JP4129617B2 - COF2 manufacturing method - Google Patents
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- JP4129617B2 JP4129617B2 JP2002117764A JP2002117764A JP4129617B2 JP 4129617 B2 JP4129617 B2 JP 4129617B2 JP 2002117764 A JP2002117764 A JP 2002117764A JP 2002117764 A JP2002117764 A JP 2002117764A JP 4129617 B2 JP4129617 B2 JP 4129617B2
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Description
【０００１】
【発明の属する技術分野】
本発明は、ＣＯＦ2（フッ化カルボニル）の製造方法に関する。
【０００２】
【従来の技術と発明が解決しようとする課題】
有機合成の試薬等として有用な化合物であるＣＯＦ2を、安全で安価に製造する新規な製造方法が求められている。
【０００３】
また、次世代ドライエッチングガスの候補として、高純度のＣＯＦ2を得る製造方法が求められている。
【０００４】
一方、ヘキサフルオロプロピレンを酸素で酸化してヘキサフルオロプロピレンオキサイドを製造する方法において副生する化合物を有効に利用する方法が求められている。
【０００５】
本発明の課題は、反応副生物等を用いて、ＣＯＦ2を安全で安価に製造する新規な製造方法を提供することにある。
【０００６】
【課題を解決するための手段】
本発明は、下記に示すとおりのＣＯＦ2の製造方法を提供するものである。
項１． 一般式（１）；
ＣＦ3Ｏ(ＣＦ2Ｏ)n−Ｒ （１）
（式中、−Ｒは−ＣＯＦ、−ＯＣＯＦまたは−ＣＦ2ＣＯＦを示し、ｎは０〜５０の整数を示す。）で表される化合物からなる群より選択される少なくとも１種の化合物を、触媒の存在下で分解反応させることを特徴とするＣＯＦ2の製造方法。
項２． 触媒が、活性炭、金属ハロゲン化物、テトラ鎖状または環状アルキル尿素および４級アンモニウム塩からなる群より選択される少なくとも１種であることを特徴とする項１に記載の方法。
項３． 金属ハロゲン化物が、一般式；ＭＸ（式中、ＭはＬｉ、Ｎａ、Ｋ、Ｒｂ、Ｃｓ、ＣｕまたはＡｇを示し、ＸはＦ、Ｃｌ、ＢｒまたはＩを示す。）で表される化合物からなる群より選択される少なくとも１種の化合物であることを特徴とする項２に記載の方法。
項４． テトラ鎖状または環状アルキル尿素が、テトラメチル尿素であることを特徴とする項２に記載の方法。
項５． 一般式（１）で表される化合物が、ヘキサフルオロプロピレンを酸化してヘキサフルオロプロピレンオキサイドを製造する方法において副生する化合物であることを特徴とする項１〜４のいずれかに記載の方法。
【０００７】
【発明の実施の形態】
本発明のＣＯＦ2の製造方法は、一般式（１）；
ＣＦ3Ｏ(ＣＦ2Ｏ)n−Ｒ （１）
（式中、−Ｒは−ＣＯＦ、−ＯＣＯＦまたは−ＣＦ2ＣＯＦを示し、ｎは０〜５０の整数を示す。）で表される化合物からなる群より選択される少なくとも１種の化合物を、触媒の存在下で分解反応させることを特徴とする。
【０００８】
本発明において用いる一般式（１）で表される化合物は、特に限定されないが、例えば、特開平６−１０７６５０号に示すような、ヘキサフルオロプロピレンを酸素で酸化してヘキサフルオロプロピレンオキサイドを製造する際に副生するフッ化カルボニルが重合して生成するオリゴマー混合物であってもよい。従って、この方法によって予め合成したものを用いてもよいし、ヘキサフルオロプロピレンオキサイド製造時の該酸化反応終了後、反応混合物からヘキサフルオロプロピレンオキサイドと未反応物のヘキサフルオロプロピレンを分離したものを用いてもよい。
【０００９】
上記一般式（１）において、ＣＦ2Ｏ繰返し単位間の結合は、頭−尾結合の外に、頭−頭結合および／または尾−尾結合をも含み、頭−尾結合の場合にはエーテル結合を形成し、頭−頭結合、尾−尾結合の場合には過酸化エーテル結合を形成する。一般式（１）で表される化合物中における過酸化エーテル結合の割合は、ヨード滴定法で測定した活性酸素濃度が０．０１〜２５重量％となるような割合であることが好ましい。一般式（１）で表される化合物がこの条件を充たす限り、一般式（１）における−Ｒが−ＣＯＦ、−ＯＣＯＦまたは−ＣＦ2ＣＯＦである化合物の割合については制限がない。
【００１０】
一般式（１）において、ｎは０〜５０の整数であり、好ましくは０〜２０の整数である。
【００１１】
一般式（１）で表される化合物の数平均分子量は、２００〜３５００程度であるのが好ましく、２００〜１５００程度であるのがより好ましい。
【００１２】
一般式（１）で表される化合物の分解反応は、触媒の存在下で行われる。触媒としては、活性炭、金属ハロゲン化物、テトラ鎖状アルキル尿素、テトラ環状アルキル尿素、４級アンモニウム塩等が挙げられる。
【００１３】
金属ハロゲン化物としては、一般式ＭＸで表される化合物が挙げられ、ここで、ＭはＬｉ、Ｎａ、Ｋ、Ｒｂ、Ｃｓ、ＣｕまたはＡｇを示し、ＸはＦ、Ｃｌ、ＢｒまたはＩを示す。金属ハロゲン化物としては、ＣｓＦ、ＲｂＦ、ＮａＦ、ＫＦ、ＡｇＦ、ＣｓＢｒ、ＲｂＢｒ、ＫＢｒ、ＣｓＩ、ＲｂＩ、ＫＩ、ＣｕＣｌ、ＣｕＣｌ2が好ましく、ＣｓＦがより好ましい。
【００１４】
テトラ鎖状アルキル尿素としては、テトラメチル尿素、テトラブチル尿素が挙げられ、テトラメチル尿素が好ましい。
【００１５】
テトラ環状アルキル尿素としては、１，３−ジメチル−２−イミダゾリジノンが好ましい。
【００１６】
４級アンモニウム塩としては、テトラメチルアンモニウムフロライド、テトラブチルアンモニウムフロライド、テトラメチルアンモニウムクロライド、テトラブチルアンモニウムクロライド、テトラメチルアンモニウムブロマイド、テトラブチルアンモニウムブロマイド、テトラメチルアンモニウムアイオダイド、テトラブチルアンモニウムアイオダイドが挙げられ、テトラメチルアンモニウムフロライドが好ましい。
【００１７】
触媒の使用量は、一般式（１）で表される化合物に対して、０．１〜２０重量％であるのが好ましく、１〜５重量％であるのがより好ましい。
【００１８】
一般式（１）で表される化合物の分解反応は、室温で行ってもよいし、加熱しながら行ってもよい。加熱する場合には、分解反応の反応温度は、５０〜４５０℃が好ましく、１００〜３５０℃がより好ましい。
【００１９】
分解反応は、常圧下、加圧下、減圧下のいずれにおいて行ってもよい。
【００２０】
分解反応後、精留等の常法により高純度（９９％以上）のＣＯＦ2を得ることができる。
【００２１】
【発明の効果】
本発明によれば、反応副生物等を用いて、ＣＯＦ2を安全で安価に製造することができる。
【００２２】
【実施例】
次に、実施例によって本発明をより詳細に説明する。
【００２３】
実施例１
２００ｍｌガラスフラスコにＣｓＦを０．６ｇ仕込み、滴下ロートから、ヘキサフルオロプロピレンオキサイドを製造する際に副生した一般式（１）で表される化合物（オリゴマー混合物、数平均分子量：３５０、活性酸素濃度：約０．１重量％）３３ｇを室温で滴下した後、１時間撹拌を続けて分解反応を行った。留出物２０ｇをメタノールトラップで採集した。採集物のＣＯＦ2純度は９８．２％（ＧＣ）であった。
【００２４】
次に、撹拌しながら加熱したところ、１１０℃で分解反応が始まった。２００℃で還流が始まり、反応を停止した。留出物２ｇをメタノールトラップで採集した。採集物のＣＯＦ2純度は９７．１％（ＧＣ）であった。
【００２５】
実施例２
ＳＵＳ製５００ｍｌオートクレーブにテトラメチル尿素を２０ｇ仕込み、これに、ヘキサフルオロプロピレンオキサイドを製造する際に副生した一般式（１）で表される化合物（オリゴマー混合物、数平均分子量：３５０、活性酸素濃度：約０．１重量％）６００ｇを室温で添加した後、９０℃まで加熱した。留出物３８０ｇを−７８℃に冷却したＳＵＳ製ボンベで採集した。採集物のＣＯＦ2純度は９０％以上（ＧＣ）であった。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing COF 2 (carbonyl fluoride).
[0002]
[Prior art and problems to be solved by the invention]
There is a need for a new production method for producing COF 2 , which is a useful compound as a reagent for organic synthesis and the like, safely and inexpensively.
[0003]
In addition, as a next-generation dry etching gas candidate, a production method for obtaining high-purity COF 2 is required.
[0004]
On the other hand, there is a demand for a method of effectively using a by-product compound in a method of producing hexafluoropropylene oxide by oxidizing hexafluoropropylene with oxygen.
[0005]
An object of the present invention is to provide a novel production method for producing COF 2 safely and inexpensively using reaction by-products and the like.
[0006]
[Means for Solving the Problems]
The present invention provides a method for producing COF 2 as described below.
Item 1. General formula (1);
CF 3 O (CF 2 O) n -R (1)
(Wherein, —R represents —COF, —OCOF or —CF 2 COF, and n represents an integer of 0 to 50), at least one compound selected from the group consisting of compounds represented by: manufacturing method of COF 2, characterized in that to decomposition reaction in the presence of a catalyst.
Item 2. Item 2. The method according to Item 1, wherein the catalyst is at least one selected from the group consisting of activated carbon, metal halide, tetra-chain or cyclic alkylurea and quaternary ammonium salt.
Item 3. The metal halide is from a compound represented by the general formula; MX (wherein M represents Li, Na, K, Rb, Cs, Cu or Ag, and X represents F, Cl, Br or I). Item 3. The method according to Item 2, which is at least one compound selected from the group consisting of:
Item 4. Item 3. The method according to Item 2, wherein the tetra-chain or cyclic alkylurea is tetramethylurea.
Item 5. Item 5. The method according to any one of Items 1 to 4, wherein the compound represented by the general formula (1) is a compound by-produced in a method of producing hexafluoropropylene oxide by oxidizing hexafluoropropylene. .
[0007]
DETAILED DESCRIPTION OF THE INVENTION
The method for producing COF 2 of the present invention comprises a general formula (1);
CF 3 O (CF 2 O) n -R (1)
(Wherein, —R represents —COF, —OCOF or —CF 2 COF, and n represents an integer of 0 to 50), at least one compound selected from the group consisting of compounds represented by: The decomposition reaction is performed in the presence of a catalyst.
[0008]
The compound represented by the general formula (1) used in the present invention is not particularly limited. For example, as shown in JP-A-6-107650, hexafluoropropylene oxide is produced by oxidizing hexafluoropropylene with oxygen. It may be an oligomer mixture produced by polymerization of carbonyl fluoride produced as a by-product. Therefore, one synthesized in advance by this method may be used, or one obtained by separating hexafluoropropylene oxide and unreacted hexafluoropropylene from the reaction mixture after completion of the oxidation reaction during the production of hexafluoropropylene oxide. May be.
[0009]
In the general formula (1), the bond between CF 2 O repeating units includes a head-to-head bond and / or a tail-to-tail bond in addition to the head-to-tail bond. A bond is formed, and in the case of a head-head bond and a tail-tail bond, a peroxide ether bond is formed. The ratio of the ether peroxide bond in the compound represented by the general formula (1) is preferably such that the active oxygen concentration measured by the iodometric titration method is 0.01 to 25% by weight. As long as the compound represented by the general formula (1) satisfies this condition, the ratio of the compound in which -R in the general formula (1) is -COF, -OCOF, or -CF 2 COF is not limited.
[0010]
In General formula (1), n is an integer of 0-50, Preferably it is an integer of 0-20.
[0011]
The number average molecular weight of the compound represented by the general formula (1) is preferably about 200 to 3500, and more preferably about 200 to 1500.
[0012]
The decomposition reaction of the compound represented by the general formula (1) is performed in the presence of a catalyst. Examples of the catalyst include activated carbon, metal halide, tetra-chain alkyl urea, tetracyclic alkyl urea, and quaternary ammonium salt.
[0013]
Examples of the metal halide include compounds represented by the general formula MX, where M represents Li, Na, K, Rb, Cs, Cu or Ag, and X represents F, Cl, Br or I. . As the metal halide, CsF, RbF, NaF, KF, AgF, CsBr, RbBr, KBr, CsI, RbI, KI, CuCl, and CuCl 2 are preferable, and CsF is more preferable.
[0014]
Examples of the tetra-chain alkyl urea include tetramethyl urea and tetrabutyl urea, and tetramethyl urea is preferable.
[0015]
As the tetracyclic alkylurea, 1,3-dimethyl-2-imidazolidinone is preferable.
[0016]
As quaternary ammonium salts, tetramethylammonium fluoride, tetrabutylammonium fluoride, tetramethylammonium chloride, tetrabutylammonium chloride, tetramethylammonium bromide, tetrabutylammonium bromide, tetramethylammonium iodide, tetrabutylammonium iodide And tetramethylammonium fluoride is preferred.
[0017]
The amount of the catalyst used is preferably from 0.1 to 20% by weight, more preferably from 1 to 5% by weight, based on the compound represented by the general formula (1).
[0018]
The decomposition reaction of the compound represented by the general formula (1) may be performed at room temperature or while heating. In the case of heating, the reaction temperature of the decomposition reaction is preferably 50 to 450 ° C, more preferably 100 to 350 ° C.
[0019]
The decomposition reaction may be performed under normal pressure, increased pressure, or reduced pressure.
[0020]
After the decomposition reaction, high-purity (99% or more) COF 2 can be obtained by a conventional method such as rectification.
[0021]
【The invention's effect】
According to the present invention, COF 2 can be produced safely and inexpensively using reaction by-products and the like.
[0022]
【Example】
Next, the present invention will be described in more detail by way of examples.
[0023]
Example 1
A 200 ml glass flask was charged with 0.6 g of CsF, and a compound represented by the general formula (1) by-produced when producing hexafluoropropylene oxide from a dropping funnel (oligomer mixture, number average molecular weight: 350, active oxygen concentration : About 0.1% by weight) After dropwise addition of 33 g at room temperature, stirring was continued for 1 hour to carry out a decomposition reaction. 20 g of distillate was collected with a methanol trap. The COF 2 purity of the collected material was 98.2% (GC).
[0024]
Next, when heated with stirring, the decomposition reaction started at 110 ° C. Reflux started at 200 ° C. and the reaction was stopped. 2 g of distillate was collected with a methanol trap. The COF 2 purity of the collected material was 97.1% (GC).
[0025]
Example 2
A SUS 500 ml autoclave was charged with 20 g of tetramethylurea, and a compound represented by the general formula (1) by-produced when producing hexafluoropropylene oxide (oligomer mixture, number average molecular weight: 350, active oxygen concentration) (About 0.1% by weight) was added at room temperature and then heated to 90 ° C. 380 g of distillate was collected in a SUS cylinder cooled to -78 ° C. The COF 2 purity of the collected material was 90% or more (GC).
Claims (5)
ＣＦ3Ｏ(ＣＦ2Ｏ)n−Ｒ （１）
（式中、−Ｒは−ＣＯＦ、−ＯＣＯＦまたは−ＣＦ2ＣＯＦを示し、ｎは０〜５０の整数を示す。）で表される化合物からなる群より選択される少なくとも１種の化合物を、触媒の存在下で分解反応させることを特徴とするＣＯＦ2の製造方法。General formula (1);
CF 3 O (CF 2 O) n -R (1)
(Wherein, —R represents —COF, —OCOF or —CF 2 COF, and n represents an integer of 0 to 50), at least one compound selected from the group consisting of compounds represented by: manufacturing method of COF 2, characterized in that to decomposition reaction in the presence of a catalyst.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002117764A JP4129617B2 (en) | 2002-04-19 | 2002-04-19 | COF2 manufacturing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002117764A JP4129617B2 (en) | 2002-04-19 | 2002-04-19 | COF2 manufacturing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2003313016A JP2003313016A (en) | 2003-11-06 |
| JP4129617B2 true JP4129617B2 (en) | 2008-08-06 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2002117764A Expired - Fee Related JP4129617B2 (en) | 2002-04-19 | 2002-04-19 | COF2 manufacturing method |
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| JP (1) | JP4129617B2 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7592484B2 (en) | 2004-04-28 | 2009-09-22 | Daikin Industries, Ltd. | Method for producing carbonyl difluoride |
| BRPI0822196A2 (en) * | 2008-01-23 | 2015-06-23 | Solvay Fluor Gmbh | Methods for manufacturing a solar cell from a silicon wafer and flat panel, solar cell, and solar panel displays |
| JP5260174B2 (en) * | 2008-08-05 | 2013-08-14 | ユニマテック株式会社 | Method for producing carbonyl fluoride |
| JP2011207767A (en) * | 2010-03-29 | 2011-10-20 | Daikin Industries Ltd | Method for producing carbonyl fluoride and hexafluoropropylene oxide |
| CN109607507B (en) * | 2018-12-24 | 2022-07-15 | 天津市长芦化工新材料有限公司 | Method for preparing carbonyl fluoride by cracking perfluorinated compounds and carbonyl fluoride |
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