JP2002088050A - Method for producing trifluoromethanesulfonic anhydride - Google Patents
Method for producing trifluoromethanesulfonic anhydrideInfo
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- JP2002088050A JP2002088050A JP2000276147A JP2000276147A JP2002088050A JP 2002088050 A JP2002088050 A JP 2002088050A JP 2000276147 A JP2000276147 A JP 2000276147A JP 2000276147 A JP2000276147 A JP 2000276147A JP 2002088050 A JP2002088050 A JP 2002088050A
- Authority
- JP
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- Prior art keywords
- trifluoromethanesulfonic anhydride
- trifluoromethanesulfonic
- trifluoromethanesulfonic acid
- amount
- anhydride
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、医療、重合開始剤
等の合成用原料として有用な無水トリフルオロメタンス
ルホン酸の効率的な製造法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an efficient method for producing trifluoromethanesulfonic anhydride, which is useful as a raw material for synthesizing medical treatments, polymerization initiators and the like.
【０００２】[0002]
【従来技術とその解決しようとする課題】一般に無水ト
リフルオロメタンスルホン酸の製造は、次式で示すよう
に、トリフルオロメタンスルホン酸に五酸化リンを添加
し反応後、蒸留することにより、粗無水トリフルオロメ
タンスルホン酸を得るものである。 ６ＣＦ3ＳＯ3Ｈ＋Ｐ2Ｏ5→３（ＣＦ3ＳＯ2）2Ｏ＋２Ｈ3
ＰＯ4 更に、これら粗製品を精留することにより、純粋な無水
トリフルオロメタンスルホン酸を製造する方法が知られ
ている。2. Description of the Related Art Generally, trifluoromethanesulfonic anhydride is produced by adding phosphorus pentoxide to trifluoromethanesulfonic acid, reacting and distilling the crude trifluoromethanesulfonic anhydride as shown in the following formula. To obtain methanesulfonic acid. 6CF 3 SO 3 H + P 2 O 5 → 3 (CF 3 SO 2 ) 2 O + 2H 3
PO 4 Furthermore, there is known a method for producing pure trifluoromethanesulfonic anhydride by rectifying these crude products.
【０００３】原料のトリフルオロメタンスルホン酸は、
一般にトリフルオロメタンスルホン酸金属塩の硫酸分
解、蒸留することにより、粗トリフルオロメタンスルホ
ン酸が得られる。[0003] The starting material trifluoromethanesulfonic acid is
Generally, crude trifluoromethanesulfonic acid is obtained by sulfuric acid decomposition and distillation of a metal salt of trifluoromethanesulfonic acid.
【０００４】しかしながら、この方法において得た粗製
品中にはＳＯ4を多く含んでいるためこのような原料を
用いて無水トリフルオロメタンスルホン酸を製造した場
合、ＳＯ4を多く含む低純度の無水トリフルオロメタン
スルホン酸を得ることなる。そのため、粗トリフルオロ
メタンスルホン酸を精留塔等で精留し、不純物を除去し
た精留品のトリフルオロメタンスルホン酸と五酸化リン
を原料として反応させる。その後、蒸留することにより
粗無水トリフルオロメタンスルホン酸を得て、これを更
に精留し、製造しているのが現状である。However, since the crude product obtained by this method contains a large amount of SO 4 , when trifluoromethanesulfonic anhydride is produced using such a raw material, low-purity trifluoroanhydride containing a large amount of SO 4 is obtained. This gives romethanesulfonic acid. Therefore, crude trifluoromethanesulfonic acid is rectified by a rectification tower or the like, and trifluoromethanesulfonic acid of a rectified product from which impurities have been removed is reacted with phosphorus pentoxide as raw materials. Thereafter, distillation is performed to obtain crude trifluoromethanesulfonic anhydride, which is further rectified and manufactured.
【０００５】また、この粗無水トリフルオロメタンスル
ホン酸中には、未反応のトリフルオロメタンスルホン酸
が残存するため、次式に示すような分解反応が進行し、[0005] Further, since unreacted trifluoromethanesulfonic acid remains in the crude trifluoromethanesulfonic acid, a decomposition reaction represented by the following formula proceeds.
【０００６】[0006]
【化１】 Embedded image
【０００７】蒸留回収した無水トリフルオロメタンスル
ホン酸にトリフルオロメタンスルホン酸エステルや原料
酸であるトリフルオロメタンスルホン酸が多く混入する
ため、不純物を多く含むものになり、品質を著しく低下
させる。A large amount of trifluoromethanesulfonic acid ester and trifluoromethanesulfonic acid as a raw material acid are mixed in the trifluoromethanesulfonic anhydride recovered by distillation, so that the trifluoromethanesulfonic acid contains a large amount of impurities, and the quality is remarkably deteriorated.
【０００８】そこで、これらの混入を防ぐため、長時間
還流を行いトリフルオロメタンスルホン酸エステルを除
去した後、精留を行っている。しかし、トリフルオロメ
タンスルホン酸は、蒸気圧が低く、還流により除去出来
ないため、細心の注意を払いながら精留を行っているの
が現状である。また、この時釜残中のトリフルオロメタ
ンスルホン酸は濃縮されるため、上記に示した式の反応
が進行する前に精留を止めなければならず、無水トリフ
ルオロメタンスルホン酸の回収率は７０％程度と効率が
悪くなっている。[0008] Therefore, in order to prevent such contamination, rectification is performed after refluxing for a long time to remove the trifluoromethanesulfonic acid ester. However, since trifluoromethanesulfonic acid has a low vapor pressure and cannot be removed by reflux, rectification is being performed with great care at present. At this time, since the trifluoromethanesulfonic acid in the bottom is concentrated, the rectification must be stopped before the reaction of the above formula proceeds, and the recovery of trifluoromethanesulfonic anhydride is 70%. The degree and efficiency are getting worse.
【０００９】また、トリフルオロメタンスルホン酸と五
酸化リンとの反応から無水トリフルオロメタンスルホン
酸を製造する際には、最初から五酸化リンの量を多く入
れることが考えられるが、多く入れると固結し撹拌でき
なくなり、蒸留した場合の回収率が著しく低下するため
好ましくない。When producing trifluoromethanesulfonic anhydride from the reaction between trifluoromethanesulfonic acid and phosphorus pentoxide, it is conceivable to add a large amount of phosphorus pentoxide from the beginning. However, it is not preferable because stirring cannot be performed, and the recovery rate after distillation significantly decreases.
【００１０】[0010]
【課題を解決するための具体的手段】本発明者らは、上
記問題点に鑑み鋭意検討の結果、トリフルオロメタンス
ルホン酸及びＳＯ4等の不純物が非常に少ない高純度の
無水トリフルオロメタンスルホン酸を容易に、かつ収率
よく製造する方法を見いだし本発明に到達したものであ
る。The present inventors have conducted intensive studies in view of the above problems, and as a result, have found that trifluoromethanesulfonic anhydride having a very small amount of impurities such as trifluoromethanesulfonic acid and SO 4 is very small. The present inventors have found a method for easily and efficiently producing the present invention, and have reached the present invention.
【００１１】すなわち、本発明は、不純物の多い粗無水
トリフルオロメタンスルホン酸に五酸化リンを添加し、
還流し、蒸留または減圧蒸留をすることでＳＯ4等の不
純物の少ない高純度の無水トリフルオロメタンスルホン
酸を経済的に得られること、さらに、粗無水トリフルオ
ロメタンスルホン酸中に残存するトリフルオロメタンス
ルホン酸と五酸化リンとが反応することで高純度の無水
トリフルオロメタンスルホン酸を製造する方法である。That is, the present invention provides a method of adding phosphorus pentoxide to crude trifluoromethanesulfonic anhydride containing many impurities,
By refluxing and performing distillation or distillation under reduced pressure, high-purity trifluoromethanesulfonic anhydride with few impurities such as SO 4 can be economically obtained, and further, trifluoromethanesulfonic acid remaining in the crude trifluoromethanesulfonic anhydride And phosphorus pentoxide to produce high-purity trifluoromethanesulfonic anhydride.
【００１２】本発明において、粗無水トリフルオロメタ
ンスルホン酸中に残存するトリフルオロメタンスルホン
酸及びＳＯ4との反応に使用する五酸化リンの量は、理
論モル比の０．１〜１０倍量である。この量より少ない
と回収率及びＳＯ4の除去率が低下し、好ましくない。
また、この範囲を超えると固結し、攪拌が困難となり、
回収率が低下し、経済的でない。In the present invention, the amount of phosphorus pentoxide used for the reaction of trifluoromethanesulfonic acid and SO 4 remaining in crude trifluoromethanesulfonic anhydride is 0.1 to 10 times the theoretical molar ratio. . If the amount is less than this, the recovery rate and the removal rate of SO 4 decrease, which is not preferable.
Also, if it exceeds this range, it solidifies, stirring becomes difficult,
Recovery rate is low and not economical.
【００１３】反応温度は、２０〜６０℃の範囲が好まし
く、この範囲を超えると不純物であるトリフルオロメタ
ンスルホン酸エステルが生成し、好ましくない。The reaction temperature is preferably in the range of 20 to 60 ° C., and if it exceeds this range, trifluoromethanesulfonic acid ester which is an impurity is generated, which is not preferable.
【００１４】還流時間は、５時間程度で十分であり、そ
の間不純物のＳＯ4を飛散させ、系外へ除去すると共に
未反応のトリフルオロメタンスルホン酸を蒸留し、回収
することにより、工業的に有利に無水トリフルオロメタ
ンスルホン酸を製造することができる。A reflux time of about 5 hours is sufficient. During that time, SO 4 as an impurity is scattered and removed outside the system, and unreacted trifluoromethanesulfonic acid is distilled and recovered, which is industrially advantageous. To produce trifluoromethanesulfonic anhydride.
【００１５】[0015]
【実施例】以下、本発明を実施例により詳細に説明す
る。DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail with reference to embodiments.
【００１６】実施例１ トリフルオロメタンスルホン酸と五酸化リンとの反応に
より生成した無水トリフルオロメタンスルホン酸を減圧
蒸留し、得られた無水トリフルオロメタンス酸中のＳＯ
4量は、イオンクロマト法より８０００ｐｐｍであり、
トリフルオロメタンスルホン酸量は、Ｆ−ＮＭＲより、
４％であった。この無水トリフルオロメタンスルホン酸
２５０ｇをガラス製の５００ｍｌフラスコ（撹拌機付
き）に入れ、攪拌しながらＰ2Ｏ5を不純物ＳＯ4量及び
未反応トリフルオロメタンスルホン酸量の１／２倍当量
にあたる計３．９ｇ添加し、窒素置換した後、４０℃、
０．０８３ＭＰａで還流を６時間行なった。その後、蒸
留して蒸留液を回収した。Example 1 Trifluoromethanesulfonic anhydride produced by the reaction of trifluoromethanesulfonic acid with phosphorus pentoxide was distilled under reduced pressure, and the resulting SO3 in trifluoromethanesulfonic anhydride was obtained.
4 amount is 8000 ppm from the ion chromatography method,
The amount of trifluoromethanesulfonic acid is determined by F-NMR.
4%. 250 g of this trifluoromethanesulfonic anhydride was put into a glass 500 ml flask (with a stirrer), and while stirring, P 2 O 5 was added to a total of 3 equivalents of 1/2 of the amount of impurity SO 4 and the amount of unreacted trifluoromethanesulfonic acid. 0.9 g was added and the atmosphere was replaced with nitrogen.
Reflux was performed at 0.083 MPa for 6 hours. Thereafter, distillation was performed to recover a distillate.
【００１７】この結果、６時間還流後の還流液中のＳＯ
4量は、５０ｐｐｍで、トリフルオロメタンスルホン酸
量は、１．１％であった。また蒸留した液中のＳＯ4量
は、３０ｐｐｍ、無水トリフルオロメタンスルホン酸の
回収率は、９３％であった。As a result, SO in the reflux liquid after reflux for 6 hours
The amount of 4 was 50 ppm, and the amount of trifluoromethanesulfonic acid was 1.1%. The amount of SO 4 in the distilled liquid was 30 ppm, and the recovery of trifluoromethanesulfonic anhydride was 93%.
【００１８】実施例２ 実施例１と同様にして減圧蒸留により得た無水トリフル
オロメタンスルホン酸２５０ｇをガラス製の５００ｍｌ
フラスコ（撹拌機付き）に入れ、攪拌しながらＰ2Ｏ5を
不純物ＳＯ4量及びトリフルオロメタンスルホン酸量の
２倍当量にあたる計１５．４ｇ添加し、窒素置換した
後、４０℃、０．０８３ＭＰａで還流を６時間行なっ
た。その後、蒸留して蒸留液を回収した。Example 2 250 g of trifluoromethanesulfonic anhydride obtained by distillation under reduced pressure in the same manner as in Example 1 was mixed with 500 ml of glass.
After placed in a flask (equipped with a stirrer), while stirring P 2 O 5 was falls 2 equivalents total 15.4g addition of the impurity SO 4 amount and trifluoromethanesulfonic acid amount was purged with nitrogen, 40 ℃, 0.083MPa Was refluxed for 6 hours. Thereafter, distillation was performed to recover a distillate.
【００１９】この結果、６時間還流後の還流液中のＳＯ
4量は、４０ｐｐｍで、トリフルオロメタンスルホン酸
量は、０．４％であった。また蒸留した液中のＳＯ4量
は、３０ｐｐｍ、無水トリフルオロメタンスルホン酸の
回収率は、９７％であった。As a result, SO in the reflux liquid after reflux for 6 hours
The amount of 4 was 40 ppm, and the amount of trifluoromethanesulfonic acid was 0.4%. The amount of SO 4 in the distilled solution was 30 ppm, and the recovery of trifluoromethanesulfonic anhydride was 97%.
【００２０】比較例１ 実施例１と同様にして減圧蒸留により得た無水トリフル
オロメタンスルホン酸２５０ｇをガラス製の５００ｍｌ
フラスコ（撹拌機付き）に入れた。窒素置換した後、４
０℃、０．０８３ＭＰａで還流を６時間行なった。その
後、蒸留して蒸留液を回収した。Comparative Example 1 250 g of trifluoromethanesulfonic anhydride obtained by distillation under reduced pressure in the same manner as in Example 1 was mixed with 500 ml of glass.
Placed in a flask (with stirrer). After replacing with nitrogen, 4
Reflux was performed at 0 ° C. and 0.083 MPa for 6 hours. Thereafter, distillation was performed to recover a distillate.
【００２１】この結果、６時間還流後の還流液中のＳＯ
4量は、１０００ｐｐｍで、トリフルオロメタンスルホ
ン酸量は、４．３％であった。また蒸留した液中のＳＯ
4量は、２００ｐｐｍ、無水トリフルオロメタンスルホ
ン酸の回収率は、７１％であった。As a result, SO in the reflux liquid after reflux for 6 hours
The amount of 4 was 1000 ppm, and the amount of trifluoromethanesulfonic acid was 4.3%. SO in the distilled liquid
The amount of 4 was 200 ppm, and the recovery of trifluoromethanesulfonic anhydride was 71%.
【００２２】[0022]
【発明の効果】本発明の方法を用いることにより高純度
の無水トリフルオロメタンスルホン酸を安価に効率よく
製造できる。According to the method of the present invention, high-purity trifluoromethanesulfonic anhydride can be efficiently produced at low cost.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 小野 浩 山口県宇部市大字沖宇部5253番地 セント ラル硝子株式会社化学研究所内 (72)発明者 西村 智 山口県宇部市大字沖宇部5253番地 セント ラル硝子株式会社化学研究所内 Ｆターム(参考） 4H006 AA02 AC61 AD11 AD40 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Hiroshi Ono 5253 Oki Obe, Oji, Ube City, Yamaguchi Prefecture Inside the Chemical Laboratory, Central Glass Co., Ltd. (72) Inventor Satoshi Nishimura 5253 Oki Ube Oaza, Ube City, Yamaguchi Prefecture, Central Glass F-term in Chemical Research Laboratories, Inc. (reference) 4H006 AA02 AC61 AD11 AD40
Claims (1)
リンとを反応させ、生成した無水トリフルオロメタンス
ルホン酸を蒸留した後、この蒸留液にさらに五酸化リン
を加え、還流し、蒸留または減圧蒸留により、無水トリ
フルオロメタンスルホン酸を精製することを特徴とする
無水トリフルオロメタンスルホン酸の製造方法。1. A reaction between trifluoromethanesulfonic acid and phosphorus pentoxide to distill off the produced trifluoromethanesulfonic anhydride, further adding phosphorus pentoxide to the distillate, refluxing, and performing distillation or distillation under reduced pressure. A method for producing trifluoromethanesulfonic anhydride, comprising purifying trifluoromethanesulfonic anhydride.
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|---|---|---|---|
| JP2000276147A JP3865577B2 (en) | 2000-09-12 | 2000-09-12 | Method for producing trifluoromethanesulfonic anhydride |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000276147A JP3865577B2 (en) | 2000-09-12 | 2000-09-12 | Method for producing trifluoromethanesulfonic anhydride |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2002088050A true JP2002088050A (en) | 2002-03-27 |
| JP3865577B2 JP3865577B2 (en) | 2007-01-10 |
Family
ID=18761664
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|---|---|---|---|
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Country Status (1)
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103450050A (en) * | 2013-09-10 | 2013-12-18 | 中国船舶重工集团公司第七一八研究所 | Purification method of trifluoromethanesulfonic anhydride |
| CN111689878A (en) * | 2020-07-14 | 2020-09-22 | 江西国化实业有限公司 | Preparation process of trifluoromethanesulfonic anhydride |
-
2000
- 2000-09-12 JP JP2000276147A patent/JP3865577B2/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103450050A (en) * | 2013-09-10 | 2013-12-18 | 中国船舶重工集团公司第七一八研究所 | Purification method of trifluoromethanesulfonic anhydride |
| CN103450050B (en) * | 2013-09-10 | 2015-11-25 | 中国船舶重工集团公司第七一八研究所 | The purification process of trifluoromethanesulfanhydride anhydride |
| CN111689878A (en) * | 2020-07-14 | 2020-09-22 | 江西国化实业有限公司 | Preparation process of trifluoromethanesulfonic anhydride |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3865577B2 (en) | 2007-01-10 |
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