JPS627893B2 - - Google Patents
Info
- Publication number
- JPS627893B2 JPS627893B2 JP54103713A JP10371379A JPS627893B2 JP S627893 B2 JPS627893 B2 JP S627893B2 JP 54103713 A JP54103713 A JP 54103713A JP 10371379 A JP10371379 A JP 10371379A JP S627893 B2 JPS627893 B2 JP S627893B2
- Authority
- JP
- Japan
- Prior art keywords
- hexafluoropropene
- reaction
- fluoride
- nickel oxide
- alkali metal
- 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
Links
- 238000006243 chemical reaction Methods 0.000 description 26
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical compound FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 15
- 229910000480 nickel oxide Inorganic materials 0.000 description 12
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 12
- 239000002904 solvent Substances 0.000 description 12
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Chemical compound [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 description 10
- 229910001515 alkali metal fluoride Inorganic materials 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000013638 trimer Substances 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000006384 oligomerization reaction Methods 0.000 description 3
- 235000003270 potassium fluoride Nutrition 0.000 description 3
- 239000011698 potassium fluoride Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000000539 dimer Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- -1 fluoride ions Chemical class 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- VJRSWIKVCUMTFK-UHFFFAOYSA-N 1,1,2,3,3,3-hexafluoroprop-1-ene Chemical compound FC(F)=C(F)C(F)(F)F.FC(F)=C(F)C(F)(F)F.FC(F)=C(F)C(F)(F)F VJRSWIKVCUMTFK-UHFFFAOYSA-N 0.000 description 1
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000003606 oligomerizing effect Effects 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000005297 pyrex Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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】
本発明は、ヘキサフルオロプロペンオリゴマー
の製法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing hexafluoropropene oligomers.
ヘキサフルオロプロペンのオリゴマー、すなわ
ちヘキサフルオロプロペンの二量体および三量体
は、自体溶媒として、また界面活性剤の中間体と
して有用である。 Oligomers of hexafluoropropene, ie, hexafluoropropene dimers and trimers, are useful as solvents themselves and as surfactant intermediates.
これまで、ヘキサフルオロプロペンオリゴマー
は、ヘキサフルオロプロペンを塩基またはフツ化
物イオン（たとえばフツ化カリウム、フツ化セシ
ウム）の存在下に非ブロトン性溶媒中でオリゴマ
ー化することによつて得られることが知られてい
る。 Hitherto, it has been known that hexafluoropropene oligomers can be obtained by oligomerizing hexafluoropropene in a non-brotic solvent in the presence of a base or fluoride ions (e.g. potassium fluoride, cesium fluoride). It is being
かかる溶媒中の反応では、溶媒が非水系である
ので、使用する溶媒を脱水乾燥することが必要で
ある。また、オリゴマーが当該溶媒には不溶で反
応槽の底部に１相をなすので、反応終了後生成オ
リゴマーを底部から抜き出すことができ、この為
オリゴマーと溶媒の分離が一見容易と思われる
が、実際には溶媒がオリゴマー中に溶解してお
り、その分離のためには水洗または蒸留の操作が
必要である。さらに、フツ化アルカリを再使用す
るにはオリゴマーからの分離回収が必要である。
これらの必要な操作はやつかいなものである。 In such a reaction in a solvent, since the solvent is non-aqueous, it is necessary to dehydrate and dry the solvent used. In addition, since the oligomer is insoluble in the solvent and forms a single phase at the bottom of the reaction tank, the oligomer produced can be extracted from the bottom after the reaction is completed. For this reason, separation of the oligomer and solvent may seem easy at first glance, but in reality The solvent is dissolved in the oligomer, and its separation requires water washing or distillation. Furthermore, in order to reuse the alkali fluoride, it is necessary to separate and recover it from the oligomer.
These necessary operations are cumbersome.
また、溶媒を用いず、この様なやつかいな操作
を必要としないヘキサフルオロプロペンのオリゴ
メリゼーシヨンは、オートクレーブ中、200℃付
近の高温で行われ、従つて反応圧力が高くなり、
しかも反応に長時間を要する。 In addition, oligomerization of hexafluoropropene, which does not use a solvent and does not require such complicated operations, is carried out in an autoclave at a high temperature of around 200°C, and therefore the reaction pressure is high.
Moreover, the reaction takes a long time.
一方、気相流通系では、実質上オリゴマーが得
られないことが知られている。すなわち、ヘキサ
フルオロプロペンを、350℃、接触時間２分でフ
ツ化セシウムの粉末上に通したとき、その転化率
は3.5％に過ぎず、また、フツ化セシウムを存在
せしめたオートクレーブ中でヘキサフルオロプロ
ペンを70％転化するには、215℃の温度、14気圧
の圧力において87時間も要するのである〔ザ・ジ
ヤーナル・オブ・オーガニツク・ケミストリー
（The Journal of Organic Chemis−try）第30巻
3524頁1965年参照〕。 On the other hand, it is known that substantially no oligomers are obtained in a gas phase flow system. That is, when hexafluoropropene was passed over cesium fluoride powder at 350°C for 2 minutes, the conversion rate was only 3.5%; 70% conversion of propene requires 87 hours at a temperature of 215°C and a pressure of 14 atmospheres (The Journal of Organic Chemistry, Vol. 30).
See page 3524, 1965].
本発明の目的は、ヘキサフルオロプロペンから
そのオリゴマーを容易に製造する方法を提供する
ことにある。 An object of the present invention is to provide a method for easily producing oligomers of hexafluoropropene.
本発明によれば、上記の目的は、フツ化アルカ
リ金属を酸化ニツケル上に担持し、これに気相で
ヘキサフルオロプロペンを接触させることにより
達成される。 According to the present invention, the above object is achieved by supporting an alkali metal fluoride on nickel oxide and contacting it with hexafluoropropene in the gas phase.
本発明の製法により、200℃付近の温度、任意
の圧力において、たとえば２分の接触時間により
数十％の転化率でヘキサフルオロプロペンオリゴ
マーを製造することができる。 According to the production method of the present invention, hexafluoropropene oligomers can be produced at a temperature around 200° C., at any pressure, and with a contact time of 2 minutes, for example, at a conversion rate of several tens of percent.
また、溶媒を使用しないので、溶媒の脱水乾燥
や反応生成物と溶媒の分離が不要であり、気相反
応であるので触媒と反応生成物の分離も極めて簡
単である。しかも、酸化ニツケルにフツ化アルカ
リ金属を担持させるには、その水溶液に酸化ニツ
ケルを浸漬して乾燥加熱するだけでよいのである
から、本発明では、従来の技術に付加された特別
に面倒な手段は不要であるという利点がある。 Furthermore, since no solvent is used, there is no need to dehydrate and dry the solvent or to separate the reaction product from the solvent, and since the reaction is a gas phase reaction, separation of the catalyst and the reaction product is extremely simple. Furthermore, in order to support an alkali metal fluoride on nickel oxide, it is sufficient to simply immerse the nickel oxide in the aqueous solution and dry and heat it. has the advantage that it is not necessary.
かかる効果を有する本発明は、ヘキサフルオロ
プロペンのオリゴメリゼーシヨンの触媒として従
来知られていたフツ化アルカリ金属を酸化ニツケ
ルに担持することにより、極めて短時間の接触時
間により数十％の転化率をもつてオリゴメリゼー
シヨンが進行するという発見に基く。 The present invention, which has such an effect, supports alkali metal fluoride, which has been known as a catalyst for oligomerization of hexafluoropropene, on nickel oxide, thereby achieving a conversion rate of several tens of percent with an extremely short contact time. This is based on the discovery that oligomerization progresses with
しかして、本発明において使用する酸化ニツケ
ルに担持したフツ化アルカリ金属は、フツ化アル
カリ金属の水溶液に酸化ニツケルを浸漬して、そ
の水溶液を含浸した酸化ニツケルを乾燥し、不活
性気体、たとえば窒素気流中、反応温度ないしそ
れより300℃高い温度で熱処理することにより調
製することができる。酸化ニツケルに対するフツ
化アルカリ金属の含有量は、酸化ニツケルの重量
を基準として５〜30重量％が適当である。 Therefore, the alkali metal fluoride supported on nickel oxide used in the present invention is prepared by immersing the nickel oxide in an aqueous solution of the alkali metal fluoride, drying the nickel oxide impregnated with the aqueous solution, and drying the nickel oxide with an inert gas, such as nitrogen. It can be prepared by heat treatment at the reaction temperature or a temperature 300°C higher than the reaction temperature in an air stream. The content of alkali metal fluoride relative to nickel oxide is suitably 5 to 30% by weight based on the weight of nickel oxide.
フツ化アルカリ金属の種類は特に制限はない
が、なかでもフツ化セシウムおよびフツ化カリウ
ムが好ましい。 The type of alkali metal fluoride is not particularly limited, but cesium fluoride and potassium fluoride are particularly preferred.
本発明にかかる反応において、反応温度は生成
されるヘキサフルオロプロペン三量体の沸点
（106℃／１気圧）ないし300℃であり、好ましく
は、150〜250℃である。 In the reaction according to the present invention, the reaction temperature ranges from the boiling point of the hexafluoropropene trimer produced (106°C/1 atm) to 300°C, preferably from 150 to 250°C.
反応圧力は、上限が制限を受ける、すなわち三
量体が気体状態を保つ圧力に制限されるほかは、
加圧でも減圧でも広い範囲から自由に選ばれる。
通常、0.1〜10気圧の反応圧力が採用される。 The reaction pressure is limited by an upper limit, i.e., by the pressure at which the trimer remains in the gaseous state.
Pressure or depressurization can be freely selected from a wide range.
Usually a reaction pressure of 0.1 to 10 atmospheres is employed.
また、接触時間は、酸化ニツケル単位重量に対
するフツ化アルカリ金属の含有量、フツ化アルカ
リ金属の種類、反応温度、反応圧力および意図す
る転化率などに依存して適宜定められる。通常、
30秒ないし10分である。 Further, the contact time is appropriately determined depending on the content of the alkali metal fluoride relative to the unit weight of nickel oxide, the type of the alkali metal fluoride, the reaction temperature, the reaction pressure, the intended conversion rate, and the like. usually,
30 seconds to 10 minutes.
さらに、本発明の製法では、窒素、ヘリウム、
アルゴンなどの希釈剤を使用することもできる。 Furthermore, in the production method of the present invention, nitrogen, helium,
Diluents such as argon can also be used.
次に実施例を示し、本発明の製法を更に具体的
に説明する。 Next, Examples will be shown to further specifically explain the manufacturing method of the present invention.
実施例 １
市販の酸化ニツケル100ｇと市販の無水フツ化
セシウム10ｇにイオン交換水30mlを加えて撹拌混
合したうえ、その混合物をノズル径５mmΦのナト
リウムプレスよりポリテトラフルオロエチレン製
シートの上に押し出した。これを乾燥器の中に入
れ、100℃で24時間乾燥後取り出し、約10mmの長
さに切断し、更に電気炉で窒素雰囲気下400℃に
５時間加熱した。このようにして得られた触媒の
85ｇを長さ１ｍの１インチパイレツクスガラス製
反応管に充填し、窒素気流中400℃に加熱、脱水
を行い、反応に供した。反応は設定温度を200℃
とし、大気圧でヘキサフルオロプロペンを20ml／
分の流速で流通させた。排出物はドライアイスで
冷却したトラツプに捕集し、ガスクロマトグラフ
イ、質量分析および核磁気共鳴により分析した。
結果は次の通りであつた。Example 1 30 ml of ion-exchanged water was added to 100 g of commercially available nickel oxide and 10 g of commercially available anhydrous cesium fluoride, mixed with stirring, and the mixture was extruded onto a polytetrafluoroethylene sheet using a sodium press with a nozzle diameter of 5 mmΦ. . This was placed in a dryer, dried at 100°C for 24 hours, taken out, cut into lengths of about 10 mm, and heated in an electric furnace at 400°C for 5 hours under a nitrogen atmosphere. The catalyst obtained in this way
85 g was filled into a 1-inch Pyrex glass reaction tube with a length of 1 m, heated to 400° C. in a nitrogen stream, dehydrated, and subjected to reaction. The reaction temperature is set at 200℃.
20 ml of hexafluoropropene at atmospheric pressure.
It was circulated at a flow rate of minutes. The effluent was collected in a trap cooled with dry ice and analyzed by gas chromatography, mass spectrometry, and nuclear magnetic resonance.
The results were as follows.
ヘキサフルオロプロペンの転化率 7.2モル％
生成物組成
二量体 80.5モル％
三量体 19.5モル％
実施例 ２
実施例１と同様の方法でフツ化セシウムの代り
にフツ化カリウムを用いて触媒を調製し、反応に
供した。反応は設定温度を220℃とし、大気圧で
ヘキサフルオロプロペンを30ml／分の流速で流通
させた。排出物を分析して次に示す結果を得た。Conversion rate of hexafluoropropene 7.2 mol% Product composition Dimer 80.5 mol% Trimer 19.5 mol% Example 2 A catalyst was prepared in the same manner as in Example 1 using potassium fluoride instead of cesium fluoride. and subjected to reaction. The reaction temperature was set at 220°C, and hexafluoropropene was passed through at a flow rate of 30 ml/min at atmospheric pressure. The discharge was analyzed and the following results were obtained.
ヘキサフルオロプロペンの転化率 71モル％ 生成物組成 二量体 83.3モル％ 三量体 16.7モル％Conversion rate of hexafluoropropene 71 mol% Product composition Dimer 83.3 mol% Trimer 16.7 mol%
Claims (1)
属にヘキサフルオロプロペンを気相状態で接触さ
せることを特徴とするヘキサフルオロプロペンオ
リゴマーの製法。 ２ ヘキサフルオロプロペンをその三量体の沸点
ないし300℃の温度で接触させる特許請求の範囲
第１項記載の製法。 ３ フツ化アルカリ金属がフツ化カリウムまたは
フツ化セシウムである特許請求の範囲第１項また
は第２項記載の製法。[Scope of Claims] 1. A method for producing a hexafluoropropene oligomer, which comprises bringing hexafluoropropene into contact with an alkali metal fluoride supported on nickel oxide in a gas phase. 2. The method according to claim 1, wherein hexafluoropropene is contacted at a temperature between the boiling point of the trimer and 300°C. 3. The production method according to claim 1 or 2, wherein the alkali metal fluoride is potassium fluoride or cesium fluoride.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10371379A JPS5629530A (en) | 1979-08-15 | 1979-08-15 | Preparation of hexafluoropropene oligomer |
| US06/170,151 US4296265A (en) | 1979-07-19 | 1980-07-18 | Process for preparing hexafluoropropene oligomers |
| DE19803027229 DE3027229A1 (en) | 1979-07-19 | 1980-07-18 | METHOD FOR PRODUCING HEXAFLUORPROPEN OLIGOMERS |
| GB8023597A GB2055824B (en) | 1979-07-19 | 1980-07-18 | Process for preparing hexafluoropropene oligomers |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10371379A JPS5629530A (en) | 1979-08-15 | 1979-08-15 | Preparation of hexafluoropropene oligomer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5629530A JPS5629530A (en) | 1981-03-24 |
| JPS627893B2 true JPS627893B2 (en) | 1987-02-19 |
Family
ID=14361347
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10371379A Granted JPS5629530A (en) | 1979-07-19 | 1979-08-15 | Preparation of hexafluoropropene oligomer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5629530A (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61234822A (en) * | 1985-04-11 | 1986-10-20 | シンポ株式会社 | Smoke distincting apparatus of roaster |
| JPS62141338U (en) * | 1986-03-03 | 1987-09-07 | ||
| JPS63123912U (en) * | 1987-02-05 | 1988-08-12 | ||
| KR20260048605A (en) * | 2023-07-31 | 2026-04-10 | 다이킨 고교 가부시키가이샤 | Composition containing a hexafluoropropene trimer |
-
1979
- 1979-08-15 JP JP10371379A patent/JPS5629530A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5629530A (en) | 1981-03-24 |
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