JP3355233B2 - Fluorinated anionic surfactant - Google Patents
Fluorinated anionic surfactantInfo
- Publication number
- JP3355233B2 JP3355233B2 JP24074593A JP24074593A JP3355233B2 JP 3355233 B2 JP3355233 B2 JP 3355233B2 JP 24074593 A JP24074593 A JP 24074593A JP 24074593 A JP24074593 A JP 24074593A JP 3355233 B2 JP3355233 B2 JP 3355233B2
- Authority
- JP
- Japan
- Prior art keywords
- anionic surfactant
- formula
- fluorine
- general formula
- reaction
- 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 - Fee Related
Links
Landscapes
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
- Detergent Compositions (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polymerisation Methods In General (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、繊維、金属、樹脂等の
表面改質剤、フッ素系高分子の乳化重合用乳化剤、帯電
防止剤、乳化剤、分散剤等として有用な２個のスルホン
基を有する新規含フッ素陰イオン界面活性剤に関する。The present invention relates to two sulfone groups useful as surface modifiers for fibers, metals, resins, etc., emulsifiers for emulsion polymerization of fluoropolymers, antistatic agents, emulsifiers, dispersants, etc. A novel fluorinated anionic surfactant having the formula:
【０００２】[0002]
【従来の技術】従来より、含フッ素陰イオン界面活性剤
は、フッ素系高分子の乳化重合用の乳化剤、インキのし
み防止剤、帯電防止剤等として用いられてきた。その中
で、ヘキサフルオロプロペンを原料とする含フッ素陰イ
オン界面活性剤としては、公開特許公報昭５７−１６４
１９９号に見られ、該含フッ素陰イオン界面活性剤は、
ヘキサフルオロプロペンの二量体、あるいは三量体を三
級アミンを反応促進剤として用い、フェノールと反応さ
せた後、スルホン化、次いで中和する方法で得られる。
しかしながら分子内にスルホン基を１個しか持たないも
のであり、このため、水に対する溶解性が悪く、水系で
の使用に限界があり、乳化剤、分散剤、及びフッ素系高
分子の乳化重合用乳化剤としての使用に限界があった。2. Description of the Related Art Conventionally, fluorine-containing anionic surfactants have been used as emulsifiers for emulsion polymerization of fluorine-based polymers, ink stain inhibitors, antistatic agents and the like. Among them, fluorinated anionic surfactants using hexafluoropropene as a raw material are disclosed in Japanese Patent Application Laid-Open No. 57-164.
No. 199, the fluorine-containing anionic surfactant is:
Hexafluoropropene dimer or trimer can be obtained by reacting with phenol using tertiary amine as a reaction accelerator, sulfonating and then neutralizing.
However, since it has only one sulfone group in the molecule, its solubility in water is poor and its use in aqueous systems is limited, and emulsifiers, dispersants, and emulsifiers for emulsion polymerization of fluorine-based polymers are used. There was a limit to its use.
【０００３】[0003]
【発明が解決しようとする課題】本発明は、従来の含フ
ッ素陰イオン界面活性剤の上記問題点を解決し、フッ素
を生かした高い界面活性を維持し、水への溶解性が良好
で、乳化剤、分散剤、表面改質剤、帯電防止剤等に使用
できるほか、低重合度のフッ素系高分子の乳化重合用乳
化剤、架橋剤、及びフッ素系試薬の水に対する可溶化剤
等の特殊な用途にも使用される含フッ素陰イオン界面活
性剤を提供する。DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned problems of the conventional fluorine-containing anionic surfactants, maintains a high surface activity utilizing fluorine, has good solubility in water, It can be used as an emulsifier, dispersant, surface modifier, antistatic agent, etc., as well as special emulsifiers for emulsion polymerization of low-polymerized fluoropolymers, crosslinkers, and solubilizers of fluorochemicals in water Provided is a fluorine-containing anionic surfactant which is also used for applications.
【０００４】[0004]
【課題を解決するための手段】本発明は、一般式
（１）：The present invention provides a compound represented by the following general formula (1):
【０００５】[0005]
【化４】 （式中、Ｘはアルカリ金属を示す。）で表される含フッ
素陰イオン界面活性剤を提供する。一般式（１）中のＸ
は、アルカリ金属を示し、リチウム、ナトリウム、カリ
ウム、セシウム等が挙げられるが、ナトリウム、カリウ
ムが好ましい。Embedded image (Wherein, X represents an alkali metal). X in the general formula (1)
Represents an alkali metal, such as lithium, sodium, potassium, and cesium, and is preferably sodium or potassium.
【０００６】一般式（１）の製造方法としては、一般式
（２）：The production method of the general formula (1) includes the general formula (2):
【０００７】[0007]
【化５】 （式中、Ｘは前記と同意義）で表されるヒドロキシベン
ゼンスルホン酸２アルカリ金属塩を非水極性溶媒中に溶
解又は分散させ、ヘキサフルオロプロペンの三量体を徐
々に滴下反応させることによって得られる。Embedded image (Where X is as defined above) by dissolving or dispersing the alkali metal salt of hydroxybenzenesulfonic acid in a non-aqueous polar solvent, and gradually dropping a trimer of hexafluoropropene to cause a reaction. can get.
【０００８】ここで非水極性溶媒としては、比較的溶解
力が大きく、極性の大きいアミド系溶媒が好ましく、
Ｎ，Ｎ−ジメチルアセトアミド、Ｎ，Ｎ-ジメチルホル
ムアミド、Ｎ,Ｎ−ジメチルイミダゾリン、Ｎ−メチル
ピロリドン等が挙げられる。[0008] Here, as the non-aqueous polar solvent, an amide-based solvent having relatively large dissolving power and large polarity is preferable.
N, N-dimethylacetamide, N, N-dimethylformamide, N, N-dimethylimidazoline, N-methylpyrrolidone and the like.
【０００９】ヘキサフルオロプロペンの三量体として具
体的には、式（３）、（４）：Specific examples of the hexafluoropropene trimer include the following formulas (3) and (4):
【００１０】[0010]
【化６】 Embedded image
【００１１】[0011]
【化７】 が示されるが、単一で用いてもよく、又混合物を用いて
もよい。Embedded image Is shown, but a single compound may be used or a mixture may be used.
【００１２】本発明では、式（４）の化合物がヒドロキ
シベンゼンスルホン酸２アルカリ金属塩と反応し、一般
式（１）の目的物を得ることが出来るが、式（３）で示
されるヘキサフルオロプロペン三量体は、塩基性条件下
で式（４）との平衡混合物を与えるため、本反応には式
（３）を用いてもよい。例えば、式（３）／式（４）＝
１／１の平衡混合物は、ジメチルホルムアミド中でトリ
エチルアミンの様な塩基の存在下では、容易に相互に異
性化して平衡混合物式（３）／式（４）＝２／１を与え
る（有機合成化学、第３９巻、第１号、Ｐ５１（１９８
１））、本発明の場合、塩基としてヒドロキシベンスル
ホン酸２アルカリ金属塩が作用している。In the present invention, the compound of the formula (4) reacts with the alkali metal salt of hydroxybenzenesulfonic acid to obtain the desired product of the general formula (1). Since the propene trimer gives an equilibrium mixture with the formula (4) under basic conditions, the reaction may use the formula (3). For example, Equation (3) / Equation (4) =
The 1/1 equilibrium mixture readily isomerizes with each other in dimethylformamide in the presence of a base such as triethylamine to give the equilibrium mixture formula (3) / formula (4) = 2/1 (organic synthetic chemistry). 39, No. 1, P51 (198
1)) In the case of the present invention, hydroxybensulfonic acid 2 alkali metal salt acts as a base.
【００１３】ヒドロキシベンゼンスルホン酸２アルカリ
塩とヘキサフルオロプロペンの三量体の反応モル比は
１：１〜５：１が好ましく、２：１〜３：１が特に好ま
しい。理論的には、ヒドロキシベンゼン２アルカリ金属
塩は、２倍当量必要であり、当量の場合は、一般式
（５）：The reaction molar ratio of the dibasic salt of hydroxybenzenesulfonic acid and the trimer of hexafluoropropene is preferably from 1: 1 to 5: 1, particularly preferably from 2: 1 to 3: 1. Theoretically, hydroxyalkane di-alkali metal salt requires twice equivalent, and in the case of equivalent, the general formula (5):
【００１４】[0014]
【化８】 が多量に生成する。また、５倍当量以上の大過剰では、
反応は進行するが経済的に好ましくない。Embedded image Is produced in large quantities. In the case of a large excess of 5 times equivalent or more,
The reaction proceeds but is not economically favorable.
【００１５】反応温度は、４０℃〜１００℃が好まし
く、６０℃〜８０℃が特に好ましい。４０℃以下では、
溶解度が低く反応速度が遅いため、原料のヒドロキシベ
ンゼンスルホン酸２アルカリ金属塩が多量に残り、１０
０℃以上では、溶媒の劣化が起こるため好ましくない。[0015] The reaction temperature is preferably from 40 ° C to 100 ° C, particularly preferably from 60 ° C to 80 ° C. Below 40 ° C,
Since the solubility is low and the reaction rate is low, a large amount of the alkali metal salt of hydroxybenzenesulfonic acid remains in a large amount.
A temperature of 0 ° C. or higher is not preferable because the solvent deteriorates.
【００１６】ヘキサフルオロプロピレン三量体の添加
は、一度に添加すると副生成物であるパーフルオロノネ
ニルオキシベンゼンスルホン酸塩（一般式（５））が多
量に生成するため、添加は徐々に行うのが好ましい。例
えば、１リットル規模での製造では、添加には１時間以上掛
けるのが好ましい。The hexafluoropropylene trimer is added gradually since a large amount of by-product perfluorononenyloxybenzenesulfonate (general formula (5)) is formed when added at once. Is preferred. For example, in the production on a 1 liter scale, the addition is preferably performed for 1 hour or more.
【００１７】[0017]
【実施例】以下実施例によって本発明を説明する。 実施例１ 冷却管、温度計、攪拌装置、滴下ロートを備えた１リットル
の４つ口フラスコに、Ｐ−ヒドロキシベンゼンスルホン
酸２ナトリウム塩１３０ｇ（０．６ｍｏｌ）をＮ，Ｎ-
ジメチルホルムアミド６００ｍｌ中に分散し、攪拌下８
０℃まで加温した後、ヘキサフルオロプロペン三量体
（式（３）／式（４）＝３８．５／６１．５の混合物）
１３５ｇ（０．３ｍｏｌ）を約４時間で滴下した。攪拌
を１時間続けた後、反応を停止し、ＮａＦを濾別し、濾
液中にトルエン１２００ｍｌを加えることによって固体
を析出させた。この固体を濾別したのち、固体を熱イソ
プロピルアルコール６００ｍｌで３回洗浄し、化合物
（１ａ）を１５７ｇ（収率６５．２％）得た。The present invention will be described below with reference to examples. Example 1 130 g (0.6 mol) of p-hydroxybenzenesulfonic acid disodium salt was placed in a 1-liter four-necked flask equipped with a cooling tube, a thermometer, a stirrer, and a dropping funnel.
Disperse in 600 ml of dimethylformamide and stir 8
After warming to 0 ° C., hexafluoropropene trimer (mixture of formula (3) / formula (4) = 38.5 / 61.5)
135 g (0.3 mol) was added dropwise in about 4 hours. After stirring was continued for 1 hour, the reaction was stopped, NaF was filtered off, and 1200 ml of toluene was added to the filtrate to precipitate a solid. After the solid was separated by filtration, the solid was washed three times with 600 ml of hot isopropyl alcohol to obtain 157 g (yield: 65.2%) of compound (1a).
【００１８】[0018]
【化９】 化合物（１ａ）の物性を表１に示す。Embedded image Table 1 shows the physical properties of the compound (1a).
【００１９】[0019]
【表１】 [Table 1]
【００２０】実施例２ 化合物（１ａ）の表面張力をウイルヘルミ法を用いて測
定した。測定温度は３０℃に設定した。各濃度における
表面張力を表２に示す。 Example 2 The surface tension of compound (1a) was measured by the Wilhelmy method. The measurement temperature was set at 30 ° C. Table 2 shows the surface tension at each concentration.
【００２１】比較例１ 冷却管、温度計、攪拌装置を備えた５リットルの４つ口フラ
スクに、Ｎ，Ｎ−ジメチルホルムアミド３ｋｇとヘキサ
フルオロプロペン三量体１．６５ｋｇ（３．６７ｍｏ
ｌ）を入れ、６０℃で加熱攪拌下、無水ｐ−ヒドロキシ
ベンゼンスルホン酸２ナトリウム塩６８７ｇ（３．１５
ｍｏｌ）を１０当分し、３０分毎に１０回に分けて加え
た。その後、２時間攪拌を続け、攪拌を停止し、７０℃
に加温した後、温度を保ちながら副生したＮａＦを濾別
し、濾液を５℃まで冷却再結晶を行った。析出した結晶
を濾別し、乾燥し、パーフルオロノネニルオキシベンゼ
ンスルホン酸ナトリウム式（５ａ）：Comparative Example 1 A 5-liter 4-neck flask equipped with a cooling pipe, a thermometer, and a stirrer was charged with 3 kg of N, N-dimethylformamide and 1.65 kg of hexafluoropropene trimer (3.67 mol).
l) and 687 g (3.15) of anhydrous p-hydroxybenzenesulfonic acid disodium salt at 60 ° C. while stirring.
mol) was added in 10 equivalents and added in 10 portions every 30 minutes. Thereafter, stirring was continued for 2 hours, and the stirring was stopped.
After heating, the by-produced NaF was separated by filtration while maintaining the temperature, and the filtrate was cooled and recrystallized to 5 ° C. The precipitated crystals are separated by filtration, dried, and sodium perfluorononenyloxybenzenesulfonate Formula (5a):
【００２２】[0022]
【化１０】 を１．６８ｋｇ（８５．３重量％）得た。反応終了時の
反応液中のパーフルオロノネニルオキシベンゼンスルホ
ン酸ナトリウムの反応液中の反応収率は、９４．８％で
あり、この反応の場合、式（１ａ）は、副生生物として
１．２重量％得られるのみである。Embedded image 1.68 kg (85.3% by weight). At the end of the reaction, the reaction yield of sodium perfluorononenyloxybenzenesulfonate in the reaction mixture was 94.8%. In this reaction, the formula (1a) was expressed as 1 by-product as a by-product. .2% by weight.
【００２３】[0023]
【発明の効果】本発明による含フッ素陰イオン界面活性
剤は、優れた撥水撥油性や防汚性等の特性を有するペル
フルオロ基と共に、親水性の強いスルホン基を２個有す
るので、水への溶解性が良好であり、フッ素系高分子の
乳化重合用乳化剤、架橋剤、及びフッ素系試薬の水への
可溶化剤等として有用である。The fluorinated anionic surfactant according to the present invention has two hydrophilic sulfone groups together with a perfluoro group having excellent properties such as water and oil repellency and antifouling properties, and therefore has a high affinity for water. Has good solubility and is useful as an emulsifier for emulsion polymerization of a fluorine-based polymer, a crosslinking agent, and a solubilizer of a fluorine-based reagent in water.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ Ｃ０９Ｋ 3/00 Ｃ０９Ｋ 3/00 Ｒ Ｚ 3/16 １０８ 3/16 １０８Ｄ (72)発明者 小濱 弘之 滋賀県甲賀郡甲西町大池町１番１ 株式 会社ネオス内 (56)参考文献 特開 昭57−164199（ＪＰ，Ａ) 特開 昭50−117727（ＪＰ，Ａ) 特開 平６−263714（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C07C 303/32,309/42 C08F 2/26 B01F 17/12 ────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 7 Identification code FI C09K 3/00 C09K 3/00 R Z 3/16 108 3/16 108D (72) Inventor Hiroyuki Obama Kosai-cho, Koga-gun, Shiga Prefecture Ikemachi 1-1, Neos Co., Ltd. (56) References JP-A-57-164199 (JP, A) JP-A-50-117727 (JP, A) JP-A-6-263714 (JP, A) (58) Survey Field (Int.Cl. 7 , DB name) C07C 303 / 32,309 / 42 C08F 2/26 B01F 17/12
Claims (2)
素陰イオン界面活性剤。1. General formula (1): (Wherein, X represents an alkali metal.) A fluorine-containing anionic surfactant represented by the formula:
ベンゼンスルホン酸２アルカリ塩を非水極性溶媒に溶
解、あるいは分散し、次いでヘキサフルオロプロペン三
量体を添加することにより得られる一般式（１）の含フ
ッ素陰イオン界面活性剤の製造方法。 【化３】 2. General formula (2): (Wherein X represents an alkali metal) Dissolve or disperse the hydroxybenzenesulfonic acid di-alkali salt in a non-aqueous polar solvent, and then add hexafluoropropene trimer to obtain a general formula ( 1) The method for producing a fluorine-containing anionic surfactant. Embedded image
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24074593A JP3355233B2 (en) | 1993-08-31 | 1993-08-31 | Fluorinated anionic surfactant |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24074593A JP3355233B2 (en) | 1993-08-31 | 1993-08-31 | Fluorinated anionic surfactant |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0760096A JPH0760096A (en) | 1995-03-07 |
| JP3355233B2 true JP3355233B2 (en) | 2002-12-09 |
Family
ID=17064078
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP24074593A Expired - Fee Related JP3355233B2 (en) | 1993-08-31 | 1993-08-31 | Fluorinated anionic surfactant |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3355233B2 (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002103103A2 (en) | 2001-06-18 | 2002-12-27 | Honeywell International Inc. | Fluorine-containing compounds and polymers derived therefrom |
| JP4428995B2 (en) * | 2003-12-03 | 2010-03-10 | 関東化学株式会社 | Etching solution composition for metal film |
| JP4750477B2 (en) * | 2005-06-08 | 2011-08-17 | 株式会社ネオス | Fluorine-containing ether compound and method for producing the same |
| US20090137773A1 (en) * | 2005-07-28 | 2009-05-28 | Andrew Jackson | Production Processes and Systems, Compositions, Surfactants, Monomer Units, Metal Complexes, Phosphate Esters, Glycols, Aqueous Film Forming Foams, and Foam Stabilizers |
| JP5329192B2 (en) * | 2008-11-27 | 2013-10-30 | 東京応化工業株式会社 | Photosensitive resin composition |
| JP5511209B2 (en) * | 2009-03-27 | 2014-06-04 | 株式会社ネオス | Fluorine-containing anionic surfactant |
| CN113549168B (en) * | 2021-08-19 | 2023-01-20 | 常熟三爱富中昊化工新材料有限公司 | Preparation method of polytrifluorochloroethylene |
-
1993
- 1993-08-31 JP JP24074593A patent/JP3355233B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0760096A (en) | 1995-03-07 |
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