JP3348879B2 - Purification method of perfluorodiene compound - Google Patents
Purification method of perfluorodiene compoundInfo
- Publication number
- JP3348879B2 JP3348879B2 JP20447692A JP20447692A JP3348879B2 JP 3348879 B2 JP3348879 B2 JP 3348879B2 JP 20447692 A JP20447692 A JP 20447692A JP 20447692 A JP20447692 A JP 20447692A JP 3348879 B2 JP3348879 B2 JP 3348879B2
- Authority
- JP
- Japan
- Prior art keywords
- compound
- perfluorodiene
- solvent
- purifying
- fluorine
- 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
Description
【０００１】[0001]
【産業上の利用分野】本発明は、パーフルオロジエン化
合物の精製方法に関する。The present invention relates to a method for purifying a perfluorodiene compound.
【０００２】[0002]
【従来の技術】フッ素置換エチレン性不飽和化合物は、
通常酸フルオリドから気相熱分解法又は液相熱分解法に
より合成されることが多い。この方法で合成したフッ素
置換エチレン性不飽和化合物は必然的に二重結合にフッ
化水素の付加した副生成物が生成する。また、フッ素置
換エチレン性不飽和化合物は重合により耐薬品性等に優
れた樹脂などが得られるため重合用モノマーとして広く
使用されている。また、従来の重合用モノマーとして使
用されていたフッ素置換エチレン性不飽和化合物はフッ
素置換エチレン性不飽和基を分子中に１個しか有してい
ないため、合成過程で副生する二重結合にフッ化水素の
付加した化合物は飽和化合物であり重合に影響を与えな
いものとして特に問題にされていなかった。2. Description of the Related Art Fluorinated ethylenically unsaturated compounds are
Usually, it is often synthesized from acid fluoride by a gas phase pyrolysis method or a liquid phase pyrolysis method. The fluorine-substituted ethylenically unsaturated compound synthesized by this method necessarily generates a by-product in which hydrogen fluoride is added to a double bond. Further, a fluorine-substituted ethylenically unsaturated compound is widely used as a monomer for polymerization since a resin excellent in chemical resistance and the like can be obtained by polymerization. Further, since the fluorine-substituted ethylenically unsaturated compound used as a conventional monomer for polymerization has only one fluorine-substituted ethylenically unsaturated group in the molecule, the double bond formed as a by-product in the synthesis process is formed. The compound to which hydrogen fluoride has been added is a saturated compound and does not particularly affect the polymerization.
【０００３】最近、フッ素置換エチレン性不飽和基を分
子両末端に有する化合物、いわゆる含フッ素α，ω−ジ
エン化合物が、環化重合により完全に非晶質なポリマー
を生成することが特開平１−１３１２１４により提案さ
れている。含フッ素α，ω−ジエン化合物のフッ化水素
１分子付加物は分子内に二重結合が１つ残っているた
め、これを含む粗含フッ素α，ω−ジエン化合物を重合
に供すると、環化重合に大きな影響を与え、目的とする
完全に非晶質の重合体が得られにくいという問題があ
る。Recently, it has been disclosed that a compound having a fluorine-substituted ethylenically unsaturated group at both molecular terminals, a so-called fluorine-containing α, ω-diene compound, forms a completely amorphous polymer by cyclopolymerization. -131214. Since a single hydrogen bond remains in the molecule of the hydrogen fluoride one-molecule adduct of a fluorine-containing α, ω-diene compound, when a crude fluorine-containing α, ω-diene compound containing the compound is subjected to polymerization, a ring is produced. However, there is a problem that it has a large effect on chemical polymerization and it is difficult to obtain a target completely amorphous polymer.
【０００４】また、含フッ素α，ω−ジエン化合物のフ
ッ化水素１分子付加物は、含フッ素α，ω−ジエン化合
物と沸点の差が小さいため、通常の蒸留法で効率よく分
離精製することは困難である。In addition, a single molecule of hydrogen fluoride of a fluorine-containing α, ω-diene compound has a small difference in boiling point from that of a fluorine-containing α, ω-diene compound. It is difficult.
【０００５】[0005]
【発明が解決しようとする課題】本発明は、従来技術の
有していた上記問題点を解決することを目的とするもの
であり、パーフルオロエチレン性不飽和基を分子両末端
に有するパーフルオロジエン化合物のフッ化水素１分子
付加物を含有する該パーフルオロジエン化合物を効率的
に精製し、工業的に高純度の該パーフルオロジエン化合
物を得る方法を提供するものである。SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems of the prior art, in which a perfluoroethylenically unsaturated group is added at both molecular terminals.
The present invention provides a method for efficiently purifying the perfluorodiene compound containing one molecule of hydrogen fluoride adduct of the perfluorodiene compound contained in the above, and industrially obtaining the perfluorodiene compound with high purity.
【０００６】[0006]
【課題を解決するための手段】本発明は、パーフルオロ
エチレン性不飽和基を分子両末端に有するパーフルオロ
ジエン化合物（Ａ）のフッ化水素１分子付加物を含有す
る粗パーフルオロジエン化合物（Ａ）を精製する方法で
あって、粗パーフルオロジエン化合物（Ａ）を、水に溶
解するケトン類、アルコール類及びエーテル類から選ば
れる溶剤の存在下に抽出蒸留し、パーフルオロジエン化
合物（Ａ）と該溶剤の共沸混合物を得、この共沸混合物
より水洗にて該溶剤を除去することを特徴とするパーフ
ルオロジエン化合物（Ａ）の精製方法を提供するもので
ある。Means for Solving the Problems The present invention, perfluoro
A method for purifying a crude perfluorodiene compound (A) containing one molecule of hydrogen fluoride adduct of a perfluorodiene compound (A) having an ethylenically unsaturated group at both molecular terminals, comprising: perfluorodiene compound (a), ketones dissolved in water, and extractive distillation in the presence of a solvent selected from alcohols and ethers, perfluorinated diene of
To obtain an azeotrope of the compound (A) and the solvent.
A purf characterized by removing the solvent by washing with water .
Ruoro diene compound purification method (A) is intended to provide.
【０００７】本発明におけるパーフルオロエチレン性不
飽和基を分子両末端に有するパーフルオロジエン化合物
（Ａ）（以下、単にパーフルオロジエン化合物と記
す。）としては、特公昭６０−４５６１９（記載内容確
認要）、特開平１−１４３８４３、特開平１−１４３８
４４、特開平２−４２０３８等に開示されている化合物
などが例示される。また、このようなパーフルオロジエ
ン化合物は、環化重合して特殊な溶媒に可溶な非晶質の
含フッ素ポリマーを提供できるため、特にフッ化水素１
分子付加物を分離除去することが重要である。パーフル
オロジエン化合物としては、パーフルオロ（ブテニルビ
ニルエーテル）、パーフルオロ（アリルビニルエーテ
ル）などが例示される。[0007] perfluoro diene compound having a perfluoro ethylenically unsaturated groups in the molecule both ends in the present invention
(A) (hereinafter simply referred to as perfluorodiene compound)
You. ) Are described in JP-B-60-45619 (confirmation of the description is necessary), JP-A-1-143843, and JP-A-1-1438.
44, compounds disclosed in JP-A-2-42038 and the like. In addition, since such a perfluorodiene compound can be subjected to cyclopolymerization to provide an amorphous fluorine-containing polymer that is soluble in a special solvent, hydrogen peroxide is particularly preferred.
It is important to separate and remove molecular adducts . The path Furu <br/> O Logistics ene compound, perfluoro (butenyl vinyl ether), perfluoro (allyl vinyl ether) and the like.
【０００８】パーフルオロジエン化合物のフッ化水素１
分子付加物を含有する粗パーフルオロジエン化合物を、
水に溶解するケトン類、アルコール類及びエーテル類か
ら選ばれる溶剤の存在下に抽出蒸留し、パーフルオロジ
エン化合物と溶剤の共沸混合物を得、その後水洗を行う
と両者を効率よく分離できる。ここで使用するケトン
類、アルコール類及びエーテル類から選ばれる溶剤とし
ては、パーフルオロジエン化合物とのみ共沸する溶剤を
選択して使用する。かかるケトン類としては、例えばア
セトン、メチルエチルケトンなど、アルコール類として
は、メタノール、エタノール、イソプロパノールなど、
エーテル類としては、テトラヒドロフラン、ジオキサ
ン、エチレングリコールジメチルエーテルなどが挙げら
れる。これらの溶剤の使用量は、パーフルオロジエン化
合物の全体量の０．０１〜１０倍量、好ましくは０．０
１〜２倍量の重量比で用いられる。Hydrogen fluoride of perfluorodiene compound 1
A crude perfluorodiene compound containing a molecular adduct ,
Ketones that are soluble in water, and extractive distillation in the presence of a solvent selected from alcohols and ethers, Pafuruoroji
When an azeotropic mixture of an ene compound and a solvent is obtained and then washed with water, both can be efficiently separated. Ketones used herein, the solvent selected from alcohols and ethers, to use to select a solvent azeotropic only perfluorodiene compound. Examples of such ketones include acetone and methyl ethyl ketone, and examples of alcohols include methanol, ethanol, and isopropanol.
Examples of the ethers include tetrahydrofuran, dioxane, and ethylene glycol dimethyl ether. The use amount of these solvents is 0.01 to 10 times the total amount of the perfluorodiene compound, preferably 0.0
It is used in a weight ratio of 1-2 times.
【０００９】抽出蒸留は、パーフルオロジエン化合物の
フッ化水素１分子付加物を含有する粗パーフルオロジエ
ン化合物に、これらの溶剤を加えて抽出蒸留し、パーフ
ルオロジエン化合物と溶剤の共沸混合物を得、この共沸
混合物より水洗にて溶剤を除去することにより高純度の
パーフルオロジエン化合物を得ることができる。[0009] Extractive distillation is a crude perfluoro diene <br/> emissions compounds containing hydrogen fluoride molecule adduct of perfluoro diene compound, and extractive distillation by adding these solvents, Pfaff
Give the Ruoro diene compound and azeotrope solvent, high purity by removing the solvent by washing with water than the azeotrope
A perfluorodiene compound can be obtained.
【００１０】[0010]
【作用】このような精製方法により高純度化されたパー
フルオロジエン化合物は、環化重合して特殊な溶媒に可
溶な非晶質のパーフルオロポリマーを得ることができ
る。しかし、パーフルオロジエン化合物のフッ化水素１
分子付加物が混入していると、それが連鎖移動剤として
作用して低分子量体を生成するばかりではなく、重合反
応の収率に著しい影響を与える。[Action] is highly purified by such purification methods par
The fluorodiene compound can be subjected to cyclopolymerization to obtain an amorphous perfluoropolymer soluble in a special solvent. However, perfluorodiene compound hydrogen fluoride 1
When the molecular adduct is contaminated, it not only acts as a chain transfer agent to produce a low molecular weight product, but also has a significant effect on the yield of the polymerization reaction.
【００１１】[0011]
【実施例】実施例 ヘリパックＮｏ．１を充填した直径１．５ｃｍ、高さ６
０ｃｍの真空ジャケット付き蒸留塔を備えた１リットル
の蒸留釜にパーフルオロ（ブテニルビニルエーテル）
［ＣＦ2 ＝ＣＦＣＦ2 ＣＦ2 ＯＣＦ＝ＣＦ2 、以下ＢＶ
Ｅという］とパーフルオロブテニル−（１，２，２，２
−テトラフルオロエチル）エーテル［ＣＦ2 ＝ＣＦＣＦ
2 ＣＦ2 ＯＣＦＨＣＦ3 、以下ＢＶＥ・ＨＦという］の
混合物（ＢＶＥ：ＢＶＥ・ＨＦ＝９７．９：２．１［重
量比］）９００ｇとエタノール９００ｇを仕込んだ。ゆ
っくり加熱し、混合液を沸騰させ３時間全還流した後、
還流比５０：２で留出させた。留出液が、４５０ｇにな
ったときの留分のフルオロカーボン層（Ａ）、１３５０
ｇになったときの留分のフルオロカーボン層（Ｂ）及び
１３５０ｇ留出時の釜のフルオロカーボン層（Ｃ）の液
をガスクロマトグラフィーで分析した結果を表１に示し
た。また、フルオロカーボン層（Ｂ）の液を同量の水で
３回水洗して得られた液（Ｄ）の成分をガスクロマトグ
ラフィーで分析した結果を表１に示した。[Example] Example Helipack No. 1.5 cm in diameter and height 6 filled with 1
Perfluoro (butenyl vinyl ether) in a 1 liter still equipped with a 0 cm vacuum jacketed distillation column
[CF 2 = CFCF 2 CF 2 OCF = CF 2 , hereinafter BV
E] and perfluorobutenyl- (1,2,2,2
- tetrafluoroethyl) ether [CF 2 = CFCF
900 g of a mixture of 2 CF 2 OCFHCF 3 (hereinafter, referred to as BVE · HF) (BVE: BVE · HF = 97.9: 2.1 [weight ratio]) and 900 g of ethanol were charged. After slowly heating, boiling the mixture and refluxing for 3 hours,
Distilled at a reflux ratio of 50: 2. The fluorocarbon layer (A) of the fraction when the distillate weighed 450 g, 1350
Table 1 shows the results of gas chromatography analysis of the liquid of the fluorocarbon layer (B) of the fraction at the time of g and the liquid of the fluorocarbon layer (C) of the kettle at the time of distillation of 1350 g. Table 1 shows the results of analyzing the components of the liquid (D) obtained by washing the liquid of the fluorocarbon layer (B) three times with the same amount of water by gas chromatography.
【００１２】比較例 実施例において、エタノールを用いなかったこと以外は
すべて同様の蒸留を行い、留出液が２５０ｇになったと
きの留分の液（Ｅ）の成分をガスクロマトグラフィーで
分析した結果を表１に示した。COMPARATIVE EXAMPLE The same distillation was carried out in the examples except that ethanol was not used, and the component of the liquid (E) of the distillate when the distillate weighed 250 g was analyzed by gas chromatography. The results are shown in Table 1.
【００１３】[0013]
【表１】 [Table 1]
【００１４】[0014]
【発明の効果】本発明の精製方法によれば、高純度のパ
ーフルオロジエン化合物が容易に得られる。また、本発
明の精製方法で精製されたパーフルオロジエン化合物
は、高収率で環化重合して特殊な溶媒に可溶な非晶質の
パーフルオロポリマーを得ることができる。According to the purification method of the present invention, high-purity Pas
Furuoro diene compound can be easily obtained. In addition, the perfluorodiene compound purified by the purification method of the present invention is an amorphous compound that is cyclopolymerized in high yield and is soluble in a special solvent.
A perfluoropolymer can be obtained.
───────────────────────────────────────────────────── フロントページの続き (58)調査した分野(Int.Cl.7，ＤＢ名) C07C 43/17 C07C 41/34 ──────────────────────────────────────────────────続 き Continuation of front page (58) Field surveyed (Int.Cl. 7 , DB name) C07C 43/17 C07C 41/34
Claims (1)
末端に有するパーフルオロジエン化合物（Ａ）のフッ化
水素１分子付加物を含有する粗パーフルオロジエン化合
物（Ａ）を精製する方法であって、粗パーフルオロジエ
ン化合物（Ａ）を、水に溶解するケトン類、アルコール
類及びエーテル類から選ばれる溶剤の存在下に抽出蒸留
し、パーフルオロジエン化合物（Ａ）と該溶剤の共沸混
合物を得、この共沸混合物より水洗にて該溶剤を除去す
ることを特徴とするパーフルオロジエン化合物（Ａ）の
精製方法。1. The method of claim 1, wherein the perfluoroethylenically unsaturated group is
A method for purifying a crude perfluorodiene compound (A) containing one molecule of hydrogen fluoride adduct of a perfluorodiene compound (A) having a terminal, comprising the step of purifying a crude perfluorodiene compound (A) the ketones to be dissolved in water, and extractive distillation in the presence of a solvent selected from alcohols and ethers, azeotropic mixed perfluoro diene compound (a) and the solvent
And removing the solvent from the azeotropic mixture by washing with water .
Method for purifying perfluoro diene compound (A), characterized in that that.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20447692A JP3348879B2 (en) | 1992-07-08 | 1992-07-08 | Purification method of perfluorodiene compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20447692A JP3348879B2 (en) | 1992-07-08 | 1992-07-08 | Purification method of perfluorodiene compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0625054A JPH0625054A (en) | 1994-02-01 |
| JP3348879B2 true JP3348879B2 (en) | 2002-11-20 |
Family
ID=16491163
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP20447692A Expired - Lifetime JP3348879B2 (en) | 1992-07-08 | 1992-07-08 | Purification method of perfluorodiene compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3348879B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3644038B2 (en) | 1996-11-26 | 2005-04-27 | ダイキン工業株式会社 | Method for purifying perfluorovinyl ether |
-
1992
- 1992-07-08 JP JP20447692A patent/JP3348879B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0625054A (en) | 1994-02-01 |
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