charged. A semi-batch method is one in which hydrogen is continuously supplied while maintaining the pressure. In this case, unreacted hydrogen is partly purged to maintain the reaction pressure, and the rest is circulated to the reactor again.
【００１１】[0011]
【実施例】本発明の方法を実施例により詳細に説明す
る。The method of the present invention will be described in detail with reference to Examples.
【００１２】〔シクロペンタジエンジカルボン酸の合
成〕シクロペンタジエン、1,5-ジアザビシクロ[5,4,0]-
5-ウンデセンおよびジメチルホルムアミドをオートクレ
ーブに入れ、二酸化炭素を圧入し、０℃、50Kg/cm2-Gで
３時間反応した。反応液を大量の０℃の塩酸水溶液へ入
れて５時間撹拌し、析出した結晶をジエチルエーテルで
洗浄し乾燥した。ＩＲ、元素分析から純度約96％のシク
ロペンタジエンジカルボン酸を得た。[Synthesis of Cyclopentadiene Dicarboxylic Acid] Cyclopentadiene, 1,5-diazabicyclo [5,4,0]-
5-Undecene and dimethylformamide were placed in an autoclave, carbon dioxide was introduced under pressure, and the reaction was carried out at 0 ° C. and 50 Kg / cm 2 -G for 3 hours. The reaction solution was poured into a large amount of 0 ° C. hydrochloric acid aqueous solution and stirred for 5 hours, and the precipitated crystals were washed with diethyl ether and dried. Cyclopentadiene dicarboxylic acid having a purity of about 96% was obtained by IR and elemental analysis.
【００１３】実施例１ 内容積 200mlのオートクレーブにシクロペンタジエンジ
カルボン酸２ｇ、5 ％Pd／C 触媒１ｇ、水20ｇを入れ、
水素を６Kg/cm2-Gを保ちながら40℃で２時間反応した。
反応後、触媒をフィルターで分離し、ガスクロマトグラ
フィーで分析した結果、シクロペンタンジカルボン酸の
収率は99％以上であり、反応液の着色はハーゼン15であ
った。また、原料の分解物と推定されるトリシクロデカ
ンはトレースであった。一方、この反応液を濃縮し、約
90％のシクロペンタンジカルボン酸を晶析させて単離し
たが結晶は白色であった。Example 1 An autoclave having an internal volume of 200 ml was charged with 2 g of cyclopentadiene dicarboxylic acid, 1 g of 5% Pd / C catalyst and 20 g of water.
The reaction was carried out at 40 ° C. for 2 hours while maintaining hydrogen at 6 kg / cm 2 -G.
After the reaction, the catalyst was separated by a filter and analyzed by gas chromatography. As a result, the yield of cyclopentanedicarboxylic acid was 99% or more, and the color of the reaction solution was Hazen 15. In addition, traces of tricyclodecane presumed to be the decomposition product of the raw material were traces. On the other hand, concentrate this reaction solution and
It was isolated by crystallizing 90% of cyclopentanedicarboxylic acid, but the crystals were white.
【００１４】実施例２ ５％Pd／C 触媒を38％Ni／シリカ・アルミナ触媒に、水
溶媒を水−メチルエチルケトン（60/40 重量比) 溶媒に
それぞれ代えて使用し、30℃で４時間反応した以外は実
施例１と同様の方法で水添した。ガスクロマトグラフィ
ーで分析した結果、シクロペンタンジカルボン酸の収率
は99％以上であり、反応液の着色はハーゼン20であっ
た。また、原料の分解物と推定されるトリシクロデカン
はトレースであった。この反応液を濃縮し、約90％のシ
クロペンタンジカルボン酸を晶析させて単離したが結晶
は白色であった。Example 2 A 5% Pd / C catalyst was used as a 38% Ni / silica-alumina catalyst, and an aqueous solvent was replaced with a water-methyl ethyl ketone (60/40 weight ratio) solvent. The reaction was carried out at 30 ° C. for 4 hours. Hydrogenation was carried out in the same manner as in Example 1 except for the above. As a result of analysis by gas chromatography, the yield of cyclopentanedicarboxylic acid was 99% or more, and the color of the reaction solution was Hazen 20. In addition, traces of tricyclodecane presumed to be the decomposition product of the raw material were traces. The reaction solution was concentrated, and about 90% of cyclopentanedicarboxylic acid was crystallized and isolated, but the crystals were white.
【００１５】比較例１ 水溶媒に変え、アセトン溶媒を使用した以外は実施例１
と同様の方法で水添した。分析の結果、シクロペンタン
ジカルボン酸の収率は86％であり、未反応のシクロペン
タジエンが残っていた。そこで、さらに水添を１時間行
った結果、シクロペンタンジカルボン酸の収率97％であ
り、この他にシクロペンタンモノカルボン酸１％、トリ
シクロデカン２％ の副生物が検出された。この反応液
は黄色に着色しており、この反応液を濃縮し、約90％の
シクロペンタンジカルボン酸を晶析させて単離したが結
晶は依然着色していた。Comparative Example 1 Example 1 except that an acetone solvent was used instead of the water solvent.
Hydrogenated in the same manner as in. As a result of the analysis, the yield of cyclopentanedicarboxylic acid was 86%, and unreacted cyclopentadiene remained. Then, as a result of further hydrogenation for 1 hour, the yield of cyclopentanedicarboxylic acid was 97%, and by-products of 1% cyclopentanemonocarboxylic acid and 2% tricyclodecane were also detected. The reaction solution was colored yellow, and the reaction solution was concentrated, and about 90% of cyclopentanedicarboxylic acid was crystallized and isolated, but the crystals were still colored.
【００１６】[0016]
【発明の効果】シクロペンタジエンジカルボン酸を水溶
媒中で水添することにより、原料の分解がなく、着色の
少ないシクロペンタンジカルボン酸を収率良く製造する
ことができる。EFFECTS OF THE INVENTION By hydrogenating cyclopentadienedicarboxylic acid in a water solvent, cyclopentanedicarboxylic acid with less coloring and less coloring can be produced in good yield.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｂ０１Ｊ 23/46 ３０１ ３１１ 23/755 25/02 Ｃ０７Ｂ 61/00 ３００ (72)発明者 高田 昇 大阪府高石市高砂１丁目６番地 三井東圧 化学株式会社内─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification number Reference number within the agency FI Technical display location B01J 23/46 301 311 23/755 25/02 C07B 61/00 300 (72) Inventor Noboru Takada Osaka 1-6 Takasago, Takaishi-shi, Mitsui Mitsui Toatsu Chemical Co., Ltd.
Claims (2)
いは水を主成分とする溶媒中で水添することを特徴とす
るシクロペンタンジカルボン酸の製造方法。1. A process for producing cyclopentanedicarboxylic acid, which comprises hydrogenating cyclopentadienedicarboxylic acid in water or a solvent containing water as a main component.
いて行うことを特徴とするシクロペンタンジカルボン酸
の製造方法。2. A method for producing cyclopentanedicarboxylic acid, wherein the hydrogenation according to claim 1 is carried out using a heterogeneous catalyst.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5244297A JPH07101899A (en) | 1993-09-30 | 1993-09-30 | Production of cyclopentanedicarboxylic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5244297A JPH07101899A (en) | 1993-09-30 | 1993-09-30 | Production of cyclopentanedicarboxylic acid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH07101899A true JPH07101899A (en) | 1995-04-18 |
Family
ID=17116649
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5244297A Pending JPH07101899A (en) | 1993-09-30 | 1993-09-30 | Production of cyclopentanedicarboxylic acid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07101899A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6377818B2 (en) | 1997-03-03 | 2002-04-23 | Kabushiki Kaisha Toshiba | Communication terminal apparatus |
| JP2016144772A (en) * | 2015-02-06 | 2016-08-12 | 内山 俊一 | Hydrogen activating catalyst |
-
1993
- 1993-09-30 JP JP5244297A patent/JPH07101899A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6377818B2 (en) | 1997-03-03 | 2002-04-23 | Kabushiki Kaisha Toshiba | Communication terminal apparatus |
| JP2016144772A (en) * | 2015-02-06 | 2016-08-12 | 内山 俊一 | Hydrogen activating catalyst |
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