JPH0952886A - Production of hexafluoropropylene oxide - Google Patents
Production of hexafluoropropylene oxideInfo
- Publication number
- JPH0952886A JPH0952886A JP20366195A JP20366195A JPH0952886A JP H0952886 A JPH0952886 A JP H0952886A JP 20366195 A JP20366195 A JP 20366195A JP 20366195 A JP20366195 A JP 20366195A JP H0952886 A JPH0952886 A JP H0952886A
- Authority
- JP
- Japan
- Prior art keywords
- hfpo
- oxygen
- compound
- reaction
- hfp
- 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
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、ヘキサフルオロプ
ロピレンオキサイド（ＨＦＰＯ）の製造方法に関する。
さらに詳しくは、ヘキサフルオロプロピレン（ＨＦＰ）
を特定の不活性溶媒の存在下で酸化することからなるヘ
キサフルオロプロピレンオキサイドの製造方法に関す
る。TECHNICAL FIELD The present invention relates to a method for producing hexafluoropropylene oxide (HFPO).
More specifically, hexafluoropropylene (HFP)
The present invention relates to a method for producing hexafluoropropylene oxide, which comprises oxidizing benzene in the presence of a specific inert solvent.
【０００２】ＨＦＰＯは、各種フッ素化合物、例えばフ
ッ素樹脂やエラストマーの中間体であるヘキサフルオロ
アセトン、パーフルオロアルキルビニルエーテルなどの
原料として重要な化合物である。またそのオリゴマーは
潤滑油や熱媒油等に広く使用されている。HFPO is an important compound as a raw material for various fluorine compounds such as hexafluoroacetone and perfluoroalkyl vinyl ether, which are intermediates of fluororesins and elastomers. Further, the oligomer is widely used as a lubricating oil, a heat transfer oil and the like.
【０００３】[0003]
【従来の技術】ＨＦＰＯの製造方法としては、従来よ
り、種々の方法が知られているが、一般的にはＨＦＰを
部分酸化して製造している。この部分酸化方法として
は、アルカリ性過酸化水素、分子状酸素、次亜塩素酸
塩、有機過酸化物などの酸化剤を使用する方法や、電解
酸化法等が知られている。2. Description of the Related Art Conventionally, various methods have been known as a method for producing HFPO, but generally, HFP is produced by partial oxidation. Known examples of this partial oxidation method include a method using an oxidizing agent such as alkaline hydrogen peroxide, molecular oxygen, hypochlorite, and organic peroxide, and an electrolytic oxidation method.
【０００４】これらの部分酸化法の中で、酸化剤として
分子状酸素を用いる方法は安価な酸素を用いる点で有利
であり、通常は、不活性溶媒の存在下にＨＦＰを酸化さ
せる方法が採用される。該方法では、Ｃ−Ｃ結合が切断
されて高次に酸化された分解物（ＣＦ3 ＣＯＦ、ＣＯＦ
2 ）が副生するものの、簡便であり高効率のため多くの
研究がなされている。Among these partial oxidation methods, the method of using molecular oxygen as the oxidant is advantageous in that inexpensive oxygen is used, and the method of oxidizing HFP in the presence of an inert solvent is usually adopted. To be done. In this method, a decomposition product (CF 3 COF, COF) in which a C—C bond is cleaved and oxidized to a higher degree is used.
Although 2 ) is a by-product, much research has been done because it is simple and highly efficient.
【０００５】[0005]
【発明が解決しようとする課題】たとえば、（１）ＵＳ
Ｐ３, ５３６, ７３３号および対応する特公昭４５−１
１６８３には、１，１，２−トリクロロ−１，２，２−
トリフルオロエタン（Ｒ−１１３）、トリクロロフルオ
ロメタン（Ｒ−１１）、四塩化炭素、窒素、ヘリウム、
炭酸ガスを不活性溶媒として用いた反応およびその成績
が明示されている。また、１，２−ジブロモヘキサフル
オロプロパン（Ｒ−２１６Ｂ２）、１，２−ジブロモ−
１−クロロ−トリフルオロエタン（Ｒ−１１３Ｂ２）、
１−クロロ−３−ヒドロ−ヘキサフルオロプロパン（Ｒ
−２２６ｃｂ）、２，２−ジクロロ−１，１，１−トリ
フルオロエタン（Ｒ−１２３）、１，３−ジクロロテト
ラフルオロアセトン、ヘプタフルオロブタン酸無水物、
パーフルオロ（２，５−ジメチル−３，６−ジオキサノ
ナノニル）フルオライド（ＨＦＰＯ二量体）、オクタフ
ルオロジチアジン、１，２−ジクロロヘキサフルオロシ
クロペンテン、パーフルオロシクロペンテン、パーフル
オロ−２−ブチルオキソラン、トリパーフルオロブチル
アミンを用いた場合も、ＨＦＰＯが生成することが記載
されているが、これらを用いた場合のＨＦＰＯの収率は
不明であり、溶媒としての特徴や優位性についてまった
く言及されていない。SUMMARY OF THE INVENTION For example, (1) US
P3, 536, 733 and corresponding Japanese Patent Publication No. 45-1
1683 includes 1,1,2-trichloro-1,2,2-
Trifluoroethane (R-113), trichlorofluoromethane (R-11), carbon tetrachloride, nitrogen, helium,
The reaction using carbon dioxide gas as an inert solvent and its results are clarified. In addition, 1,2-dibromohexafluoropropane (R-216B2), 1,2-dibromo-
1-chloro-trifluoroethane (R-113B2),
1-chloro-3-hydro-hexafluoropropane (R
-226cb), 2,2-dichloro-1,1,1-trifluoroethane (R-123), 1,3-dichlorotetrafluoroacetone, heptafluorobutanoic acid anhydride,
Perfluoro (2,5-dimethyl-3,6-dioxanonanonyl) fluoride (HFPO dimer), octafluorodithiazine, 1,2-dichlorohexafluorocyclopentene, perfluorocyclopentene, perfluoro-2-butyl It is described that HFPO is also produced when oxolane and triperfluorobutylamine are used, but the yield of HFPO when these are used is unknown, and the characteristics and superiority as a solvent are not mentioned at all. It has not been.
【０００６】また、（２）ＵＳＰ３, ６００, ４０９号
にはベンゼン、ニトロベンゼンまたはハロゲン化ベンゼ
ン等の芳香属化合物をＲ−１１３等の溶媒に添加するこ
とにより、ヘキサフルオロアセトンのような副生成物を
抑制し、ＨＦＰＯを高収率で得る方法が記載されてい
る。しかし、芳香属化合物は臭気や毒性等の作業環境の
点で好ましくない問題がある。(2) USP 3,600,409 describes a by-product such as hexafluoroacetone by adding an aromatic compound such as benzene, nitrobenzene or halogenated benzene to a solvent such as R-113. And a method for obtaining HFPO in a high yield is described. However, aromatic compounds have an unfavorable problem in terms of work environment such as odor and toxicity.
【０００７】（３）ロシア文献Izvestia Akademii Nauk
(10,2230-2234,1975,UDC542.943 号,UDC547.413 号) お
よび特開平１−１３５７８０では、パーフルオロエーテ
ルを用いる方法が記載されている。しかし、パーフルオ
ロエーテルを用いた場合には、収率が低く、反応操作が
しにくい問題が認められた。また、パーフルオロポリエ
ーテル類（商品名フォンブリンの名で知られている。）
は、半導体用途の真空ポンプ等の限定された用途に使わ
れるきわめて高価なオイルである。(3) Russian literature Izvestia Akademii Nauk
(10,2230-2234,1975, UDC542.943, UDC547.413) and JP-A-1-135780 describe a method using perfluoroether. However, when perfluoroether was used, the yield was low, and there was a problem that the reaction operation was difficult. Also, perfluoropolyethers (known under the trade name Fomblin).
Is an extremely expensive oil used in limited applications such as vacuum pumps for semiconductor applications.
【０００８】また、先のロシア文献には、Ｒ−１１３を
用いる方法も記載されており反応溶媒をリサイクル使用
すると、該溶媒中に含まれるＨＦＰ酸化時の副生物であ
る高沸点有機過酸化物が混入することにより、反応誘導
期を消滅できると記載されている。しかしＲ−１１３
は、オゾン層を破壊する恐れがある化合物として今後は
使用できなくなる問題がある。Further, the above-mentioned Russian document also describes a method using R-113, and when the reaction solvent is recycled, a high-boiling-point organic peroxide which is a by-product at the time of HFP oxidation contained in the solvent is used. It is described that the reaction induction period can be eliminated by mixing with. But R-113
Has a problem that it cannot be used as a compound that may destroy the ozone layer in the future.
【０００９】（４）（３）と同様の技術として特開平６
−１０７６５０には、ＨＦＰの酸素酸化時に副生するポ
リ（パーフルオロオキシメチレン）酸フルオライド由来
の過酸化物が、反応の誘導期を無くして反応を安定化さ
せ、収率を向上させることが示されている。(4) As a technique similar to (3), Japanese Patent Laid-Open No.
-107650 shows that a peroxide derived from poly (perfluorooxymethylene) fluoride, which is a by-product during oxygen oxidation of HFP, stabilizes the reaction by eliminating the induction period of the reaction and improves the yield. Has been done.
【００１０】また、ＨＦＰの酸化には、従来Ｒ−１１３
等のオゾン層破壊の懸念されるパークロロフルオロカー
ボンのなかで、特定フロンを溶媒にすることが一般的で
あったが、（５）近年の公開特許には、１，１，３，４
−テトラクロロ−ヘキサフルオロブタン（Ｒ−３１６ｌ
ｂｃ）等の、規制を受けていない溶媒を使用することが
記載されている。しかし、Ｒ−３１６ｌｂｃは、規制は
受けていないがオゾン層破壊が懸念される物質であると
いう問題がある。In addition, conventional R-113 is used for the oxidation of HFP.
Among the perchlorofluorocarbons, which are concerned about ozone layer depletion, it is common to use specific CFCs as a solvent. (5) Recent published patents include 1, 1, 3, 4
-Tetrachloro-hexafluorobutane (R-316l
It is described to use non-regulated solvents such as bc). However, there is a problem that R-316lbc is a substance that is not regulated but may cause ozone layer depletion.
【００１１】本発明者らは、ＨＦＰを酸素で酸化してＨ
ＦＰＯを製造するにあたり、以下の条件を検討した。 (1) ＨＦＰＯが高収率で得られること。 (2) 原料が安価であること。 (3) 設備が複雑でないこと。 (4) 安全性が確保できること。 (5) オゾン層破壊、地球温暖化等、地球環境へ与える影
響の少ない原料を使用をすること。The present inventors oxidize HFP with oxygen to produce H
The following conditions were examined in manufacturing FPO. (1) HFPO can be obtained in high yield. (2) Raw materials are inexpensive. (3) Equipment is not complicated. (4) Safety can be secured. (5) Use raw materials that have little effect on the global environment such as ozone depletion and global warming.
【００１２】本発明は、安価かつ高収率でＨＦＰＯを製
造する方法を確立するためになされたものであり、具体
的には、地球環境等に影響の少ない安価な溶媒を使用す
る製造方法を確立することを目的とする。The present invention was made in order to establish a method for producing HFPO at a low cost and in a high yield. Specifically, a production method using an inexpensive solvent which has little influence on the global environment and the like is described. The purpose is to establish.
【００１３】[0013]
【課題を解決するための手段】本発明は、ＨＦＰＯの高
収率化を達成すべく鋭意検討を重ねた結果、ＨＦＰＯの
二量体、ＨＦＰＯの製造時に副生するＨＦＰＯの多量
体、あるいはそれらの混合物である下記の構造を有する
化合物を用いてＨＦＰを酸素酸化を実施すると、Ｒ−１
１３など従来の溶媒に比べ、ＨＦＰの高転化率域におけ
るＨＦＰＯ選択率の低下を抑制できることを見いだし本
発明に至った。Means for Solving the Problems In the present invention, as a result of intensive studies to achieve a high yield of HFPO, a dimer of HFPO, a multimer of HFPO produced as a by-product during the production of HFPO, or those Oxygen oxidation of HFP using a compound having the following structure, which is a mixture of
The inventors have found that it is possible to suppress a decrease in the HFPO selectivity in the high conversion region of HFP, as compared with a conventional solvent such as No. 13 and the like, and thus reached the present invention.
【００１４】すなわち、本発明は、ヘキサフルオロプロ
ピレンと酸素を式（１）で表される化合物（以下、化合
物（１）と記す。）の存在下で反応させることを特徴と
するヘキサフルオロプロピレンオキサイドの製造方法を
提供する。ただし、下式において、ｎは０〜４の整数を
示す。That is, the present invention is characterized by reacting hexafluoropropylene and oxygen in the presence of a compound represented by the formula (1) (hereinafter referred to as compound (1)). A method for manufacturing the same is provided. However, in the following formula, n represents an integer of 0 to 4.
【００１５】[0015]
【化３】 ＣＦ3 （ＣＦ2 ）2 Ｏ［ＣＦ（ＣＦ3 ）ＣＦ2 Ｏ］n ＣＦ（ＣＦ3 ）ＣＯＦ ・・・・（１）Embedded image CF 3 (CF 2 ) 2 O [CF (CF 3 ) CF 2 O] n CF (CF 3 ) COF ... (1)
【００１６】化合物（１）のうちｎが０であるものは、
汎用フッ素樹脂として量産されているＰＦＡの原料であ
るパーフルオロ（プロピルビニルエーテル）［以下、Ｐ
ＰＶＥと記す。］の原料であり、容易かつ安価に入手可
能な化合物である。また、ｎが１、２、３、および４の
化合物は、ＰＰＶＥ製造時の副生物として入手可能な化
合物であり、これまで、有用な用途が知られていなかっ
た化合物である。したがって、ｎが１〜４の整数である
化合物（１）は、安価に入手可能であり、経済的な点か
らも特に好適である。また、化合物（１）は、ｎの値が
異なる２種以上の混合物であってもよく、また、ｎの平
均値が１〜４の範囲にある混合物であってもよい。本発
明は、これまで実質的に用途が知られていなかった化合
物の有用な用途を見いだしたという側面も有する。Compounds (1) in which n is 0 are
Perfluoro (propyl vinyl ether), which is a raw material of PFA mass-produced as a general-purpose fluororesin [hereinafter, P
It is written as PVE. ], And a compound that can be easily and inexpensively obtained. Further, the compounds in which n is 1, 2, 3, and 4 are compounds that can be obtained as a by-product during the production of PPVE, and their useful uses have not been known so far. Therefore, the compound (1) in which n is an integer of 1 to 4 is available at low cost and is particularly preferable from the economical point of view. In addition, the compound (1) may be a mixture of two or more kinds having different values of n, or may be a mixture having an average value of n in the range of 1 to 4. The present invention also has an aspect of finding a useful use of a compound whose use has been unknown so far.
【００１７】さらに、式（１）で表される化合物は、極
めて揮散しにくく、空気中でカルボン酸となり、オゾン
層への影響もなく、地球環境へ与える影響が少ない化合
物である。また、酸素をよく溶解させる性質も有する。
また、化合物（１）は、酸フルオライドとしてエポキシ
化反応の中間体としての役割も示唆される。Further, the compound represented by the formula (1) is a compound which is extremely difficult to volatilize, becomes a carboxylic acid in the air, has no effect on the ozone layer, and has little effect on the global environment. It also has the property of dissolving oxygen well.
Further, it is suggested that the compound (1) also functions as an acid fluoride as an intermediate in the epoxidation reaction.
【００１８】本発明の反応においては、反応容器とし
て、内部の撹拌可能な加圧反応容器を使用するのが好ま
しく、特にステンレス、ハステロイ等の耐酸性金属材質
のオートクレーブが好ましい。本発明においては、ＨＦ
Ｐと酸素と式（１）で表される化合物とを耐圧製反応器
に導入しながら連続して反応させるのが好ましい。化合
物（１）、ＨＦＰ、および酸素は、それぞれ、ノズルよ
り反応器に導入し、生成物は、容器上部より化合物
（１）と共に抜き出し（気液混相）、安全性の理由か
ら、さらに反応器出口には窒素を導入できるようにす
る。反応圧力は反応器出口で制御し、反応温度は加熱浴
を用いて制御する。In the reaction of the present invention, it is preferable to use a pressure-reacting vessel capable of stirring inside, as an autoclave made of an acid-resistant metal material such as stainless steel or hastelloy. In the present invention, HF
It is preferable that P, oxygen and the compound represented by the formula (1) are continuously reacted while being introduced into a pressure resistant reactor. The compound (1), HFP, and oxygen are introduced into the reactor through a nozzle, and the product is taken out together with the compound (1) from the upper part of the container (gas-liquid mixed phase). Allow nitrogen to be introduced into. The reaction pressure is controlled at the reactor outlet and the reaction temperature is controlled using a heating bath.
【００１９】本発明において使用する酸素は、酸素その
ものでも、他の不活性ガスで希釈したもの等であっても
よい。たとえば、窒素で希釈した酸素や空気等が挙げら
れる。また、ＨＦＰと酸素の使用割合は、ＨＦＰの１モ
ルに対して酸素の１〜５モルが好ましく、特に、１〜２
モルが好ましい。また、化合物（１）の量は、特に限定
されず、いかなる量であってもよいが、通常は、ＨＦＰ
１モルに対して、１〜２０モル程度が好ましく、特に１
〜５モルが好ましい。また、反応圧力は２０〜５０ｋｇ
／ｃｍ2 が好ましく、特に２５〜４０ｋｇ／ｃｍ2 が好
ましい。反応温度は１００〜２００℃が好ましく、特に
１２０〜１８０℃が好ましく、さらに１４０〜１７０℃
が好ましい。反応の滞留時間は、特に限定されないが、
通常５〜２４０分程度であり、実質的な反応速度を得る
ためには、２０〜１００分程度が好ましい。The oxygen used in the present invention may be oxygen itself or one diluted with another inert gas. For example, oxygen or air diluted with nitrogen can be used. Further, the use ratio of HFP and oxygen is preferably 1 to 5 mol of oxygen with respect to 1 mol of HFP, and particularly 1 to 2 mol.
Molar is preferred. The amount of the compound (1) is not particularly limited and may be any amount, but usually HFP
About 1 to 20 mol is preferable per 1 mol, and particularly 1
-5 mol is preferable. The reaction pressure is 20 to 50 kg.
/ Cm 2 is preferable, and 25 to 40 kg / cm 2 is particularly preferable. The reaction temperature is preferably 100 to 200 ° C, particularly preferably 120 to 180 ° C, and further 140 to 170 ° C.
Is preferred. The residence time of the reaction is not particularly limited,
It is usually about 5 to 240 minutes, and preferably about 20 to 100 minutes in order to obtain a substantial reaction rate.
【００２０】[0020]
【実施例】以下に本発明を例を挙げて具体例的に説明す
るが、これらによって、本発明は限定されない。ただ
し、例１〜５は、本発明の実施例に該当し、例７および
例８は、比較例に該当する。EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto. However, Examples 1 to 5 correspond to Examples of the present invention, and Examples 7 and 8 correspond to Comparative Examples.
【００２１】［例１］２リットルのハステロイ製オート
クレーブに溶媒として、パーフルオロ−２，５−ジメチ
ル−３，６−ジオキサノナノニルフルオライド（化合物
（１）におけるｎが１の化合物：沸点１１３℃）を６．
０ｍｏｌ／ｈｒで導入しながら、ＨＦＰを３．４ｍｏｌ
／ｈｒ、酸素を２．５ｍｏｌ／ｈｒで導入し、反応開始
後、圧力を３３ｋｇ／ｃｍ2 、内温を１６３℃に制御し
た。抜き出し口直前より連続的に窒素を２．５ｍｏｌ／
ｈｒで供給し、抜き出した反応ガスと溶媒の混合物を、
数回サンプリングし、ガスクロマトグラフで分析した。
ＨＦＰの導入量および反応ガスのＨＦＰ、ＨＦＰＯ量よ
り、ＨＦＰ転化率６８％およびＨＦＰＯ選択率６８％の
結果を安定して得た。Example 1 Perfluoro-2,5-dimethyl-3,6-dioxanonanonylfluoride (compound in which n is 1 in compound (1): boiling point 113) was used as a solvent in a 2 liter Hastelloy autoclave. ℃) 6.
3.4 mol of HFP while introducing at 0 mol / hr
/ Hr, oxygen was introduced at 2.5 mol / hr, and after starting the reaction, the pressure was controlled at 33 kg / cm 2 and the internal temperature was controlled at 163 ° C. Nitrogen was continuously added at 2.5 mol / min immediately before the outlet.
The mixture of the reaction gas and the solvent, which was supplied by the hr.
It sampled several times and analyzed by the gas chromatograph.
From the amount of HFP introduced and the amounts of HFP and HFPO in the reaction gas, the results of HFP conversion rate of 68% and HFPO selectivity rate of 68% were stably obtained.
【００２２】［例２〜５］溶媒として、パーフルオロ−
２，５−ジメチル−３，６−ジオキサノナノニルフルオ
ライドのかわりに式（１）におけるｎが０の化合物（Ｈ
ＦＰＯ二量体）、ｎが２の化合物（ＨＦＰＯ四量体）、
ｎが３の化合物（ＨＦＰＯ五量体）、ｎが４の化合物
（ＨＦＰＯ六量体）をそれぞれ表１に示すような量で導
入すること以外は、例１と同様に反応を実施した。抜き
出し口より反応ガスと溶媒の混合物を数回サンプリング
し、ガスクロマトグラフで分析した。いずれの場合も反
応は安定し、連続的に反応させることができた。ＨＦＰ
の導入量および反応ガスのＨＦＰ、ＨＦＰＯ量より、Ｈ
ＦＰ転化率とＨＦＰＯ選択率を算出した結果を表１に示
す。[Examples 2 to 5] As a solvent, perfluoro-
Instead of 2,5-dimethyl-3,6-dioxanonanonyl fluoride, a compound in which n in formula (1) is 0 (H
FPO dimer), a compound in which n is 2 (HFPO tetramer),
The reaction was carried out in the same manner as in Example 1 except that the compound of n = 3 (HFPO pentamer) and the compound of n = 4 (HFPO hexamer) were introduced in the amounts shown in Table 1, respectively. The mixture of the reaction gas and the solvent was sampled several times from the outlet and analyzed by gas chromatography. In any case, the reaction was stable and could be continuously reacted. HFP
Of HFP and HFPO in the reaction gas
Table 1 shows the results of calculating the FP conversion rate and the HFPO selectivity.
【００２３】[0023]
【表１】 [Table 1]
【００２４】（ＨＦＰＯ）2 ：ＨＦＰＯ二量体［パーフ
ルオロ（２−メチル−３−オキサヘキサノイル）フルオ
ライド］ （ＨＦＰＯ）4 ：ＨＦＰＯ四量体［パーフルオロ（２，
５，８−トリメチル−３，６，９−トリオキサドデカノ
イル）フルオライド］ （ＨＦＰＯ）5 ：ＨＦＰＯ五量体［パーフルオロ（２，
５，８，１１−テトラメチル−３，６，９，１２−テト
ラオキサペンタデカノイル）フルオライド］ （ＨＦＰＯ）6 ：ＨＦＰＯ六量体［パーフルオロ（２，
５，８，１１，１４−ペンタメチル−３，６，９，１
２，１５−ペンタオキサオクタデカノイル）フルオライ
ド］(HFPO) 2 : HFPO dimer [perfluoro (2-methyl-3-oxahexanoyl) fluoride] (HFPO) 4 : HFPO tetramer [perfluoro (2,
5,8-Trimethyl-3,6,9-trioxadodecanoyl) fluoride] (HFPO) 5 : HFPO pentamer [perfluoro (2,2
5,8,11-Tetramethyl-3,6,9,12-tetraoxapentadecanoyl) fluoride] (HFPO) 6 : HFPO hexamer [perfluoro (2,
5,8,11,14-pentamethyl-3,6,9,1
2,15-Pentaoxaoctadecanoyl) fluoride]
【００２５】［例６］２リットルのハステロイ製オート
クレーブに溶媒として、ＨＦＰＯ三量体のかわりに１，
１，２−トリクロロ−１，２，２−トリフルオロエタン
（Ｒ−１１３）を１４．２ｍｏｌ／ｈｒで導入する他
は、実施例１と同様に制御した。抜き出し口より反応ガ
スと溶媒の混合物を数回サンプリングし、ガスクロマト
グラフで分析した。反応は安定し、連続的に反応させる
ことができた。ＨＦＰの導入量および反応ガスのＨＦ
Ｐ、ＨＦＰＯ量より、ＨＦＰ転化率６７％およびＨＦＰ
Ｏ選択率５５％の結果を得た。Example 6 In a 2 liter Hastelloy autoclave, the solvent was 1, 1, instead of the HFPO trimer.
Control was performed in the same manner as in Example 1 except that 1,2-trichloro-1,2,2-trifluoroethane (R-113) was introduced at 14.2 mol / hr. The mixture of the reaction gas and the solvent was sampled several times from the outlet and analyzed by gas chromatography. The reaction was stable and could be reacted continuously. Amount of HFP introduced and HF of reaction gas
From the amount of P and HFPO, HFP conversion rate 67% and HFP
A result with an O selectivity of 55% was obtained.
【００２６】［例７］２リットルのハステロイ製オート
クレーブに溶媒として、ＨＦＰＯ三量体のかわりに以下
の構造式を示す平均分子量３２００のパーフルオロポリ
エーテルを０．９３ｍｏｌ／ｈｒで導入する他は、例１
と同様に反応させた。[Example 7] A perfluoropolyether having an average molecular weight of 3200 having the following structural formula was introduced as a solvent into a 2-liter Hastelloy autoclave at a rate of 0.93 mol / hr instead of the HFPO trimer. Example 1
The reaction was carried out in the same manner as described above.
【００２７】[0027]
【化４】ＣＦ3 （ＯＣＦ2 ）n ［ＣＦ（ＣＦ3 ）ＣＦ2
Ｏ］m Ｃ2 Ｆ5 Embedded image CF 3 (OCF 2 ) n [CF (CF 3 ) CF 2
O] m C 2 F 5
【００２８】抜き出し口より反応ガスと溶媒の混合物を
サンプリングしたが、溶媒が発泡し反応圧力を安定して
運転するのが困難であった。ＨＦＰの導入量および反応
ガスのＨＦＰ、ＨＦＰＯ量のガスクロマトグラフ分析結
果より、ＨＦＰ転化率５５％およびＨＦＰＯ選択率６３
％の結果を得た。A mixture of the reaction gas and the solvent was sampled from the outlet, but the solvent foamed and it was difficult to operate at a stable reaction pressure. From the gas chromatographic analysis results of the amount of HFP introduced and the amounts of HFP and HFPO in the reaction gas, HFP conversion rate 55% and HFPO selectivity 63
% Results were obtained.
【００２９】[0029]
【発明の効果】本発明方法によれば、反応溶媒として、
地球環境に影響を及ぼさない安価な溶を用いて、高収率
でヘキサフルオロプロピレンオキサイドが製造可能であ
る。また、本発明の方法は、副生物も少なく、反応操作
も容易であり、工業的に有利な連続的製造方法にも採用
できる利点もある。According to the method of the present invention, as a reaction solvent,
Hexafluoropropylene oxide can be produced in high yield using an inexpensive solution that does not affect the global environment. Further, the method of the present invention has few by-products, is easy to carry out the reaction operation, and has an advantage that it can be applied to an industrially advantageous continuous production method.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 江畑 研一 神奈川県横浜市神奈川区羽沢町1150番地 旭硝子株式会社中央研究所内 ─────────────────────────────────────────────────── --- Continuation of the front page (72) Inventor Kenichi Ebata 1150 Hazawa-machi, Kanagawa-ku, Yokohama, Kanagawa Prefecture Asahi Glass Co., Ltd. Central Research Laboratory
Claims (4)
（１）で表される化合物の存在下で反応させることを特
徴とするヘキサフルオロプロピレンオキサイドの製造方
法。ただし、下式において、ｎは０〜４の整数を示す。 【化１】 ＣＦ3 （ＣＦ2 ）2 Ｏ［ＣＦ（ＣＦ3 ）ＣＦ2 Ｏ］n ＣＦ（ＣＦ3 ）ＣＯＦ ・・・・（１）1. A method for producing hexafluoropropylene oxide, which comprises reacting hexafluoropropylene and oxygen in the presence of a compound represented by the formula (1). However, in the following formula, n represents an integer of 0 to 4. Embedded image CF 3 (CF 2 ) 2 O [CF (CF 3 ) CF 2 O] n CF (CF 3 ) COF ... (1)
請求項１の製造方法。2. The method according to claim 1, wherein n in the formula (1) is an integer of 1 to 4.
製造方法。3. The method according to claim 1, wherein n in the formula (1) is 1.
（１）で表される化合物とを耐圧製反応器に導入しなが
ら連続して反応させることを特徴とするヘキサフルオロ
プロピレンオキサイドの製造方法。ただし、下式におい
て、ｎは０〜４の整数を示す。 【化２】 ＣＦ3 （ＣＦ2 ）2 Ｏ［ＣＦ（ＣＦ3 ）ＣＦ2 Ｏ］n ＣＦ（ＣＦ3 ）ＣＯＦ ・・・・（１）4. A method for producing hexafluoropropylene oxide, which comprises continuously reacting hexafluoropropylene, oxygen and a compound represented by the formula (1) while introducing them into a pressure resistant reactor. However, in the following formula, n represents an integer of 0 to 4. Embedded image CF 3 (CF 2 ) 2 O [CF (CF 3 ) CF 2 O] n CF (CF 3 ) COF ... (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20366195A JP3785654B2 (en) | 1995-08-09 | 1995-08-09 | Method for producing hexafluoropropylene oxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20366195A JP3785654B2 (en) | 1995-08-09 | 1995-08-09 | Method for producing hexafluoropropylene oxide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0952886A true JPH0952886A (en) | 1997-02-25 |
| JP3785654B2 JP3785654B2 (en) | 2006-06-14 |
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ID=16477763
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP20366195A Expired - Fee Related JP3785654B2 (en) | 1995-08-09 | 1995-08-09 | Method for producing hexafluoropropylene oxide |
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| Country | Link |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003040879A (en) * | 2001-07-31 | 2003-02-13 | Asahi Glass Co Ltd | Method for producing hexafluoropropylene oxide |
| CN104557797A (en) * | 2013-10-28 | 2015-04-29 | 浙江蓝天环保高科技股份有限公司 | Method for shortening induction period of epoxidation reaction of hexafluoropropylene |
| CN104557788A (en) * | 2013-10-28 | 2015-04-29 | 浙江蓝天环保高科技股份有限公司 | Preparation method of hexafluoropropylene oxide |
-
1995
- 1995-08-09 JP JP20366195A patent/JP3785654B2/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003040879A (en) * | 2001-07-31 | 2003-02-13 | Asahi Glass Co Ltd | Method for producing hexafluoropropylene oxide |
| CN104557797A (en) * | 2013-10-28 | 2015-04-29 | 浙江蓝天环保高科技股份有限公司 | Method for shortening induction period of epoxidation reaction of hexafluoropropylene |
| CN104557788A (en) * | 2013-10-28 | 2015-04-29 | 浙江蓝天环保高科技股份有限公司 | Preparation method of hexafluoropropylene oxide |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3785654B2 (en) | 2006-06-14 |
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