JPS6217586B2 - - Google Patents
Info
- Publication number
- JPS6217586B2 JPS6217586B2 JP54080685A JP8068579A JPS6217586B2 JP S6217586 B2 JPS6217586 B2 JP S6217586B2 JP 54080685 A JP54080685 A JP 54080685A JP 8068579 A JP8068579 A JP 8068579A JP S6217586 B2 JPS6217586 B2 JP S6217586B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- fluorine
- carbon atoms
- hydroxybetaine
- formula
- 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
- 229910052731 fluorine Inorganic materials 0.000 claims description 39
- 239000011737 fluorine Substances 0.000 claims description 39
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 37
- 239000002280 amphoteric surfactant Substances 0.000 claims description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000002947 alkylene group Chemical group 0.000 claims description 2
- 125000000129 anionic group Chemical group 0.000 claims description 2
- 150000007942 carboxylates Chemical group 0.000 claims description 2
- 125000005647 linker group Chemical group 0.000 claims description 2
- 125000000587 piperidin-1-yl group Chemical group [H]C1([H])N(*)C([H])([H])C([H])([H])C([H])([H])C1([H])[H] 0.000 claims description 2
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 claims description 2
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- KWIUHFFTVRNATP-UHFFFAOYSA-N glycine betaine Chemical compound C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- 238000000921 elemental analysis Methods 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 235000019441 ethanol Nutrition 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 229960003237 betaine Drugs 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 150000002924 oxiranes Chemical class 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 3
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 2
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- VEUUMBGHMNQHGO-UHFFFAOYSA-N ethyl chloroacetate Chemical compound CCOC(=O)CCl VEUUMBGHMNQHGO-UHFFFAOYSA-N 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 150000002221 fluorine Chemical class 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 239000005871 repellent Substances 0.000 description 2
- 230000002940 repellent Effects 0.000 description 2
- FDRCDNZGSXJAFP-UHFFFAOYSA-M sodium chloroacetate Chemical compound [Na+].[O-]C(=O)CCl FDRCDNZGSXJAFP-UHFFFAOYSA-M 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- PSBDWGZCVUAZQS-UHFFFAOYSA-N (dimethylsulfonio)acetate Chemical compound C[S+](C)CC([O-])=O PSBDWGZCVUAZQS-UHFFFAOYSA-N 0.000 description 1
- SDNHELSTPFCXTG-UHFFFAOYSA-N 1,1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-octadecafluorooctane sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O.FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F SDNHELSTPFCXTG-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 238000005684 Liebig rearrangement reaction Methods 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- VEZXCJBBBCKRPI-UHFFFAOYSA-N beta-propiolactone Chemical compound O=C1CCO1 VEZXCJBBBCKRPI-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229910052799 carbon Chemical group 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 150000002443 hydroxylamines Chemical class 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- RRRXPPIDPYTNJG-UHFFFAOYSA-N perfluorooctanesulfonamide Chemical compound NS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F RRRXPPIDPYTNJG-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 229960000380 propiolactone Drugs 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- VWHYHPPXJSBSNK-UHFFFAOYSA-M sodium;3-chloropropane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CCCCl VWHYHPPXJSBSNK-UHFFFAOYSA-M 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229940117986 sulfobetaine Drugs 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
- C23F11/14—Nitrogen-containing compounds
- C23F11/149—Heterocyclic compounds containing nitrogen as hetero atom
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- 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)
- Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Description
本発明は新規な含フツ素ヒドロキシベタイン型
両性界面活性剤に関する。
パーフロロアルキル基含有ベタインのあるもの
は既に米国特許第2764602号明細書により公知で
あるが、本発明のヒドロキシル基を有する含フツ
素ベタインは公知の含フツ素ベタイン化合物とは
明確に区別される。
含フツ素ヒドロキシベタインを公知技術に基づ
いて製造しようと試みると、まずその前駆物質で
ある含フツ素ヒドロキシアミンが次のようにして
製造されなければならない。
即ち、パーフロロアルキルカルボン酸、パーフ
ロロアルキルスルホン酸またはそれらの酸ハライ
ドもしくはエステルにヒドロキシ基含有ジアミン
を縮合反応させなければならない。
しかしながら、アミン分子中のヒドロキシル基
は種々の複雑な好ましくない副反応を惹起し、目
的とする含フツ素ヒドロキシアミンは、ほとんど
得られないことは良く知られている（例えば、文
献H.Niederprumら、Liebigs Annalen der
Chem.、1973巻11頁（1973年））。
従つて、公知技術の応用展開においては含フツ
素ヒドロキシベタインは製造されるはずがないの
で、その実在は全く知られていなかつたが、本発
明者等は別のルートを見い出した結果、初めて含
フツ素ヒドロキシベタインを得、またそれが優れ
た界面活性特性を発現することを発見し、本発明
を完成するに至つた。
本発明によれば、次の一般式：
で示される新規にして有用なる含フツ素ヒドロキ
シベタイン型両性界面活性剤が提供される。
ここにおいて、上記一般式中のＲfは４ないし
12個の炭素原子を含有するフツ素化脂肪族基、た
とえばパーフロロアルキル基を表わすものとする
が、かかるフツ素化脂肪族基は直鎖状、分枝状、
環状（たとえば、シクロヘキシルのような基）ま
たはこれらを適宜組み合わせたもののいずれであ
つもよく、さらには主鎖中に酸素原子が介入され
た形の、たとえば（CF3）2CFOCF2CF2−のよう
なものも本発明に包含される。
次に、Ｙは−SO2−または−CO−なる二価の
連結基を表わすものとする。
また、Ｒは水素原子あるいは炭素数１ないし12
のアルキル基、またはヒドロキシル基もしくは炭
素数１ないし３のアルコキシル基により置換され
た炭素数１ないし８のアルキル基を表わすものと
するが、これら置換ないしは非置換の各アルキル
基は直鎖状、分枝状、環状（たとえば、シクロヘ
キシルあるいはベンジルのような基）またはそれ
らを適宜組み合わせたもののいずれであつてもよ
く、さらには主鎖中に酸素原子が介入された形
の、たとえばCH3CH2OCH2−、CH3OCOCH2−
またはCH3COOCH2−のようなものも本発明に包
含される。
さらに、前掲の一般式において、R1およびR2
はそれぞれ同一であつても異なつていてもよい。
水素原子あるいは炭素数１ないし６のアルキル
基、またはヒドロキシル基もしくはω−ヒドロキ
シ−ポリエトキシ基により置換された炭素数１な
いし６のアルキル基、たとえば−CH2CH2OHま
たは−（CH2CH2O）oＨ（但し、ここにおいてｎは
１〜20の整数であるものとする。）を表わすもの
とし、あるいはこのR1とR2とが互いに連結して
隣接する窒素原子と共にピペリジノ環を形成して
もよいものとする。
他方、R3は炭素数１ないし４のアルキレン基
または−CH2CH（OH）CH2−なる基を表わすも
のとし、そしてＷはカルボキシレート基（−
COO）またはスルホネート基（−SO3）なる
陰イオン性の親水基を表わすものとする。
本発明の含フツ素ヒドロキシベタイン型両性界
面活性剤の代表的な例としては次のようなものが
挙げられる。
または
このような本発明の含フツ素ヒドロキシベタイ
ン型両性界面活性剤は次のような調製方法によつ
て得ることができる。
まず通常容易に入手される反応性のパーフロロ
アルキルカルボン酸、パーフロロアルキルスルホ
ン酸またはそれらの酸ハライドもしくはエステル
を出発原料とし、これと式RNH2（但し、式中の
Ｒは前出した通りであるものとする。）で示され
るアミンとを反応させ、次いでかくして得られる
酸アミド
ＲfYNHR（但し、式中のＲf、ＹおよびＲは前出
した通りであるものとする。）を式
The present invention relates to a novel fluorine-containing hydroxybetaine type amphoteric surfactant. Certain perfluoroalkyl group-containing betaines are already known from U.S. Pat. No. 2,764,602, but the hydroxyl group-containing fluorine-containing betaine of the present invention is clearly distinguished from known fluorine-containing betaine compounds. . When attempting to produce fluorine-containing hydroxybetaine based on known techniques, a fluorine-containing hydroxyamine, which is a precursor thereof, must first be produced in the following manner. That is, a hydroxy group-containing diamine must be subjected to a condensation reaction with perfluoroalkylcarboxylic acid, perfluoroalkylsulfonic acid, or an acid halide or ester thereof. However, it is well known that the hydroxyl group in the amine molecule causes various complicated and undesirable side reactions, and the desired fluorine-containing hydroxyamine is hardly obtained (for example, in the literature H. Niederprum et al. , Liebigs Annalen der
Chem., vol. 1973, p. 11 (1973)). Therefore, fluorine-containing hydroxybetaine cannot be produced in the application and development of known technology, and its existence was completely unknown. However, as a result of finding another route, the present inventors were able to produce fluorine-containing hydroxybetaine for the first time. The present inventors obtained fluorine hydroxybetaine and discovered that it exhibits excellent surfactant properties, leading to the completion of the present invention. According to the invention, the following general formula: A novel and useful fluorine-containing hydroxybetaine type amphoteric surfactant is provided. Here, R f in the above general formula is 4 to
shall represent a fluorinated aliphatic group containing 12 carbon atoms, such as a perfluoroalkyl group, but such fluorinated aliphatic groups may be linear, branched,
It may be cyclic (for example, a group such as cyclohexyl) or an appropriate combination of these, and furthermore, it may have an oxygen atom interposed in the main chain, such as (CF 3 ) 2 CFOCF 2 CF 2 −. Such materials are also included in the present invention. Next, Y represents a divalent linking group of -SO2- or -CO-. In addition, R is a hydrogen atom or a carbon number of 1 to 12
or an alkyl group having 1 to 8 carbon atoms substituted with a hydroxyl group or an alkoxyl group having 1 to 3 carbon atoms, and each of these substituted or unsubstituted alkyl groups may be linear, branched or It may be branched, cyclic (for example, a group such as cyclohexyl or benzyl), or a suitable combination thereof, and furthermore, it may have an oxygen atom interposed in the main chain, for example, CH 3 CH 2 OCH 2 −, CH 3 OCOCH 2 −
or CH 3 COOCH 2 − and the like are also included in the present invention. Furthermore, in the above general formula, R 1 and R 2
may be the same or different.
a hydrogen atom or a C1 -C6 alkyl group, or a C1 -C6 alkyl group substituted by a hydroxyl group or an ω-hydroxy-polyethoxy group, such as -CH 2 CH 2 OH or -(CH 2 CH 2 O ) o H (where n is an integer from 1 to 20), or R 1 and R 2 are connected to each other to form a piperidino ring with the adjacent nitrogen atom. may be used. On the other hand, R 3 represents an alkylene group having 1 to 4 carbon atoms or a group -CH 2 CH(OH)CH 2 -, and W represents a carboxylate group (-
COO) or a sulfonate group ( -SO3 ), which is an anionic hydrophilic group. Representative examples of the fluorine-containing hydroxybetaine type amphoteric surfactants of the present invention include the following. or Such a fluorine-containing hydroxybetaine type amphoteric surfactant of the present invention can be obtained by the following preparation method. First, a normally easily available reactive perfluoroalkylcarboxylic acid, perfluoroalkylsulfonic acid, or their acid halide or ester is used as a starting material, and this is combined with the formula RNH 2 (where R is as described above). ), and then the acid amide R f YNHR obtained in this way (where R f , Y and R in the formula are as defined above) is reacted with an amine represented by formula
【式】（但し、式中のＸはフツ素
以外の、塩素、臭素またはヨウ素なるハロゲン原
子を表わすものとする。）で示されるエポキサイ
ドと縮合させて式[Formula] (However, X in the formula represents a halogen atom other than fluorine, such as chlorine, bromine, or iodine.)
【式】（但
し、式中のＲf、ＹおよびＲは前出した通りであ
るものとする。）で示される含フツ素エポキサイ
ドを調製する。
しかるのち、この含フツ素エポキサイドに式
HNR1R2（但し、式中のR1およびR2は前出した通
りであるものとする。）で示されるアミンを作用
させることによりエポキシ環を開環せしめて式
A fluorine-containing epoxide represented by the formula (in which R f , Y, and R are as defined above) is prepared. Afterwards, the formula was added to this fluorine-containing epoxide.
HNR 1 R 2 (However, R 1 and R 2 in the formula are as described above.) The epoxy ring is opened by reacting with the amine represented by the formula
【式】
（但し、式中のＲf、Ｙ、Ｒ、R1およびR2は前出し
た通りであるものとする。）で示される含フツ素
ヒドロキシアミンを調製する。
次いで、該ヒドロキシアミン中の末端アミノ基
にモノクロル酢酸（あるいはモノクロル酢酸ナト
リウムまたはモノクロル酢酸エチルエステルなど
の各種誘導体）、プロピオラクトン、プロパンサ
ルトン、モノクロルプロピルスルホン酸ナトリウ
ムまたはアクリル酸などの如き公知慣用の四級化
剤を作用せしめて、目的とする含フツ素ヒドロキ
シベタイン型両性界面活性剤を得るという方法で
ある。
この場合、モノクロル酢酸アルキルエステルの
ように親水基がマスキングされた四級化剤を使用
したときには、反応後酸もしくはアルカリでエス
テル基を加水分解させることにより、両性イオン
構造をもつた含フツ素ヒドロキシベタイン型両性
界面活性剤を製造することができる。
本発明の含フツ素ヒドロキシベタイン型両性界
面活性剤は、水あるいはアルコールのような極性
媒体中で優れた界面活性特性を発揮するだけでな
く、オイル、ワツクス、グリースあるいはワニス
のような低誘電率の媒体中においても、優れた界
面活性特性を発揮し得る。
次の表は各種含フツ素ベタイン型両性界面活性
剤水溶液の表面張力をPHを変えて測定した結果で
ある。公知の含フツ素ベタイン型両性界面活性剤
に比較して本発明の含フツ素ヒドロキシベタイン
型両性界面活性剤は広いPH領域で優れた界面活性
を発揮する。A fluorine-containing hydroxyamine represented by the formula: (in which R f , Y, R, R 1 and R 2 are as defined above) is prepared. Next, the terminal amino group in the hydroxyamine is treated with a known compound such as monochloroacetic acid (or various derivatives such as sodium monochloroacetate or ethyl monochloroacetate), propiolactone, propane sultone, sodium monochloropropylsulfonate, or acrylic acid. In this method, a desired fluorine-containing hydroxybetaine type amphoteric surfactant is obtained by applying a quaternizing agent. In this case, when using a quaternizing agent whose hydrophilic groups are masked, such as monochloroacetic alkyl ester, by hydrolyzing the ester group with an acid or alkali after the reaction, fluorine-containing hydroxyl with a zwitterion structure can be used. Betaine type amphoteric surfactants can be produced. The fluorine-containing hydroxybetaine type amphoteric surfactant of the present invention not only exhibits excellent surfactant properties in polar media such as water or alcohol, but also has low dielectric constant properties such as oil, wax, grease, or varnish. It can exhibit excellent surfactant properties even in medium of The following table shows the results of measuring the surface tension of various fluorine-containing betaine type amphoteric surfactant aqueous solutions by varying the pH. Compared to known fluorine-containing betaine type amphoteric surfactants, the fluorine-containing hydroxybetaine type amphoteric surfactant of the present invention exhibits superior surface activity over a wide pH range.
【表】【table】
【表】
したがつて、本発明の含フツ素ヒドロキシベタ
イン型両性界面活性剤は起泡剤、湿潤剤、乳化
剤、洗浄剤、防錆剤、帯電防止剤、液状炭化水素
蒸発抑制剤、水成膜形成剤、レベリング剤、塗料
用添加剤、撥水剤、撥油剤、プラスチツクス用添
加剤または離型剤などに広範に用いることができ
る。
次に本発明をさらに具体的に説明するために実
施例を示す。
実施例 １
パーフロロオクタンスルホニルクロライド
C8F17SO2F100ｇ（0.2モル）とｎ−プロピルアミ
ン35.4ｇ（0.6モル）との粗製縮合物をクロロホ
ルム／エタノール混合溶媒で再結晶して融点85〜
87℃の白色固体パーフロロオクタンスルホンアミ
ドC8F17SO2NHC3H797ｇを得た。これをメタノ
ール中に溶解し、等モルのナトリウムメチラート
を加えてドライアツプし、[Table] Therefore, the fluorine-containing hydroxybetaine type amphoteric surfactant of the present invention can be used as a foaming agent, a wetting agent, an emulsifier, a detergent, a rust preventive agent, an antistatic agent, a liquid hydrocarbon evaporation inhibitor, and an aqueous hydrocarbon evaporation inhibitor. It can be widely used as a film forming agent, leveling agent, paint additive, water repellent, oil repellent, plastics additive, mold release agent, etc. Next, Examples will be shown to further specifically explain the present invention. Example 1 Perfluorooctane sulfonyl chloride
C 8 F 17 SO 2 A crude condensate of 100 g (0.2 mol) of F and 35.4 g (0.6 mol) of n-propylamine was recrystallized from a chloroform/ethanol mixed solvent to give a melting point of 85~
97 g of white solid perfluorooctane sulfonamide C 8 F 17 SO 2 NHC 3 H 7 was obtained at 87°C. This was dissolved in methanol, added with an equimolar amount of sodium methylate, and dried up.
【式】に転
換した後、エピクロルヒドリン82.8ｇ（0.00895
モル）と11時間還流温度で反応させた。塩を別
し、過剰エピクロルヒドリンを留去した後、減圧
蒸留し、相当する含フツ素エポキサイド
After converting to [formula], 82.8 g of epichlorohydrin (0.00895
mol) at reflux temperature for 11 hours. After separating the salt and distilling off excess epichlorohydrin, distillation is performed under reduced pressure to obtain the corresponding fluorine-containing epoxide.
【式】84ｇを得た。
この含フツ素エポキサイド84ｇ（0.141モル）
に50％ジメチルアミン水溶液63.3ｇ（0.704モ
ル）を加え、５時間室温で撹拌した後、イソプロ
ピルエーテルで抽出水洗し、無水硫酸ナトリウム
で乾燥させた。エーテルを留去した後、減圧蒸留
し、目的とする含フツ素ヒドロキシアミン
[Formula] 84g was obtained. 84g (0.141mol) of this fluorine-containing epoxide
63.3 g (0.704 mol) of a 50% aqueous dimethylamine solution was added thereto, and the mixture was stirred at room temperature for 5 hours, extracted with isopropyl ether, washed with water, and dried over anhydrous sodium sulfate. After distilling off the ether, it is distilled under reduced pressure to obtain the desired fluorine-containing hydroxyamine.
【式】79.3ｇを得
た。
上記含フツ素ヒドロキシアミン64.2ｇ（0.1モ
ル）およびクロル酢酸エチル24.5ｇ（0.2モル）
をトルエン50ml中で撹拌しながら80〜90℃に3.5
時間加熱した。室温まで冷却後、生成した白色析
出物を別し、イソプロピルエーテルで洗浄し
た。残存溶媒を減圧し除去し、白色固体64.5ｇを
得た。このものは元素分析、IRおよびNMR分析
により、
なる化合物であることが確認された。
Γ原料含フツ素ヒドロキシアミンに対する収率：
84.5％
Γ元素分析
Ｃ Ｈ Ｎ Ｆ Cl
計算値（％） 31.4 3.0 3.7 42.2 4.6
分析値（％） 31.5 3.1 3.5 41.9 4.4
ΓIRスペクトル：1745cm-1に−CH2COOC2H5の
エステルカルボニルの吸収が見られた。
ΓMNRスペクトル：
(1) ４級窒素原子に結合したメチル基の水素原子
……3.4ppm
(2) ４級窒素原子とカルボニル基にはさまれたメ
チレン基の水素原子 ……4.5ppm
実施例 ２
実施例１の生成物57.3ｇ（0.075モル）を、イ
ソプロピルアルコール100ml中において25％
NaOH水溶液24ｇ（0.15モル）と共に70〜80℃で
２時間加熱撹拌することにより、加水分解した
後、過剰の水酸化ナトリウムを希塩酸で中和し、
ドライアツプした。エチルアルコール200mlを用
いて加熱抽出した後、不溶部分を別し、再びド
ライアツプすると白色固体51.5ｇが得られた。こ
のものは元素分析、IRおよびNMR分析により目
的物であることが確認された。
Γこの例に於ける出発原料に対する収率：99％
Γ元素分析
Ｃ Ｈ Ｎ Ｆ
計算値（％） 30.9 3.0 4.0 46.1
分析値（％） 30.8 2.8 4.0 46.0
ΓIRスペクトル：1630cm-1に−CH2COOの吸
収が見られた。
ΓNMR
(1) ４級窒素原子に結合したメチル基の水素原子
……3.33ppm
(2) ４級窒素原子とカルボニル基にはさまれたメ
チレン基の水素原子 ……3.94ppm
実施例 ３
12.4ｇ（0.025モル）の含フツ素ヒドロキシアミ
ン
をトルエン50ml中で、プロパンサルトン3.1ｇ
（0.025モル）と共に90〜100℃にて７時間加熱撹
拌した。このとき反応が進行するにしたがい白色
固体が析出してきた。室温まで冷却した後吸引
過し、残をイソプロピルエーテルで洗浄した。
残存する溶媒を除くと、目的とする含フツ素スル
ホベタイン（白色固体）12.7ｇが得られた。
Γ含フツ素ヒドロキシアミンに対する収率：76.5
％
Γ元素分析
Ｃ Ｈ Ｎ Ｆ Cl
計算値（％） 30.7 3.7 4.2 37.2 9.6
分析値（％） 30.5 3.8 4.4 36.9 9.8
実施例 ４
64.2ｇ（0.1モル）の含フツ素ヒドロキシアミン
および12.8ｇ（0.11モル）のモノクロル酢酸ナト
リウムをエタノール100ml中において６時間還流
下撹拌した。反応終了後生成する塩を別し、
液をドライアツプすると目的とする含フツ素ヒド
ロキシベタイン68.6ｇが得られた。このものの外
観は白色吸湿性固体である。
Γ含フツ素ヒドロキシアミンに対する収率：98％
ΓIRスペクトル：1630cm-1に−CH2COOの吸
収が見られた。
ΓNMRスペクトル
(1) ４級窒素原子に結合したメチル基の水素原子
……2.7ppm
(2) ４級窒素原子とカルボニル基にはさまれたメ
チレン基の水素原子 ……3.5ppm
Γ元素分析
Ｃ Ｈ Ｎ Ｆ
計算値（％） 30.9 3.0 4.0 46.1
分析値（％） 31.0 3.2 3.8 45.9
実施例 ５
29.2ｇ（0.05モル）の含フツ素ヒドロキシルアミ
ン
をテトラヒドロフラン50mlに溶解し、これにアク
リル酸7.2ｇ（0.1モル）を加え、40℃で25時間加
熱撹拌した。析出した白色固体を別し、さらに
テトラヒドロフランで洗浄した後、真空乾燥し
て、目的とする含フツ素ヒドロキシベタイン（白
色固体）29.8ｇを得た。
Γ含フツ素ヒドロキシアミンに対する収率：91％
ΓIRスペクトル：1620cm-1に−CH2CH2COOの
吸収が見られた。
Γ元素分析
Ｃ Ｈ Ｎ Ｆ
計算値（％） 36.6 4.4 4.3 37.7
分析値（％） 36.8 4.7 4.0 37.4
実施例 ６
26.4ｇ（0.05モル）の含フツ素ヒドロキシアミン
および10.8ｇ（0.55モル）のエピクロルヒドリン
スルホネート
をエタノール100ml中において６時間還流撹拌し
た。反応終了後生成した塩を別し、液をドラ
イアツプすると、目的とする含フツ素ヒドロキシ
ベタイン（白色固体）32ｇを得た。
Γ含フツ素ヒドロキシアミンに対する収率：96％
Γ元素分析
Ｃ Ｈ Ｎ Ｆ
計算値（％） 28.8 3.5 4.2 37.1
分析値（％） 29.0 3.8 4.1 36.9
実施例 ７〜11
以上の実施例と同様な操作で本発明に関る含フ
ツ素ヒドロキシベタインを合成し実施例７〜11と
し、これらと実施例３〜６の化合物の0.1％水溶
液の表面張力を測定し結果を表−２にまとめた。
尚、表面張力は酸性（PH３）、中性（PH7.5）、
塩基性（PH11）において、25℃にてウイルヘルミ
ー法で測定した。[Formula] 79.3g was obtained. 64.2g (0.1mol) of the above fluorine-containing hydroxyamine and 24.5g (0.2mol) of ethyl chloroacetate
3.5 to 80-90℃ with stirring in 50ml of toluene.
heated for an hour. After cooling to room temperature, the white precipitate formed was separated and washed with isopropyl ether. The remaining solvent was removed under reduced pressure to obtain 64.5 g of a white solid. This item was determined by elemental analysis, IR and NMR analysis. It was confirmed that the compound was Yield based on Γ raw material fluorine-containing hydroxyamine:
84.5% Γ elemental analysis C H N F Cl Calculated value (%) 31.4 3.0 3.7 42.2 4.6 Analysis value (%) 31.5 3.1 3.5 41.9 4.4 ΓIR spectrum: Absorption of ester carbonyl of -CH 2 COOC 2 H 5 at 1745 cm -1 It was seen. ΓMNR spectrum: (1) Hydrogen atom of methyl group bonded to quaternary nitrogen atom
...3.4ppm (2) Hydrogen atom of methylene group sandwiched between quaternary nitrogen atom and carbonyl group ...4.5ppm Example 2 57.3 g (0.075 mol) of the product of Example 1 at 25% in 100 ml of isopropyl alcohol
After hydrolysis by heating and stirring at 70 to 80°C for 2 hours with 24 g (0.15 mol) of NaOH aqueous solution, excess sodium hydroxide was neutralized with dilute hydrochloric acid.
It was dry. After heating and extraction with 200 ml of ethyl alcohol, the insoluble portion was separated and dry-up again to obtain 51.5 g of a white solid. This product was confirmed to be the desired product by elemental analysis, IR and NMR analysis. Γ Yield based on starting material in this example: 99% Γ Elemental analysis C H N F Calculated value (%) 30.9 3.0 4.0 46.1 Analyzed value (%) 30.8 2.8 4.0 46.0 Γ IR spectrum: -CH 2 COO at 1630 cm -1 absorption was observed. ΓNMR (1) Hydrogen atom of methyl group bonded to quaternary nitrogen atom
...3.33ppm (2) Hydrogen atom of methylene group sandwiched between quaternary nitrogen atom and carbonyl group ...3.94ppm Example 3 12.4g (0.025mol) fluorinated hydroxyamine in 50 ml of toluene, 3.1 g of propane sultone
(0.025 mol) and heated and stirred at 90 to 100°C for 7 hours. At this time, as the reaction progressed, a white solid precipitated. After cooling to room temperature, the mixture was filtered under suction, and the residue was washed with isopropyl ether.
After removing the remaining solvent, 12.7 g of the desired fluorine-containing sulfobetaine (white solid) was obtained. Yield to Γ fluorine-containing hydroxyamine: 76.5
% Γ elemental analysis C H N F Cl Calculated value (%) 30.7 3.7 4.2 37.2 9.6 Analysis value (%) 30.5 3.8 4.4 36.9 9.8 Example 4 64.2g (0.1mol) of fluorine-containing hydroxyamine and 12.8 g (0.11 mol) of sodium monochloroacetate were stirred in 100 ml of ethanol under reflux for 6 hours. Separate the salt produced after the reaction is complete,
When the liquid was dry-uped, 68.6 g of the desired fluorine-containing hydroxybetaine was obtained. The appearance of this product is a white hygroscopic solid. Yield based on Γ fluorine-containing hydroxyamine: 98% Γ IR spectrum: -CH 2 COO absorption was observed at 1630 cm -1 . ΓNMR spectrum (1) Hydrogen atom of methyl group bonded to quaternary nitrogen atom
...2.7ppm (2) Hydrogen atom of methylene group sandwiched between quaternary nitrogen atom and carbonyl group ...3.5ppm Γ elemental analysis C H N F Calculated value (%) 30.9 3.0 4.0 46.1 Analytical value (%) 31.0 3.2 3.8 45.9 Example 5 29.2g (0.05mol) of fluorinated hydroxylamine was dissolved in 50 ml of tetrahydrofuran, 7.2 g (0.1 mol) of acrylic acid was added thereto, and the mixture was heated and stirred at 40°C for 25 hours. The precipitated white solid was separated, further washed with tetrahydrofuran, and then vacuum dried to obtain 29.8 g of the desired fluorine-containing hydroxybetaine (white solid). Yield based on Γ fluorine-containing hydroxyamine: 91% Γ IR spectrum: -CH 2 CH 2 COO absorption was observed at 1620 cm -1 . Γ elemental analysis C H N F Calculated value (%) 36.6 4.4 4.3 37.7 Analysis value (%) 36.8 4.7 4.0 37.4 Example 6 26.4g (0.05mol) fluorinated hydroxyamine and 10.8 g (0.55 mol) epichlorohydrin sulfonate The mixture was stirred under reflux in 100 ml of ethanol for 6 hours. After the reaction was completed, the salt produced was separated and the liquid was dried up to obtain 32 g of the desired fluorine-containing hydroxybetaine (white solid). Yield based on Γ fluorine-containing hydroxyamine: 96% Γ elemental analysis C H N F Calculated value (%) 28.8 3.5 4.2 37.1 Analytical value (%) 29.0 3.8 4.1 36.9 Examples 7 to 11 Same operation as in the above examples The fluorine-containing hydroxybetaines of the present invention were synthesized as Examples 7 to 11, and the surface tensions of 0.1% aqueous solutions of these and the compounds of Examples 3 to 6 were measured, and the results are summarized in Table 2. In addition, the surface tension is acidic (PH3), neutral (PH7.5),
Measured by Wilhelmy method at 25°C under basic conditions (PH11).
【表】【table】
Claims (1)
有するフツ素化脂肪族基を、Ｙは−SO2−または
−CO−なる二価の連結基を、Ｒは水素原子ある
いは炭素数１ないし12のアルキル基、またはヒド
ロキシル基もしくは炭素数１ないし３のアルコキ
シル基により置換された炭素数１ないし12のアル
キル基を表わすものとし、R1およびR2はそれぞ
れ同一であつても異なつていてもよい、水素原子
あるいは炭素数１ないし６のアルキル基、または
ヒドロキシル基もしくはω−ヒドロキシ−ポリエ
トキシ基により置換された炭素数１ないし６のア
ルキル基を表わすものとし、このR1とR2とが互
いに連結して隣接する窒素原子と共にピペリジノ
環を形成してもよいものとし、R3は炭素数１な
いし４のアルキレン基または−CH2CH（OH）
CH2−なる基を、Ｗはカルボキシレート基または
スルホネート基なる陰イオン性の親水基を表わす
ものとする。） で示される含フツ素ヒドロキシベタイン型両性界
面活性剤。[Claims] 1. General formula (However, in the formula, R f is a fluorinated aliphatic group containing 4 to 12 carbon atoms, Y is a divalent linking group such as -SO 2 - or -CO-, and R is a hydrogen atom or Represents an alkyl group having 1 to 12 carbon atoms, or an alkyl group having 1 to 12 carbon atoms substituted with a hydroxyl group or an alkoxyl group having 1 to 3 carbon atoms, even if R 1 and R 2 are each the same. R 1 and R 2 may be linked to each other to form a piperidino ring with the adjacent nitrogen atom, and R 3 is an alkylene group having 1 to 4 carbon atoms or -CH 2 CH(OH)
In the group CH2- , W represents an anionic hydrophilic group such as a carboxylate group or a sulfonate group. ) A fluorine-containing hydroxybetaine type amphoteric surfactant.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8068579A JPS565897A (en) | 1979-06-28 | 1979-06-28 | Fluorine containing hydroxybetaine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8068579A JPS565897A (en) | 1979-06-28 | 1979-06-28 | Fluorine containing hydroxybetaine |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS565897A JPS565897A (en) | 1981-01-21 |
| JPS6217586B2 true JPS6217586B2 (en) | 1987-04-18 |
Family
ID=13725188
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8068579A Granted JPS565897A (en) | 1979-06-28 | 1979-06-28 | Fluorine containing hydroxybetaine |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS565897A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58201752A (en) * | 1982-05-19 | 1983-11-24 | Dainippon Ink & Chem Inc | Fluorine-containing tricarboxylic acid-type amphoteric compound and its preparation |
| JP5136826B2 (en) * | 2007-03-20 | 2013-02-06 | Ｄｉｃ株式会社 | Antistatic agent |
| JP5610209B2 (en) * | 2010-09-08 | 2014-10-22 | Dic株式会社 | Antistatic agent and coating composition using the same |
-
1979
- 1979-06-28 JP JP8068579A patent/JPS565897A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS565897A (en) | 1981-01-21 |
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