JP2001220374A - Fluorine-based surfactant compound and method for producing the same - Google Patents
Fluorine-based surfactant compound and method for producing the sameInfo
- Publication number
- JP2001220374A JP2001220374A JP2000030522A JP2000030522A JP2001220374A JP 2001220374 A JP2001220374 A JP 2001220374A JP 2000030522 A JP2000030522 A JP 2000030522A JP 2000030522 A JP2000030522 A JP 2000030522A JP 2001220374 A JP2001220374 A JP 2001220374A
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- fluorine
- atom
- nitrogen
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、新規なフッ素系界
面活性化合物、及びその製造方法に関するものである。
更に詳しくは、本発明は、高い表面張力低下能を有し、
界面活性剤として有用な、含窒素ペルフルオロアルキル
基を持つ新規なカチオン型界面活性化合物、及び該化合
物を簡便かつ有利に製造する方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel fluorine-containing surface active compound and a method for producing the same.
More specifically, the present invention has a high surface tension reducing ability,
The present invention relates to a novel cationic surfactant compound having a nitrogen-containing perfluoroalkyl group, which is useful as a surfactant, and to a method for easily and advantageously producing the compound.
【０００２】[0002]
【従来の技術】アルキル基中の水素原子を全てフッ素に
より置換したペルフルオロアルキル基を有する界面活性
剤（以下、含フッ素界面活性剤と記載することがある）
は、ハイドロカーボン系の界面活性剤では達せられない
優れた界面活性能力を有することが良く知られており、
これまで、種々の含フッ素界面活性剤が産業上広く利用
されている。フッ素系界面活性剤として、ペルフルオロ
カルボン酸（ＲｆＣＯＯＨ）を合成原料として、アミド
結合で連結した界面活性剤、なかでも、ペルフルオロオ
クタンアミドプロピレンジメチルアミン誘導体が広く利
用されている。例えば、Ｃ7 Ｆ15ＣＯＮＨ（ＣＨ2 ）3
Ｎ（ＣＨ3 ）3 + Ｉ- 、で表されるカチオン型界面活性
剤は、水溶液の２５℃におけるＷｉｌｈｅｌｍｙ法によ
る表面張力の測定結果より、ｃｍｃ（臨界ミセル濃度）
が４．０６ｍＭｏｌ／ｌであり、その時の表面張力値が
１６．５ｍＮ／ｍである〔油化学、３１，４６４（１９
８２）〕 。しかしながら、ペルフルオロカルボン酸
は、電解フッ素化反応により合成されているが、その収
率は、一般的に、他の合成反応に比べ低く、満足できる
ものではない。また、このため価格が高くなり、界面活
性能も通常の炭化水素系界面活性剤と比べれば高いもの
の、更に、より優れた界面活性能を有する化合物の探索
が進められている。2. Description of the Related Art All hydrogen atoms in an alkyl group are converted to fluorine.
Activity with more substituted perfluoroalkyl groups
Agent (hereinafter sometimes referred to as fluorine-containing surfactant)
Cannot be achieved with hydrocarbon-based surfactants
It is well known that it has excellent surface active ability,
Until now, various fluorine-containing surfactants have been widely used in industry
Have been. Perfluorinated surfactants
Amide using carboxylic acid (RfCOOH) as raw material for synthesis
Surfactants linked by bonds, especially perfluoro
Cutanamid propylene dimethylamine derivatives are widely used
Have been used. For example, C7 FFifteenCONH (CHTwo )Three
N (CHThree )Three + I- , Cationic surfactant represented by
The agent was prepared by the Wilhelmy method at 25 ° C of an aqueous solution.
Cmc (critical micelle concentration)
Is 4.06 mMol / l, and the surface tension value at that time is
16.5 mN / m [Oil Chemistry, 31, 464 (19
82)]. However, perfluorocarboxylic acid
Is synthesized by an electrolytic fluorination reaction.
The rates are generally lower and satisfactory compared to other synthetic reactions
Not something. In addition, this increases the price and increases surface activity.
Higher performance than ordinary hydrocarbon surfactants
For compounds with even better surface activity
Is being promoted.
【０００３】従来、より高機能・高性能な含フッ素機能
性化合物を得る方策として、通常のペルフルオロカルボ
ン酸の代わりに含窒素ペルフルオロカルボン酸類を使用
して、含窒素ペルフルオロアルキル基を導入せしめて含
フッ素機能性化合物を得ること知られている。このよう
な方法により、例えば、液晶化合物（特開平９−２２７
４７５）、含フッ素オリゴマー型界面活性化合物（特願
平１０−２４３５６８）などが合成されているが、低分
子系含フッ素界面活性剤を得る方法は知られていない。Heretofore, as a measure for obtaining a fluorine-containing functional compound having higher functionality and higher performance, a nitrogen-containing perfluoroalkyl group has been introduced by using a nitrogen-containing perfluorocarboxylic acid in place of a usual perfluorocarboxylic acid. It is known to obtain fluorine functional compounds. By such a method, for example, a liquid crystal compound (JP-A-9-227)
475), and a fluorine-containing oligomer-type surfactant compound (Japanese Patent Application No. 10-243568), but a method for obtaining a low-molecular-weight fluorine-containing surfactant is not known.
【０００４】[0004]
【発明が解決しようとする課題】このような状況の中
で、本発明者らは、上記従来技術を踏まえて、有用な新
規含窒素ペルフルオロアルキル基を置換せしめた含フッ
素カチオン型界面活性化合物を開発することを目標とし
て鋭意研究を積み重ねた結果、含窒素ペルフルオロカル
ボン酸フルオリドあるいは酸フルオリドのフッ素を他の
ハロゲンで置換した含窒素ペルフルオロカルボン酸ハロ
ゲン化物をジメチルアルキレンアミンと反応せしめ、続
いてアルキルハロゲニドと反応せしめることにより、高
い界面活性能を有する新しい含フッ素カチオン型型界面
活性化合物が得られることを見出し、本発明を完成する
に至った。本発明は、界面活性剤として有用な新規な含
フッ素カチオン型界面活性化合物、及び該化合物を、容
易に入手し得る試薬を用いて、簡便な操作で収率良く製
造する方法を提供することを目的とするものである。す
なわち、本発明は、一般式（Ｉ）Under such circumstances, the present inventors have developed a useful fluorine-containing cationic surfactant compound having a useful nitrogen-containing perfluoroalkyl group substituted based on the above prior art. As a result of intensive research aimed at development, nitrogen-containing perfluorocarboxylic acid fluoride or a nitrogen-containing perfluorocarboxylic acid halide obtained by substituting fluorine of acid fluoride with another halogen is reacted with dimethylalkyleneamine, followed by alkylhalogenation. The present inventors have found that a new fluorine-containing cation-type surfactant compound having high surface activity can be obtained by reacting with nide, and the present invention has been completed. The present invention provides a novel fluorine-containing cationic surfactant compound useful as a surfactant, and a method for producing the compound in a simple operation with high yield using a readily available reagent. It is the purpose. That is, the present invention provides a compound represented by the general formula (I):
【０００５】[0005]
【化３】 Embedded image
【０００６】（式中のＲｆ1 及びＲｆ2 は、それぞれ同
一又は互いに異なる炭素数１〜５のペルフルオロアルキ
ル基であって、それらは直接に、あるいは酸素原子又は
窒素原子を介して結合し、両者が結合している酸素原子
又は窒素原子とともに複素環を形成していてもよい。ｍ
は１又は２の、ｎは２から４の、ｌは１から２０の整
数、Ｘは塩素原子、臭素原子、ヨウ素原子などのハロゲ
ン元素）で表されるフッ素系界面活性化合物、及び該化
合物の製造方法を提供するものである。(In the formula, Rf 1 and Rf 2 are the same or different perfluoroalkyl groups having 1 to 5 carbon atoms, which are bonded directly or via an oxygen atom or a nitrogen atom. May form a heterocyclic ring together with the oxygen atom or nitrogen atom to which m is bonded.
Is 1 or 2, n is an integer of 2 to 4, 1 is an integer of 1 to 20, X is a halogen element such as a chlorine atom, a bromine atom, an iodine atom, etc.) It is intended to provide a manufacturing method.
【０００７】[0007]
【課題を解決するための手段】上記課題を解決するため
の本発明は、以下の技術的手段からなる。 （１）一般式（Ｉ） （式中のＲｆ1 及びＲｆ2 は、それぞれ同一又は互いに
異なる炭素数１〜５のペルフルオロアルキル基であっ
て、それらは直接に、あるいは酸素原子又は窒素原子を
介して結合し、両者が結合している酸素原子又は窒素原
子とともに複素環を形成していてもよい。ｍは１又は２
の、ｎは２から４の、ｌは１から２０の整数、Ｘは塩素
原子、臭素原子、ヨウ素原子などのハロゲン元素）で表
されるフッ素系界面活性化合物。 （２）前記（１）記載のフッ素系界面活性化合物を製造
する方法であって、一般式（ＩＩ） （ただし、Ｒｆ1 及びＲｆ2 及びｍは前記したものと同
じ、Ｙはフッ素、塩素、臭素、ヨウ素などのハロゲン原
子）で表される含窒素ペルフロオロカルボン酸ハロゲン
化物とジメチルアルキレンアミンとの反応生成物をアル
キルハロゲニドと反応させることを特徴とするフッ素系
界面活性化合物の製造方法。The present invention for solving the above-mentioned problems comprises the following technical means. (1) General Formula (I) (wherein Rf 1 and Rf 2 are the same or different and are different perfluoroalkyl groups having 1 to 5 carbon atoms, and they are directly or via an oxygen atom or a nitrogen atom. And m may be 1 or 2 to form a heterocyclic ring together with the oxygen atom or the nitrogen atom to which both are bonded.
Wherein n is an integer of 2 to 4, l is an integer of 1 to 20, and X is a halogen element such as a chlorine atom, a bromine atom and an iodine atom). (2) A method for producing the fluorine-containing surfactant compound according to the above (1), wherein Rf 1, Rf 2 and m are the same as those described above, and Y is fluorine, chlorine, A process for producing a fluorine-containing surfactant, comprising reacting a reaction product of a nitrogen-containing perfluorocarboxylic acid halide represented by a halogen atom such as bromine or iodine) with dimethylalkyleneamine with an alkyl halide. .
【０００８】[0008]
【発明の実施の形態】以下、本発明を更に詳細に説明す
る。前記一般式（Ｉ）で表される本発明の含フッ素カチ
オン型界面活性化合物は、文献未載の新規な化合物であ
って、該一般式（Ｉ）中のＲｆ1 及びＲｆ2 は、それぞ
れ炭素数１〜５のペルフルオロアルキル基であり、それ
らは同一であってもよいし、互いに異なっていてもよ
く、また、直接にあるいは酸素原子又は窒素原子を介し
て結合し、両者が結合している酸素原子又は窒素原子と
ともに五員環、六員環又は七員環を形成していてもよ
い。すなわち、該一般式（Ｉ）における（Ｒｆ1 ）（Ｒ
ｆ2 ) Ｎ−の例としては、以下のものが例示される。BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. The fluorine-containing cationic surfactant compound of the present invention represented by the general formula (I) is a novel compound not described in any literature, and Rf 1 and Rf 2 in the general formula (I) each represent a carbon atom. 1 to 5 perfluoroalkyl groups, which may be the same or different from each other, and are bonded directly or via an oxygen atom or a nitrogen atom, and both are bonded. It may form a 5-, 6- or 7-membered ring with an oxygen atom or a nitrogen atom. That is, in the general formula (I), (Rf 1 ) (R
f 2) Examples of N-, it is exemplified as follows.
【０００９】[0009]
【化４】 Embedded image
【００１０】一般式（Ｉ）の含フッ素カチオン型界面活
性化合物は、下記一般式（ＩＩ）The fluorine-containing cationic surfactant compound of the general formula (I) has the following general formula (II)
【００１１】[0011]
【化５】 Embedded image
【００１２】（式中のＲｆ1 及びＲｆ2 、 ｍは、一般式
（Ｉ）記載のものと同一、Ｙはハロゲン元素）で表され
る、含窒素ペルフルオロカルボン酸ハロゲン化物と、下
記一般式（ＩＩＩ）(Wherein Rf 1, Rf 2 and m are the same as those described in the general formula (I), and Y is a halogen element), and a nitrogen-containing perfluorocarboxylic acid halide represented by the following general formula ( III)
【００１３】[0013]
【化６】 Embedded image
【００１４】（ｎは、２ないし４の整数）で表されるジ
メチルアルキレンアミンとを反応させることにより、簡
単かつ高収率で製造することができる、下記一般式（Ｉ
Ｖ）By reacting with dimethylalkyleneamine represented by (n is an integer of 2 to 4), the compound can be produced simply and in high yield.
V)
【００１５】[0015]
【化７】 Embedded image
【００１６】で表される化合物（式中のＲｆ1 及びＲｆ
2 、 ｍ及びｎは、一般式（Ｉ）記載のものと同一）を、
下記一般式（Ｖ）A compound represented by the formula (Rf 1 and Rf
2 , m and n are the same as those described in formula (I))
The following general formula (V)
【００１７】[0017]
【化８】 Embedded image
【００１８】（ｌは１から２０の整数、Ｘは塩素原子、
臭素原子、ヨウ素原子などのハロゲン元素）で表される
アルキルハロゲニドと反応させることにより、簡便かつ
高収率で得ることができる。前記一般式（ＩＩ）中のＹ
で示されるハロゲン原子としては、フッ素原子、塩素原
子、臭素原子、ヨウ素原子が挙げられる。このＹがフッ
素原子である含窒素ペルフルオロカルボン酸フルオリド
は、例えば、対応する含窒素カルボン酸のエステル又は
ハロゲン化物を、フッ化水素中で電解フッ素化すること
により容易に得ることができる。また、必要に応じて、
前記一般式（ＩＩ）で表される含窒素ペルフルオロカル
ボン酸ハロゲン化物として、Ｙがフッ素原子以外のハロ
ゲン原子であるものを用いる場合には、例えば、前記電
解フッ素化により得られた含窒素ペルフルオロカルボン
酸フルオリドを加水分解処理して、対応する含窒素ペル
フルオロカルボン酸を生成させた後、適当な酸ハロゲン
化剤を反応させて、対応する含窒素ペルフルオロカルボ
ン酸ハロゲン化物に誘導すればよい。(L is an integer from 1 to 20, X is a chlorine atom,
By reacting with an alkylhalogenide represented by a halogen element such as a bromine atom or an iodine atom), a simple and high yield can be obtained. Y in the general formula (II)
Examples of the halogen atom represented by include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. The nitrogen-containing perfluorocarboxylic acid fluoride in which Y is a fluorine atom can be easily obtained, for example, by subjecting the corresponding ester or halide of a nitrogen-containing carboxylic acid to electrolytic fluorination in hydrogen fluoride. Also, if necessary,
When Y is a halogen atom other than a fluorine atom as the nitrogen-containing perfluorocarboxylic acid halide represented by the general formula (II), for example, the nitrogen-containing perfluorocarboxylic acid obtained by the electrolytic fluorination is used. The acid fluoride may be hydrolyzed to generate the corresponding nitrogen-containing perfluorocarboxylic acid, and then reacted with an appropriate acid halogenating agent to derive the corresponding nitrogen-containing perfluorocarboxylic acid halide.
【００１９】一般式（ＩＶ）で表される化合物を生成せ
しめる反応におけるジメチルアルキレンアミンと含窒素
ペルフルオロカルボン酸ハロゲン化物との使用割合は、
通常、モル比で１：０．１ないし１：１０、好ましくは
１：０．２ないし１：２の範囲で選ばれる。反応は溶媒
中で行うのが有利であり、溶媒としては反応に不活発で
両成分を溶解し得るものが好ましい。このようなものと
しては、例えば、塩化メチレン、エチレンジクロリド、
クロロホルム、四塩化炭素、モノクロロベンゼン、ジク
ロロベンゼンなどのハロゲン化炭化水素、ベンゼン、ト
ルエン、キシレン、エチルベンゼンなどの芳香族系炭化
水素、ジエチルエーテル、ジプロピルエーテルなどのエ
ーテル系化合物などが例示される。また、反応液中にハ
ロゲン化水素補足剤を加えることも可能であり、このハ
ロゲン化水素補足剤としては、例えば、ピリジン、トリ
エチルアミンなどの有機塩基が好適なものとして挙げら
れる。The proportion of dimethylalkyleneamine and nitrogen-containing perfluorocarboxylic acid halide used in the reaction for producing the compound represented by the general formula (IV) is as follows:
Usually, the molar ratio is selected in the range of 1: 0.1 to 1:10, preferably 1: 0.2 to 1: 2. The reaction is advantageously performed in a solvent, and a solvent that is inactive in the reaction and can dissolve both components is preferable. Such include, for example, methylene chloride, ethylene dichloride,
Examples thereof include halogenated hydrocarbons such as chloroform, carbon tetrachloride, monochlorobenzene, and dichlorobenzene, aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene, and ether compounds such as diethyl ether and dipropyl ether. It is also possible to add a hydrogen halide scavenger to the reaction solution. As the hydrogen halide scavenger, for example, organic bases such as pyridine and triethylamine are preferable.
【００２０】反応温度は、通常、−５０〜１００℃、好
ましくは−２０〜５０℃の範囲で選ばれる。また、圧力
については特に制限はないが、通常は常圧下で反応が行
われる。反応時間は、含窒素ペルフルオロカルボン酸ハ
ロゲン化物の種類、ポリエチレンイミンの重合度、ポリ
エチレンイミンと含窒素ペルフルオロカルボン酸ハロゲ
ン化物との使用割合、反応温度、その他の要因で異な
り、一概に定めることはできないが、通常は１０分ない
し５時間程度で十分である。一般式（Ｉ）で表される本
発明の含フッ素カチオン型界面活性化合物を、生成せし
める反応で、一般式（ＩＶ）で表される化合物は、蒸留
などの操作により、精製したものを用いることが、より
好ましいが、反応粗生成物をそのまま用いることも可能
である。一般式（Ｉ）で表される化合物を生成せしめる
反応における一般式（ＩＶ）で表される化合物とアルキ
ルハロゲニドとの使用割合は、通常、モル比で１：０．
２ないし１：２、好ましくは１：０．５ないし１：１．
５の範囲で選ばれる。反応は溶媒中で行うのが有利であ
り、溶媒としては反応に不活発で両成分を溶解し得るも
のが好ましい。このようなものとしては、例えば、ジエ
チルエーテル、ジプロピルエーテルなどのエーテル系化
合物、アセトン、２−ブタノンなどのケトン系化合物、
酢酸エチルなどのエステル系化合物などが例示される。The reaction temperature is generally selected in the range of -50 to 100 ° C, preferably -20 to 50 ° C. The pressure is not particularly limited, but the reaction is usually performed under normal pressure. The reaction time varies depending on the type of the nitrogen-containing perfluorocarboxylic acid halide, the degree of polymerization of the polyethyleneimine, the use ratio of the polyethyleneimine and the nitrogen-containing perfluorocarboxylic acid halide, the reaction temperature, and other factors, and cannot be determined unconditionally. However, usually about 10 minutes to 5 hours is sufficient. In the reaction for producing the fluorine-containing cationic surfactant compound of the present invention represented by the general formula (I), the compound represented by the general formula (IV) may be purified by an operation such as distillation. Is more preferable, but the crude reaction product can be used as it is. The ratio of the compound represented by the general formula (IV) and the alkyl halide used in the reaction to produce the compound represented by the general formula (I) is usually 1: 0.
2 to 1: 2, preferably 1: 0.5 to 1: 1.
5 is selected. The reaction is advantageously performed in a solvent, and a solvent that is inactive in the reaction and can dissolve both components is preferable. Such compounds include, for example, ether compounds such as diethyl ether and dipropyl ether, ketone compounds such as acetone and 2-butanone,
Examples include ester compounds such as ethyl acetate.
【００２１】反応温度は、通常、−５０〜１００℃、好
ましくは０〜５０℃の範囲で選ばれる。また、圧力につ
いては特に制限はないが、通常は常圧下で反応が行われ
る。反応時間は、反応物の種類、使用割合、反応温度、
その他の要因で異なり、一概に定めることはできない
が、通常は１時間ないし１ヶ月程度である。反応粗生成
物は、通常、再結晶操作により、高純度な精製物にする
ことができる。再結晶操作に使用する溶媒としては、反
応に不活発であるものが好ましい。このようなものとし
ては、例えば、塩化メチレン、エチレンジクロリド、ク
ロロホルム、四塩化炭素、モノクロロベンゼン、ジクロ
ロベンゼンなどのハロゲン化炭化水素、ベンゼン、トル
エン、キシレン、エチルベンゼンなどの芳香族系炭化水
素、ジエチルエーテル、ジプロピルエーテルなどのエー
テル系化合物、酢酸エチルなどのエステル系化合物など
が例示される。当然、溶媒としてこれらの化合物の混合
液を用いることも可能である。The reaction temperature is usually selected in the range of -50 to 100 ° C, preferably 0 to 50 ° C. The pressure is not particularly limited, but the reaction is usually performed under normal pressure. The reaction time depends on the type of reactants, the proportion used, the reaction temperature,
It differs depending on other factors and cannot be unconditionally determined, but is usually about one hour to one month. The reaction crude product can be usually converted into a highly purified product by a recrystallization operation. As the solvent used for the recrystallization operation, those which are inactive in the reaction are preferable. Such substances include, for example, halogenated hydrocarbons such as methylene chloride, ethylene dichloride, chloroform, carbon tetrachloride, monochlorobenzene, dichlorobenzene, aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene, and diethyl ether. And ether compounds such as dipropyl ether, and ester compounds such as ethyl acetate. Of course, it is also possible to use a mixture of these compounds as a solvent.
【００２２】[0022]
【実施例】次に、実施例により本発明を更に詳しく説明
するが、本発明はこれらの実施例によって何ら限定され
るものではない。 実施例１ 界面活性化合物（１）EXAMPLES Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. Example 1 Surfactant (1)
【００２３】[0023]
【化９】 Embedded image
【００２４】１００ｍｌフラスコにＮ，Ｎ−ジメチルア
ミノプロピルアミン３．０ｇとエーテル１００ｍｌを加
えて、アルゴン気流下で氷冷しながら、ペルフルオロ
（モルホリノプロピオン酸）フルオリド１２．５ｇ（純
度７０％、電解フッ素粗生成物）を滴下し、約２時間反
応させた。反応終了後、不溶物を濾別して反応液を回収
した。回収液を約３．０ｗｔ％炭酸水素ナトリウム水溶
液約１００ｍｌ、続いて、飽和食塩水約１００ｍｌで洗
浄した後、無水硫酸マグネシウムを加えて、約１０時間
放置した。無水硫酸マグネシウムを濾別し、溶媒を留去
して、高粘性な淡黄色液体、４．９ｇを得た。これを１
００ｍｌフラスコ移して、２−ブタノン約３０ｍｌを加
え完全に溶解した後、ヨウ化メチル１．６ｇを加え、室
温で約３０時間攪拌した。反応終了後、溶媒を留去し
て、粗成生物を回収した。この粗成生物を、２０％酢酸
エチル／ｎ−ヘキサン液約５０ｍｌからの再結晶操作に
より、淡黄色粉末固体の化合物（１）、４．７ｇを得
た。以下にその物性値を示す。 （物性値） ｍｐ：１３５〜１３６℃ ＩＲ（ＫＢｒ：ｃｍ-1）：１７１５（νＣ＝０），１１
００〜１３００（νＣＦ） Ｈ ＮＭＲ（ＣＤＣｌ3 ，ｉｎｔ．ＴＭＳ；δｐｐ
ｍ）：１．３（２Ｈ），３．３（９Ｈ），３．７（２
Ｈ），３．８（２Ｈ） Ｆ ＮＭＲ（ＣＤＣｌ3 ，ｉｎｔ．ＣＣｌ3 Ｆ；δｐｐ
ｍ）：−８７．５（４Ｆ），−９２．６（４Ｆ），−９
３．８（２Ｆ），−１１２．０（２Ｆ）． この化合物の水溶液の２５℃におけるＷｉｌｈｅｌｍｙ
法による表面張力の測定結果は以下の通りであった。To a 100 ml flask were added 3.0 g of N, N-dimethylaminopropylamine and 100 ml of ether, and 12.5 g of perfluoro (morpholinopropionic acid) fluoride (purity 70%, electrolytic fluorine) while cooling with ice under an argon stream. (Crude product) was added dropwise and reacted for about 2 hours. After the completion of the reaction, insolubles were removed by filtration to collect a reaction solution. The recovered liquid was washed with about 3.0 ml of an aqueous solution of about 3.0 wt% sodium hydrogencarbonate and subsequently with about 100 ml of a saturated saline solution, and anhydrous magnesium sulfate was added thereto and left for about 10 hours. The anhydrous magnesium sulfate was filtered off and the solvent was distilled off to obtain 4.9 g of a highly viscous pale yellow liquid. This one
After transferring to a 00 ml flask and adding about 30 ml of 2-butanone to completely dissolve, 1.6 g of methyl iodide was added and stirred at room temperature for about 30 hours. After completion of the reaction, the solvent was distilled off, and a crude product was recovered. The crude product was recrystallized from about 50 ml of a 20% ethyl acetate / n-hexane solution to obtain 4.7 g of a pale yellow powdery solid (1). The physical properties are shown below. (Physical properties) mp: 135-136 ° C IR (KBr: cm −1 ): 1715 (νC = 0), 11
00 to 1300 (νCF) 1 H NMR (CDCl 3 , int. TMS; δpp
m): 1.3 (2H), 3.3 (9H), 3.7 (2H)
H), 3.8 (2H) F NMR (CDCl 3 , int. CCl 3 F; δpp
m): -87.5 (4F), -92.6 (4F), -9
3.8 (2F), -112.0 (2F). Wilhelmy at 25 ° C. in aqueous solution of this compound
The measurement results of the surface tension by the method were as follows.
【００２５】[0025]
【表１】 [Table 1]
【００２６】実施例２ 界面活性化合物（２）Example 2 Surfactant (2)
【００２７】[0027]
【化１０】 Embedded image
【００２８】１００ｍｌフラスコにＮ，Ｎ−ジメチルア
ミノプロピルアミン３．０ｇとエーテル１００ｍｌを加
えて、アルゴン気流下で氷冷しながら、ペルフルオロ
（Ｎ，Ｎ−ｎ−プロピルアミノプロピオン酸）フルオリ
ド１５．０ｇ（純度７０％、電解フッ素粗生成物）を滴
下し、約２時間反応させた。反応終了後、不溶物を濾別
して反応液を回収した。回収液を約３．０ｗｔ％炭酸水
素ナトリウム水溶液約１００ｍｌ、続いて、飽和食塩水
約１００ｍｌで洗浄した後、無水硫酸マグネシウムを加
えて、約１０時間放置した。無水硫酸マグネシウムを濾
別し、溶媒を留去して、高粘性な淡黄色液体、５．５ｇ
を得た。このものを１００ｍｌフラスコに移し、２−ブ
タノン約３０ｍｌを加えて、完全に溶解した後、ヨウ化
メチル１．５ｇを加え、室温で約３０時間攪拌した。反
応終了後、溶媒を留去して、粗生物を回収した。粗成生
物を２０％酢酸エチル／ｎ−ヘキサン液約５０ｍｌから
の再結晶操作により、淡黄色粉末固体の化合物（２）、
５．１ｇを得た。以下にその物性値を示す。 （物性値） ｍｐ：１２７〜１２８℃ ＩＲ（ＫＢｒ：ｃｍ-1）：１７０５（νＣ＝０），１１
００〜１３００（νＣＦ） Ｈ ＮＭＲ（ＣＤＣｌ3 ，ｉｎｔ．ＴＭＳ；δｐｐ
ｍ）：１．３（２Ｈ），３．３（９Ｈ），３．７（２
Ｈ），３．８（２Ｈ） Ｆ ＮＭＲ（ＣＤＣｌ3 ，ｉｎｔ．ＣＣｌ3 Ｆ；δｐｐ
ｍ）：−８１．９（６Ｆ），−８４．０（２Ｆ），−８
５．２（４Ｆ），−１１３．０（２Ｆ），−１２２．５
（４Ｆ）． この化合物の水溶液の２５℃におけるＷｉｌｈｅｌｍｙ
法による表面張力の測定結果は以下の通りであった。To a 100 ml flask, 3.0 g of N, N-dimethylaminopropylamine and 100 ml of ether were added, and 15.0 g of perfluoro (N, Nn-propylaminopropionic acid) fluoride was added while cooling with ice under an argon stream. (Purity: 70%, crude electrolytic fluorine product) was added dropwise and reacted for about 2 hours. After the completion of the reaction, insolubles were removed by filtration to collect a reaction solution. The recovered liquid was washed with about 3.0 ml of an aqueous solution of about 3.0 wt% sodium hydrogencarbonate and subsequently with about 100 ml of a saturated saline solution, and anhydrous magnesium sulfate was added thereto and left for about 10 hours. The anhydrous magnesium sulfate was separated by filtration, and the solvent was distilled off.
I got This was transferred to a 100 ml flask, and about 30 ml of 2-butanone was added to completely dissolve the mixture. Then, 1.5 g of methyl iodide was added, and the mixture was stirred at room temperature for about 30 hours. After completion of the reaction, the solvent was distilled off, and a crude product was recovered. The crude product was recrystallized from about 50 ml of a 20% ethyl acetate / n-hexane solution to give the compound (2) as a pale yellow powder solid,
5.1 g were obtained. The physical properties are shown below. (Physical properties) mp: 127 to 128 ° C IR (KBr: cm −1 ): 1705 (νC = 0), 11
00 to 1300 (νCF) 1 H NMR (CDCl 3 , int. TMS; δpp
m): 1.3 (2H), 3.3 (9H), 3.7 (2H)
H), 3.8 (2H) F NMR (CDCl 3 , int. CCl 3 F; δpp
m): -81.9 (6F), -84.0 (2F), -8
5.2 (4F), -113.0 (2F), -122.5
(4F). Wilhelmy at 25 ° C. in aqueous solution of this compound
The measurement results of the surface tension by the method were as follows.
【００２９】[0029]
【表２】 [Table 2]
【００３０】[0030]
【発明の効果】以上詳述したように、本発明は、新規な
フッ素系界面活性化合物に係るものであり、本発明のフ
ッ素系カチオン型界面活性化合物は、その水溶液におい
て、ｃｍｃが０．１ないし１ｍＭｏｌ／ｌであり、その
時の表面張力値が１０ないし１３ｍＮ／ｍである、極め
て高い界面活性能を有する化合物である。本発明方法に
よれば、このような新規な含窒素ペルフルオロアルキル
基を有するカチオン型界面活性化合物を、簡単なプロセ
スにより製造することができるので、この方法は、新規
な含フッ素カチオン型界面活性化合物の工業的製法とし
て有用である。また、該含窒素ペルフルオロアルキル基
置換カチオン型界面活性化合物は、文献未記載の新規化
合物であって、高い界面活性能を有し、工業的価値の高
いものである。As described above in detail, the present invention relates to a novel fluorinated surfactant, and the fluorinated cationic surfactant of the present invention has an aqueous solution having a cmc of 0.1%. To 1 mMol / l, and the surface tension value at that time is 10 to 13 mN / m. According to the method of the present invention, a cationic surfactant compound having such a novel nitrogen-containing perfluoroalkyl group can be produced by a simple process. It is useful as an industrial production method. Further, the nitrogen-containing perfluoroalkyl group-substituted cationic surfactant compound is a novel compound which has not been described in the literature, has high surface activity, and has high industrial value.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 阿部 隆 愛知県春日井市押沢台７丁目６番４号 (72)発明者 渡辺 雅生 秋田県秋田市茨島三丁目１番６号 株式会 社トーケムプロダクツ内 (72)発明者 佐藤 幸生 秋田県秋田市茨島三丁目１番６号 株式会 社トーケムプロダクツ内 (72)発明者 大森 浩太 秋田県秋田市茨島三丁目１番６号 株式会 社トーケムプロダクツ内 Ｆターム(参考） 4C056 AA02 AB01 AC03 AD01 AE01 AF05 EA01 EB02 EC06 4H003 AA02 AE04 4H006 AA01 AA02 AB68 AC52 AC53 BB11 BB12 BB16 BC10 BC31 BM10 BM71 BV30 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Takashi Abe 7-6-4 Oshizawadai, Kasugai-shi, Aichi Prefecture (72) Inventor Masao Watanabe 3-6-1, Ibarimashima, Akita-shi, Akita Prefecture Inside Tochem Products Co., Ltd. (72) Inventor Yukio Sato 3-6-1 Ibarjima, Akita-shi, Akita Prefecture Inside Tochem Products Inc. (72) Inventor Kota Omori 3-6-1 Ibarjima, Akita-shi Akita Prefecture Inside Tochem Products Inc. F term (reference) 4C056 AA02 AB01 AC03 AD01 AE01 AF05 EA01 EB02 EC06 4H003 AA02 AE04 4H006 AA01 AA02 AB68 AC52 AC53 BB11 BB12 BB16 BC10 BC31 BM10 BM71 BV30
Claims (2)
異なる炭素数１〜５のペルフルオロアルキル基であっ
て、それらは直接に、あるいは酸素原子又は窒素原子を
介して結合し、両者が結合している酸素原子又は窒素原
子とともに複素環を形成していてもよい。ｍは１又は２
の、ｎは２から４の、ｌは１から２０の整数、Ｘは塩素
原子、臭素原子、ヨウ素原子などのハロゲン元素）で表
されるフッ素系界面活性化合物。1. A compound of the general formula (I) (In the formula, Rf 1 and Rf 2 are the same or different and are each a C 1-5 perfluoroalkyl group, which are bonded directly or via an oxygen atom or a nitrogen atom, and May form a heterocyclic ring together with the oxygen atom or the nitrogen atom.
Wherein n is an integer of 2 to 4, l is an integer of 1 to 20, and X is a halogen element such as a chlorine atom, a bromine atom and an iodine atom).
を製造する方法であって、一般式（ＩＩ） 【化２】 （ただし、Ｒｆ1 及びＲｆ2 及びｍは前記したものと同
じ、Ｙはフッ素、塩素、臭素、ヨウ素などのハロゲン原
子）で表される含窒素ペルフロオロカルボン酸ハロゲン
化物とジメチルアルキレンアミンとの反応生成物をアル
キルハロゲニドと反応させることを特徴とするフッ素系
界面活性化合物の製造方法。2. A method for producing the fluorine-containing surfactant compound according to claim 1, wherein the compound has the general formula (II): (Where Rf 1, Rf 2 and m are the same as those described above, and Y is a halogen atom such as fluorine, chlorine, bromine or iodine). A method for producing a fluorinated surfactant, comprising reacting a reaction product with an alkyl halide.
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