JPH0764765B2 - Fluorolysis method of polytetrafluoroethylene - Google Patents
Fluorolysis method of polytetrafluoroethyleneInfo
- Publication number
- JPH0764765B2 JPH0764765B2 JP63002073A JP207388A JPH0764765B2 JP H0764765 B2 JPH0764765 B2 JP H0764765B2 JP 63002073 A JP63002073 A JP 63002073A JP 207388 A JP207388 A JP 207388A JP H0764765 B2 JPH0764765 B2 JP H0764765B2
- Authority
- JP
- Japan
- Prior art keywords
- polytetrafluoroethylene
- gas
- fluorine
- fluorolysis
- fluoride
- 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.)
- Expired - Lifetime
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
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明はポリ四フッ化エチレンのフッ素化分解法に係わ
り、更に詳しくはポリ四フッ化エチレンのフッ素化分解
により四フッ化炭素、六フッ化エタン、八フッ化プロパ
ン等のフルオロカーボン類を効率良く得る方法に関する
ものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial field of use] The present invention relates to a method for fluorinating and decomposing polytetrafluoroethylene, and more particularly to carbon tetrafluoride and hexafluoride by fluorinating and decomposing polytetrafluoroethylene. The present invention relates to a method for efficiently obtaining fluorocarbons such as ethane oxide and octafluoropropane.
本発明により得られるフルオロカーボン類は、例えば半
導体工業におけるエッチングガス、気相絶縁体、リーク
テスト剤等に幅広い用途を有するものである。The fluorocarbons obtained by the present invention have a wide range of uses, for example, as etching gas, gas phase insulator, leak test agent, etc. in the semiconductor industry.
フルオロカーボン類の製造方法としては、従来より、
（１）炭素または炭化水素のフッ素ガスによるフッ素
化、（２）ハロゲン化炭素のフッ化水素によるフッ素置
換、及び（３）炭化水素又はハロゲン化炭化水素の電解
フッ素化等が知られている。As a method for producing fluorocarbons, conventionally,
Known are (1) fluorination of carbon or hydrocarbon with fluorine gas, (2) fluorine substitution of halogenated carbon with hydrogen fluoride, and (3) electrolytic fluorination of hydrocarbon or halogenated hydrocarbon.
しかし、（１）の方法においては、反応性に富むフッ素
ガスを使用するため、水素が全部フッ素で置換されるま
で反応を進行させようとすると、炭素−炭素の解裂、そ
して場合により爆発を引き起こす危険性をはらんでい
る。そのため特殊な装置を用いたり、フッ素を不活性ガ
スにより大幅に希釈して行う等の工夫がなされている
が、収率の向上は望めず、また完全に爆発の危険性を排
除するまでには至っていない。However, in the method (1), since a highly reactive fluorine gas is used, if the reaction is attempted to proceed until hydrogen is completely replaced with fluorine, carbon-carbon cleavage and, in some cases, explosion may occur. There is a risk of causing it. For this reason, special devices have been used and measures have been taken to dilute fluorine with an inert gas to a large extent, but improvement in yield cannot be expected, and it is necessary to completely eliminate the risk of explosion. I haven't arrived.
また、（２）の方法ではハロゲンを水素によって完全に
置換するのは困難であり、例えば四塩化炭素のフッ化水
素によるフッ素置換では第四番目の塩素原子のフッ素へ
の置換が極めて困難である。さらに、四フッ化炭素が得
られたとしても微量のクロロトリフルオロメタンが残存
し、これを完全に除去することは不可能に近い難事であ
る。しかるに半導体エッチング用としては、塩素含有化
合物が全く含まれていないことが要求されており、斯か
る方法は未だ満足し得るものではない。Further, in the method (2), it is difficult to completely replace halogen with hydrogen, and for example, in the case of fluorine replacement of carbon tetrachloride with hydrogen fluoride, it is extremely difficult to replace the fourth chlorine atom with fluorine. . Furthermore, even if carbon tetrafluoride is obtained, a trace amount of chlorotrifluoromethane remains, and it is almost impossible to completely remove this. However, for semiconductor etching, it is required that a chlorine-containing compound is not contained at all, and such a method is not yet satisfactory.
（３）の電解フッ素化に至っては、副反応が多く起こ
り、目的生成物以外に数多くの副生物が生成するため、
分離精製が困難である上に、収率が大幅に低下する。In the electrolytic fluorination of (3), many side reactions occur and many byproducts are produced in addition to the target product.
Separation and purification are difficult, and the yield is significantly reduced.
本発明の目的は、上記従来法の欠点を排除し、完全に、
効率良くフルオロカーボン類を製造することにある。The object of the present invention is to eliminate the drawbacks of the above-mentioned conventional methods, and completely,
It is to efficiently produce fluorocarbons.
本発明者等はかかる目的を達成すべく鋭意検討した結
果、本発明に到達した。The present inventors have arrived at the present invention as a result of intensive studies to achieve such an object.
即ち本発明は、ポリ四フッ化エチレンをフッ素ガスによ
りフッ素化分解するにあたり、アルカリ金属フッ化物及
び／又はアルカリ土類金属フッ化物の存在下でフッ素化
分解を行うことを特徴とするポリ四フッ化エチレンのフ
ッ素化分解法である。That is, the present invention is characterized in that, when fluorinating and decomposing polytetrafluoroethylene with fluorine gas, fluorinative decomposition is carried out in the presence of an alkali metal fluoride and / or an alkaline earth metal fluoride. It is a fluorination decomposition method of ethylene oxide.
本発明の方法によれば、完全に、そして効率良くフルオ
ロカーボン類を得られるもので、アルカリ金属フッ化物
及び／又はアルカリ土類金属の内でもフッ化ナトリウ
ム、フッ化カリウム及びフッ化カルシウムの存在下で行
う場合が特に好ましい結果が得られる。According to the method of the present invention, fluorocarbons can be obtained completely and efficiently, and in the presence of sodium fluoride, potassium fluoride and calcium fluoride among alkali metal fluorides and / or alkaline earth metals. Particularly preferable results can be obtained in the case of (1).
また、ポリ四フッ化エチレンは特にその分子量に限定は
なく、形状もチップ、フィルム片、粉末等、細かにされ
ているものであれば良い。The molecular weight of polytetrafluoroethylene is not particularly limited, and any shape such as a chip, a film piece, or a powder may be used.
反応温度は300〜600℃の範囲が好ましく、目的生成物に
応じて温度を変化させれば良い。またフッ素ガスは希釈
せずに、或いは不活性ガスにより希釈して使用するが、
これも目的生成物により適宜選択することができる。The reaction temperature is preferably in the range of 300 to 600 ° C, and the temperature may be changed according to the desired product. Fluorine gas is used without dilution, or diluted with an inert gas,
This too can be appropriately selected depending on the desired product.
以下、実施例及び比較例により本発明をさらに詳しく説
明する。Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples.
実施例 １ 撹拌機付きのニッケル反応器（直径20cm、長さ250cm）
にフッ化ナトリウム（NaF）粉末30kg、テフロン屑（ポ
リ四フッ化エチレン）10kgを仕込んだ。テフロンは成
型の際できる屑を純粋機で解枠しチップ状にしたものを
用いた。撹拌機の回転数は4rpmとした。Example 1 Nickel reactor with a stirrer (diameter 20 cm, length 250 cm)
Then, 30 kg of sodium fluoride (NaF) powder and 10 kg of Teflon scrap (polytetrafluoroethylene) were charged. The Teflon used was a chip that was formed by unraveling scraps produced during molding with a pure machine. The rotation speed of the stirrer was 4 rpm.
窒素雰囲気で昇温し、400℃になった時点でフッ素ガス
を10/minの割合で送入した。このフッ素ガスは電解発
生させたもので約11％（容積）のフッ化水素を含有して
いる。反応ガスを10％水酸化ナトリウム水溶液が循環し
ているアルカリ洗浄塔に通し、フッ化水素及び微量の未
反応フッ素を除去し、ガスクロマトグラフィーを用いて
組成を分析した。置換に用いた少量の窒素を除去した分
析値は次の通りであった。The temperature was raised in a nitrogen atmosphere, and when the temperature reached 400 ° C., fluorine gas was fed at a rate of 10 / min. This fluorine gas is generated electrolytically and contains about 11% (volume) of hydrogen fluoride. The reaction gas was passed through an alkali washing tower in which a 10% aqueous sodium hydroxide solution was circulated to remove hydrogen fluoride and a small amount of unreacted fluorine, and the composition was analyzed by gas chromatography. The analytical values after removing a small amount of nitrogen used for the substitution were as follows.
CF4 93.2％ C2F6 4.4％ C3F8 0.9％ その他 1.5％（面積パーセント） ６時間反応を続けた後、フッ素ガス送入を止め、窒素雰
囲気中で冷却後テフロンチップ10kgを仕込み、昇温後上
記の条件で反応を再開し、適時反応ガス組成を分析した
が、上記と同様の結果であった。CF 4 93.2% C 2 F 6 4.4% C 3 F 8 0.9% Others 1.5% (area percent) After continuing the reaction for 6 hours, stopping the fluorine gas feed, cooling in a nitrogen atmosphere and charging 10 kg of Teflon chips, After the temperature was raised, the reaction was restarted under the above conditions, and the reaction gas composition was analyzed at appropriate times, but the same results as above were obtained.
実施例 ２ 実施例１と同じ反応器を用い、NaFの代わりにフッ化カ
リシウム（CaF2）30kg、テフロンチップ10kgを仕込み、
320℃に昇温した。次にフッ素ガスをヘキサフルオロエ
タン（C2F6）で希釈したもの（F2;50vol％）を10/min
の割合で反応器に送入した。反応ガスをアルカリ洗浄
後、ガスメーターで計量し、ガスクロマトグラフィーに
よって組成を分析した。その結果、希釈用C2F6を除外し
た組成は次の通りであった。Example 2 Using the same reactor as in Example 1, 30 g of calcium fluoride (CaF 2 ) and 10 kg of Teflon chips were charged instead of NaF.
The temperature was raised to 320 ° C. Next, dilute fluorine gas with hexafluoroethane (C 2 F 6 ) (F 2 ; 50vol%) at 10 / min.
Was fed into the reactor at a rate of. After the reaction gas was washed with alkali, it was measured with a gas meter and the composition was analyzed by gas chromatography. As a result, the composition excluding C 2 F 6 for dilution was as follows.
CF4 49.3％ C2F6 34.8％ C3F8 11.6％ C4F10 3.2％ その他 1.1％ 比較例 １ 上記実施例１と同じ反応器を用いNaFを仕込まず、他は
実施例１と同様の条件で反応させた。その結果、反応系
の圧変動が大きく、しばしば大小様々の爆発音が聞かれ
た。また、アルカリ洗浄水中にカーボン状の黒状粉末が
みられ、ガス生成量も実施例の約72％であった。CF 4 49.3% C 2 F 6 34.8% C 3 F 8 11.6% C 4 F 10 3.2% Other 1.1% Comparative Example 1 NaF was not charged using the same reactor as in Example 1 above, but otherwise the same as Example 1. It was made to react on the conditions of. As a result, pressure fluctuations in the reaction system were large, and explosion sounds of various sizes were often heard. In addition, carbon-like black powder was found in the alkaline washing water, and the gas generation amount was about 72% of that in the example.
以上の如く、テフロン屑単味をフッ素化分解してCF4、C
2F6等を得ようとしても円滑な製造は困難である。As described above, the Teflon scrap is fluorinated and decomposed into CF 4 , C
Even if you try to obtain 2 F 6 etc., it is difficult to manufacture smoothly.
実施例に示した通り、本発明の方法によれば、完全に、
効率良く、所望のフルオロカーボンを得ることができ
る。As shown in the examples, according to the method of the present invention, completely,
A desired fluorocarbon can be efficiently obtained.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 佐藤 四郎 群馬県渋川市金井425番地 関東電化工業 株式会社研究開発センター内 (56)参考文献 特開 昭51−75001（ＪＰ，Ａ) 特開 昭47−1491（ＪＰ，Ａ) 特開 昭61−118331（ＪＰ，Ａ) 特開 昭49−39642（ＪＰ，Ａ) ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Shiro Sato 425 Kanai, Shibukawa City, Gunma Kanto Denka Kogyo Co., Ltd. Research and Development Center (56) References JP-A-51-75001 (JP, A) JP-A-47 -1491 (JP, A) JP 61-118331 (JP, A) JP 49-39642 (JP, A)
Claims (1)
フッ素化分解するにあたり、アルカリ金属フッ化物及び
／又はアルカリ土類金属フッ化物の存在下でフッ素化分
解を行うことを特徴とするポリ四フッ化エチレンのフッ
素化分解法。1. When fluorinating and decomposing polytetrafluoroethylene with fluorine gas, fluorinative decomposition is carried out in the presence of an alkali metal fluoride and / or an alkaline earth metal fluoride. Fluorolysis method of ethylene oxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63002073A JPH0764765B2 (en) | 1988-01-08 | 1988-01-08 | Fluorolysis method of polytetrafluoroethylene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63002073A JPH0764765B2 (en) | 1988-01-08 | 1988-01-08 | Fluorolysis method of polytetrafluoroethylene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01180839A JPH01180839A (en) | 1989-07-18 |
| JPH0764765B2 true JPH0764765B2 (en) | 1995-07-12 |
Family
ID=11519165
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63002073A Expired - Lifetime JPH0764765B2 (en) | 1988-01-08 | 1988-01-08 | Fluorolysis method of polytetrafluoroethylene |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0764765B2 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4202906A1 (en) * | 1992-02-01 | 1993-08-05 | Solvay Fluor & Derivate | PRODUCTION OF HEXAFLUORETHANE BY PYROLYTIC DECOMPOSITION OF CF (ARROW DOWN) 3 (ARROW DOWN) BR |
| EP2418227B1 (en) * | 2009-03-31 | 2018-12-19 | Daikin Industries, Ltd. | Method for producing stabilized fluoropolymer |
| EP3741736B1 (en) | 2018-01-17 | 2023-08-02 | Resonac Corporation | Method for producing tetrafluoromethane |
| JP7198780B2 (en) * | 2018-01-19 | 2023-01-04 | 昭和電工株式会社 | Method for producing tetrafluoromethane |
| CN117024245B (en) * | 2023-08-07 | 2024-06-18 | 浙江大学 | A method for producing tetrafluoromethane by thermal plasma pyrolysis of waste polytetrafluoroethylene |
| CN121155597A (en) * | 2025-11-20 | 2025-12-19 | 昊华气体有限公司 | Catalyst for cracking hexafluoroethane in crude carbon tetrafluoride gas, preparation method, carbon tetrafluoride production device and production method |
-
1988
- 1988-01-08 JP JP63002073A patent/JPH0764765B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01180839A (en) | 1989-07-18 |
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