JPS622848B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a fluoroalkyl group-containing surfactant and a method for producing the same, and more specifically, to a surfactant comprising a new compound containing a polyfluoroalkyl group and a method for producing the same. Conventionally, various surfactants such as anionic, cationic, and nonionic surfactants have been known, and fluorine-based surfactants having a fluoroalkyl group such as a perfluoroalkyl group are also known. Fluorine-based surfactants exhibit unique surfactant properties, so they can be used as evaporation inhibitors (extinguishing agents) for volatile liquids,
It is suitable for use as a leveling agent for photographic gelatin layers, as a paint additive, as a wax additive, and for various other uses.
Fluorinated anionic surfactants are also widely used as emulsifiers in the production of fluorinated resins. Although amphoteric surfactants generally have characteristics such as being less affected by pH changes and less affected by salts, there have been few proposals for suitable fluorine-based amphoteric surfactants. . Previously, the applicant has discovered that an amphoteric surfactant with a specific structure containing a polyfluoroalkyl group has the general characteristics of an amphoteric surfactant, has a small critical micelle formation concentration, and is effective in lowering surface tension even at low concentrations. It was proposed that it exhibits excellent surfactant effects such as large and low minimum surface tension values.
For example, JP-A-53-45683, JP-A-53-45683,
See Publication No. 45684, Japanese Unexamined Patent Publication No. 1983-62990, etc. According to the research of the present inventors, an amide can be synthesized by using a perfluorocarboxylic acid chloride, a perfluorocarboxylic acid alkyl ester, etc. as a starting material and reacting it with an alkoxyamine compound such as hydroxyaminoethoxypropylamine. When reacted with β-lactone or monochloroacetic acid, a new compound containing a perfluoroalkyl group can be obtained. It has thus been discovered that such a new compound is extremely effective as a fluorine-containing surfactant. In other words, the surface tension of an aqueous solution is 16
We have obtained new knowledge that it is a surfactant that can be reduced to dyne/cm or less, has a low critical micelle formation concentration as a fluorine-based surfactant, and can act effectively even at a concentration as low as 0.001% by weight. It is something. Thus, the present invention has been completed based on the above findings, and is based on the general formula

[Formula] (However, R _f in the formula is a polyfluoroalkyl group having 1 to 20 carbon atoms,
R ₁ is a hydrogen atom or an alkyl group, A has 1 or more carbon atoms
10 divalent alkylene groups, B is a divalent alkylene group having 1 to 10 carbon atoms, Q is a divalent alkylene group having 1 to 5 carbon atoms, R ₂ is an alkyl group or a hydroxyalkyl group, M The present invention provides a novel fluoroalkyl group-containing surfactant comprising a compound represented by a hydrogen atom, _-NH4 , or an alkali metal, respectively. The fluorine-based surfactant of the present invention having a specific structure can lower the surface tension of an aqueous solution more than the surfactant disclosed in JP-A-53-45684, which has a similar structure. , it also has the characteristic of having a large ability to lower surface tension even at lower concentrations. For example, as is clear from the Examples described below, the present invention Compounds such as C ₉ F ₁₉ CONH(CH ₂ ) ₃ 〓
(CH ₃ ) ₂ CH ₂ It lowers the surface tension of water more than compounds such as COO (16 dynes/cm
(below), it can reduce the surface tension of water to around 17.8 dynes/cm at very low concentrations (0.001% by weight).
Furthermore, since it is an amphoteric surfactant, it is stable even in hard water and is not easily affected by pH, making it an excellent product that can be effectively used in various applications. In the novel compound of the present invention, firstly, the number of carbon atoms is 1.
It is important to have ~20 polyfluoroalkyl groups (R _f groups). Usually the R _f group has 3 carbon atoms
The perfluoroalkyl group preferably has 18 to 18 carbon atoms, particularly 6 to 12 carbon atoms. Of course, the R _f group may be linear or branched, and may also be a polyfluoroalkyl group partially containing a hydrogen atom, a chlorine atom, or the like. Such polyfluoroalkyl groups, particularly perfluoroalkyl groups, can exhibit various properties as a fluorosurfactant. Second, it is important to contain an ether bond within the molecule, and such a structure allows

Compared to those containing [Formula] etc., the ability to lower the surface tension of aqueous solutions is increased. Thirdly, it is important that the -Q-COOM group is bonded to the nitrogen atom, and by such an embodiment, various properties as an amphoteric surfactant can be exhibited. Q
is a divalent alkylene group having 1 to 5 carbon atoms,
It may be linear or branched, but usually has 1 to 1 carbon atoms.
Two linear alkylene groups, i.e. -CH ₂ - or -
_CH2CH2- is _a preferred embodiment. R ₁ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and usually a hydrogen atom is preferred. R ₂ is an alkyl group or a hydroxyalkyl group, particularly a lower alkyl group having 1 to 5 carbon atoms or a lower hydroxyalkyl group such as -CH ₂ CH ₂ OH. Thus, A is a divalent alkylene group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, and B is a divalent alkylene group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms.
divalent alkylene groups, which may be linear or branched. Usually, from the viewpoint of surfactant ability, easy availability, etc., an embodiment in which B is -CH ₂ CH ₂ - is particularly desirable, and A is -CH ₂ CH ₂ - or -
It is particularly desirable that CH ₂ CH ₂ CH ₂ -. The novel fluorosurfactant compound of the present invention is
Although it can be produced by various synthetic methods, it is usually produced by the general formula

It can be easily synthesized by reacting a polyfluoroalkylamide compound represented by the formula with a carboxylating agent such as monochloroacetic acid, β-propiolactone, or acrylic acid. For example, it can be synthesized by the following specific reaction example. That is, etc. Therefore, the general formula

A compound of the formula can be easily obtained by an amidation reaction between a polyfluoroalkylcarboxylic acid and a specific alkoxyamine compound. For example, it can be synthesized by the method shown by the following chemical reaction formula. That is, the present invention provides the general formula

[Formula] (However, R _f in the formula is a polyfluoroalkyl group having 1 to 20 carbon atoms as described above, and Z is -OR, X, or

[Formula], R represents a hydrogen atom or a lower alkyl group, and X represents a halogen atom) and the general formula NHR ₁ -A-O-B-NHR ₂ (However, R ₁
is a hydrogen atom or an alkyl group, A is a divalent alkylene group having 1 to 10 carbon atoms, B is a divalent alkylene group having 1 to 10 carbon atoms, and R ₂ is an alkyl group or a hydroxyalkyl group, respectively) By performing an amidation reaction with an alkoxyamine compound represented by the general formula

A polyfluoroalkylamide compound represented by the formula (in which R _f , R ₁ , A, B, and R ₂ are the same as above) is produced, and the amide compound is reacted with a carboxylating agent. general formula

[Formula] (However, R _f , R ₁ , A, B, and R ₂ in the formula are the same as above, and Q
is a divalent alkylene group having 1 to 5 carbon atoms, and M is a hydrogen atom, -NH ₄ , or an alkali metal. It also provides new laws. In the synthesis methods such as (1) to (3) of the present invention,
The reaction is preferably carried out in an inert solvent such as dioxane, tetrahydrofuran, chloroform, carbon tetrachloride, toluene, xylene, cyclohexane, acetonitrile, ethyl acetate, etc., and in methods (1) or (3) etc., ethanol, Lower alcohol solvents such as isopropanol may also be used.
The amount of solvent to be used is approximately 1/2 to 3 times (volume) the amount of the polyfluoroalkylamide compound. In methods (1) and (3) above, the reaction temperature is 40 to 100°C.
℃, preferably 50 to 90℃ for about 1 to 30 hours, and in method (2), the reaction temperature is 10 to 100℃.
C., preferably 20 to 50.degree. C. for about 5 to 15 hours. According to such a method, it is possible to achieve a yield of almost 100% of the target compound.
The carboxylating agent can be used in an amount of about 1 to 2 moles per mole of the polyfluoroalkylamide compound, but preferably about 1 to 1.5 moles per mole of the amide compound. In the present invention, the carboxylating agent is not particularly limited as long as it can replace the active hydrogen atom of -NHR ₂ of the polyfluoroalkylamide compound with a -Q-COOM group, and various examples can be used. . Suitable carboxylating agents include, firstly, halogen-substituted hydrocarbons such as Y-W-COOM (where W is the same as Q, Y is a chlorine atom or a bromine atom, and M is the same as above); These are carboxylic acids, such as monochloroacetic acid, β-chloropropionic acid, and δ-chlorocaproic acid. Secondly,

[Formula] (where W is the same as Q), such as β-propiolactone and γ-butyrolactone. Thirdly, W'-COOM (where W' is an alkenyl group having a carbon-carbon double bond and has the same number of carbon atoms as Q except that it has 2 or more carbon atoms, or M is an unsaturated hydrocarbon carboxylic acid (same as above), such as acrylic acid, vinyl acetic acid, methacrylic acid, etc. In the present invention, monochloroacetic acid, β-propiolactone, acrylic acid, and the like can be particularly preferably employed as the carboxylating agent. In the method of the present invention, the raw material polyfluoroalkylcarbonyl compound for the amidation reaction has the general formula

It is represented by [Formula]. R _f is as described above, and Z is -OR, X, or

[Formula]. and R is a hydrogen atom or a lower alkyl group,
It is usually a lower alkyl group having 1 to 5 carbon atoms.
X is a halogen atom, preferably a chlorine atom or a bromine atom. For example, R _f COOH, R _f
COCl, R _f COBr, R _f COOCH ₃ , R _f COOC ₂ H ₅ ,
R _f COOC ₃ H ₇ ,

Examples include [Formula]. In addition, alkoxyamine compounds have the general formula
Represented by NHR ₁ -A-O-B-NHR ₂ , R ₁ ,
A, B, and R ₂ are as described above, for example, hydroxyethylaminoethoxypropylamine (NH ₂ (CH ₂ ) ₃ O(CH ₂ ) ₂ NHCH ₂ CH ₂ OH), methylaminoethoxypropylamine (NH ₂ ( _CH2 ) _3O
(CH ₂ ) ₂ NHCH ₃ ), etc. In the present invention, amidation reactions such as those mentioned above also include alcohols such as ethanol and isopropanol, toluene, xylene, cyclohexane,
It is preferably carried out in an inert solvent such as chloroform, carbon tetrachloride, acetonitrile, ethyl acetate, dioxane, tetrahydrofuran, and usually

1/2 to 3 times (volume) of the solvent may be used relative to the carbonyl compound of the formula. reaction temperature 40
Conditions are employed at ~100°C, preferably 50~80°C for about 1~30 hours. In the above and the like, the reaction molar ratio is about 1 to 2 moles, preferably about 1 to 1.5 moles, of the amine compound per 1 mole of the carbonyl compound;
2 to 4 moles of amine compound per mole, preferably 2
~3 moles may be employed. The fluorine-containing surfactant of the present invention thus obtained has the general formula:

It is expressed by [Formula], and the following are typical examples. That is, For example, The structure of the novel compound of the present invention can be determined by infrared absorption spectrum, elemental analysis, and NMR.
This has been confirmed by means such as measurements. The novel fluorine-containing surfactant of the present invention has various excellent properties, as shown in the Examples below. That is, in addition to the general properties of an amphoteric type and a fluorinated type, such as hard water resistance, pH change resistance, heat resistance, and chemical resistance, it also has a remarkable ability to lower the surface tension of water. Furthermore, since the critical micelle formation concentration is very low, the above-mentioned effects can be satisfactorily exhibited even at very low concentrations. Therefore, the fluorine-containing surfactant of the present invention can be widely employed in various applications utilizing such properties. For example, since it acts effectively even in an aqueous gelatin solution, it can be used as a wetting improver for the emulsion base material of photographic film or photographic paper. In addition, it is stable in hard water and is not easily affected by pH, so it can be effectively used as a fire extinguisher for fires with flammable liquids such as gasoline. In addition, leveling agents for waxes, wetting agents for fiber processing,
Penetrants for agricultural chemicals and pharmaceuticals, mist prevention agents for plating tanks,
It also exhibits excellent effects as an etching additive, plastic modifier, anti-fogging agent, paint additive, shoe cream additive, etc. Next, embodiments of the present invention will be described in more detail, but it goes without saying that the present invention is not limited by such explanations. In the following examples, surface tension was measured by the Wilhelmy method while maintaining a sample solution diluted to a predetermined concentration at 25°C. Example 1 100 gr of perfluoroalkyl isopropyl ester (C ₉ F ₁₀ COOC ₃ H ₇ ) was added to a 300 ml flask equipped with a stirrer, reflux condenser and thermometer.
and 100g of isopropanol (IPA) solvent, and stirred the contents at room temperature to dissolve hydroxyaminoethoxypropylamine (NH ₂ (CH ₂ ) ₃ O
After gradually dropping 27.0gr of (CH ₂ ) ₂ NHCH ₂ CH ₂ OH), the yield was increased by reacting at 70°C for about 20 hours.
_C9F19CONH ( _CH2 ) _3O at 98% _or more
(CH ₂ ) ₂ NHCH ₂ CH ₂ OH was synthesized. Next, 18.5 g of monochloroacetic acid is added to the mixture and kept under the reflux temperature of IPA (approximately 83° C.) for 30 minutes. Then, while stirring the contents vigorously,
26.1 gr of 30% by weight aqueous NaOH solution was added dropwise and reacted for about 20 hours. As a result, the objective 101gr was obtained. The yield based on the raw material C ₉ F ₁₉ COOC ₃ H ₇ is 85%. Example 2 An amide compound was synthesized in the same manner as in the first part of Example 1. Next, the solvent IPA was removed by distillation, 100g of acetonitrile solvent was added, and 13.6g of β-propiolactone was charged, followed by reaction at 20°C for 20 hours with stirring. As a result, the objective 109gr was obtained. The yield based on the raw material C ₉ F ₁₉ COOC ₃ H ₇ is 90%. When the infrared absorption spectrum of the target compounds obtained in Example 1 and Example 2 was measured, it was found that at 1680 cm ^-1

There was an absorption of [formula], indicating that amide was synthesized. Furthermore, the presence of -COOH absorption at 1710 cm ^-1 confirms that carboxylation is occurring. Furthermore, the results of elemental analysis are
The compound of Example 1 had C32.7%, H2.9%, N4.0%,
F51.0%, the compound of Example 2 has C33.8%, H3.1
%, N3.9%, F50.4%, and the respective calculated values (Example 1 is C32.5%, H2.7%, N4.0%, F51.5
%, Example 2 is C33.6%, H2.9%, N3.9%,
F50.6%), and it was confirmed that each compound had the above structure. Example 3 100 g of perfluoroalkyl isopropyl ester (C ₉ F ₁₉ COOC ₃ H ₇ ) and 100 g of isopropanol (IPA) solvent were charged into a 300 ml flask equipped with a stirrer, a reflux condenser, and a thermometer, and the contents were Hydroxyethylaminoethoxy(n-ethyl)propylamine (NH ₍ CH2CH3) _{.(CH2)3O ( CH2 ) 2-)} at room temperature with stirring.
After gradually dropping 38.8gr of NHCH ₂ CH ₂ OH), 70
By reacting at ℃ for about 20 hours, C ₉ F ₁₉ CON(CH ₂ CH ₃ )・(CH ₂ ) ₃ O was produced with a yield of 98% or more.
(CH ₂ ) ₂ NHCH ₂ CH ₂ OH was synthesized. Next, 18.5 g of monochloroacetic acid was added to the mixture and kept at the reflux temperature of IPA (approximately 83° C.) for 30 minutes. Then, while stirring the contents vigorously, add 26.1gr.
A 30% by weight aqueous solution of NaOH was added dropwise and reacted for about 20 hours. As a result, the objective 105.4gr was obtained. The yield based on the raw material C ₉ F ₁₉ COOC ₃ H ₇ is 85%. Next, regarding the surface tension lowering ability of these compounds, we will discuss similar compounds C ₉ F ₁₉ CONH(CH ₂ ) ₃ 〓
(CH ₃ ) ₂ CH ₂ COO was measured as a comparative example.
The results of measuring the surface tension of the aqueous solution by varying the concentration added are summarized in Table 1 below.

[Table] (*Weight%)
Next, the foaming properties of these compounds were measured. The measurement method was the Ross Miles method at 20°C. The results are shown in Table 2.

[Table] (*Weight%)

Claims (1)

[Claims] 1 General formula [Formula] (wherein R _f is a polyfluoroalkyl group having 1 to 20 carbon atoms, R ₁ is a hydrogen atom or an alkyl group, A
is a divalent alkylene group having 1 to 10 carbon atoms, B is a divalent alkylene group having 1 to 10 carbon atoms, Q is a divalent alkylene group having 1 to 5 carbon atoms, and R ₂ is an alkyl group or Hydroxyalkyl group, M is hydrogen atom, -
A fluoroalkyl group-containing surfactant consisting of a compound represented by NH ₄ or an alkali metal, respectively. 2. The surfactant according to claim 1, wherein R _f is a perfluoroalkyl group having 3 to 18 carbon atoms. 3. The surfactant according to claim 1, wherein A is a -( _CH2 ) _3- group. 4. The surfactant according to claim 1, wherein B is _{a -CH2CH2-} group. 5. The surfactant according to claim 1 _, wherein Q is _-CH2- or _-CH2CH2- . 6. The surfactant according to claim 1, wherein R ₂ is a lower alkyl group. 7 General formula [Formula] (However, R _f in the formula is a polyfluoroalkyl group having 1 to 20 carbon atoms, and Z is -
OR, X, or [Formula _] , where R is a hydrogen atom or a lower alkyl group, _and
(However, R ₁ in the formula is a hydrogen atom or an alkyl group,
is a divalent alkylene group having 1 to 10 carbon atoms, B is a divalent alkylene group having 1 to 10 carbon atoms, and R ₂ is an alkyl group or a hydroxyalkyl group, respectively). Amidation reaction is carried out to produce a polyfluoroalkylamide compound represented by the general formula [Formula] (wherein R _f , R ₁ , A, B and R ₂ are the same as above), and the amide compound is By reaction with a carboxylating agent, the general formula [Formula] (in the formula, R _f , R ₁ , A, B and R ₂ are the same as above, M is a hydrogen atom, -NH ₄ or an alkali metal, Q represents a divalent alkylene group having 1 to 5 carbon atoms. 8 As a carboxylating agent, general formula Y-W-
Claim 7 using a halogen-substituted hydrocarbon carboxylic acid represented by COOM (where W in the formula is the same as Q, Y is a chlorine atom or a bromine atom, and M is the same as above). Manufacturing method described in section. 9. The manufacturing method according to claim 8, wherein monochloroacetic acid is used as the carboxylating agent. 10. The production method according to claim 9, which employs a carboxylation reaction temperature of 40 to 100°C. 11. The production method according to claim 7, which uses lactones represented by the general formula [Formula] (where W in the formula is the same as Q above) as the carboxylating agent. 12. The production method according to claim 11, wherein β-propiolactone is used as the carboxylating agent. 13. The production method according to claim 12, which employs a carboxylation reaction temperature of 10 to 100°C. 14 As a carboxylating agent, the general formula W'-
COOM (However, W' in the formula is an alkenyl group having a carbon-carbon double bond and has the same number of carbon atoms as Q above, except that it satisfies the requirement that the number of carbon atoms is 2 or more. M is the same as above Q. 8. The method according to claim 7, which uses an unsaturated hydrocarbon carboxylic acid represented by: 15. The manufacturing method according to claim 14, wherein acrylic acid is used as the carboxylating agent. 16. The production method according to claim 15, which employs a carboxylation reaction temperature of 40 to 100°C. 17. The production method according to claim 7, wherein the amount of the carboxylating agent used is 1 to 2 mol per 1 mol of the polyfluoroalkylamide compound. 18. The method according to claim 7, wherein the reaction with the carboxylating agent is carried out in an inert solvent. 19. The production method according to claim 7, wherein the amidation reaction is carried out in an inert solvent. 20. The production method according to claim 7, which employs an amidation reaction temperature of 40 to 100°C. 21 Claim 7, wherein the amidation reaction is carried out using a carbonyl compound represented by [Formula] or [Formula] as [Formula], and employing a ratio of 1 to 2 moles of the alkoxyamine compound per 1 mole of the carbonyl compound. Manufacturing method described in section. 22 Using a carbonyl compound of [formula] as [formula], the carbonyl compound 1
8. The method according to claim 7, wherein the amidation reaction is carried out at a ratio of 2 to 4 moles of alkoxyamine compound per mole. 23 [Formula] is a lower alkyl ester of polyfluorocarboxylic acid represented by the general formula [Formula] (where R' represents a lower alkyl group having 1 to 5 carbon atoms, and R _f is the same as above) The manufacturing method according to claim 7 or 21, which uses.