JPS61277645A - Production of hexafluoroacetone - Google Patents
Production of hexafluoroacetoneInfo
- Publication number
- JPS61277645A JPS61277645A JP12032285A JP12032285A JPS61277645A JP S61277645 A JPS61277645 A JP S61277645A JP 12032285 A JP12032285 A JP 12032285A JP 12032285 A JP12032285 A JP 12032285A JP S61277645 A JPS61277645 A JP S61277645A
- Authority
- JP
- Japan
- Prior art keywords
- hexafluoroacetone
- alkyl ether
- produced
- production
- product
- 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.)
- Granted
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Physical Or Chemical Processes And Apparatus (AREA)
Abstract
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、ヘキサフルオロアセトンの製造法に関する。[Detailed description of the invention] [Industrial application field] The present invention relates to a method for producing hexafluoroacetone.
更に詳しくは、オクタフルオロイソブチンまたはそのア
ルコール付加物の有効利用をも兼ねたヘキサフルオロア
セトンの製造法に関する。More specifically, the present invention relates to a method for producing hexafluoroacetone that also effectively utilizes octafluoroisobutyne or its alcohol adduct.
ヘキサフルオロアセトンは、合成樹脂、合成コムなどの
製造用単量体として、あるいはビスフェノール人７など
の架橋剤の中間体、医薬、農薬などの中間原料などとし
て用いられている。Hexafluoroacetone is used as a monomer for producing synthetic resins and synthetic combs, as an intermediate for crosslinking agents such as bisphenol 7, and as an intermediate raw material for medicines, agricultural chemicals, and the like.
このような各種の用途を有するヘキサフルオロアセトン
は、従来法のような方法によって製造することが提案さ
れている。Hexafluoroacetone, which has such various uses, has been proposed to be produced by conventional methods.
Ｃａｎ、 Ｊ、 Ｏｈｅｍ、第３３巻第４５３頁（１９
５５）米国特許第３，３２１，５１５号明細書米国特許
第４，３３７，３６１号明細書特公昭４０−２７１７３
号公報
しかしながら、上記の各方法には、次のような欠点がみ
られる。Can, J, Ohem, vol. 33, p. 453 (19
55) U.S. Patent No. 3,321,515 U.S. Patent No. 4,337,361 Japanese Patent Publication No. 40-27173
However, each of the above methods has the following drawbacks.
（１）過マンガン酸カリによる酸化反応は、反応が激し
くまた副生する二酸化マンガンが容易には処置できない
産業廃棄物となること
（２）へキサフルオロプロペンよシ合成されるそのオキ
サイドは高純度のものが得られ難く、従って生成物たる
ヘキサフルオロアセトン中にヘキサフルオロプロペンな
どが混在すること
（３）ジチェタンの硝酸酸化では、得られるヘキサフル
オロアセトン水和物中に１７０２およびＳ０２が含まれ
、それの除宍に手間がかかること
（４）へキサクロルアセトンの使用は、合成上塩素が重
量を増加させるだけで効率的ではなく、また有毒な五塩
化アンチモンを必要とし、更に高純度の生成物が得られ
難いこと
〔発明が解決しようとする問題点〕
本発明者らは、かかる欠点がみられるこれらの従来技術
とは全く発想を異にし、それの有効利用が強く求められ
ているオクタフルオロイソブチンまたはそのアルコール
付加物を原料物質として用い、それを酸化することによ
シ、目的とするヘキサフルオロアセトンを得ることに成
功した。(1) The oxidation reaction with potassium permanganate is violent, and the by-product manganese dioxide becomes industrial waste that cannot be easily disposed of. (2) The oxide synthesized from hexafluoropropene has high purity. (3) In the nitric acid oxidation of dichetane, the resulting hexafluoroacetone hydrate contains 1702 and S02, (4) The use of hexachloroacetone is not efficient as chlorine only increases the weight of the synthesis, and it also requires toxic antimony pentachloride, which further increases the purity of the product. Difficulty in obtaining a product [Problem to be solved by the invention] The present inventors have developed an octave product which is completely different from the conventional techniques that have such drawbacks, and whose effective use is strongly desired. By using fluoroisobutyne or its alcohol adduct as a raw material and oxidizing it, we succeeded in obtaining the desired hexafluoroacetone.
〔問題点を解決するための手段〕および〔作用〕従って
、本発明はヘキサフルオロアセトンの製造法に係シ、ヘ
キサフルオロアセトンの製造は、ヘプタフルオロイソブ
テニルアルキルエーテルを光照射下に酸素と反応させる
ことにより行われる。[Means for Solving the Problems] and [Operation] Therefore, the present invention relates to a method for producing hexafluoroacetone, and the production of hexafluoroacetone involves combining heptafluoroisobutenyl alkyl ether with oxygen under irradiation with light. This is done by reacting.
オクタフルオロイソブチンは、含フツ素共重合体の重要
な原料の一種であるヘキサフルオロプロペン製造時の副
生成物であシ、この毒性の強いオクタフルオロイソブチ
ンは、一般に低級アルコール、例えばメタノール、エタ
ノール、ｎ−プロパノ−；、イソプロパツール、ｎ−ブ
タノールなどとのアルコール付加物を容易に形成する性
質を有している。Octafluoroisobutyne is a by-product during the production of hexafluoropropene, which is an important raw material for fluorine-containing copolymers.This highly toxic octafluoroisobutyne is generally used in lower alcohols, such as methanol. It has the property of easily forming alcohol adducts with ethanol, n-propanol, isopropanol, n-butanol, etc.
このアルコール付加物たるオクタフルオロイソブチルア
ルキルエーテルは、第４級アンモニウム塩などの相関移
動触媒の存在下に、アルカリ金属またはアルカリ土類金
属の水酸化物または炭酸塩あるいはトリアルキルアミン
などの塩基と共に攪拌することによシ脱７ツ化水素化反
応され、ヘプタフルオロイソブテニルアルキルエーテル
を与える。This alcohol adduct, octafluoroisobutyl alkyl ether, is stirred with an alkali metal or alkaline earth metal hydroxide or carbonate or a base such as a trialkylamine in the presence of a phase transfer catalyst such as a quaternary ammonium salt. This dehydrogenation reaction is carried out to give heptafluoroisobutenyl alkyl ether.
かかるヘプタフルオロイソブテニルアルキルエーテルは
、光照射下に酸素と反応させると、次式に示されるよう
にヘキサフルオロアセトンの水和物を与える。When such heptafluoroisobutenyl alkyl ether is reacted with oxygen under light irradiation, it gives a hydrate of hexafluoroacetone as shown in the following formula.
この反応は、石英製の反応容器々どを用い、そこにヘキ
サフルオロイソブテニルアルキルエーテルを加え、好ま
しくは水の存在下で、激しく攪拌しながら酸素をパルプ
リングさせ、水銀ランプなどで紫外線などを照射するこ
とによって行われる。In this reaction, hexafluoroisobutenyl alkyl ether is added to reaction vessels made of quartz, oxygen is pulped with vigorous stirring, preferably in the presence of water, and ultraviolet rays are emitted using a mercury lamp or the like. This is done by irradiating.
照射光源としては、例えば波長約１００〜６００皿、好
ましくは約１５０〜４００ ｎｍの紫外線が用いられ、
酸素はヘキサフルオロイソブテニルアルキルエーテルに
対して約２〜２０ 、好ましくは約４〜１０のモル比で
供給され、その反応温度としては一般に一５０〜１００
℃、好ましくは一１０〜６０℃の゛温度が用いられる。As the irradiation light source, for example, ultraviolet light having a wavelength of about 100 to 600 nm, preferably about 150 to 400 nm is used,
Oxygen is supplied in a molar ratio of about 2 to 20, preferably about 4 to 10, to hexafluoroisobutenyl alkyl ether, and the reaction temperature is generally 150 to 100.
℃, preferably from -10 to 60℃ is used.
この反応の際、水を添加すると、ヘキサフルオロアセト
ンへの転化率は低いものの選択率が良好なため、水の不
存在下での反応と結局はほぼ同じ収率で目的物を得るこ
とができ、しかも回収された原料はくシ返して使用する
ことができる。When water is added during this reaction, the conversion rate to hexafluoroacetone is low, but the selectivity is good, so the desired product can be obtained in almost the same yield as the reaction in the absence of water. Moreover, the recovered raw materials can be recycled and used again.
ｉられたヘキサフルオロアセトンは水和物の形をとって
おシ、水和物自体ポリエステル、ポリアミドなどの溶媒
として使用できるが、それの脱水を行なう場合には、五
酸化リン、濃硫酸、無水硫酸あるいはモレキュラシーブ
などを用いる方法によって容易に行なうことができる（
特開昭５７−８１ 、４３３号公報、同５９−１５７，
０４５号公報）。The hydrated hexafluoroacetone can be used as a solvent for polyester, polyamide, etc., but when dehydrating it, phosphorus pentoxide, concentrated sulfuric acid, anhydrous This can be easily done using methods such as sulfuric acid or molecular sieves (
JP-A No. 57-81, No. 433, No. 59-157,
045 Publication).
ヘキサフルオロアセトンが、ヘプタフルオロイソブテニ
ルアルキルエーテルの酸化という全くの新規な反応方法
によシ得ることができ、これはオクタフルオロイソブチ
ンまたはそのアルフール付加物の有効利用としても有意
義である。Hexafluoroacetone can be obtained by a completely new reaction method of oxidation of heptafluoroisobutenyl alkyl ether, which is also significant as an effective use of octafluoroisobutyne or its alfur adduct.
次に、実施例について本発明を説明する。 Next, the present invention will be explained with reference to examples.
実施例１
球入シ冷却管およびガス導入管を備えた容量３００ ｄ
の石英製円筒状容器に、ヘプタフルオロイソブテニルエ
ーテル１５り（０，０７モル）、水１（１（０，５５モ
ル）、光増感剤としてのローズベンガル０、Ｏ３５り（
３，４Ｘ １０−’モル）および第４級アンモニウム塩
（ローズベンガルがへブタフルオロイソブテニルエーテ
ルに不溶、水に可溶であるため、これら不拘−系２成分
間の相間移動触媒として使用）少量をそれぞれ仕込み、
スターラーで激しく攪拌しながら、酸素を４０時間の間
に約３０ ｔバブリングさせた。その間、５０℃で５０
０Ｗの中圧水銀ランプを照射し続けた。照射終了後、反
応容器内の反応混合物は２層に分離していたので、それ
らを分液した。Example 1 Capacity 300 d with bulb cooling pipe and gas introduction pipe
In a cylindrical container made of quartz, 15 mol of heptafluoroisobutenyl ether (0.07 mol), 1 mol of water (1 (0.55 mol)), 0 mol of rose bengal as a photosensitizer, and 35 mol of O3
3,4X 10-' mol) and a quaternary ammonium salt (used as a phase transfer catalyst between these two unbound components since rose bengal is insoluble in hebutafluoroisobutenyl ether and soluble in water) Prepare a small amount of each,
While vigorously stirring with a stirrer, approximately 30 t of oxygen was bubbled over a period of 40 hours. Meanwhile, 50℃ at 50℃
Irradiation was continued with a 0W medium pressure mercury lamp. After the irradiation was completed, the reaction mixture in the reaction vessel was separated into two layers, which were separated.
その結果、上層にはヘキサフルオロアセトン水和物の１
９重量％水溶液（ｙ−ＮＭＲ内標法による）が１３．０
ｆ７得られ、下層には未反応へブタフルオロイソブテ
ニルエーテル（？−ＮＭＲによる）が９．７り回収され
、またドライアイス・メタノールトラップにはへブタフ
ルオロイソブテニルエーテル６重量％−オクタフルオロ
イソブチルエーテル３３重量％混合物（ｐ−ＮＭＲ内像
法による）が０．８ｇ得られ念。As a result, the upper layer contains 1 of hexafluoroacetone hydrate.
9% by weight aqueous solution (according to y-NMR internal standard method) is 13.0
f7 was obtained, 9.7% of unreacted hebutafluoroisobutenyl ether (?-NMR) was recovered in the lower layer, and 6% by weight of hebutafluoroisobutenyl ether was recovered in the dry ice/methanol trap. 0.8 g of a 33% by weight mixture of fluoroisobutyl ether (according to p-NMR internal imaging method) was obtained.
回収原料量 ９．７ ＋ ０．８ Ｘ Ｏ，６６−１０
，２９１５，０−１０，２
全転化率 □Ｘ １００−３２％
１５．０
２１２： へブタフルオロイソブテニルエーテルのｍ１
９．２
選択率 □Ｘ １００−６０％
２ｈＯ
実施例２
実施例１において、ヘプタフルオロイソブテニルエーテ
ル３０．５ ｇ（０，１４モル）を用い、水の不存在下
に、酸素を４８時間の間に約２０ ｔバブリングさせた
。Amount of recovered raw material 9.7 + 0.8 X O, 66-10
,2915,0-10,2 Total conversion □X 100-32% 15.0 212: m1 of hebutafluoroisobutenyl ether
9.2 Selectivity □X 100-60% 2hO Example 2 In Example 1, 30.5 g (0.14 mol) of heptafluoroisobutenyl ether was used and oxygen was added for 48 hours in the absence of water. Approximately 20 t of bubbles were bubbled during this period.
その結果、反応容器内の反応液として、ヘキサフルオロ
アセトン水和物２９重量％および副反応物を含有する水
溶液が１７．７ ｇ得られ、またドライアイス・メタノ
ールトラップにはへブタフルオロイソブテニルエーテル
１５重量％−オクタフルオロイソブチルエーテル８５重
量％混合物（Ｆ −ＮＭＲ内標法による）が１０．Ｏり
得られた。As a result, 17.7 g of an aqueous solution containing 29% by weight of hexafluoroacetone hydrate and side reactants was obtained as the reaction liquid in the reaction vessel, and hexafluoroisobutenyl was placed in the dry ice/methanol trap. A mixture of 15% by weight ether and 85% by weight octafluoroisobutyl ether (according to the F-NMR internal standard method) was 10. I got it.
Claims (1)
照射下に酸素と反応させることを特徴とするヘキサフル
オロアセトンの製造法。 ２、水の存在下で反応させる特許請求の範囲第１項記載
のヘキサフルオロアセトンの製造法。 ３、ヘキサフルオロアセトンが水和物として得られる特
許請求の範囲第１項または第２項記載のヘキサフルオロ
アセトンの製造法。[Claims] 1. A method for producing hexafluoroacetone, which comprises reacting heptafluoroisobutenyl alkyl ether with oxygen under irradiation with light. 2. The method for producing hexafluoroacetone according to claim 1, wherein the reaction is carried out in the presence of water. 3. The method for producing hexafluoroacetone according to claim 1 or 2, wherein hexafluoroacetone is obtained as a hydrate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12032285A JPS61277645A (en) | 1985-06-03 | 1985-06-03 | Production of hexafluoroacetone |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12032285A JPS61277645A (en) | 1985-06-03 | 1985-06-03 | Production of hexafluoroacetone |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61277645A true JPS61277645A (en) | 1986-12-08 |
| JPS6411624B2 JPS6411624B2 (en) | 1989-02-27 |
Family
ID=14783382
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12032285A Granted JPS61277645A (en) | 1985-06-03 | 1985-06-03 | Production of hexafluoroacetone |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61277645A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4885398A (en) * | 1987-07-21 | 1989-12-05 | Nippon Mektron Limited | Process for producing hexafluoroacetone or its hydrate |
| JP2001081056A (en) * | 1999-09-13 | 2001-03-27 | Nippon Mektron Ltd | Production of hexafluoro acetone or its hydrate |
| US6274005B1 (en) * | 2000-05-26 | 2001-08-14 | Halocarbon Products Corporation | Method for the preparation of hexafluoroacetone |
| WO2007142110A1 (en) | 2006-06-05 | 2007-12-13 | Daikin Industries, Ltd. | Novel carboxylic acid compound, use thereof, and process for producing the same |
| WO2008004466A1 (en) | 2006-07-06 | 2008-01-10 | Daikin Industries, Ltd. | NOVEL α-FLUOROMETHOXYCARBOXYLIC ESTER, PROCESS FOR PRODUCING THE α-FLUOROMETHOXYCARBOXYLIC ESTER, AND PROCESS FOR PRODUCING SEVOFLURANE |
| WO2009063783A1 (en) | 2007-11-13 | 2009-05-22 | Daikin Industries, Ltd. | Novel carboxylic acid ester, use of the same, and method for producing the same |
| US7598425B2 (en) | 2004-04-19 | 2009-10-06 | Daikin Industries, Ltd. | Method for producing hydrate of fluoroalkyl ketone |
-
1985
- 1985-06-03 JP JP12032285A patent/JPS61277645A/en active Granted
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4885398A (en) * | 1987-07-21 | 1989-12-05 | Nippon Mektron Limited | Process for producing hexafluoroacetone or its hydrate |
| JP2001081056A (en) * | 1999-09-13 | 2001-03-27 | Nippon Mektron Ltd | Production of hexafluoro acetone or its hydrate |
| JP4534274B2 (en) * | 1999-09-13 | 2010-09-01 | ユニマテック株式会社 | Method for producing hexafluoroacetone or hydrate thereof |
| US6274005B1 (en) * | 2000-05-26 | 2001-08-14 | Halocarbon Products Corporation | Method for the preparation of hexafluoroacetone |
| WO2001092270A3 (en) * | 2000-05-26 | 2003-10-16 | Halocarbon Prod Corp | An improved method for the preparation of hexafluoroacetone |
| US7598425B2 (en) | 2004-04-19 | 2009-10-06 | Daikin Industries, Ltd. | Method for producing hydrate of fluoroalkyl ketone |
| US7985877B2 (en) | 2006-06-05 | 2011-07-26 | Daikin Industries, Ltd. | Carboxylic acid compound, use thereof, and process for producing the same |
| WO2007142110A1 (en) | 2006-06-05 | 2007-12-13 | Daikin Industries, Ltd. | Novel carboxylic acid compound, use thereof, and process for producing the same |
| EP2479161A1 (en) | 2006-06-05 | 2012-07-25 | Daikin Industries, Ltd. | A novel process for producing 1,1,1,3,3,3-hexafluoro-2-methoxypropane |
| WO2008004466A1 (en) | 2006-07-06 | 2008-01-10 | Daikin Industries, Ltd. | NOVEL α-FLUOROMETHOXYCARBOXYLIC ESTER, PROCESS FOR PRODUCING THE α-FLUOROMETHOXYCARBOXYLIC ESTER, AND PROCESS FOR PRODUCING SEVOFLURANE |
| US8022245B2 (en) | 2006-07-06 | 2011-09-20 | Daikin Industries, Ltd. | Alpha-fluoromethoxycarboxylic ester, process for producing the alpha-fluoromethoxycarboxylic ester, and process for producing sevoflurane |
| WO2009063783A1 (en) | 2007-11-13 | 2009-05-22 | Daikin Industries, Ltd. | Novel carboxylic acid ester, use of the same, and method for producing the same |
| US8013182B2 (en) | 2007-11-13 | 2011-09-06 | Daikin Industries, Ltd. | Carboxylic acid ester, use of the same, and method for producing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6411624B2 (en) | 1989-02-27 |
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